ORGANIC SYNTHESES 1 ACETAMIDINE HYDROCHLORIDE OCs CHEN --CatOH+CI + CHACON HL cals Ais HCL cae SRF Hota = cncZNt i Oton Suite by A.W Doe Gack by Panes C, Wevon, 1. Procedure Dax hydrogen corde (Or. Sy. 2,39) (Note) spss Jato a sltion of 1 g. (2-4 oles) of throughly ry son tlle (Note 2) in 225g. of abte ety sel (Notes) com {sind in a3 weghed suction fs (Note 3) surmnded by 3 fering mistre of ee and alt uni an incteate a weight of 95 & (26 mola) fe obtained. "This requires about four hous (ote 4) Yat the tine i diminished considerably if proper rechanicl sting is wd.” The fas snow tightly stoppere, the sie arm bung stacked to eal chloe taba, and allowed to stand until the mixta ha set slid mass of ery tal Unally this roqies to or three days "A seltio of dey ammonia gas in abst cyl alcool is prepared and titrated agaist standard hydrochloric a, wing ‘ethyl orange ss the indicator. ‘The solution sould contain at leat 9p ent of ammonia by weight (Note 9) “he slid eystaline mass af acetinido ety! ether hydro orl is broken up aed traneerted to dry sorte ia hich2 ‘ORGANIC S¥IvTHESES it fs ground to « paste with s00 cc. of absolute alcohol and ‘returned to the ask (Note 6). Te is then stirred mechanically ‘with an exces of the alcoolic ammonia solution (500 ce. of 9 per cet solution or an equivalent amount of a more concen: tiated solution). "The cystals gradually dissolve and amme- lum chloride separates. After stirring for three hours the smamonium chloride I tered by suction and the trate evap trated on the steam bath to a volume of about 200 cc. when 4 considerable quantity of crystals separates. On cooling, the acetamidine hydrochloride separates In long colorless prisms ‘These ate filtered by suction, washed with roc. of cold aleoal, and dried ina desicator over sulfuric acid, Concentration of ‘the mother liquor gives a second crop. The prodact malts at 164-166 and fs ready soluble in alcobol and in water. The yield varies from 285-210 g. (Go-gr per eent ofthe theoretical mount), "The product is somewhat deliquesent and should ‘be kept in tightly stoppered bottle 2, Notes 2. The dryness of the reagents affects the yield sriously Decne af the case with Which the intermediate imido ether is hydrolyzed. ‘The hydrogen choeide mast be thoroughly dried ‘bypassing it through ‘iro wash botles containing ealfurie acid. TE the wash bottles are not effective, a tube containing ss beads mixed with photphorus pentoxide should be wed After the wach bottles, Te i wel to protect the sidearm of the ask by means of a calcium chloride tube. The absolute aleo- hol used should be a leat 99.5 per cent (Org. Sym. 6) 2. 1f commercial scetonte & used directly, the yields are poor. It should be dried over calcium chloride for atleast ‘wes, fitered, and disiled, the faction bailing at 75-817 being sed 3: Wea thinner flask ie used, there is danger of its being czadked during the experiment. ‘4. Ifa proper salty bottle ic placed between the drying train andthe Aask of acctonite, the teeatment with hydrogen Chloride does not require constant attention during this time, ACETAMIDINE HYDROCHLORIDE 3 When weaker slutions of ammonia were sed, the yells were lower 6. The grinding of the imido ether hydrochloride ts very Simportant,s lamps ofthis material become costed with ammo nium chloride, which prevents the complete action of the 8. Methods of Preparation ‘The only practical method of preparation is that of Pinner! on which the present directions are based, Phy, Br 488) 8 ab,uw ‘ALLYL CYANIDE 2CuS04+ sNaCN + s0uCN+(CN)at oNas804 (CH= CHCHaBr +CuCN > CHe=CHCHLCN + Cube ‘Sina by JV. Sepa end Sicha Car 1. Procedure A. Preparation of Cuprous Cyenide. (Note 1) —In x 64 round-bottom ask Sted with a slopper carrying a mechanical timer, a separatory funnel, and» gas ext tube lending to a good hood (Note 2), is placed « solution af 650 g. (2.6 moles) of crystallized copper sulfate in 41 of water. The fla is rr rounded by an oll bath and heated to about So°.‘The ster ie started anda solution of 255 g.(.2 moles) of sodium cyanide (ote 3) in 650 cc. of water sade from the separatory funnel ‘over a period of about one-half hour. Then the mixture i boiled until no more cyanogen gus i evolved, This requires aout Sve to ten minute “The cuprous cyanide, which begins to separate a¢ a Hight tan precipitate as soon as any of the cane salution ie added, ix lowed to settle and the solution is decanted, ‘The precipitate fs ltered, then washed with water (¢ 1) aad nally with alcool (Goo ex) and ether (joo ec). Afte? drying at 210° for about thirty sic hours, the product weighs zoo” arog. (85-90 per cent of the theoretical amount), B. Preparation of Alls Cyonide-—In a x, round bottom fas ted witha condenser (Note 4) and a mechanical ste placed 220g. (1.83 mols) of all! bromide (Note 5) snd 270 g ALIYL CxAMIDE 5 (69 mes) of dey eaprovs cyanide (Note 6). ‘The mixtre i ested ina wate bath andthe stir ttated slowly hy Had tant the enc start (oot feen to thy mane) ‘When the rection ones og, i Decne Nguou al he eating bath mut be replaced by 2 ling mare of fe and ‘ater ia ort to avid ls of product though te coins ‘Ar the vigorous reaction fat sie, the water ball tpi the meta ier staan Ge tae is nist unl ao more allyl bromide rete. "This egies about one hour. 7 bee iat ‘he coaetser the for dition and the al yan feist rom the das by heating it in en bath neh terng (Sots 7 and 8). Ujonailation te aly eynie poe fd bie st 16-r21" nth almost no "Th yd ob 105 6 (SoBe percent o the theoreti moun) 2. Motes 1. Techical cuprous cyanide dried at 11 gives at res as the secly pepe sane. 2. The cyanogen evolve inthis ection shoud be Td nt 4 fe with good suction draft Tt may te bumed i's wap Paced in the system to slo te moisture to olen { The odinary tein sodium eyanie fe. 4A very ecient condensers ead a the misters vigorously dang the fst part of the reaction. A conden the bl type about yo em. lenge etectony “Trt Tes ficient condenter ud, the appt end should Be ted wilt 4 toe leing into an empty fatto catch ey materiale 4 The aly bromite (Ore. Sym. 3) shoul be ded over calcium ctor, ftered and reid, the recto bang SE Gor7 being te 6: The cupros cyanide mast be dy, as snl amounts of tmostre reduce the pid considerably bout 1g\ per cen ‘With some samples of technical euprous cyanide a lager amount must be wel6 ocantc sunrises 41 Toward the end of this distillation itis advisable to con rect with the suction to remove the last of the ally cyanide from the sold reside in the ask. ‘8 The residue in the flask is very tary. Tt is best removed by careful eatment with strong alte acid, then with water, and finally with hot alcohol. TE necesary, the treatment is repeated several tines. 8. Methods of Preparation Allyl eyanie has been found in oil of mustard and has been prepared from allyl chloride and potassium cyanide? allyl bromide end. potasium cyanide? alll iodide and_ potas cyanide! and silver cyanide. The method decribed in the procedure is essentially that of Bruylants, who has shown that the yields are much etter when dry cuprous cyanide is treated with allyl bromide "ead ey, A325 (86 Romney ig nd 2 26 (ge plan Bl oe tim (3) 9528 2d. ine a on So TEI Kitty th "Deiat lee: Be, B19 (2.i i OO sates ol Dee é «i ete by JB Cote Wn 1. Procedere Tv 4 #1. round-botom ask Sitted with # reflux condenser, 105 & (2.3 mole) of antheaquinone, mp. 236-280" (Cor), is mixed with 109 g (0.86 mole) of granulated tin, and 750 ce of glacial acetic acid is added. The contents of tho atk aze Iheated to boiling, and in the course of two hours, 250 ce. of| x. hydrochlore add (3p. gr, 1-9) fs addin 20 ce. portions to the boiling mixture. At the end ofthis time al ofthe enthra- ‘quinone should have gone into solution; if ot, more tin and hydrochloric acid are added ‘The liquid is filtered with suction through a Gooch erucle swith a fixed porous plate (Note 1), and s00 ce, of water is added ‘The anthrone crystallizes at about 40%. After being dried on 44 porous plate, kt melts at about 153° (core). The yield fs 0g, (Gas per cent of the theoretical amount). On reerystal- zation from a 3: x mixture (Note 2) of benzene and petroleum ether about 60g. of antbrone melting at 154-135° (oom) ie obtained (62 per cent of the theoretial amount). sermon ° 2. Notes 1. The liquid can also be fltered through alate filter paper, but this is slower, 2 The proportions do not make much diffrence as far a8 the yield i concerned, but the substance is more soluble In mixtures rch in benzene. About ro-r2 ce of the 3 : 1 mixture fs requred for each gram of anthrone. ‘The anthtone may be ‘more readily disved if iis added to the estimated quantity ‘of hot benzene on the stam bath, and the petroleum ether is then added. About two-thirds of the tother liquor may. be lstlled off through a condenser and used in later runs. ‘The Fesidual mother iquor deposis about 12g. of rather impure snthrone. ‘3. Wlothods of Preparation Anthrone has been prepared by the reduction of anthe ‘guinone with tin and hydrochlouie acid! and with alumina Drone? Mee, Aan a8 5 Gor he at ay Mah 8 ehw APPARATUS FOR CATALYTIC REDUCTION Sst y Roses Anus a ¥. Vooeeens ‘Ghniel ty Hawn Gumnend $A Hae 1. Procedure L. The Apparatus (Fig. x). A Prestolite tank A from ‘which the filing has been removed (Notes), or any’ other aimar| tank of bout S101. capacity, may De conveniently sed 5 a container for hydrogen. The top of the teak contains ‘wo openings B and C. In Bis weldad «tube holding a gauge and valve, and through this tube the hydrogen from a large cylinder D is intreduced into the tank. Tn C is welded another tubo contelled by a necile valve, E is used for the vacuum, manometer G being introduced into this systom, and F for a tube leading to the reaction bottle H. Thee outlets are 20 arranged that it is posible to shut off the tank from either outlet and also to make a direct connection between the vacuum and the bottle Hy, leaving tank A out of the crit. The cons nection between the tank A ad the botle H isa heavy taped rubber tube (Note 2) which sin turn connected to's glass tube inserted through the stopper of the bottle, The rubber tube snd stopper should be high-grade and must be carefully balled with alkall before being used (Note 3). The aeangement for faking the bottle is shown In the diagram (Note 4), ‘The diving pulley is connected to the reaction botle by a wooden for preferably a metal rod. Tae rod in ura is attached by a. yoke to. metal ring which circles the botiom of the bolle. The ing opens on the back side of the bottle and fs held together bya wing:nut and bolt, In order to hold the stopper in the APPARATUS FOR CATALYTIC REDUCTION u bottle when the latter {filled with hydrogen under presure fetal stip Tis damped tightly over the stopper. Tis stip fs screwed to the Tong wooden bottle holder which extends Detween the beatings, and short wooden piece which Sts around the neck ofthe botlefsattached tothe fonger one by {beans of screws held by wingnuts. This arangemest per ‘Bis removal of the botle from the apparates without detach ing the metal strip. 1m ne chet precetions in setting up thie rection out are2 ORGANIC SvITHESES fist, 1 have every piece fee fom catalytic potons and second, to be curtain that there are ne leaks (Note 5). The later are sometimer an annoying fector and the complete apparatus should be carefully tested before attempting any reduetons for Staudazdisng theliydeogen tank, ‘The apparatus put together fn nal form with the empty reduction bottle attached to the Inydeoger tank exactly as itis arranged in a reduction, The tank is then filled with hydrogen unl the gauge cea 2.5") atm Go-45 Ibe) and the temperature of the tank recorded. "The ead ofthe gauge is observed as soon as equilibrium is reached and the bottle is then shaken for six to eight hours. Observa- tons are mae ofthe drop in pressure, taking into account any change of temperature which may occur during this time. In| sgeneral ifthe drop th pressure i less than 03 atm. (o.§ 1b) fn the time indicated the apparatus mey be considered sul ciently free fom leaks for ordinary work. For some ractians it is advantageous to heat the mixture, and the following arrangement is very satisfctory for this pur pow. The bole H is wrapped with moltened asbesus paper toa thicknes of about 5 man. and the paper is the allowed to dry. When the asbesot i thoroughly dry the bole fs wound swith a col of No. 2g Nichrome wire besinning the cll at the bottom of the bottle and making the turns about 9 me. apart. ‘The wise is then covered with & 3 mm. layer of asbestos, wh {s mobstened and allowed to dry, alter which the wire fs wound around the botile in another col from top 40 bottom, - The second col is covered with asbestos as before, and the ens of the wite are connected to the terminal wins from a source of current. These wie are led slong the bottle to the neck end held by means of tape in order to avoid excessive shaking. A variable restance in the eicuit is used to roglate the tea perature. TE Te of the Apporatns.—The tank A is fils with bydo- gen to-a pressure of 3-3.§ atm. from the eylinder 1 (Nate 6) ‘The solution, ina suitable solvent, ofthe suwlance to be reduced [soured into the bottle TT andthe plating oxi (valida (Nowe 7) The bette tach to he append eva MATUS FOR CATALYTIC REDUCTION ry sted by opening valves B and F and closing C, In the case of Jon-boiling solvents, the evacuation is continued only until the folvent begins to bel; in other cases itis continued until the Pressure as recorded hy the manometer remains fily constant. ‘The valve Eis then closed and hydrogen is admitted tthe bottle HE from the tank A by opening valve C (Notes 8 and), When the pressure in the bottle has Deeome adjusted the pressure of the daydiogen and the temperature of the tank A ste recorded, Shaking is started. Within a few minates the brown platinum oxide tums black (se Note 5, p. 93) and the absorption of hydrogen begins. The shaking is continued until the theoretical amount of hydrogen hasbeen absorbed, The hydrogen remain: ing in the bottle is removed, alr fs admitted and the mixture allowed to stand or, if necessary, shaken for few mites in ‘order to aid the settling ofthe catalyst. Ta certain cases where the catalyst setiles spontaneously at the end of the reduction it snot necesary to shake the mixtute with at. The solution ray be decanted from the main portion of the catalyst and second reduction carried out. In cases where the catalyst ca tol be used dizeey for snother rueion (ne Note 8, p- on) the solution is filtered, preferably throagh an aebestoo filter (Note se) and fresh slvent fs wel for washing. The reduction product i isolated fram the filtrate, usally hy stilling off the solvent. ‘The reduction of ethyl pritrobenzoate to ethyl ‘paminobenzoate (p, 66) and Densalacetopbenone 10. benzyl- ‘cetophenone (p36) are describe in detail inthis volume, TIL Stondardiaton of te Apporatu.— Alter making ccr- tain that there are no leaks inthe apparatus (Notes) the Byro- gen tank may be standardiued fy reucng 11.6 g (o4 mol) of pure maleic acd (Note 12) disoWed in 250 x. of 95 per cent sleobol using org. of catalyst (p. 9). ‘The reduction i carted cout according to the procedure desribed in part IL, Shaking ofthe misture i continaed until no more hydrogen i absorbed, the theoretical amount is absorbed by o.r mole of male acd within twenty or thity minutes. ‘The temperature of the tank Js recorded. The decrse in presute cormsponds to ot mole ‘of hyrlogen atthe observed temperature. If the suecnke ac“ loncasre syerHeses fs desired Ht may be recovered merely by filtering the pt rum, evaporating the alcohol and. crysaliing from about ro-ts cc. of boiling water. The yield of preduct is 10-115 g (Gu-98 per cent of the theoretical amount) depending on the care used in rystallizaton 2, Not 2. The bottom of the tank is ext off the filing removed, ‘nd the bottom welded on agi, 2. copper tube may be used for this connection bat is loss saisactory se Uh aking tends to wear it ont at the joint, 3; It is advisable to bol the tube and stopper with several portions of 20 per cent sodium hydroxide until the soltion fs ‘bo longer colored yellow, after which the boling is cared out several ties with distilled water. 