4551558 1 2 Lower alot and parsley scl ave also BROMINATION OF susrrruTED tbcen employed at Gromination renson snd (fF TDENZALDEHYDES ‘Tema tH Bet, 7618 (1474) Toe coal form hoa af recssersbie met! brcmide or ey bromide CROSSREFERENCE TO RELATED 5 ich may be dificult ostily economically lnge- "ABPLICATION ‘cate praductan of bromo makes thi prcces Our copending appleation Sez. No. 644.72, Waa Sutactve, cocareny Berean tigod tothe signee ver nace the eat eds othe oan feet BACKGROUND OF THEAWENTION —” Blowing rn 1. ld af be inven oe {OY ie 2 Dever of the Pe Art fnestenmissnyae being Ryeosy andor ale LG cay sbsonents av nowt et a ane as: Seen Soctmyteanedc | Rrameeswacas Skye mh ie tar hl frming tyre oats pie) aidan ihe saben Sime bonged epening ton = cpanel ay pein ‘tee of ssh purmacesia a tnetnopen ‘rican = of ch Purmacesals ws tamatbopti 24" Fjom th napus ofthe se of the att allows amin. ‘bere that tb conn formation of HB eng one mecca of ycrobeomic aid pet molec 10 frombenzaiesydes produced accordance With the “Toe present invention relates tothe preparition of OR romabenraidehydes Beans tacrosy aador aly 5 saben, aed i parielar she compound Sremavaailin til compounds eset at nermediies ia atiow ot "1 found tat i aca roc cay cna af he 'S coomumed to form brometes roms, Recovery Sipontion i he preparation of 4 coo SY cic vadce the tral ike of procest whatever | Promuenaalichyes are abo wit in tbe peeparaion rose ana ronieatng ape pests (€ bromophenynanines having hypocracy © 9 ee cfs va tromiaing gsm Pee (se, French Pat No. 4392238) kenown proces “Te alkeny and/or hsrony sbwinwed bromaben- sabres ply prpered oy rersing ome SUMMARY OF THE INVENTION ‘ah the correpending aldehyde, 28 Ascoeaimgly a mae ojet fhe present invention eke ensens = os stacey Tite pepeeieceny peel erates et soamreitiee Petiemersrosicce? ieee! erin, whch md ‘nyes in various reaction media The soiventemployed §— Grsviaycis above outlined with respect to the coajoiat cE aT sme ante maiel Shrine eal fm Chem’ Sac. $1, JIS, RA. ag Melvor etal Cox 4 of Chem, 32, 270502 (933% Henry eas here Se, 2279-89 (0), Moan ct oe 2, Ort Chem 10,326 949%, R. Pacha, a 39, *gi 4551558 4 2. The peosess as deine by clan 1, whersin sad 9. The peccen at defined by chim 11nd bromiation benalscte snlaoconty contacted wih the Me Se cut te potnee of x cartane or est. an sokehiometele amount of Ted the organsc acd ro — 1. The process defied ky cai I, said beom being tasted oat xu qu anos acd (0.43 