4 The motor, pulley and the supports for the reaction vessel rust be attached fimly to a heavy wooden stand which will, allow as litle motion as powble in the apparetus during shak ing, thus reducing to 4 minimum the posbily of the gradual formation of leas. "The ereangement for shaking should be so made that the reaction bottle i agitated at a rate above which no dliference in the speed of reduction is observed. Ia this laboratory the rotor used is 3/30 hp., 1760 rpm, the pulley onthe motor 2.5 nin aus, and the wooden diving plley 7 em. fn radian. ‘The distance from the center of the pulley tothe ole for attach: fing the rod to the reaction bottle is 2 em, the distance from the centr of the pulley an the motor tothe center of the diving pulley tothe bottle sttachment i 30cm. Considerable latitude 1 possible in these measurements. Although the apparatus in Fig «ie readily set up in any laboratory, a more compact tnd more stable form is shown ia Fig. >. The uprights which Support the bot consist of 15cm. (one-half inch) piping sur mounted by T-couplings. The uprights, deiving pulley, and motor are firmly serewel down to heavy wink sand, An apparatus similar to this can he purchase! complete from the Standard Calorimeter Cn, Hast Moline, I ADPARATUS FOR EATALYTIC REDUCTION 18 5, Teisquite necesary thatthe welding ofthe tank i pect tnd foe from pin holes Leaks frquetly appear where the tubes are welded in the top of the tank. These may be elim inated by brazing the joints. A Tess satfactory way is to use 1 cement of lidharge and giyerel. This cement may also be ‘sed with succor on leaky velves, Occasionally Teak coca in the rubber ting o its connections with Uke botle ota, but these are unas 6, Electrolytic hydrogen was used in all expeiments, This hydrogen ie essentially fre from all impurities except oxygen, Since oxygen in general has no harmful effect upon the reduc lon pureaton isnecessary. Hf however oxygen-free hy semis needed, it must be passed overheated platinized asbestos, 1 This procedure may be varied In certain cases where it seems advantageous to reduce the platinum oxide to platinum black fa the preonce of the solvent alone (ee Note 12, p. 98).6 loncawe svxrnsses 8, During the reductions i i usually advauble not to allow the pressure in the tank Ato drop below about 2 atm. ifthe ‘eduction i to be caried out in minimum time, When the sgnuge registers 2 atm. the tank is loved off fom the reducing bottle and the presaure is increased to about 5-3. tm, by the [admission of more hylogen from D. 5, Ordinarily traces of at In the hydrogen have no deletes ‘ous efect upon the reductins. If in any experiment, absolute freedom ftom air i desir the bottle may be evacuated and refilled with hydrogen two or more tines, In this way the alt |sall washed out of the bottle ro, Whea paper filters are used the rapid auction of ir ‘through the paper In the presence of the catalyst often causes spontancous combustion of the filter. Paper filters may be sed, Dowever, if care is taken to keep the filter covered with solvent while suction i being applied; just before the last portion of solvent has run throagh, the sulin f stopped 1. Tnstead of pure maleic acd, 106g. (.2 mol) of pe ben- zallehyde may be use for the standardisation, In this ase ree of ox molar ferrous sllate Ie add to the mixture of benzalde hyde, slehol and catalyst before the reduction is started (ce Note 15, p. 98). The reduction is complete in fifteen to thirty rainutes, 1. Forms of Apparatus Other forms of catalytic weluction apparatus which may bbe used inthe laboratory have been described inthe following stiles! alan Arb, Bt 88, sp pF and Gru De, (8 iter, eter Deate ds Croce tomate Zinc tres tap er iy tans es et ah 3 fy Gon), Reman Zone, Be Bo 918) Hane ad Vane Ds om Chom Se Hts as hima Ce Bg 4s ton ana amev PARABINOSE Hytroiyisof Mesquite Gum (Gece ir 1s Canes at Be 1 Procedure ‘Five hunted grams of mesquite gum (Note 1) is dlsalved (Note 2) in 31 of cold water in a 5 round-bottom Mask; cal solution of 125g. of concentrated sulfuric acid in 89 ce. of water is added and the mixture warmed at 60° for six hours (Note 3) ina Iarge water bath. The acid i neutralized by ‘gradual addition of 140g, of powdered calcium carbonate (Note 4), and the solution with excess calcium carbonate is heated in 4 boing water bath for an hour to complete the neutralization ‘The calcium sulfate i fered off aul washed with about 21 ‘of hot water. The filtrate is concentrated in an eveporating| dish (Note 3) on the boiling water bath to a volume of 650° yoo ce. ‘The solution is transfered to a flask, using about 50 ce. of wats for rinsing, an toitis add, with wolent (Note ) shaking, twcets volume (r420-1500 ce) of 95 per cent ethyl Aleabol. The solution is decanted fom the gurmy residue and the latter extracted three times with methyl alcohol under reflux, each time with soo cc. of the selvent. In order to remove all the arabinose from the salts the precipitate ia die telved in 200-220 ce. of wate, tranaerred to an evaporating Aish and 4oo ce. of 9§ por cent chy slobol ie ered in with a heavy rom The car sleol sation is decantel and the soli terunel ice with joo e-portians of methyl aleabol PaRanisose 0 Al the alsoic extracts (both ethyl and meth) are com ined, shaken thoroughly, and 95 per cont ethyl alcohol added as long as any appreciable precipitate forms (Note 7). The folution i alowed to stand for some hours unt i & clea, decanted, and concentrated in vacuo on a boling water bath two 2 thin syrup (Note 8). Crystallization asually begins «8 soon as the syrup is col though itis sometimes neceaary to seed with arabinose, Alter crystallization has begun 109 cc. of 95 per cent ethy alcohol is sted i, taking care not to precipitate any sppe- able amount of gum. Crystallization is allowed to become complete ina coo pace, occasionally string witha heavy rod. After about two days the crystalline arabinose i Stered of and washed with 209 ce of 95 per cont ethyl aleal, To secure further crops of arabinose from the mother liquor and washings, the solvent is distilled off under reduced pressure on the boting water bath, and the resual gum dissolved in 200 = of hot methyl alcohol (Note 9). Te solution is cooled, seeded with arabinowe if mocesary, set in the refrigerator for atleast one day and the arabinose fered of, "After the Best. to crops of crystals have been secured, the organic salts that ‘orginally dissolved along with the arabinoge begin to interfere ‘with the crystallization. To remove these, the solvent dis tile off n vacuo on the bing wate bath, the ese disalved in approximately 209 ce f boiling methyl alcohol and 95 per cent ethyl alcohol added slowly with shaking until no more precipitate forms (about 40 ev ie necessary). The solution allowed to cool and is decanted from the gummy salts; the solvent is then disfled ftom the sugar on the steam bath, finally under reduced presure. ‘The sugar is dieolved in a minimum yolume of hot methyl alcahol, cooled, seeded with arabinose if necessary, st in the religerator to crystallize and the arabinose filtered of If an appreciable amount of mother liquor is obtained, a fourth crop of crystals canbe secured with ‘out aguin removing the gummy alts In this way «total yild of o-2309 of cride arabigabatag te obtained from the gum. ‘The fst two crops of erystala are easily obtained and amount2» ‘onaune s¥THEsEs ‘o approximstsly go por cet of the toa yall, The meling Din ofthe erate rogue vais rom ry 1015" “he crate powdered sae puri by beating 20 oft foe frye minster onthe boing water bath with 30 of shail acti ci allowing to cos, Hering af the seins, ‘ashing it with sco ce of of pe cnt ethyl alcool in fat os, and ding at soo", Te thn wei about 9 ieia at agar Ie may be reaped from fe ‘imc tego 7 po cet eh aol wih th eof tog ti declan charcoal, Nie, “The yald ana tay ad is the cna are now prety 2. Notes 1. Mesquite gum is collected by the natives in the south- ‘western United Stues and northern Mexico, Tt scarred by most drug stores inthis regi and may be purchased from the Martin Drug Company of Tucson, Arizona 2. If the mixture of mesquite gum end water is allowed to stand for ten hours with frequent shaking it wil form a lear felution. If dhe mistare of gum and water i heated in the Doiing water for an howr with frequent stising the gum will lio disslve but the resulting solution is turbid. 5 Most of the arabinose fs berated during the fst three hour’ heating. The longer heting fs necessary only in case the highest yield of arabinose is desired or the salts are to bbe uscd later for the preparation of galactose. No galactose Js Uberated by beating to 86° for six hour. However, rome of this sugar is produced st r00" and seriously interferes with crystallization ofthe arabinose ‘4 The salution is apt to foam over during neutralization. ‘This may be prevented by adding to the fouming solution irom time to time small amounts of rebutyl alcohol to break up the bubbles '. The solution may foam so aly that it dificult to dis Ul off he water under reduced prewar. Th checking, has paxnanrvase 2 been found possible todo wo if as much a8 200-500 ce. of butyt sleobol as been added during neutralization, 6, Mf the mixture is merely gently shaken at this point such srabinose fs contained wih the precipitate, and the yield fale to.as low as jo per cent of the amount obisined otherwise 4 Appreciable amoun's of organic salts dissolve during the ‘extraction of the sugar ard interfere sectously with the erytal liction of the latte Bost of the ste ate precipitate by audition of 95 percent ethyl alcokl, leaving the sugar in sol ‘8, If all the water is removed at this stage by heating tho ‘gum in vacuo for some ime, the sugar wil not erystallie eal. 5 Methy! sleohol, puried by distilation over qucklime, fs the most satisfactory solvent for use in crystlising, the arabinose from the gummy mixture; ethyl eleobol at this stage ‘sally causes the precipitation of gum 8, Methods of Preparation ‘The preparation of srabinoee from various plant products dna been repeatedly desried in the iterture The most ezrin: es recy inf up and recently been hown by the present author meng es, ‘he chet advantage ofthe preparation fe meno a that the material ready avaiable in large amv he ee «csp, aed the ye comparatively Lage The peent procedure isa modification of the original method of Adroon snd Sands lat ad DJ Am Chem Sz 9 so) Chr BKB. yt), oie ot Sani ee yh SES Bon eas aaah 92 8, se Handing, Sugar B, 636 (x923) [C. A. 17, 1164 (0929) ? Shs nt Sg Ch a,a BENZALANILINE (CoBl{CHO}-CeltgNEs > CeHeCH NCA HILO ‘Chciod by ese Guar tnd, Reno, 1. Procedure Tx a sone. threcneck, round:bottom flak provided with ‘ mechanical ster is placed 105 g(t mole) of benzaldehyde (ote 1), and 93. (r mole) of aniline is added. with rapid Stirring. | Aftcr a few seconds 2 reaction occurs with evolution otheat and separation of water. The mixture i allowed to Sta Hiltoen minutes and i then poured, with vigorous string, into 163 cof 95 percent alco in aGeowe. beaker. Crystal- lation begins in about five minutes, and the mixtuce i allowed to stand, frst ten minutes at room temperate, and the thirty minutes in ice water, ‘The almost solid mess i next tans- ferred to a largo Buchner funnel, Sltered by suction, pressed fut, and air did. The yldd of pure bensalaniline melting at j2° i 152-198 g. (8-87 percent of the thooretical amount) By concentrating the mother Tiquor to about half of it ‘xginal volume at room temperature or lower, under reduced pssuze by means of « water pump, aa addtional 10g. of bet Zlaniline may be obtained, Tais i of good quality and melts at sr (Note 2). 2 Notes 1. Freshly distilled reagents must be wed to obtain the ys descabed. Disilation through a column is recom: ‘mended. The benzaldehyde should be washed with § per cent sodium carbonate solution before being vacuum sted 2 Remove of the slesbol by dtilaton at oniary pee ‘sure gives a much darker product, Ee 3, Methods of Prepacation ‘These are discussed in Org. Syn. 8,13. The present method f simpler than that descetbed there and although the yells ae approximately liken the two methods, the product obatned here is purer. Excluding the drying of the crystal, the etiee roosdure may be completed in abost two fou, Benzalanlline has also been prepared! by the condensation of online and benzaldehyde in ‘iltte alcool saturated with carbon dios! 1 Be 8 ogvr BENZOHYDROL (CAB COCGH, + 2H (da-+ NaOH) > Cal:CHONC Hs (Casio! Wy}. B.Com al @M,lnnanes 1 Procedure ‘va 51 Unee-neck, round: bottom Sask ted witha mechane fea stirer and a reflux condenser with a wide inner tube, ate placed a solution of 200 g (5 moles) of pare sodium hydroxide Ina of 95 per cent alcohol (Note 1) and aco (tc moles) of benzophenone (p. 26). The stver is started and the solution iS heated to boiling unl thas trod dark brown (about twenty minutes) (Note 2). To thie brown solution 00 g, (about 2.6- § moles) of technical zine dust (about 85 per ent pure) fe added ‘over & period of twenty minutes, The solution is heated and sticed after all of the zine has been added until the brown calor has disappeared (usually about one hour). ‘The hot solution istered and Ue residue fs washed twice with a litle hot aleobol (too ec.).. The fkrate fs pourel ito five wokumes of ice water acid with about 425 cc, of concentrated hydrochloric acid (ep. gt 1.19). ‘The beazobydrol separates as white crystalline ‘mas and is filtered by suction. The yield of crude air-dried product melting at 65" is ro2-200 g (93-99 per cent of the Useoretical mount). From 300 g. of erude pvt in 200 ce of hot alcohol there is obtsined, after cooling in an esl mixture, itering and drying, 140-143 g of product multing st 68". The henzohydeol remaining in the’ mather liquors ray be provpitated with water, ENzoHYDROL Pa ¥. The directions in the Hterature usally cll for the use af absolute alcohol and potassium hydroxide. "The water present ‘in ordinary alcohol does not interfere and soliam hydronide can be substituted for potassium hydroxide. The alcohol alkalis mos easly prepared by cisolving the sodium hydroside {in 10 c. of water and then adding 1900 ce. of absolute alco, 2, Unless the benzophenone i heated with the slosolic alkali until a brown colar is produce itis imposible to get 9 reduction, Several runs were made in whic the alll was solved in the hot alcohol the benzophenone putin and the ine dust added immediately in portions, "No teluction took place. 8. Methods of Preparation ent us net he! by aan een ws inna i ee She a i Stepan ‘toa sg in ye ‘nisin bree {Marchal Ber 4, 649 (1920 oe atin, Gg hen Zot yeast Te? Amc 1 meena Save aSvi BENZOPHENONE Cilla CCW, + AIC) > CelTeCCHCHM +H CasCCUCali +140 + CotlsCOC Is +aHICL (Coke by Conary nd @ 30 Banas 1. Procedure Is a 54 twoneck, round-bottom flask Stel with a good mechanical stirrer (Note 2), a separatory funnel, «thermometer, fd a reflux condenser connected with a trap (Note 2) for absorbing the hyeogen chore evolved, ate placed 455 8. (3.4 ‘mole) of anhydrous aluminium chloride (Note 3) and 1. (102 sole) of dey eatbon tetrachloride (Note 4). The fask is sur- rounded by an ice bath (Note s). ‘The stirrer started and twhen the femperature ofthe carbon tetrachloride has dropped to 10-15", sace of dry thiopbenetree benzene (Note €) is aude ail st once. The reaction begins immediately as is indi- tated hy the evolution of hydrogen chloride and ing tem perature. As soon as the reaction has started, salt is added to the ie in Ue cooling bath im onder to get more effective coling. When the temperate bins to fall aftr the reaction hasstartd, ‘mixture of $30 ce-(atotalot 6. mole) of thiophene-free benzene and soc. (a total of 14.5 moles) of carbon tetrachloride iran in at auch 4 rate that the temperature is kept between s* and rot (Note 4). If eficiene cooling fe maintained, this addition requires ont ‘0 two hours, The sicring is continued for bout hee hours after the benvene-carbon tetrachloride Solution has been added, while the temperature ished at about ro’. The stiring is then discontinued and the mixture is aENZoRUENONY a allowed to stand about twelve hours, Daring this tne the aixture comes fo room temperature. ‘The stn i then gain started and bout soo ce. of water i slowly added. External cooling fs used in order that the water may be added store rapidly, “The exces catbon tetrachloride wualyreflaxes during tls part of the procefure. ‘The reaction mixture & then Best heated on a sicam bath to remove most ofthe execs of ean tetrachloride, then the mixture ie disled with steam to cary ‘over the remaining casbon tetrachloride (Nate 7), and to hydee: lyse the benzophenone dichloride ta benzophenone. The carbon tetrachloride comes over in about thirty minutes but the steam istlation is continued for about ane hout to lace complete hnydtolyss. The upper benzophenone layer is then separated from the aqueous layer and the latter i extracted with shout 200. of benzene. The benzune zoltion and the benzophenone are transfered to a 14. modiied Calsen fask (Ore, Sy fs) for distilation. ‘The beazeae and any water thet i presnt are removed under ordinary presure and the benzophenone fs listed under reduced pressre (Note 6). ‘The yd i 4po> 5506. (Go-Bo per cent ofthe theoretical amount based on the Denzene) of» product boting at s87-1g0°/1s mam, and soli, ing to a white solid melting at 47-48". ‘The material some- times has a blush tinge. This may be removed by mofsteing with benzene and centrifuging 2. Notes 1, The siiter should be very efficient as otherwite the suminium chloride tends to cake on theses of the ask. ‘TA makes cooling very dificult and thus increases the time neces, sary forthe ation ofthe henzenecarbon tetrachloride minfore 2, A convenient trap (Fg. 3) devised by John I Johnaon for the absorption of hydrogen chloride, o for the elination of sulfur dioride, hydrogen cyanide, et, may be arranged as shown in the figure. The gases ar Ted into a chamber in which {stream of water (frm the rex condenser in this cas) Aows downward into a large botde. The botile is provided with a2 oxcante syeriests beat tube which serves asa siphon drain, The ges are thus Drought Sato cantact witha fowing stream of water 0 that the heat of solution is dicpated, and the level of the water in the lower bottle serves a5 seal to prevent excape of the gise ito the atmosphere. Water soluble gaece sre drawn out through the siphon drain direty into the sink, ‘Ifthe gas chamber is of suticent capacity ther ie practically tno danger of water being drawn back iato the reaction ves) taut care shold he exercised when the reaction flask is cone For the reaction described here, a gas chamber about 2-5 cm, in diameter and 20-25 cm. in Tength was found tobe satisfactory ‘3A good grade of technical enbydeous aluminium chloride vas used to obtain the results given in the procedure. "The {eld falls of considerably when the quality of this reagent is ot god : 4.No diferonce in yiold fe noticed in ucing the ordinary “pare” gras of carbon tetrachloride amt the sulfurfree fms graie. TL i esl dred hy listing the commercial pode uct and rejeting the Brat 0 pr vent of the ie ‘DeNZoERENONE 0 5. This necessary to allow the reaction to stat before pack- ing in an icesalt mixture. I he temperate i too low (oelow 10°) the eaction does nat start. Ate the reaction has stated, ‘the cooling shouldbe as efficient as possible so that the mixture fof benzene and carbon tetrachloride may be added in the min ‘mum amount of time.. If the temperature drops. below the reaction is too slow. TF the temperature gues above 10° there is increasing formation of tarry matter and lowering of the yield. 6, The yield sto x0 pe cent lower if the ordinary technical aude of Benzene is used. The benzene is dred in the same ‘manner asthe carbon tetraclorle (Note 4) 7 About 1050-1139 eof carbon tetrachloride is recovered ‘This contains s small amount of benzene, However, it may bbe used in succeeding run if it dried over ealefum chlorite and distlled. No diference inthe yield is otic! when recov. fro carhon tetrachloride i wed 8, There is conslerable tendency for the beszapbenone to foam over during the eumy part of the vacuum distillation and care must be taken to prevet this 3. Methods of Preparation Fenzophonone has been prepared by the disilation of eal: cium benzoate by the action of beaaty] chloride on benzene in the presence of aluminium chlorde* by the action o phosgene ‘on benzene in the presence of aluminium chloride by the action ‘of carbon tetrachloride on benzene ia the presence of aluminium thlorde followed by Bydealysis Palit an 4), Chao 29 "Pal an GA thn 0 fs 0 Baa, Ra te hy ha sl Olver 65 Non Ts ‘ots lee aie Gua, Cha a. Fl nd Crt an cin fy() 8GB Pael Ctc ant dee er 94) e se si Ra hi) oi ing JA ChemBr BENZOYLHYDROPEROXIDE (Cut,00)/0r+Cs14ONa + CHCOOANa+ CHTTCOLCH ‘CaHsCOO:Ne+Hs$04 + CeHCOO4H+ NadiSO4 Sate by Tena, 1. Procedure Ties 5 ound bition Aa, Ste with an cent mechan ical stiner end sounded by an lost iste, ir plead SC oluon of tg. (os mol) af poe dry Sndy-pordred Benseyipeonie (up. 04") (Note 4) about fchene The temperate shoal be bow fsa ethlate, prepared by calving 29 (1 mole) of ‘ean in once of abt lesbo, and cose too, intro ‘feed fom a seperatny fennel whe the mitre vgoouly ‘tinea Ths oprtin should not require more than okt fr tn minnes “The itd whens and thicken onsiderbly gn aceount ofthe formation of voli beseypeonde ‘iter the wal eylte han een ade the sdium ben aoylproide i daalved by pouring 2 Lee ce water into the feat, wile contig he sng a kesping the tte ol (Nee) When sete mano mre an ae of on Trncyipernie, as evidenced by the fact that won of « Sel quantity of ie water profes no fortron, the talcne layer ib separated io a prviowly cole separtary ftw The aqurou solution ‘extracted with ether which takes up the etyl Bnaote, the eee is spratd, and the [BENZOVLIEVDROPERONIDE, a squcous portion placed in the orginal dask surrounded by the trcling mixture. ‘The liquid should be clear and absolutely foe from unchanged benzoylprexide. “The solution is cooled to 2° and then a cold solution of 54g. of sulfur acid (sp. gr. 1.84) in go ce. of water (lightly more than the theoretical amount) fs slowly introduced from the segaretory funnel during vigorous string. The soltion becomes tubid and whitens ava result ofthe formation ofthe hydroperoxide, but no sold should appear. There should be no evolution of gas. Oxygen & evolved if the cooling isi sufficient. The hydrpercnide appears in the form of thick ature fs poured into a separatory funnel and ex- tracted three times with 250-c portlons of eal chloroform. (Note 3) which disclves the hydroperoxide. The chloroform Js poured into a graduated cylinder, the volume noted, then poured into carefully dried Sask containing anhydrous sodium sulfate. The yield is 750-820. of «solution containing 40 8. of benzoylnydroperoride (go per cent of the theoretical amount) (Notes 4 ahd s). The use of thie reagent in oxida tion reactions is Mlustrated by the formation of styeene oxide from styrene (p. 8). 2 Notes 1. Tho benaoylpereside used eas analyzed by dislving 1g in ag cx of dry ether and adding 2c, of § per oont sum ttiylate solution, Keeping the temperature bdow ~5". The eter solution was extract with exactly 100 ce of cold water and an aliqut part ofthe aqueous extract taken.” To this was ‘added 2 ce, of § pee cent potassium iodide and 2 ce. of dilute Inydrochovic acid and the liberated, iodine was titrated with fox N sodium thiosullate solution. ‘The peroride analyzed go per cent pure 2. Generally ie notced that tle ofthe benzoylperoxide remains undscolved, causing « turbidity in the bottom of the ask. This docs not interfere with the reseton ‘3 Ethereal solutions of the hydroperonide areas stable as2 ‘ORGANIC SHITHESES chloroform solutions, but have been found to be notably Tess {Determination of active axygen: ‘The equation CARCOO:H + 2 KI-+HCL-CAECO-K + Ie + KCL+ HO see och cree oe aT calc te ee ae St cre a ee tema ete eee tom th rig cman: $= 2 we p= SE ” te hit sot apn th Weyer tet ee eee accede erates ee eee eee re ieee a ET et at ole real con Se ee bbe ad Bar har meld Peete eee et eee ae Ce “gn obese an eacgie hie ar and or oe cocina eter enon se Se ee oalis k's pom tka cade peeparstion must thercfore be card ot such a ey ue ipa bin we vo Se am le bested tn pecely por re cy edge al Soe ee ame Saiun troy When he cee naga ere aaa Seema eee vee mere cee Sr ac icy net fee alba Bs ae ea tk beers ont a8 Set at raat [MENZOYLYDROPEROXIDE = Hibbert and Bure dissolved the benzoyiperoxide in dry ether, cooled to —5" and added the ealulatd amount of 9 10 per cent sodium ethylate solution, sitainng the low tempera ture during the procalure. Sufcient ice water was added to five 2 clear solution, the ether containing the ethyl benzoate Separated and the aqueous sodiam benzoylperoxide solution fulded slowly with string to twice the necesary amount of ald 20 percent sulfuric acid (reaction mixture alrays ato). ‘The oily layer of benzoylhydtoperosde was then extracted thre times with chloroform and the extract dred over anhydrous sodium sulfate. This procedure was enrricd out by the checkers and com- prod with Tifenes's procedure, Tilloncu’s directions soem preferable for the following reacons, ‘There was much less tendency to form an emulsion when the sodium salt was extracted with eter. The emulsion in Hibbert’ methods was frequeatly persistent and the solution bacarse warm before the aqueous Solution could be separated fom the ether, thus causing decom position. A zo percent solution of sodium ethylate is dificult to handle fort erystallises and cannot be added from a sep ratory funnel. If more alcbol & added the tendency tomard formation of the emulsion is increased Th seems to the checkers that any fee alkali were present with the sodium beazoyperoxie this would certainly be new tralzed frst when acd is added before any {eee benzoylhydro peroxide i formed. AL any rate the yields by both procedures ‘were exellent. 7- Evaporation of a ehlorofore solution of benzoylhydro peroxide under reduced pressure yields a paste containing 20-50 percent of hydroperoxide. On further evaporation this soa poses into Benzole acd. A chloroform sotion of benzayl- Ihydroperoxide when careflly dvied over anhydrous sdium sulfate nto” may be Kept exposed t ight at room temperature for a number of days without appreciable decomposition, In ‘order to obtain bensoylydroperoide fee fom the eageats use in ite preparation, it is noctssary to extract the product with chloroform, such extzactonresultingin aloes of about vo per cent,3 loncante syieieses 8. Methods of Preparation Renzoylhydroperoxide has always been. prepared by the action of sodium ethylate on benaoylperoaide and subsequent acidification with dilute sulfuric acl? be nd Bat, J. Chon. S36, 24 (9. "Baer and Vil, Br 888 a5 Gox BENZYLACETOPHENONE (CUHLCH = CHOC +114) + CaLCHCH COCA: Sette Hope. J.W- Ras nd Se 4. Procedure A soucrion of 208 (0 mole) of benzalacctophenone (ote 1) (Org. Syn. a, 1) In 250¢e. of Cm, ethyl acetate (Note 2) is placed in the reaction bottle of the eatalytic reduction 'pparauus (p. 10) and 0.2 of platinum enige catalyst (p. 9a) is added. The apparatus fs evacuated, then filed with hydro- set, and the mitre shaken with aydrogen until ont tate has ‘been absorb. The time requis usally about Afteen to ‘twenty-five minates (Note 3). Tae platinum istered ff and the solvent removed fron the filtrate by distillation, The benaylacetophenone is recrystallized from about 25 cof leohol and melts at 72-73%. The yield is 17-208, (Gt-95 per cent (of the theoretical amount). 2. Notes 1. The benzalacetophenone should be freshly rerystalized from alcohol just before using and should melt at 57" 2. Owiag to the comparatively slight solubility of bencalacet- ‘ophenone in alcohol, ethyl ncetate is used as a solvent doting the reduction. 5: Hong of catalyst is used the reduction requires about ‘three hours; an increase i catalyst to 05 causes the reduction to take place in three or four minutes. The exact ime depend to a considerable extent on the grade of benstlactophenone use adit isnot certain that the very purest will neceosarly be rectuced in the shortest time, 8. Methods of Preparation ‘Benzylacetophenone has been prepared by the rection of benzalacetophenone with tine and acti acid and catalytic ally with palladium and hydrogen? by the reduction of duplo- bengylidene acetophenone manosulde;* by the oxidation of the corresponding carbinl with chromic acid « by the hydvoly- sis of ethyl benzyl benanplaetate;® from acetophenone aad benzyl horde by the action of sodamide; ® and from benzoic and hydrocinnamie acids using as catalysts manganese ov and feric oxide Seinen, Bet Msg HE) a a Hon, Aa. 28 337 ce Sas and Gin Am $8, (5. ronm,Bru acy Can a op (9 Mette Cle, er ie) Hae and Bats Cap ad, 8s) ‘Sater aod Male, Camp. in 2895 ‘ee awe cin ysxt [BENZYLANILINE CalgCHACI+ ColfaN Ha CLCHEANHCHe HCE Stal y HO, Wasa T.§ Was (Gheba by Miss Gioc at BcC we 1. Procedure A rsoorce. Bask is Gtted with a rellus condenser, « mechan- fal stiner, and x too. separatory funnel Inthe ase ave placed 372, (4 moles) of aniline (Note 1), 105g (1-25 tole) of sodium bicarbonate (Note 2) and roo. of water ‘The Sask and contents are then heated on a steam bath 10 o9-95°, and 127 g (+ mle) of benzyl ehlorde (Note 5) ran i Slowly from the separatory funnel, vigorous agitation being ‘maintsined. The addition of benzyl chloride shoald take aot Tess than one and one-alf to two hours, and the reaction is com plete in four hours. "The mixture i then cooled, tered with suction the layers of water and organle liquid separated, and the latter washed swith saturated salt solution (Note 4). ‘The araines are hen tied by shaking wth about 20, of ankytrous sodium sulphate, and ayain filtered with suction. The excess of aniline fs removed bby vacuum distillation (Notes) using « modied Claisen Mask with a fractonating side arm (Org. Syn. 1, 40). The aniline Alistls ot 81°/12 mm, and then the temperature rises quickly tw the Boling point of benzylanline,r8"/12 mim. oF 190°/16 mm. ‘When the temperature as risen to within about s* of the bol ing point of the erzaaline, the nee and the bencylaniine collect from 172 EXEVLANILINE, 2 tically all boiling at 178-182"/12 mmm. ‘The anne recovered amounts. 10 2507260g. (8o-o2 per cent of the theoretical Amount), and the yield of benzyaniline is u55-s60 g. (85-87 Der cant ofthe theoretical amount basod on the benzyl chore) The product soles oa cooling and melts at 35°36". Tt i practically colorless and suficiently pure for most synthetic purposes. A pure compound melting at 36° may be obtained by crystallizing the praact from about 120 ee of lignan (bp, 85-00"). The solution is could in freezing mixtre to cause crystallization, the crystals Sltered with suction, washed wi a litle cold ligroin,presed, and dried. ‘The recovery i aboat 99 por cent ofthe original product. 2, Notes 1. Benzylaniline reacts with benzyl cMoride to form diben- 2planiline. Tf the proportion of anne used less than that sven, the yield of benzylniine i+ lowered, and separation rnidered more dificult, 2 Sodium bicarbonate is used om account ofits high pasity and convenience in handling. Ax equivalent amount of the normal carbonate may’ be substituted, but reagents of stronger basicity inrease the proportion of high-boling by-product, ‘3 The benzyl chlovie should be frely stile! and cal- lected at 176-178". ‘Saturated alt solution is wod here in preference to water, as separation of the liquide is more rapid a lew, '. The aniline may also be quite satisfactorily removed by Aisillaion under atmospheeis pressure, axing an efient frac tionating column, the dsilacon being interupted when the thermometer in the still head registers 255° 6, Benzylanline dstis without appreciable decompastion at atmospheric presure at 296-300". It asuines, however, yellow colo, and separation from any highet-bllingimpurt more ditcult than when distillation is cieried out under reduce pressure0 ‘oRanste synTises 8. Methods of Preparation Fehr yout haa by ings ith ven ad "Ea ayy en Spe titans "an pete Sect‘ yl nl ea srt Ticks natn i son SDR i Nev sd fr evista al nd ie Bsn of Wheat fate he ptin {SSeS sis nr sae ie oye mm rete SEs Pe eo sts ES Onesxt p-BROMODIPHENYL prBrCallNaCl+ Cally + NAOH —> PBeCuH.CeHo+ Net NaC 3,0, ected tp CS Atwood Sans 1 Procedare Fonsvomnmer grams (0.25 male) of pobromouniline (Note 1) and 20 cc of water are warmed in a 4oo-e. beaker until the bromoaailine melts, and then s0ec. of concentrated. hydeo- chlorie acid ip. gf. 1-9) ie added with mechanical stiring ‘The misture ie hentod and stirred until solution & practically complote (Note 2). ‘The boaker is then set in « dish of i trate and the solution is steed ast cools inorder to precipitate the promonniline hydrochloride in fine crystals. A few small pieces of ice are added and the cold (about o-s") suspension is Aiszotized with a solution of 28 x of sodium nitrite in 36 c fof water to an end pant with starch-idide paper. “The diazotiaed solution is poured into a 1.54. widemouth Aaak or bottle which is surrounded by ice water. Tree hundred = of cold benzene is now poured into the diazonium solution, fnd by meats of «good stiver the two liguds are intimately mixed, “The mixture, which is at the temperature of melting Ienzane, is now ready forthe edition of alkali "To this well-stired mixture is added 38 cc. of 5 N sodium Inydronide solution over a period of onehall to uhre-quarters| fof an hour. ‘This may beaded drop by sop fom a separatory funnel or in portions of few euie centimeter. The addition | fof the alkali ears the formation of «yl prsiptate which, paRowoDIeHEYL “ on being stirred into the benzene, reacts with the latter and ives p-bromodipheny. 1 to much ofthis reactive “oxide” fs precipitated at onetime, some of i may decompose to dark brown product. ‘The alkali is, therefore, adled at such a rate that the amount of precipitate is at no vime greater than can readily reat with the benzene andthe sting must be eficent "The temperature during the reaction is kept at about §¢; when ll the alkali has boon added, tho mixtre i allowed to warm 1 room temperature an emulsion has formed, it may be broken by eciiying with bydruchlori acid, whereupon tm cleat layers ate obtained, ‘The benzene selution may be deed and then fractionated or preferably, it may be steam distilled In the latter case it is transferred to a t.Clsisen fk, the ask set in an of bah (Note 3) and the benzone distled. Steam is then pessed in, and after the last of the benzene is removed, the »-bromed phenyl distis withthe seam. The temperature of the ol bath held at 170" in onder to hasten the tiation, The product solids in the condenser and receiving Sask. There is obtained 25-24 g. of pBromoripheny| which melts at 5-865" ‘The crude product ie ually yellow of orange in coor ‘The color may be readily removed by dieolving the crude product in 200 ec of hot ethyl alcool ab trating this solution with s@. of zine dust and about sc, of concentrated kydro- cori acid (sp. gr. r19). This solaion is then Eltered and the Prbcomodiphenyt allowed to crystallce, This gives a. white Doduct melting at 89.5-00°. The yield is 0-21 g. 4-35 Per fet of the theoretical amount), 2. Notes +. The pbromoaniline used was somewhat colored and malted at Gag-63" 2. The volume of the diazonium solution is Kept as small ss possible in order that the proportion of benaene t water may bens large us posible. The bromoanine docs not completly sve in this quantity but i eatiey converted tothe sal“a ‘oncANIC SUNTHESES 45. There i some tendancy toward fonming during the steam istlition, To avoid thio the Bask should be submerged almost completely in the oil bath. 3. Methods of Preparation ‘pRromodiphenyl has boon obtained along with some of the ortho derivative from the bromination of diphenyl How- ever, according to Sclenk,? the product so obtained is contam- inated with some p, p-llbromediphenyl which is wery dient to remove, ‘Bamberger obtained pbromodipheny! from the faction of benzene on solid prbromobenzane diazoanhydride? ‘The method described in the procedure has recently been Aescibe in the iterature "Sel, Ane T4270 Se, or a4 mee ee ho 89 onbr bd aca J Am Chem. Se, 3990xu ‘n-BROMONTTROBENZENE CaHENO,+ Be ( Pe) > meBECHANOL HABE ‘oti by Jom Romo aed CG. GasvaRe ‘chee by Pe © Watrons nT Oreo 1. Procedure Jv a jc. threeneck, round-bottom ask, provided with an ficent fetlux condenser bearing an outlet tube held above a Suslae of water, a reo-e. separatory funnel, and a mercury ‘ele mechanical ster (Note s), is placed 270 g (2.2 moles) of freshly distil dry nitrobenzene (Note 2). ‘The jolts inthe apparatus are made of asbestos paper covered with water gass (Org. Syn, )- The Bask is heated in an oil bath maintained st 1gs-t45% and 26 of iron powder and 180 ce. (55 moles) of ‘ry bromine (Note 3) are added in che following manner: Eight grams of fron powder (“ferram reductum ") (Note 4 is added through the side neck to the stirred nitrobenzene. "From the separatory fannel Go cc. of bromine i added at such 2 rate that the bromine vapors do not traverse the condenser. ‘This addition requires about one hour, and the mixture fs timed and heated for another hour before the addition of & second portion of iron and bromine. Two portions, ech fof 8, of fron powder and Goce. of bromine ae aided der the same conditions as the frst addition, and che mixture {is sted and heated for one hour between the completion of one addition and the begining of another. The evlutin of hydro- fea bromide sackensconsklerably toward the last ofthe heating, snd there is practically no more bromine vapor condensed. * se BRONOSITROBENZENE ‘Aina addition of 2g of irom pode continued for one hour longer. ‘The reaction product, which ia datk reddish-brown liguid, is poured or siphoned (Notes) into 2. Lof water to which go cc cf a saturated solution of sodium bislGte hae been added (ote 6). The misture is dstied with steam (Org. Syn 2, 80) and the fst porton ofthe distillate ts collected separately «0 remove a stall amount of unchanged nitrobenzene, Tt is necessry to cllect about 121. of distillate in order to obtain all of the mr-bromonitrbeazene. The yellow crystalline sold is Stored with suction and press well on the funnel to remove ‘water and tracts of nitobemsene, The yield of cride product ‘ties fom 270-340 (6-75 Pr centof the theoretical amount). We melts at grs-s2” and bolls at 117-118"/9 mm. This oduct is satisfactory for most purposes If a pre mae terial fs desired, the crade aebromonitobenzene may be dis- tiled under reduced presuce. The recovery on purification is bout 8s per cent, Bribl recorded the b.p- a x38"/28 mm. and the mp. as 56° for pure w-bromonitrobenzene.! ‘made, and the heating 2, Notes +. With small amounts, upto goof nitrobenzene, mechan- rng isnot essential, and occasional shaking is suficien. 2, The nitrobenzene i dred by distillation under etmaspherc for redo presute, by rejecting the fint 5 per cent of the sitll 55. The Bromine is difed by shaking with an equal volume of concentrated slic ack and separating “4A number of other forms of iron were used, but none gave as good zesult a the “ ferrum eeductum.” 5, 11 series of sueosive ran eto be made, i is convenient to spon the resetion prodact, and cary outa second prepara: fon in the sume apparatus without dismantling i. “6, The sodium blslite faded to temove any free bromine. ‘A large excess should not be used secondary reactions may occur during the steam dsillaton. ial6 oncaNIC svNTHESEs 8. Methods of Prepersion ‘m-Bromonitrobenzene has been obtained through maito- benzene diazonium salts and by slimination of the amino sroup from 4-bromo--nitoanline* Tt has beett prepared by the bromination of altobenzere in the presence’ of various catalysts ‘The procedure given is adapted ftom that described by Wheeler and McFarlane ® "eh 2 py Cham. 883. 1 Tr yo 61, Je, ‘Rani Br ah Water and Grea, De, *Wheer and Fuk Am Chem. J. 66 (850. osexv JA BUTYL, CHLORIDE tart CHOW + HCI + te CHC HD Sebel by fas F None od Asan W. eae, (Ghee ty ee Grand He 1. Procedure Tx a sooce. separatory funndl are placed 74, of 95 (4 mole) of tersbutylaleabol (Note #) and 247 02 (5 eles) of ‘x. concentiated hydrochloric ack (p. gr. 1.19). After shaking, the layers are allowed to separate (ifteen to twenty minates) and the upper layer is drawn off and washed first with a 5 per ‘ent sodium bicerbonate solution, then with water until neutral to moist tmus paper (Note 2). ‘The chloride is treated with tog. of ealsium chloride and shaken Unoroughy, then trans ferred to. 125-ce.distligg fask Te ie then distilled, using & Jong water condenser. The fraction biting at 40.5-53° weighs 172-82 &, (78-88 per cent of the theoretical amount) 1, As itis difcat to prepare trcbutyl alooho free from water, 84 of the constant baling mixture of the alcabol and water can be used. Tais mixture bolls at 80°, contains 88.24 per cent alcaol when the ditilation is catied out at 760mm. and can be readily obtained by distiling a sample of the dilute aleobol 2. The chloride is very slowly hydrolyze hy cold water, tesnrvt ctconan ot 3. Methods of Preparation fertButyl chloride has been prepared by pessing hydrogen, lorie into the aleohol kept cold ina frecaing mixture and by isting a miacure of the kohol and a lage exces of com centrated hydrochloric acd? The method given i an in provement ofthe latter asi takes less time and largely avolds Tos of the very volatile product by seducing the number of operations involved, “edt, Ball win) 8,05 "er A: Cham 35 4xv ‘-CHLOROBUTYRONITRILE (CICH:CHACHaBe + KCN — CICHSCH:CHLCN+KBr ‘Cocke 976, Maes a © G, Groene 1. Procedure Ia 24, threeneck, ound-bottom fas, ited with sie, 4 refux condenser and a separatory funnel are placed 82, (2 moles) of potassium eyanide (95 per cent) (Note 1) ant teocc, of water. The mistue is warmed and stirred until the crnide is completdy disolved ‘To this solution is added 350.e. of 95 per cont alcohol, follomed by 158g. (t mole) of ti ‘methylene chlorobromide (Note 2), and the milxture i heated under a reflux condenser (best on a water bath) with sting for about ane and one-half hours. ‘The solution is cooled and then luted with 450. of water. ‘The oily layer of chlocontrile is collected in about. 80 ce. of chloroform anil Separated from the water solation, The chloro form solution is washed with about 125-1s0.cc. of calcium chloride solution (prepared by adding one volume of water to fn equal volume of a saturated solution of crystallized calcu chore) and once with 125-150 ce. of water, and then dried ‘over fuse calcium chloride, ‘The dried solution is then fractionally distilled in a modi fd too-ce. Caisen Aask (Org. Syn. x, 40). The chloroform is removed by distiing at ordinary pressure until the temperature reaches 120° (Note 3). ‘The remainder may be fractionated ‘under ordinary pressure but itis beter to we reduced pressure -remonosurvRostrRILe ey After two or three dsilatons the yield of pare product baling at 93-96"/26 mm. (Notes 4 ands) is 42-499. (50-70 per cent of the theoretical amount baeed on the clorobromie sod, or 42-47 per cont based on the total amount of chlorobromide taken). (Notes sand 6) 2. Notes 1 An equivalent amount (58g, 1.2 moles) of sodium ey: nid dissolved ia go ce. of water may be sed instead ofthe potas- slum salt wichout materially altering the ie, 2. The trimethylone chlorobromide used boiled at 142-147". Te may be prepared ia 75-85 per cont yislds from trimetbylene chlorohydrin (p.rr2) by the general method forthe preparation of allyl bromides deserbed in Org Sy. 1. 5 The chloroform fraction has 8 vey sttong odor of isnt tule, Only a trace is noted in the rodistiled product. “4 When the distlaton is carved out under ordinacy pre. sures (about 745 mm.) the product bolls at 194-197" The lower boling faction fs inky unchanged tsmethyl- ‘ne chiorobromide and amounts to 15-20. Tt may be reac: tionated or used directly in a subsequent ean. The high boiling residue is mainly tuimethylene cyanide, If the residues from several uns are combined and redsilled an average of 6-7 ‘er run of product boiling at 60-165"/26 mi. is abtaind, 6, Langer runs have been made and the yields are propor. tional; thus a five-mole run gives 230-245 g of chlorobutyron tile and 30-35 g of trimethylene cyanide, 3, Methods of Prepartion srChlorobutyronitle has always been prepared by the acifon of potassium cyanide on trimethylene chlorobromide + ey, Cony: en 1, 4}, Bl oe.) 4 (8805 ales 8, iti sop Con, Sear and Rae, J A Gem ei yoXVI #CHLOROPROPIONIC ACID CHs=CHCHO-HHICI— CH:CICHACHO (CH,CICHTsCHO+OCINOs) —+ CH:CICH,COH Shite y Moun ad R. Cans concede. 8 Mine an Fae 1. Procedure \ ‘a tared Erlenmeyer flask surrounded by an icesalt bath fsplaced 109 g (1-73 moles) ofacroten (Org, Syn. 6,1) (Note 2). When the temperature has dropped to ~r0 €9 15" & curent of dry hydrogen chlorie (Ore. Syn 6,64) passed ino the ato ein until it shows a gain in weight of ds g. (1.78 moles). This requies about two hous. The product thus obtained is lea, viscous, slightly yellow liquid which becomes very turbid and dack cole on standing one or two days (Note 2). ‘The oxidation of the crude g-chloropropionaldehyde is car ried out in a 2o0ce. Mask Stted with a cork stopper held by a lamp about 2 em. hove the opening of the neck. The stopper caries a mechanical ster, a sepuratery fannel, a thermometer tnd a glass delivery tube about so mm. in diameter which i connected to « water pump. The space between the stopper and the Mask is closed by winding « stip of asbestos paper around it (Note 3). Tn the flask ic placed Gg. of fuming nici aid (epg. 1.49) (Note 4), theater ix started and about one-sixth (Note $) of the crude a-chlorypopionaldehyde fs added (Note 6) very slowly through the separatory funnel. About x ec. ofthe ade hyde is added to the seid. The temperature remains constant for one or two minutes and then slowly vscs. As the oxidation somonorromoste cio es begins, oxides of nitrogen are evelved and are drawn off by ‘means of the watee pump. “When the temperature of the reac- tion mixture reaches about go* (Note 7), the flack i immersed ina water bath (at about x5-70") and the rte of aition ofthe sled is eeguated eo that the temperature of the reaction imieture fs about 3o-35°. After the addition ofthe last of the portion of the alchyie,stering i continued until the tem perature drops below 25°, This exidation requires about ‘twenty-five minutes, “The products of six successive oxidations are combined in fo. longneck Sask.” Oxides of nitrogen ate often evolved but there i 20 dangcr of violent reaction. The entre quam tity of liquid is heated gradually on 3 water bth unt the bath is boiling. "This should be done under a hood as large quant- tis of oxides of nitrogen aze evolved. After about an hour and 4 half the oxidation is complete and a yellow-brown, liquid ‘The quid is placed in « modiied Clason fask (Org Syn. t, 42) and disiled (Note 8) on an oll bath with saver pump, ‘are being takea to protect the manometer (placed in sant in fonder to avoid the pasage of a current of vapors) by a tube containing solid sodium hydroxide. A water condenser 4o- seem. long should be used. AC ist oxides of itrogen are evolved and it i dicat to obtain «low pressure. Then the pressure drops (to about 20-25 mm) and atric acid dist at 40-70". When the distilacon has neatly stopped, the tm perature ofthe bath is rabed until the baling pont ofthe die Ailing vapors reaches too". "This fraction weighs 160-170. tnd i tie acid having asp. gt. of 125-130. Tt may oontain ‘small amount of aeryic acid. ‘The condenser is now removed ‘rom the apparatus, a distling ask attached as recive, and the residue is factonated at 0mm, collecting about 4-5 g. bling up to 105° and 116-125 of f-choroproprnic acd bil Ing at :05-107° (60-05 per cont ofthe theoretical amount), The product melts at 35-g0° (purest acd melts at 42") The frac tion boiling bslow 105° contains large proportion of chlor propionic acl and shoul be redisled with a subsequent run6 loncaste SyTHESES 2. Notes 4. The acroein usad by the checker was that ebtained by isting the commercial material (stabilized by hydeoquizone) purchased from Poulene Fes, BChioropropionaldchyde is a very unstable substance which polymeriaee rapidly especially inthe prsence of traces ff hydrochloric ackd. The crude material must be oxidized Without delay ae sanding before oxidation will ese a lower- fg of the yield {5 This constitutes a safety devi, since it prevents dif san of the oxides of nitrogen, but in case the reaction becomes ‘lent it permits fee expansion ofa sudden wave of gases ‘The concentration and purity of the faming nitric acid is of considerable importance, It should have a sp. ge of not Tess than 1.9 and should leave no residue on distillation. ‘Te fs tot advantageous to work with larger quantities asan explosive reaction is liable to occur if stirring is stopped. (eis absolutely necesacy to Introduce the aldehyde into lhe tse acid. When the reverse is ettemptod the reaction starts slowly but soon becomes explosive. ‘The temperature interval mest favorable for the reaction gorss* 8. The reaction mixtere may also be worked up by pouring ft into water and extacting the Schloroprpionie acid with tether. This is less satisactory as the nitric acid is lst and ‘Some ofthe f-chloropropionic seid remains in the water. 3. Methods of Preparation ‘-Chloropropioni ac has been prepared by the hydelysis of ethylene eyanohydin with hydrococe acid and by the ‘oxidation of fechloropeopionaldehyde? or of trimethylene loroydin by nti acid. xs ant Mee, J. A. Che Sa 2, 25 or tort, Ber B87 Lio Mowe, Hall ch, 88 (os chimp 9) Bs es Mawes nd Che, a chm (OMRoiin er 843, 316 vor); Mame and Mare, Ome Ch eset so 1 en (ge Pom JA Cemxvi SCHLOROPROPIONIC ACD (ICH CH,CHOH +20(HNO}) + CICH.CH,COsH +0 Sait by Sane, Fons Cort by 08 ne a See 6 Fo 1. Procedure Is a 1, widemouth, narrow bottle immersed in running ‘water and ited with a-hole rubber stopper hong a mechan- Fea ster, a separatory funnel and reflux condenser is placed 220 of concentrated nisi acd (ep. ge. 142). "The condenser should be connected with a hood or tap to catch the oxides of nitrogen berated during the oration, The stirer is started and og. (052 moles) of trimethylene chlorohydrin (p. 112) is added om the separatory funnel during the course of fone hour. String continued for half an hour longer. Dur- Sng Ula part of the oxidation the reaction vestl is cooled with running water. The reaction {s completed by waning the reaction mixture on a seanv-bath for one hour. "The fecloropropionic acid is best isolated by direct ditl- lasion under eedced pressure (Note 1) using a 250-c. modified inion flack (Ong. Sym. 1, 40). The nitric acid ls elected up to sos"/20mm. using a water condenser. The condenser is then removed and the reskdual g-chloropropionic acid is frac- tionated,calleting as pure product the portion balling at $05 o7"/20mm. ‘The yield is 31-315 6 (54-55 pet cent of the {oretial amount) (Note 2). The product slides on cooling and melts at 48-415" emonorrorioxte Acro oo 2 Motes 4, About 30 ce. of altel acid ep. ge. 1.27) obtalned. TE ‘desired the oxidation mixture may be diluted with water and the #-chloropropionic acid extractod with ether and distilled. Some material is lost in the water by this procedure. ‘2, Larger runs may be cazred out without loweting the yield. “When a run of four times that described was made, the time of adding the trimethylene chlorohydrin was only doubled 8, Methods of Prepartion ‘These are given on ps6xv DIBENZOYLMETHANE (Phenyl-o-hydroxystyeyiketoe) CelIsCHBsCHBrOOCae + NeOCHy + CasC(OCH,) = CHCOCAH, + NaBe+ CHO CeHlsC(OCH,) ~CHCOC +110 + (CiH:C(OH) =CHCOC.H.+-CHLOH CCeHsC(OMD = CHCOCGH = CoHsCOCTSCOCate A. Procedure I a 24. roundbottom Mask, fitted with stimer and a reflux condenser, and surrounded by a cold water bath, ate placed 184g. (05 mole) of bensalacetophenone dibromide (Note 1) and 165 ce. of absolute methy alcohol (Notes 2 and 3) A solution of sodium methylate, previously prepared by die. selving 23.2 g. of sodium (s.or moles) in 23000. of absolute ‘methyl alcool, fs aided domly throogh the condenser, stising being begun as soon as the mass is fluid enough. When the addition has been completed, the whole is heated to boling and refluxed for three hours. To the brown liguid is then added 140. of water to dissolve the precipitated sodium bromide, and cough concentrated hydrochlaric acd (@p. ge. 1.39) to aeiity| the solution, when the eolor changes to a light yolow and an ‘ll separates. The acid sation is refxed two hours longer, then coo in fee-mater, siting rapidly to cause formation of| small erystals (Note 5); the Titer are acparated by filtration ‘DENADYLMETIANE a and washed once with so cc. of cold 50 per cent alcohol and then with water until ire. from acid. The iid (Note 1) of the crude, air-dried dibenzoylmethane, mp. 70-78" i 165-69 g. (59-6 per cent of the theoretical amount) (Note "The erde product f quite pre but i desired it may be rer tallied from 160 ce. of bot 9s percent alcohol. The fst erop weighs 58-62. (mp. 77-78") and on partial evaporation of the selvent leas pare soond crop of 2-3 (mp. 14-75") can be obtain 2. Notes 1. The yield depen largely upon the quality of the dbo: mide. ‘The product which gave the results deselbed in the ‘procedure was prepared by dimolving 208 g (1 mola) of benzal ‘cetaphenone (Org. Sym. 2,2) in oo ce. of carbon tetrachloride, ‘oolng the solatfon in an ie bath and edn with sirsing x60 (ile) of bromine. After the rwuction was complete the Aibromide was fltered off and washed with two as-ce potions fof hot alcool, The product obtained in this way melted at 136-157° and weighed about 510g 2 Uf eadinary methyl aleahol is used, the iol agree with the lower figures. ‘The dikstone is also contaminated by an cily substance that persists through several recrystalizations ‘The presence of water favors the climination of bromine and regeneration ofthe unsaturated Letone ‘3 The use of ethyl clasol results in an inferior prodct, mp. 65-65% “The se of sted spatula should be avoided, as traces of inom sas cause the product to be of a reddish colar. This can be removed either by a vacuum dstiltion, or by disolving in concentrated sulfuric acd and reprepitating by pouring the cid solution upon cracked ie ‘5 The mother liquor contains only 2-3 g, mote of the dike- tone, which can be urate as the copper derivative by shake ing an ethereal extract with « saturated aqueous solution of copper acetate@ oncaNic SveTHESES % Methods of Preperation Dibenzoylmethane has been prepared by the hydrolysis of “benzoyl acetic acid; by the slow epontancous decomposition ‘of aceyl dibenzoyl methane; *by the ation of metallic sodium,” sodium ethylate? sodium methylate* alchobolic potash or sdamide* on mixtutes of acetophenone and ethyl benzoate; and by the action of alcohelie potash, sodium methylte,” of sodium ethylate # on benzalacetophenone dibromide, ‘ue and Psi Bes 1034188; Pein Chem. Sa, 290 (08). Chk, Raw Sy ey A. 2). ‘iw and vo Sey 9,02) Shins, Be 3 6 oe Wise As,B yon; Se Abe J Chen So. 1, 8) ‘Hon atl and Noman An. Chen 836 (9 ce te im 8 908 ie)XIX Di-e-NMTROPHENYL DISULFIDE 2 @CICAHEANOs + Nas + NOAH SSCHNO2+ aNaCt ‘Checked by Panne C. Watewoae, W,F, Sitaram and FE Sooo 1 Procedure Iva 54, round-botiom flack fitted with @ refioe condenser are placed 360 , (15 moles) of crystalline vu sulde [Note 1) and 11 of 95 per eeat alcoho. ‘The flask i heated on s steams bath until the sulide solves. ‘Then 48. (1.5 moles) of finely ground sulfur 1 added, nd the heating fs continged wnt the sulfur has dissolved, forming brownish redsolation of sodium disulfide (Note 2). A solion of 315. (2 moles) of ‘chlorontrobenzene (Note 3) in so0 ce. of 95 per cet alcohel 's prepared in a 1. round:bottom ask fitted with a yell condenser. The sodium disulide solution is added slowly to this solution through a funnel placed in the tep of the rear ‘onvenser. The aiton should be slow until the violence of the reaction abutes somewhat. The mixture i then heated ‘ona steam bath, gently at frst (Note 4), and then at fll beat for mo hours. “After cooling, i i tend! by suction. The risture of the organie disulfide and the sodium chlcide fs transfered to rl, beaker and sted thoroughly with goo ce of water to remove the sodium chloride, It thea filtesed by suction and the crystalline residue is washed on the Ste with 100€c, of elcchol toremove any echloronitrcbengene.."The pro. uct melting at 192-195" weighs #Bo-210g. (8-66 per cent ofthe theoretical amount) Die NtrRoMMENYL DISLLEIDE 65 2. Notes 1. Crystals a dry as posible shouldbe selected. If desired, an equivalent amount of analyzed fused eodium sulide may be ‘sed. this can, solution takes a longer time. Since en excess of sodium sulfide added light inaceraces inthe amount sed are not important. 2. In eate © small amount of sodium disulfide separates in a layer atthe bottom, it should be taken up with « litle more aleahol ind added to the chloonirobenzene olution. 4 Commercial e-cloronitroberzene containing 95-98 per ‘ent of the ortho compound was used. 4 TF too muuch beat is applied st fst, the reaction becomes 8. Methods of Preparation Diconitropheny! disulfide was fest prepared by the action ‘of hydriodic acid on e-nitrobenzene slfocloride." Tt has alo been prepared by the raluction of enitrbenne sullinie ack with hydrogen bromide;? by the reduction of ethyb-nito Phenylulfonscetate with ammonium sollde;> and by the deamination of 44'-diamino-2,2-dnitrodiphenyldsallie The procedure given isthe method of Blanka as elaborated by: Woblfabr.® "ee, Be 954 (8) Che a foro Mil, 2 Fett fam Zot 36,8 ‘int, etc Sse Gao oma Chom (3 456 asexx ETHYL p-AMINOBENZOATR. 1 Procedure A souotioN of 19.56, (ext moe) of ethyl pnitrobenzoate (ote 1) in 150. of 95 per eet alcobo is placed in the reset Bottle of the catalytic reduction apparatus (p. 19) and 0. g of platinum oxide catalyst (p. 93) is added. The miztare taken with hydrogen un three molecular equivalents have bea absorbed, The time required is about seven minutes, ‘The platinum is filtered off and the slcobol removed from the Aitrate by distilation. The ethyl p-aminobenzoate, reerystal- lized from about 40. of ether, melts at 89-90". The yield 15-16.5, (91-100 percent of the theoretical amount}, 2. Notes +. The ethyl prnitrobenzoate should be fred from acd and recrystallized frm alcohol until it mes at 57" 8. Methods of Preparation Ethyl paminobenzoate has been prepared by the esterifca- tion of paminobenaoie acid and By the rection of ethyl Pasitrobenzoate with ammonium sulfide? Although commet- laly the reagent used io usually irom and water in presence of 4 litde cid, in the laboratory the catalytic reduction as described in the procedre is by far the most convenient. "Sow, 8 0 (or, Voda Meyer, Aan, 35 (6 Dime em 88 8 ah,XxI BTHYL BENZOYLFORMATE (CHHACHOMCO3H+-O(KMn0g) + CQHSCOCORE-+ 1:0 (CxHCOCO at + CoHLOH(HS0,) —+ CH1,COCO.CaHls+ 20 CuHCOCO:CsHe-+NaHSOs Call{COM(SOINS) COM CaHCCOH GONG) CONG +H.S04—+ CeHeCOCO.CaHe + NaHSO4 S024 HL Sein 2. cn Rem Da ‘Cute by CS Manor aod FB Kanone 1, Procedure ‘bea ro, carthenware crock equipped with an ecient ster and a strong motor are placed 375g, (2-5 moles) of mandeic acid (Org. Syn. 6, 38) and soo c.of water. The stirrer started, and a cool solution of 120g, (28 moles) of sodium hylroide (or 145g. of technical sulism hydroxide) in soa ee. of water is Added. This is followed by the ation of 2000 g. of cracked fce and then after a few minutes by 275g. (1.74 moles) of finely aground vs. potassium permanganate in portions over a period ofhalfan hour. The misture i stirred for one anda half hours, the temperature beisg” maintained at —2 to 4°. About Ske. of ice is nocesary. At the end of one and a balf hours the mixture is tested for excess permanganate by placing a drop fon a piece of filter paper; there i formed a black or brown, center of manganese dioxide, @ gronish ring around this, and fn outer ring which is eolreas in the abyence and pink fa the presence of excess permanganate, Any excess is removed by ding ey leo}, generally about 200-soo ce When the permanganate Bas been destroyed the aie is stopped and the manganese dice allows! to coagulate for an hour. The misture ix filtered through to so-cm, Bich ret funnel, the Alter cakes washel with soo ce. af ues (ote 1) and sucked dey agin (Note 2). The sete is ewep ated to Boo-1o00 cover & fee Bane. While the vame ‘of solution is age, two go-em. evaporating dies are sed, but tovard the ead the two slutins ae combined in one ih ‘The evaporation requis ero to thee hours. Sonus 4 lide manganese side wil be eragulated dung the rape kn and this should be removed by fie, "The yelonshsaleton fe trunsered to 51. round bottom widened Mak and cooled with runing water while fo cf encentatol sulfuric aid faded only from a separatory fanncl. "This aciicaion pros regis thirty minute and the temperature should notre much above 25% The lid froth ad aus 595, of Deni ald separates but i not ‘tered. Extraction ofthe restion mixture with 20066 por tions of ether at 1go0 ce. of extract has Ben alee snow cated out in a eparatery funnel. The cher i dled on steam buth from 11 round ottom wide neck flask con: ected witha ater condense, the extract being ade tom Sparatony fonpel a fast a4 the eter dist After meet of of the ethers been removed the heating i entnued fra tcdonl alf hour. ‘The crude liquid ac (about goog) is exoled with ranaig vate and 156 of eamentatd sfc gid i added; the Alar yellow od becomes cowl. The aid teed by the Iethod described in Org Syn. 3, sy, with the following changes all three fash, the slcobol Bas che tap, and the Cctrfetion ask are ound-ottom widened fests The sleobol fask and the usp are set on adjacent steam bath. ‘he estrieation Gas place fan ol ath which i eated Uy fre fame. A safety tbe leads from the lao Bak and dips under 7m, of mercury conan im seam tube70 oncaNIC SYNTHESES ‘This mercury safety valve avolds all dangers which from the development of excess pressure within the system (Notes). The temperature ofthe esterification mixture f kept at 105-110" and eliyl alcohol vapor is passed through ‘until so0cc. of distillate has been collected. This requires about thyce hous. ‘The distillate consists of lcobo, water, and litle erber. ‘The crude ester is cooled, an equal volume of benzene Is auded, then the free acid is neutralized by shaking with about 250¢c. of 10 per cent solution of sodium carbonate (Note 4). ‘The benzene solution is poured into 1300 ce. of «saturated solu tion of sodium bisulte (about 6g of technical sodium bisulite per 100 c), contained In a wide-neck bottle equipped with an ‘iclent stirrer, and the mixture tired for two and half hour. ‘The mixture soon yarms up a litle and becomes semi-solid 1c is filtered through a 20-cm. Buchner funnel and careflly washed, fst with 209.2. of «saturated solution of sodium bisulite, finally with two 150-ce. portions of benzene (Notes 5.and 6). ‘The white pratly aes ofthe sodium bisulfite adi tion product are transfered to a 31. round-bottom wide neck ‘ask equipped with # mechanical stirrer and containing yoo ce. of water, 175 cof concentrated sulfure acd, and s00.¢- of Denzene.’ The ask is heated on steam bath under © hood, the temperature being kept at 55°, and the mixture fs stirred for thirty minutes (Note 7). ‘The Solution is then poured into separatory fannel, the benzene separated and the water layer fextracted with a soo. portion of benzene. ‘The combined Dbenzene solution ie shaken with excess of 10 per cent sodium carbonate solution to remove free add and sulfur dioxide (ote 8). The benzene is washed witha Htle water and then dried over anhydrous potassium carbonate (Note 9). The benzene i distilled at ornary pressure over a free fame frm fa soo-cc Clasen fas, the solution being added from a separa: tory funna as fast a the benzene dit. T is advisable to dit the ester under reduced pressure although it can be done under ordinary pressure. The fraction distilling around r18*/s mam, nyot/iomm, 138/15 mm, 48/35 mm, 155°/35 mM, oF [ETHYL BEN2OVLFORMATE n 254"/76o mm, is eallected. The yield of ethyl bensuytormate Bassas & sae pet cont of the there amount) (Note ze) 2. Notes 4. In order to wash the manganese donde cake it mast bbe removed from the funnel and sired into thin paste with 2. Tk fs advisable not to stop the experiment until after Slwation since manganese diase slowly oxidizes benzoyformie ito benzo 3: If it ib nocomary to generate the stein from a can or similar contrivance, the steam generator should be connected with a safety tube dipping under 20-25/em, of mercury 4, The sodium carbonate solution contains #15. of ‘unestered acd which can be easly recovered by acication with concentrated hydrochloric acid followed by extraction vith ether ‘The benzene contains So. of impure ethyl benzoate boiling at 180-260" and containing about 20 per ceat of ethyl benzoylformate, Tn the case of the methyl cater the benzene ‘contains 6o g, of impure methyl benzoate, boiling at 170-250" and containing about 20 per cent of methyl benzoylformate, 6, If the string is not very efiient the lenzene layer shouldbe sired wih the bisulte solution second time. Longer contact with acid tends to hydrolyze the ester ‘The reaction shouldbe performed under a hood since considerable sulfur dioide is generated. ‘8. This sodium carbonate solution contane about 4 g. of Impure benzyformic ae 9, The potasium carbonate holds some ester which may bbe recovered by ading water and separating the ester layer. to. The methylester is easly made by subrtituting methyl for ethyl alcohol It bos at 250-255°/760 mm. The yield is about 175 (4s per cent of the theoretical amount) 11. This work was done with the aid of 2 grant from the2 oncante svrHeses CCyras M. Warren fund of the American Academy of Arts and Sciences, ‘3. Methods of Preparation Ethyl benaoylformate has boon prepared by the diest exter ication of the acd and by the action of oxides of nitrogen on| an alcoholic suspension of indigo? The acid has been prepared bby many clferent reactions but the mort practical are the Dbydrlysis of benzoyl cyanide, the onidaton of scstophenone + and the oxidation of mandeicack.® "chen, Ber 1438) 1, 9 Gr Sims An i.) 1 an Kalan Moan 38, soy ees a Cam Sean oo ‘Pie ast Aaermany, Be 5,3 heen a1 ta 8) Bn ny Bub, Be, 3658 ‘Sin, hi tye (9. 08). "intima, Mena, 8) Ca (odio un. cn nk, eH 48 (is. Ae Arm Ce. J. 8,50 Noakns, Jp. Chem,xxi ETHYL CYANOACETATE (CICHsCOsNa -NSCN > CNCH.CONa+ NaCI (CNCHsCOsH-+CsH1,01f —+ CNC! Conky 68 Mant, WF Touryaed SY Povtanon, 1. Procedure Isa 54. round-bottom flask 0 (5-3 moles) ofeloroacetic acid is dissolved in yoo ce. of water. The eolution is warmed to 5° and neutralized with anhydrous sodium carbonate of which About 290g. (2.6 moles) fs eequied (a alight exces of sodiom grbonate fs npt_ disadvantageous). Meanwhile ay4g. (58 oles) of soium cyanide (o7 per cent) f dissolved in 759 cc of water warmed to 55°. The diam cyanide solution then Added to the sodium chloroacetate action, which bas been ‘cooled to room temperature, with rapid rising of the two sos tions and cooing undee the water tap. The temperature rapidly rises; when it reaches 95% the solution should be cooled by adding 209 ce. of cold water and this repeated i necesay, ti the temperature no longer ries (Note a). The solution is Ineated tothe boing point and hailed for five minates (ote 2), and Gnally cooled with running water for a half hour. ‘The solution is tered if not dea, and the cyanoscetic acid set fre (hood) by adding with thorough string Gao ec. (@ slight excess) of commercial hydrochloric acid (6p. gr. 1-13) ‘The solation fe evaporated on a water bith at 60-76" (Note 3) tuner pressure of 20 jomm, and the evaporation continued tnt prarteally uo move distillate (Note 4) comes over. To ETHYL C¥ANOACETATE 16 the rsd added 600 ce. of 95 per cea aleabol. The soluion {is filtered (Note s) from the sodium chloride, and the residue [s washed with another score. portion of aleohol. ‘On evaporating the aleoholie solution under reduced pressure from a water bath held at so~6o° (Note 6) the residue weighs shout sof A mixture of 6o0cc. of absolute alcohol and to ce. of concentrated sulfur acid (Note 7) then added. The mixture fs then Heated on the water bath under a relax con ‘denser for three hours. The excess of alecbol and some of the crater formed are removed by distillation under reduced pres fare and the reside again heated for two hours with 300 ce. of| absolute alcohol and an addtional 4 ce. of concentrated sulfuric acid. The alcohol ip removed by distillation under reduced pssure nd when the eto has cole to rom temperate the follri aeid neutralized with eonowntrated solution of soda carbonate; th ester (apper Iyer) s separated a the aqueous solution extracted with ether, or preferably’ benzene; about ‘one-tenth ofthe ys rn the extract. The combined products fre phced in « 14. distilling fask and distilled under reduced pressure after the solvent and alcohol and water have boon Femoved. The ester ie collected st 94-99", chiely at 97 98"/s6 mm, (Note 8). "The ylld of a product analyzing abot 7-98 per cent ethyl cysnoaeetate amunts to 474-4926 (7 Bo per cent ofthe theoretical amount) (Note g} 2 Notes 1 If the reaction between the cyanide and chloroacetate bcomes too vigorous, Iydrogen cyanide is sot Sree and partly changed to brown material and a corerpondiag amount of pfyoolate fs formed. 2 The colar at tit stage should be yellow o light brown 43. the msture is heated to a higher temperatare there is «considerable lass due to decomposition of the eyanouctic ai ‘t Tovard the end of the dstilation, hydrochloric acd should be present in the dsilte if exes was added in the fst place. During the ailiion ofthe hydrochloric acid the 1g off hydrogen eyane,6 ORGANIC SvITHESS 5: Tels much easier to remove the st by means of a cents: fuge. Tr this method is used the sale should be washed fst with sao ec ad then with a o.ofaleabol. 6. The solution containing mineral acid must not be evap. ‘rated at high temperature or ethyl malonate wll be formed. 7. The aulditlon of sulfuric acid will probably produce slg precptate, but eis may’ be ignored ifthe orignal treat ment with hydrochloric ald was properly carved ott 8, Eihyh cyanoacetate boils at 97°/16mm., ro1*/9 mm, vor" /27 am. o, The product was analyzed for nitrogen by the Kjeldahl method, % Methods of Preparation ‘The method desc dilfers fromm that given ia. Ong. Sym. 43, 58 mainly i the use of hydrochloric acd in pace of le furie acd, in the liberation of the eyanoucetic acid from the sodium salt and in the simplified esterification process. Those ae ight but very important diferenoes an make the procedure much easier to cary out In the laboratory, Moreover, the syed age higherxxU [NITROANTHRONE o ] +10, 5| +0 toh wf Nos Shae by Kens He coed by FB Cova al Ba 1. Procedure Iiva rl beaker equipped with «separatory funnel a mechan- eal stiner, and a thermometer, 20 g. (0-+ mole) of anthrone (p. 8) B adsolved in goo ce. of glacal acetic acd. While the rixture fs kept at 6o? and sige a solution of 7 ce. of fuming nitric ack (ap. ye. 1.8) ia g0.e- of glacial acti acid is run in Aluring ane hour ‘On cooling (o about 10°) 15, of nltcanthrone separates cout in long yellowish-white needles. After the addition of roc. fof water to the mother liquor 6. more, somewhat darker in Color, crystallizes in three to four hours ‘a recrystaliztin from about joo ce. of a 1: r benzene petmoleum ether (40-60") mixture, 165 of altroanthrone melting at 142" (coe) i obtained (67 per exnt ofthe theoretical mount) (Note 1). 2, Notes 1. Ry dissolving in bot alka (about joo ce. of water and 30g ‘of sodium hysrosie per gram of nitroanthrone) and precipita ITROAN THRONE » ing with acid below 10°, the rd itroanthranol may be obtained, ‘which cn standing slowly changes bck to the ntroanthrone. 18, Methods of Preparation ‘Nitroanthrone has been prepared by the stration of anthr ene in cobuty alcool and by the nitration of anthrone.* rein wet Mace, J. Chen. Soc 1 68 (0; Mente and contr, R297). Mle and Sede som 3,490xxv PHENYLETHYLENE (Styreae) CeHLCH =CHOOAH — CallCHCH,+003 Shee by TW Ato nd Jas Jom 1. Procedure Iva soot. flask fitted with « 2¢-em. frctionating column (Notes v and 4) attached to a water jacketod condenser, are placed 148 8. (F mele) of dry pondered cinneiic acy 2 of hydroquinone and several small pices of clay plate. One-half ram of hydroquinone is alco placed inthe fask in which the dis- ‘late isto be collected (Note 2). ‘The ack is sapidly Beated ‘over a wire guuze with free fame until phenylethylene begins to dist, the heating being regulated so that the temperature of the vapors at the head of the caluran never exceeds 136°, and mmalnly remains below 120° (Notes j and 4). The elanamic acid refuxes, but very Ute should escape and cllect in the condenser. ‘The decomposition is complete jn thre nd oae half to ve hours, when no more phenyethylene disils and the lumpersture atthe head of the column rises rapily. The dis: tilate consists ofa straw-eolored ol and a lite water; « dark tary residue (50-€0.) remains in the reaction ask. About 09 eof water I added to the distilate and the aqueogs mix ture i distiled. The phenylethylene ie easly volatile with steam and separates inthe distillate ass colores ol. The oil s-18 g) is separated, dried with a small amount of calcium lode, and eatfuly dated under diminished presure, col PRENYLETHYLENE 86 {ng the condenser and reesver to o-5° by means of eed (or very cold) water. The phonylethylene i cllected at 44-45"/40 ‘or 6o-632/6omm, (Note 3). The yield fe 4o-gz GPa" per ant ofthe theoretical amount) (Note 6) 2, Notes 1 The colums consists of glass tube of 15-14 mm, internal diameter, 24 om. lng from lower end to the side sem, whic has an intemal diameter of ym, Iti Important that thee dimensions be observed in order to avoid polymerization ofthe product. Te has been found in checking that better resus are obtained by making indentations in the tube at fequent inter vals and a different anges; thee tend to reduce the number of ‘danainic acid particles which ere carried over with the vapor. ‘Acolumn ofthe Vigreux type would no doubt leo be sutable. ‘> An antioxygen such as catechol ot hydroquinone iy used to prevent polymerization, ydroquinone should be added in the ratio of one part per thowsanel unless the phenylethylene is to be used immediatly. 5: Tt the temperate ofthe escaping vapor ses above 132" appreciable amounts of cinnamic acid pass into the condenser snd the yield falls materially 4. the fractionating column does not have the exact dimensions deagnated in Note 1 the temperature of the vapors ft the head of the column will vary from thove given, How fever, no diiclty wil arise in obtaining the yield of product indicated if the general directions for heating the canamic acid, 0 as to avoid the carrying ofthe ennamic ad into the dis late, are followed 5. Phenylethylene should not be distilled under stmospheric pressure shoe the temperature (246°) eequred for the distaion| causes a considerable lose by polymerization, The decompoxt tion of cinnamic acid eannet be fected by disilation under dliiished pressure, since the acid under thew conditions dist Tolow the temperature require for decomposition (approxi nately 3007)xxiv ‘e-NITROPHENOL pe NOCAINHe + HeSO¢-+ NOs > NO;CN:OSO3H. [NOsCuHLN,O8Og1I-+120 — m NOLCHLOH-+No HHO 1, Procedure Thy a 44. beaker i place 230 of finely powered mento: aniline (Note 1), cad mixture of 450. of water and 330 cr of concentrated sulfrie acid is added with hand or mechanical string and then about Soo of finely crushed ie, When @ homogeneous mixture has rested, solution of vos. of advan trite in 250 cc. of water is added rapidly over « period of sight to ten minutes at the bottom af zhe mitre through a separacory funnel (Note 2) until a permanent color is given to sarch- lode paper (about 25-30 c. of nitrite solution eemains unused) ‘The tumperacure during dizotization should be maintained at o-5°._ Sting ie continued for five to ten minutes longer and the solution allowed to settle for another five minutes. A heavy crystalline deposit of m-aitrobenzene diazonium sulfate settles At the bottom of the beaker, from wich Uhe supernatant liquid fs decanted (Note 3) ‘While the dissbtvation isin progress 1. of concentrated sulfuric ac i added to 730 c. of water in a 51, round-bottom flask and the mixture heated to boiling (160°) with «Tage ring Dbumer. The liguar from the diaotization fs then added from 4 ccparatory funnel at such arate that the acd mixture boils very vigorously. About fly minutes is required for this addi- ‘mNITROPENOL st tion, The crstalnedazonum slate is then ad in salt portions at wich arate thatthe eld atogeh doce not cause Tos of materia by exeve foaming. Boing i continue for 2 Tow minutes longer and the contents of the ask ae potted into’ lage beaker (Note 4) set i runing cal water, a ‘igwrouly sted to obtain a bomogeacous ysl magma, ‘When completly col, the nittphenl istered, torughly posed out drained wilh sc, and meshed with several por ions of ced water, 450 in all ng ud Tei mead on large shove of ter pap and deed in warm tum. Av ts Prepare it hs a yells row appeacance with dar pa ties fntemized. "The ytd lo 1yo-80g (1-86 per eet of the theoreti! amouct) (Note) Te may be pred by reerpstalisation from hot hydo- ‘Moric ai, as recommended in Org. Sym. 3,87, bt on acount ‘ofthe dificult of tration this prcadure ie tatsactory on 4 Sal wale only. Tel preferably dite in aoorg. ot from sgoee Chien fk under so-1s mim. presre, bp 16o~ 165/23 mm, Te is Tnportant that ao ais inlet be ased to prevent bumping, sac ander thes conn It pry sublines Ent causes eouble by stopping up the connections, A ltr or Aisling fask i wed ana ociver and only sort but wide bore (1omm) alt condense is necessary. This producti pale Yolow and melts st 95-96% The pil fom soo. of crude Prt Is 180-185 2, Notes +. The mnitrosniline used in these experiments was com smercal spectnen of $84 percent rity. A les pure specimen didnot give a greatly decreased yield ‘The mnitroanline may also be added to the mixtre pee- pared by adding the ice tothe Alued acd, bu this proceure {snot quite so satisfactory. 2. The addition ofthe Sodium nitrite sluton should be a rapid as posible, If udded too rapialy, however, considerable foaming occurs@ foxcante serueses ‘5 The filtration ofthis solution fs low and usually unnaces sary. Occasionally undetermined impurities are present and then washing ofthe dazoniar salt with end water by decanta- tion, followed by filtation, comes desirable “Inthe fist part ofthe addition the solution remains pale yellow to brown but when the solution becomes saturatad with the nitropherol the latter separates as a dare oil which is not filtered of. The final volume of the eoutin i about 3.51. and the boiling temperature about 120, 5. By sing the sare molecular proportions te following ‘penitrophenls were prepared in equally goed yields fom the cor responing menttoaniliacss j-methoxy-snitopienol snd 5 nito- ‘séayleno. In the former case it eadvisable to we sighlly ‘hore ice inthe dinzotization and ad the diazonium eoktion to ‘mista of equal volames of sulfuric acid and water. 4. Methods of Preparation smNitrophenol has recently been made inthe laboratory of, ‘one ofthe editors by boiling maitrophenetle (Irom phenace {ia by nitvation, hydelyss, and diazotiation in aleobol) with Inydsabromic al, a method which fe better than that given in (fe. Sym. 3, 87, but far inferior tothe present method,% ‘onGAse SYIeTHESES 6. On increasing the scale of the preparation, the yield is somewhat higher. 1, Mothods of Preparation ‘The method given is that of Béoecken and Bostet? Phen: lene has also been prepaed by the addition of hydro tromic oF hyriodic acid to clnnamic acld and subsequent treatment with alkali? This method f slated to give higher Yylelds ut it raguires more tzme and reagents. Phenylethylene bas been prepared from phenylmethyl catbinol by distillation of the beazoie ester or by the action of phosphoric acd; flso by distiling @ phenylethyl phenyl acetate.” Phexylehy- Tene may be prepated ffom ethyl benzene by pyrogenic de- comporiton or by conversion into phensldibromoethane and tueatment of the Inter with magnesia? "ea a ante ete he Be ona oes, US anne eA Be ‘und nian. 38 ‘Kite oot Aen er tony, 108 (80. ‘ad art J ie Ch ac ae 2 ‘Onan a hepa, Sp nes (6 A240 i). ‘Situs ae Mate er B48 osXxVE PHENYLSUCCINIC ACID cance 0) )O0s1+Csll,OH+HCI + CoHsCH~C(CN)COsCaHs +HCI4-H.0 CaCH = C(CN)CO4CaH s+ NaCN + HCI» CAHACH(CN)CH(CN)COMCHH (CaHECH(CN)CH(CN) COACH y+ 540+ 2EC1 + (CA HACH(COsH)CH.CO:H + CsHAOH+ COs + sNHACI cat ‘Gnehed by B Cova snd Main Bs, 1. Procedure A. Estericaion of wCyanot-Phenslaryte Acid: —Tn soot, ound-bottom ask aitted with a eax condenser, 506. of dry a-cyanos-phenylacrylic acid (Org. Syn. 7, 20) i belad for four and a half hours with 100 ce. of absolute alchl con taining 5-4 g. of anhydrous hydrogen chloride, The resulting solution is filtered rapidly while hot and allowed to stand over: night. Long, ft, colores prisms separate which are filtered off ‘with auetion, washed with litle cold alcool and dred in air. A further small quantity may be obtained by working up the mother liquor. The melting point of the ethyl ecyanors-penylacryate is go" and the yield 45.5-53 g. (82-94 percent ofthe theoretical amount). B. Addition of Sodium Cyanide io Ett e-Cyaners-phensl- acrsate:—Twenty grams of Cyanophenylacrytic ater f treated with 40cc. of 50 per cent alcohol and 10g. of finely pow PUEXYESUCCINIE ACID ered sodium cyanide The mixture becomes warm and the ‘ester rapidly dissolves, the reaction bing completed by heating fon thesteam bath fortwo minutes, To this i adel 200 cx of Water and the resulting clear, colores sluton of the edition roduc is decomposed with hydrochloric sei. This eases the Drecpitation of ethyl «, Sieyano-# penylropionate as a yel Towish ol, which on standing overnight and blag stirred vigor. ‘oui, or seeded if possible, sets to a yllowish slid mass, "This is filtered off with suction ual wait with col water. C. Myolyis of Eth, 8-Dieyano--hemsl Propionate — ‘The product thus obtained is hydrulyzed by boiling under a reflux condenser for four hours with Soc. of concentrated Inydrochlorc acd (ap. gr- x29). "The substance goes into soe tion and this clear solution, on cooling, deposits phenylstcinic acid in small crystals which are nearly colores. These are flteted of. washed with cold water and dried. The yield of product melting at 164-166" fe 17.6-18. g. (01-95 per cent of te theoretial amount based ot the weight of ester asa) (Notes rand 2). 2. Nowe 4. The phenysuecinic acid, if slightly off color, maybe recrystallized easly fom a hot water solution by rap cooling. Five grams is dislved in goa ce. of bot water and then 6o ce more of hot wate i added. ‘This solution is Slered and cole nice water with stirring unl crystals separate, Alter standing the erystals are filtered off. The yield is 45 (90 per cent) of product melting at +672 2, The quantities of material used. may be doubled from (B) on, in which case the reoxng in (C) requires at leat a half ‘hou longer for complete solution, One run with double quant ties yielded 326 8. Methods of Preparation ‘Phenylsucinic acid has ben prepared bythe action of potas slum cyanide and alcohol upon sechorostyrene* by the tction0 foncavte sywTHESES of ethoxyphenylmalele anhydride and fuming hyo ac at 165°;* by the hydrolysis of phenyleyanopropionic acid, obtained by heating ethy! benzyidene malonate and aqueous potassium ‘yanide;? by the action of potassium cyanide on ethyl benzal ‘malonate and saponification of the product with potassium hydroxide; ¢ by the addition of hydrogen cyanide to etnyl ben- . Commettial cp. chlorplatinge acid varies somewhat fn its purity. In this work that from the Mallinckrodt Chemical Works, St. Lous, was used and gave very satisfactory results Since small amounts of impurities a the ctalyt are important factors in the rate of redtion of certain type of compounds, this question of impurities in the chloropltinic acid must be taken into account (Note 13). In a large proportion of the reductions studied, platinum aide prepared rom the ebro platinic acd mentioned gave as good results as that from spec- tuoscopically pure chloropatinc acid made according to the Alirectons of Wishers! only platinum metal is availble this ie dissolved in aqua regia and evaporated to dryness several times with hydrochloric acid, until fee from nitrates (Note 9) and the product purified cconding to the method of Wishers, (TINUM CATALYST ¥OR REDUCTIONS 9% Usp. sodium sitate could probably be wed in place of dhe co. grade im mort instances, but in one type of reduc ‘ton at least (that of aminophenols to cyclic amino alebls) the stall amount of impure in the ws. gade affected the activity of the catalyst. ‘The relation of temperature of fusian to the propetis of ‘the catalyst produced was determincd by carrying out the fusion at Vavous temperatures which were recorded by string continuously with a thermocouple encased in a Fytex glast tube, and reading tho temperature on a pyrometer, The product prepared at loner temperatures & usally Fight brown Sa color and hs a greater tendency to become calla on wast- jing. ‘The catalyst prepared at intermediate temperatures is brown in color and at 6oo* as a very deep brown color, ‘The color may vary even when the catalyst f prepared under con ditions which aze esentially the same, but ifthe temperature indicated in the procedure is used the oxide wl be satisfactory. ‘The products prepare a temperatures below 430° and above 600" have a lower activity and require a greater length of time for reduction to platinum black than those prepared temper stares between 430° and 60 1 the fasion temperature i about sco", the yield of platinum. ‘oxide is very low, at higher temperatures the yield increases, and ft temperatures of 450" and higher its practialy quantitative, ‘With a proper fasion a slightly lower ylld chan quantitative senerlly not due to nomprccptation of the platinum but 20 loss by spattering and to deposition of a small amount on the caserole 's. The brown oxke is «heavy granular powder which sets to the bottom ofthe solution in the bots in which the reduction fs cased out (p10). Te must be reduced to platinum Black before it becomes a catalyst for the seduction. When the Ihydeogen is admittal an the bote shaken the brown oxide ‘becomes black and whips up into a fine suspension, ‘The time _nccessary for the change ofthe oxide to platinum Back is called the lg. The time of lag varies usually from several seconds to {oo oF tree minutes, depenling upon thevonulitons under mb% ConcANIC SYICTHESES the platinars oxide reduced o platinum lack. In general the lag Ss short provide the reduction of the exide & carried out rmerly inthe presence of solvent if carved out in the presence ‘of solvent and substance tobe reduced, as is more fequent the fase, the character of the substance being reduced bas a consid- trable efec, and sometimes a lag of ten to Sfteen minutes bceurs. Tn eapertmeats where foreign salts are added as pro- moter of poisoas the lag varies widely, though generally within a maximum of ten to Glen minutes; exceptions occur and it teas found that the lg wat forty to sixty minutes more when the Platinum oxide was reduced in the presence of a Hite sodium Iitrite and an alcoboli solution of benzaldehyde, It s probable tlso that the temperature at which the platinum oxide sformed from the chloroplatini acd and the slvent present have some tffect on the ease with which itis reduced to platinum black. 6. Tt advisable to test for platinum in all the fltates before discarding any of them, since there is sometimes a tex- dency for small amounts of platinum to remaia i solution ‘A vory satisfactory and delicate test for platinum, descebed by Wahler, consists in making the solution acid with hyeo- chlorie acid and ating few diops of stannous chloride. A yellow color develops when platinum is present and. brown Galor when it i ia large amount. If any doubt exists as to whether or not the solution is yellow, it should be shaken with {small amount of ether; the yellow color concentrates in the ther layer, Indiating the peesence of platinum. From the Secium nitrate filtrates a large proportion of the platinum can he recovers by adding excess of formaldehyde and sodium ‘hydroxide and heating. Upon standiag, platinum black sepa- rates and may be fltered and worked up with other platinum black residues. ‘The platinum which stl remains in solution ator this precipitation can be recovered by acidifying the soe tion and heating with zine 7. Quantitative analyses show the oxide to he PiOs. #03" 1 ually contains very small amount of glaze from the eas serole, but thi docs not allect its ase or activity. The exide PLATINOM EXTALYST FOR REDUCTIONS w lisolves ony slightly in hot agua ey even after Jong heating: {ts insolube in bling concentrated ntsc ach and only slightly, for at ast only slowly, soluble in boiling concentrated Bydro- chloe acid, Constant-oling hydrobeomic acid, on the other hhand, dissolves it completely Ia the cold with the evolution af bromine and the formation of a solution of bromepatile ad from which the red potassium salt ean be readily precipitated or the solution may be evaporated and the residue used directly In a subsequent fusion '8, The platinam-oride platinum Blac, ike aay other plat- num black, gradually lose its ativiey with use._In the roc tion of certain types of compounds, notably aldehydes the fatalyat can be revived by shaking with alr or oxygen fora few minutes. Frequently this mest e done in crder to ave ‘the ceduction go to completion and often it fs deeable to do so doring 2 reluction s0 as to increase the rate of reaction In other reductions attempted reactivation as descitbed re- salts ia the complete inactivation and frequently the cong Tation of the catalyst. In reducing certin substances, the catalyst tends to cougulate in Tumps during the reduction, par- ticularly toward the end of the reduction. Tn these instances reworking of catalyst f neessary’ (Note 9) before i canbe use ‘atsfictorly fora second run. On the other hand in the reduc- tion of many substances the catalyst des not coagulate but after the reduction is complete it gradally settles if allowed to stand, land the supernatant liquid may be decanted; when a second zn i made with this catalyst fi frequently tot much inferior to now catalyst and forms a fine suspension 1 soon as shaking fs gala stated. > Platinum residues may be reworked by disoling them fn aqua regi, filtering, evaporating the Strate to dryness aking ‘up ith litle water and fosing with sodium nitrate. If organic Inaticr is present inthe chloropatinie acid, a9 is generally the fase when recover platinum aed, i wl be exis’ during the fusion and, exept in eases requiring a spectroscopially pare platinum, ssoms to have no deleterious elect. Repeatedremorking docs sem to cause an aecumulation of polson In the Catalyst_and under these conditions it should be pure as Aleseibed by Wichers? 10, Thote is always a certain amount of the oxide which ‘adheres to the ‘ter paper during filtration, so thet these ‘papers shouldbe ignited and the residue added to any platinum fatayit which has aleeady become inactive and eequire rede solving snd reprecipitation (Note 9). "tT thin lm of oxide which remains inthe caserle dlisaved by treating with a ite eonstunt-baling hyeecbro cid (Note pl; the ection obtained may: then be evaporated nd the rsd added to the next fasion mixture 2 Tr certain reductions itis an advantage to reduce the platinum oside to platinum black by shaking with Bydrogen in| the presence of sclvent only, before the substance to be reduced fs added to the mixture. More often the catalyst fe reduced fn the presence ofthe substance tobe reduced; with aldehydes for crample the platinum black is wsslly more finely divided and generally more active if prepared in presence of the aldehyde. 13. Certain inorganic salts have the eect of promoting oF retarding the action of the catalyst. 36E™ERG EE THe fa the reduction of aldehydes, fon salts ia mere traces have a remarkable efict in increasing the rate of reduction and in Inhibiting the tendency of the catalyst to lose its activity. To ‘loser extent manganese, nickel, and oer salts have the sine ‘ect, On the other hand, with the majority of substances Studied, the flect ofthese salts sto retard the reduction. ‘14. The solvent used i an important factor infuencing the rate of euetion ® and no generalization cam be made beyond the one that alcoho, either 9s percent or absolute has proved to be the best solvent for most of the compounds thus fa Studia. Ethyl acetate and glacial acetic seid may be used to advantage in some cases, 15, Palladous oxide” PAO, may be prepared by the fusion of palladous chloride with sodium nitrate, and is an fective Catalyst in hydrogenation, the mort active form being produced ‘when the fusion temperature is eo", PLATINUM CATALYST FOR REDUCTIONS ~” 3. Methods of Preparation Patnic oxide has been prepaced previously by the inter ction of platiniechoede and excese sadam hydroxide Since the catalyst itt is platinum black, the other methods for is preparation are given below: Platinum black has been prepared chiely by the reduction of chlorplatinke acid with formaldehyde; "the details have Inen improved by Wilstitter and. Hatty® Wilstitter and Waldschmidt Leitz” and by Feulgen* Wir, J A. Cha, Sc 186 (ee) Wao Cham 2p 3 98 ae "Ae hs Boe) Vos and Adis J. Am Cha Si 4, hr) Cather Ada ts ih 6 ad Se 1G, Sn ees Haun Adm ty np 9) 0) Caen ad ‘aos nep (oa) Sher an Aa hy aC) Came: tt Slane, scr tne i Pe and Adame ap oh (Ker, ee and Aus Ay spn (i) Heckel tt ham 42 Ls (QT and Any 2 ey ) Aan ad a {ep Mera Ae yop) Adem Coe ‘Gn Seton) ies aA a9 lone sy estat a ton gt ese Sense iy 7g Chan onl alist rg, he a8 (een Weber at Py, 2 tan 9 0 “Lien be Bhp be ‘Sitter mi te er A, 2 ae) ‘iianes 24 Wace te, Br 159, ‘teen er axxv SODIUM p-ARSONO-N-PHENYLGLYCINAMIDE, (Peppers) pHLO)AsCHNHy +CICHCONH.+ NaOH > pULOsAeCaH1,NHCHACONH, + NaCl HzO pHsO4AsCuHf,SHICHACONT,+2NaOH pNsgDsAeCgHANHCH,CONB s+ =110 Sid ty W. A scone aM, Hapa, 4. Procedure ‘To a solution of 139. (@6 mole) of arse acd (Ore. Sym. 13:13) n foo ce. (06 mole) of normal sodium hydroxide is added Sew (062 mol) of sodium bicarbonate and 704. (0.75 mol) at ehlovoucetamie (Org, Sym. 7, 16). The misture is heated fon a water bath to go-r60" and a steady evolution of carbon SGoside occur, At the ead of two hours, when gas evolution thas practically ceased, the mixture is cooled to 40° C, steed orowsly and 1s0cc. of «1+ hydrochloric aid poured in rap- idly. p-Arsonophenylelycnanide crystallizes at once an, after Cuoling to roo temperature, is tered by suetion and washed fee with 2 pet cent hydrochloric aeid (Note 2), then with eold tater, Tue crude product thus obtained is contaminated with ome arsnilie acid and postbly other products. These are rrmoved during purileation, The crude preduct is suspended fm about joo e- of water and with vigorous stirring, treated Carefully with 25 percent aqueous sodium hyeioxide until sla tion Is Jost complete, At this point the mixture is still acid to Titmas and an exces of sodium hydroxide is to be avoided t0 prevent decompenition ofthe product. About 15g. of boneblack SODIUM. pARSONO S:IHENYLELYCINAMIDE 101 fs added, the mixture stirred for five minutes without heating tnd sitered, The filtrate i treated during vigorous string With too.e ofr x hydrochloric acid and the pare ac at once feparnten. After colin, ite sltered by suction and washed ‘horoaghly with small portions of ice-cold water unl the iteate is pratially halogen-rce (Note 2). "The eid, without dying, is suspended i about 200 cof dis ‘led water ond with vigorous scring, cautiously (Note 3) treated with 25 por cent sodium hydroxide soltion unt de alved aad the solution reacts neutral to litmus. The solution fs then flteed through folded filter paper which should be free from soluble caeiam silts, otherwke the ilteate ill remain clouded by « suspension of the calcium sat. The dear, flatly yellow or colotss flteate fs then vigorously steed and treated with 1.5 volumes of 95 per cent alcohol. Crystallization is induced by rubbing with « rod and then an editionl volume of aloo! ie added, ‘The misture should be allowed to cool to bout 20° and stand for atleast two ous to complete the pe ‘Sptation of the salt, which shen Steed by action and was ‘horoughly with 8 per eet alcool The salt i then air-dried "The yield 75°77 & (48-40 per cent of the theoretical amount) 2. Notes 1. Frota this filtrate approximately 15-30. of ersnii acid may be recovered by just neutralizing to Congo Red. with sodium hydroxide 2 If the fre acids desired it may be obtalned by drying the product at this stage. The yield of free acd is about 109g, (60 percent ofthe Leoreteal amount) 5. If sodium hydroxide is aed too rapidly some solid pre Gpitates which doesnot rodisslve 8, Methods of Preparation ‘This procedure for the preparation of tryparsamide as Down destin the iterate cna sae J Am. Cl Se. Ay 9 satann'h Behxxx STYRENE OXIDE (CallgCH = CHs + Cel sCOO3H + CECH CH, + CoHCOLH. No” "Chee by Rovee Aout al Fes 1, Procedure To a solution of 42. (033 mole) of benzoylbydroperoxide (p. 30) in sooe, of chloroform is added 30g (6) mol) of syrene (bp. 141-143") (p. 8). The solution is kept at o* for twenty-four hours and is shaken frequently during the first hou, At the end of twenty-four hours, titration of en aliquot prt of the solution shows that only the excess of benzoylhytro- peroxide remains (Note 1). ‘The benzoic acid i removed from the chloroform solution by shaking with an excess of 10 per cent sodium hydroxide solution, the alkali is removed by washing with water, and the chloroform solution is ded with anhydrous sodium sulfate, It is then fractionated through an ecient ditling column (Org. Syn. 2, 4). Removal of the chlorofuem leaves ® practically coloress liquid which distits at 188-102° (ancorr) (Note 2). The yield is 24°26 g (70-75 percent ofthe theoretical amount). 2. Notes 1. The benzoythydroperoxide may be analyzed by mixing ‘with an excess of acidifed potassium fodide and titrating the Wberated iene with sodium thiosal ate (p. 30. 2 Tf the styrene ose iy distilled over & free fhme some STYRENE OXIDE ue decomposition takes place, indicated by the formation of water. ‘This is not observed if the products distilled from an ol bath 8. Methods of Preparation Styrene oride has previously been prepare by the action of fodine, water and mercuric oxide on styrene description of Hibbert’s method * using benzoylhydroperonde has appeared {in the literature "Founea an Tia, Canpt a8 1,196 ) ‘hier ad ur, Js Chom Se yexxx, TRIMETHYLACETIC ACID (CHa CC Mg > (CH CMe? (Ci)CMxC1+COs > (CHO CCO-M ECE (CHa'xCCO:MgCE+ 11,0 —+ (CH) COEF MeOHCL Seite SV. Persia EA. Zora, Chel by Jk Conor and tsa Bua 4. Procedure Ix a gy threeneck, round-bottom ask, fitted with mechanical strer and mercury seal soo-ce, separatory funnel land an eficient redux condenser, Is placed 6 g. (2.5 moles) of ‘magnesium turnings or powder (Note 1). The magnesium is then covered with 200 ce. of anhydrous ether, Five ce of pure fer-batyl chloride (with a erytal or two of lang) is added to start the reaction. tiring is begun and a sokation of 227 g. (21s mole) of pure er-butsl chloride (p50) in 1100 ce. of any drous ether is dropped slowly (Note 2) on the magnesium during six to eight hours. The reaction is practically complete when all the hale has been added, but stirring shouldbe eontined for ‘teen minutes anges, ‘The reaction mixture is now surrounded by an ke and salt amisture, The separatory funnel is replaced by a two-hole rubber stopper containing a thermometer (bulb immersed in the reaction mixture) ani a glass tube the outer end of which is connected to 2 mercury trap (Note 3). When the temperature ofthe reaction mixture has fallen to 0°, the condenser is replaced by a tube 10 mm. in diameter and adjuster so the end i go mm, above the surace of the eacton mixture. The reaction mix: ‘TaMETNLACENe ACD 105, ture fs stlered and carbon dioxide is added through this tube directly from a eslinder after passing through two bottles con ‘taining concentrated sulfuric acd. The carbon dioxide is added as rapidly asi s used up. The temperature is contrlled by the tate of string and should not go above +8". After two and ‘one-half to three hours the temperature falls below ‘Then the addition is continued for one-alf hour under « presure of 445 mm. (Note 3), The temperature falls to —3° to 5° at the fend ofthis time and the reaction is complete After surrounding the Dask with fc, the reaction minture is Inydeolyzed (Note 4) with 25 per cent sulfuric eid. “The seuss ton mirture fs transferred to a 2-4. separatory fanael and the ether layer separated (Note 4). The weter lyer fs extracted with our 100-e- portions of ether. The combined ether extracts are then washed with four 100-c. portions of 25 percent sodium hhydroide solution to remove the trimethylacett aid from the ether ‘The aqueous alkaline extract ie bested to 100° to remove ether and volatile imparites. The solution is then coiled with ice and acidified with 25 per cnt safari acid and the organic acid separated. The water layer eds from a 21 fask unt ao more oll solution eames over. The distillate is saturated with salt and the ac layer separated. This water layer together with the low boiling fraction from distillation of the erude tr methylacetic acd is distilled and the distilate salted out as before. ‘The combined acid layers ate distil frm a 250-e. Chisen flask connected to an sir condenser, which in tuea fe connected to a side-arm flask cooled by running water. ‘The trimethy- ascetic aii cllete at 162-165"/atm. press, 110-143/124 mm, ‘The yield, which depends somewhat on the form of magnesium, is 157-152. (61-63 per cen of the theoretical amount based on ‘er:butyl corde) when ordinary magnesium turnings ae used and 177-178 g (6-7 percent) when 2oosmesh megnesiam pow der is'used. “The acid malts at 34-355108 ‘onaamie svimses 2, Notes 1. The yield of product depends to a considerable extent upon the form of magnesium used. Either the finer commer. dal grade of tumings should be wsed or the 30 to 200-mesh povedered magnesiam that is kept in a tightly stoppered bottle ‘when not in use. The powdered magnesium makes posible @ 5-8 per cant increase in Yel, 42. The rate of ation of the halide solution is important. ‘The slower the rate the better the yleld. A delivery constant should be determined of the separatory funnel so that the solu- ‘ton can be added uniformly aver a period of sx to elght hous ‘5 The mercury trp enables the operator to adjst the fow ofthe carbon douide according to the rate of absorption, and to apply a pressure of 45 mm. during the lst half-hour. The pres- sure itself has practically no effect. The trap eansists merely ‘of a narrow glass test-tube containing mercury, and the tube fs ‘made to extend beneath the surface 4 The hydrolysis of the reaction mixture and subsequent ‘separation of the acd is the procedure given by Gilman and Parker (Org. Syn. g, 23). Sulfuric acid should be added during ‘he hydrolysis as long as any particles of magnesium are present. ‘The water layer does aot become clear, due to solidification of the ongunie aed 3. Other Methods of Prparstion See p. 110XXXI ‘TRIMETHYLACETIC ACID (CHa aCCOCHs + NaOH Bee (CHs)sCCOsNa-+H40+-CHB ro sNaBr (CHa CCOANa +1504 (CHy)CCOAH + NaTISO4 Sate by fT Sons and EW, Boss 1. Procedure Iva 5. ound-bottom flask ited with « mechanical ster is placed a solution of 530g. (8 moles) of stick sodium hydroxide (ear) in 281 of water snd the solution is cooled to 6° in an icesilt bath, To the wellstired solution 480g. (3 moles) of bromine is added from @ separatory funnel at such arate as to keep the temperature below 10" (Note 1) (fiften to twenty minutes). The solution is cooled agin too” and roo g. (1 mole) ‘of pinacolone (Org. Syn. §, 9) eaded from a separatory funnel, keeping the temperature below 10". After the solution is deol rized (about an hour) it is stirred for three hours at room temperature, "The ask is then fitted sith a separatory funnel and a con ener for distillation, and heated sith 4 Meker burner to steam ‘dsl the bromoform aad carbon tetrabromide (Notes 2 and 3). ‘The burner is then removed, the mixture Is cooled to 32°, and 4o0 cc. of concentrated sulfuric acid (Note 4) is added through the separatory funnel. The heat of neutralization causes some trimethylicetic seid to distil with water. When all the add is added the flask is heated again and the ti rthylacetc acid comes over with about 40 ce. of water. When [TRINETHYLACETIC ACID 10 all of the trimethylacetle acid (70-80 :) has dstiled, a lguid heavier than water begins to come over. The dstilation I stopped and the ald separated from the water in separatory funnel and dried cither with calcium ehovide or by dsiling with benzene which cares overall water (Note 3). The tt tnethylacetic aid is farther purified by distillation under reduced pressure. Tk boils at 5-78°/20 mm. and the yields 63-65 smelting at 34-35". ‘The water loyer is extracted with two roo-ce. portions of ther, ‘The combined ether solutions are dried with calcium chloride, the ether distilled, and the residue fractionated under rechced presse, sing 2 modified Claisen flask (Ong Syn, 40) ‘Ten to twelve grams ray be obtain in this way. The total syed ie 72-75 @ (74-74 per cunt ofthe theoretical amount) 2. Notes 1 The temperature must be Rept low duving the reaction to prevent formation of sodium brome, 2 The reaction between sodium hydroxide and tibromo- pinacolone is ot complete at room temperature. Heating in| {his manner, rather than separation in the cld, results in an ease of 10-15 percent in he yield. ‘The bromoform passes over withthe steam rather rapidly In some runs some carbon tetrabromide was also obtaine ‘Toward the cn of the steam distilation a heavy ofl that more or les ofa lachrymator may come over. This is undoubt tly brominated pinacoloae. The bromoform may be puried by vacuum estilation, One run gave 115 of product, boing at 78-79"/22 mm, “4 An equivalent amount of hydrochloric acid may be used without affecting the yield {5 The trimethylaceie acid is dred very esily by distling vith about 50ce of benzene at ordinary pressure nti all ofthe tater is removed and then the residue is dist under reduced pressure10 oncasie s¥meses 3 Methods of Preparation ‘Trimethylcetic acd may be made by the hydrolysis of tr: butyl cyanide with weak hydrochloric acid at 100°! It ie also obtained by oxidation of trimethylpyroracemic acid with silver oxide or potassium dichromate and sulfuric acd,® by ‘oxidation of ter-butylethylene with permanganate solution,” ‘ot by oxkation of dimethyl 2,z-propanol with chromic aid Schrocter reports the formation of trimethylaceic acid by rear rangement of the oxime of trimethylacetephenone to give the anilde of trimethylacetic acid, which can be hydrolyzed to sive the a "The method given in these directions © may be modified by ‘using potasium hypochorte* or chromic acid * as the oxidising agent. ‘The dizcetions given in Exp, XXX by the restion of kr Dbuty! magnesiam chloride and cazbon dioxide are an improve- ‘ment on those desribed by Bouveaut.” Dato, Ane 16 sr "len tr 187 (et) ‘Panis Scans 4) or) ‘Penton 9s Gt) ‘Sco, Ber Hyco ‘Mid ed any Blk im 7, 0 "Dame, Rech 59 "sell and Sv Bee (99) ‘Dect, Cape ea 18,08 (omXXXIE ‘TRIMBTHYLENE CHLOROHYDRIN HOCH.CHsCH,OH-+HCt— CICH.CH.CH.OH-+1,0 1. Procedure A too, round-bottom wide-mouth fask (or a large test- tube 18 cm. long and 4.5 em. wide) is ted with a rubber stopper carrying separatory funnel, a thermometer, a inlet tube reaching almost to the bottom af the flask and an outlet tube leading to a condenser se for downward distillation. A receiver consisting of suction flask is attached tightly to the end of the condenser and the side arm of the receiver fs attached to 1 efux condenser. A tube isle from the top ofthe condenser to the hood in order to take care of excess hydrogen chloride during the distillation, or better the apparatus described in Note 2, p. 27, is used. About 25-so.e. of trimethylene glycal (up. 210-215") bs placed in the Bask and heated by means of an ofl or metal bath to 130-170". A sery rapid stream of dry hydrogen chloride (Note :) is now led into the hot glycol through the inlet tube A reddish distilate consisting of wate, t ethylene chlorohydrin, hydrogen chloride and some unchanged slyeal begins o dist” As rapidly as the glyo! is used “up in the reaction ask, more is added fom the separatory funnel Tt is always advibable to Keep the amount of material in the reaction flask as small as possible The rate at which the Ihydrogen chloride is pased through the flask contrcs the seace tion and also has « marke effect on the yk! (Note 2). The Dest resus are obtained by passing In the gas rapdly enough ‘TRIMETHYLENE CHLOROHYDRIN 413 to use up 23 of trimethslene glycol in one minute, The proces continuous and ean bern nde without change {ng the apparatus "The weight of crude distil fom 1800 of trimethylene glycol i esualy 2300-2300 "To obtain the Winethyene clorkydrn the dilate from this operation i heated for about one howe on a seam Dath inorder to deve out must of the aces hydrogen chlor, The dstilate Ys then factionated. under relued presure (Note 5) ia a modifed Clase Mask (Org. Syn r, 40). The fratonting sie ar soul be 25min length,” The actions collected under om. are: 10-55% 55-57% 51-65, 65-85% 5-15", residue. Belo a frther fractionation is cari ox the residue is discarded the portion bong at 85-105", costing chil of ‘nchanged triethylene gy, bse aside for we ima Inter preparation; the ow-boing portion p to 55° consating relay Sfwater and bydrogen corde with sme timethylene chlre (Note 4) and trimethylene chloahyésin, enewtrlind carefully ‘with powdered safum carbonate. Two layers form and te Upper containing the chlorohydrin ie separate, died over suhydrovs potassium carbonate and agin replaced a the portion Toting up to 55%. Another cpetefrsctonal dilaton, carved out in te usual may, is now’ made excep that te high (st fraction baila at 6 8"/s0 mm. ‘The material bolingsbove Gs" /so mm. chil trimetylene sXyel and is wad in seceding experiment. The fal ped ff triethylene chlorohydrin [Note boiling a 60-4" 10, is 835-1000, from Boog. of trnetiyene gly (50-6 per cent ofthe theoretical amu) and s0-450 6 of trimetiyene ye i recovered 2, Notes 1. The hydrogen chloride msy be generated by any method osined. Since a large quantity of gas is required, the procedure deveibed (Org. Syn. 2,20) is rather expensive. A more satis factory arrangement isto hal il a 121. tsk with @ paste of sale and concentrated hydrochloric acid al rn ft this comesmorcal sulfuric acid. The gas ie died by a single wash bottle of sulfur acd Ti sulfuric and hydrochloste ack are wed then for the con- version of 1800 of trimethylene glyeal, a 204. bottle hall- filles with concentrated sulfure acids treated with concentrated Inydrochlric acid introduced through a tube reaching 10 the bottom. The hydrochloric acd is adda at the rate of 52-40 drops per minute, Two charges of sulfuric acd ere needed and 2 total of about 24 ky. of hydrochloric acid 2 The yield of chlorohydrin is largely determined by the rate at which the reaction carried out. A very rapid stream of hydrogen chloride is absolutely esenial for obtaining the yiekis mentioned. Moreover, it x very important to keep as Small an amount of glyeol as posible in che reaction fask. If Jacger amounts of glycal are present at any one time, the yield of produc is lowered and considerable tar is produced 3: Trimethylene chlorohydrin cannot be distilled under atmospheric pressure without seme decomposition, The frac ‘onation can be carried out at ordinary pressres when the fractions collected ae up 10 125°, 125-138, 158-164", 164 go", 1go-210" and residue, This’ procedure i less desirable as some hysrogen chloride is evolved and the product turns dark on standing 4 The portion boiling up to 55*/1omm., obtained after the second fractionation, was washod with concentrated sulfuric acid, then water, and finally red and distil. A certain ‘amount of trimethylene chloride was sometimes obtained, boiling fat 115-120" and amounting to about jo pet cent ofthe total ‘action ‘5 The chlorohydrin contains a very sll atnount (les then 5 per cent) of waterinsluble material, which is probably ‘timethylene chloride and dl-y-cbloropropyl ether. 3. Methods of Preparation ‘Trimethylene chlorohydvin has been prepared from tr- methylene ilyeol by the action of dry’ hydrogen chloride [TRIMETHVLENE CHLOROHYDRIN us ‘under various conditions; * by the action of aquecus hydrochloric acid; and by the action of sulfur chloride? Tt has also been prepared from y-chloropropyl acetate and methyl alecbalic hydrochloric acid "Reo Aan. chi poe (6) M, op (809: Maken a Leb yl Chen 7 rol, arene A ace Fone AL, 0) (Chm. Zme Ui sp, Der tnd Bash AmCham. Son 3h oi) Raton each Fee AL (ot) CAH ses Noni aod Ali, J Ay Chem So 88, mee Hama, Dar, se Cathe, Am Chon 8 90. "Desa Bl, Am Cee ab (0. ‘rer, all A oy Bel ik 8 38 Ge)xxx ‘TRIPHENYLAMINE (Cells aNT1 4 2CoHl+ 52005 + o(Calle)N'$2KTLHLO-LCOs 1. Procedure Is #1 throonec, round bottom dak, ited with very stint mechaial ser, a robe, sepacaary Tanne aad Jnrge aicovted res conenser (Note), the upper art ct ist owned staal to vera ae oe lense, are placa 176 (so4 mus) of pond diphenfasae (Note) 044 {0 mol) of othenten, 11 of alcubensene (Note 3) 138 g (F mol) of nny powdered. anbydeous Pet rat i pe er Nae) reaction mintte then sted wey” igrouy Dota at sud a sate thatthe hlvobnene Condens fa the upper third of th src eh condense and ows back ian almost steady team. The water formed in he seaton sss over, fogether wits all umount of alttobenzen ae Idobenzene, and is condensd by the water-cooled con lense ‘This slate fe of water by aking mith smal quay of soi waliate and retort intervals tough he spar tory fanael to the reecton flask Tating i ontnucl for about twenty four oars or unt te ection is completa aa enced by the no evoltin of water (Note 5 The reaction mine i lowe to col somewhat and ie ‘hen transfer to 51 fas, al the nluobensne tapther vith a Title of the exc digheaplmine is moved by steam Aistacion Dering dita the lack shou be he to ‘rmummexyLAnone 7 prevent excesive condensation of steam (Note 6). Steam dis tllsion should be continsed until liter of distillate contains Tess than 3 cc, of water-insoluble material (Note 7) “The reaction mixture & cooled and che crude amines which separate are collected on a sction funnel and washed twice ‘with goo-e, portont of water. ‘The filtrate and washings Thould be saved for the recovery of fine (Note 8). The pre- Cipitate on the funnel ls transferred to a 2. beaker, dissolved fn about 11. of benzene, filtered, and the benzene-insoluble pert washed three times with 73: portions of benzene. The benzene solution and washings are combined and separated ‘mechanically from as much water aa is possible. ‘The water is thea completely removed by distiling wat the distillate comes lover cleat, If nccessay, dry benzene is added to the solution Sn onder to ave a inal volume of about 1200. ‘When the water is entirely removed, the benzene solution is cooled anda excess of dry hydrogen eblorde is paseed into i to precipitate the diphenylamine asthe hydrochloride (Note 9). ‘After standing about three hours, the diphenylamine hydro- oride is filtered and wathed with benzene (Note 10}. The benzene is distilled from the fate (Note 11) and the residual triphenylamine is transfered toa s20-c. modi Claisen Mask (Org. Syn. 40) and cited under reduced pressure. The first fraction ‘consists of some benzene, then the temperature rises rpily and a few cubic centimeters of deeply colored di tillate comes over just before the amine faction, which i cl lected at 195-203%/t0-12 mm. The distlate is «yellow liquid which soon sles toa light yellow slid, The side arm of the distling Bas should be of rather large bore (about to mm.) to prevent clogging by the amine which sldies. The crude product weighs 220-235 g- and malts at 120-124% Tn order to obtaia pure product the amine is disalved fn about 700 ce of boing ethyl acctate under a reflux condenser ‘When the amine has dieolved the solution is rapidly cooled and stired, whereupon the amine separates ia almost white rystals Further crops of crystals may be obtainel om concentrating the solution and cooling. The last portions may be colored, ut oneus foncawic sunmueses ceystallization from ethyl acetate gives «nearly colorless product (Note 12). The total yield of pale yellow product which melts at 126" is 200-240 g. (82-85 per cant of the theoretical amount) (ote 23). 2. Notes 1. The sis condenser used here was 65 em, long and of gnu. bore and the vertical water condenser, 4o em. in length, Cork stoppers were used and it was found desirable to protect their exposed surfaces by coating them with water glass, allowing these to dry, and then coating with ead foil. Tes best to bol the mixture on a sand bath and to cover with asbestos that part of the flask not finmersed in the sand 2 Technical diphenylamine which has been vac di Ail and collected over a 5" range (159-263°/4 mm) is sat- istactory 45 The nitrobenzene should not contain eny five act ‘Should there be fre acd present, i can be removed by shaking ‘with sli potassium carbonate. 4. “ Natur Kupfer "is a good catalyst, but ordinary cop: per Bronze may be sed 5 The time requited forthe completion of reaction varies withthe rate of sting, When the string is very vigorous ‘most ofthe water comes over within twelve hous, 6, This heating should be done carefully, preferably on sand bath, because of the danger of bresking the flask due to the caking of some undiselved potassium carbonate. 1 Tn generat, about 10. of aqueous dstiiate is required, and practically all but about 25 ec. ofthe nitrobenaene is recov” cred. It is recommended that the removal of nitrobenzene by steam disilation be fey complete in onder to avoid a gummy residue 48. Most ofthe iodine can be recovered as potassium fodide sized with some potassium carbonate. A litle cuprous fodide also present, 9. The hydrogen ehovie fe introduced through a. delivery tube at lest 25mm. in diameter an! about soem, under the ‘rerenEYLAMINE 19 surface of the lig, f the esis intduce apd enough fn the mature occasoaly aie there ie one with Slgging ofthe dalvery to fo The crude diphnyamine may be recovered by decom ving the hydnchlre nh water an tring the mitre Te A lange amount of Byogn erie is eave ing the dilaton and some provision mst ae to Ke ot ofthe eo Be iis Bees of the loser city of rphenplamine in ethyl lei his salvent may be asd advantageous fn wh ing the cytls and in recrystalising small anuants of the compound wy N Phenyl easasle ay be made in an analogous man ner by wing crust in pace of dghenaine. It srng Ed eating are Doth very goo, eve oor sac for he feacton, The ye of pied oct i abt 83 per cent {nd thecompoutd melts at 88-897 ‘The rsa when ered, Si tong vot ih 8, Methods of Preparation ‘This procedure is a mosifcation of the method of Goldberg and Nimerovsky.)Triphenylamine has also been prepared by the treatment of anne or diphenylamine with potassium and then bromobenzene ? and by the action of sodium on dipheny- aunine and bromobenzene* ahr and Nimoy, Bet 2489). era Wey assy Ryka, Be sesLATER REFERENCES TO PREPARATIONS IN PRE- CEDING VOLUMES ein soa a ate pute pre a a St seaport the we page Ogee Sy Acrolea (6,1) By heating glycerol with anhydrous magnesium sulfate Evans and Hass, J.Am. Chem. S00, 48,2703 (1926). ‘Benzene sulfonyl ehlorde (1, 2) From sodium benzene sulfonate and ehlorosulfonic acid ‘Rop1oxov, Bll 00. chim. (4) 39, 365 (1926) Beasil (2, 25) By th oxidative catalytic dehydration of benaoin. Zersca and Zava, Helvetica Chim. Aeta 9, 288 (2926) Bene acid (, 29): By heating bensil in tolucne with sodamide and treatment ith water. Kastwact, Bul. Chem. Soc. Japan ¥, 68 (1936) [C.A. 20, 291 (2526) Butyl butyrate (5,23): A by-product fn the preparation of butyraldehyde by the dehydrogenation of butyl alcohol with a copper catalyst. Lee and Bociy, U.S. pat. 1,380,243 (1926) [C. A. 20, 1813 (2926)) [Ethyl Bromide (1,6) From ethyl ptoluene sulfonate and potassium bromide, Rorowaw, Bul. sc. chim. () 39, 395 (2936). EATER REFERENCES TO PRECEDING VOLUMES 121 Btuyl oxalate (2 2, and 5,55) (@) To oxalic acid is added suicient alcohol to remove as the aseotropic mixture all of the water formed in the reaction fd then the mixture is heated until the water is removed Covraew-Caower, Bull. we. chim, Belg. 36,165 (1026) (@) Essentially the method given in Orgunic. Syntheses ‘Wost, Bull. oe. chim. (3) 97,713 (0939) ‘2-Furancarboaylic acid and 2-Furlcarbinol (6, 44) By heating furfural in toluene with sodamide. Kasrwact, Bull: Chem. Soe. Japan 1, 65 (2936) [C. A. 20, 2401 (1920) Furfural (149) () From peanut hulls, De Butsoves, Ball. mat. grasses 1936, (G@) By the oxidative catalytle dehydration of fufureleohol ‘Derascam. and Zaza, Helvetica Chim. Acta 9, 288 (1926). 2Gistamie ald (5,63): (@) By the electrolysis of beet sugar residues. TaRavasc, Brit pt. 233,196 (1924) [C. A. 20,675 (1920). (@) By the hydolyssof the resides from alaholcfermenta- tion, Trzba, U.S. pat, 1,583,472 (1920) [C. A 20, 1996 (1926) () From acrolein through aldehydobutyric acid. KEK arse and Suoasawa, J- Pham. Soe. Japan st, 369 (1925) [CA 20, 2824 (2926 ‘Mesiyt oxide (, 3): (@) From acetone and sulfuric aid, YuuweR, Svensk. Kem. Tid. 97,227 (1925) [C. A. 20,739 (10260) (@) From acetone and phorphorss onychlorde. Gasopoutos, Ber. 99, 2188 (1926). Myris ald (6, 66): ‘An improvement over the general procedute given in organic syntheses is desribed, Viakave and Coors, Rec, trav chim. 45.598. (90)m oncaste svyTisES Phenglacetic acid (2,63) By the action of carbon dioxide on benzyl magnesium Dromide, Ivanov, Bull. oe. chim. (4) 37, 287 (4923). Pheaglacetyene (2,67): By the action of sodamile on styrene dibromide and on sebromostyrene, Bovxcuxt, Ann. chim. (10) 3225, 228 (1929) Plaacol hydrate (, 87): ‘A general study of the reduction of acstone to pinacol Cavan, India Rubber Rev, 26, No. 9, «8 (1926). Quinone (2,85) ‘By the oxidation of hydroquinone in 6o per cent acetic acid with chromic acid. Ceavaw and Duweam, J. Chem, Soc. 127, 1489 (1925) 1 2,g-Tibromopropane (s, 99) By the bromination of 1,2 ocean Fs is; 64 | Day FB re Bowne ats bay @ 0 38 anor iy Davi Ant W658 9570 Pane Bom Fm Bs TEN Raaae | men haat Tse"Sv 1, 038,58 196 0a Fora Ba Gn 848 Gormae Rr 9 Gaaswoin, Ay 8,8 26, 86 sean 18208 gs 6887 a a 048 5 98 nce ago oct 108 #8488 oman, dbs Teton. ©5264 orm RW at etm J ie Bote 1 cone EA 2; ap0 | Seer R189) Bens Soman oo Bay 9, 6 85 Those romans HLH, 9.98 soa ati Koen WP As rs, Paste 35, 46509 | ea E855 ison Sas Than 8A, 68; Rm gon Heng Potato ssn Jo C409 1m sn Rewvurootn® So 88 Lawsure, Ba ter AvrHIOR INDEX a Tenuta Pana, 68453 Bat hn Pane, HH. 76 mercy Ryo) G20 a8 | Pano 3, 4558 8 Lior e.7 a Tanah own SS iy fast Cae Lao ewe, Wee 3 Sara Tony ka we 8 72 Bar own 6.8 Pomme V8.4 305 Dorensca bt, 4 2 a (oan 0, 8 8,550.85 ans £3 2 eee 48 8 Res 4, he Moria Sia be | Remme S Mckee tegisy | Remon te Ronee Ce eer 6 59,85 into J.D 8 8 Browse 28 Mermae TP, a Aan a : wes Seung 824 Staion Lope 8s 95 a Sse enw Bis 76 Stele Wt, sewoa, Js a3 Sense Brat as Newest Somes Fy iss ns e NOUEG RIB Konan in| Sean Led Fry soos Pot a5 Bke Soe | Simm Rey 34 6 Nonwow Adak Sao Nome Wear 3 ssaro« WP. 36516 8 6 Sine 4 Well io Rin ares 5 Sit. 8 3 ae asa 8 SrmnF 8 Sem WB as a Sion jie Gramma ind ss toe | SrmeAckw reves 1 ook Soh 2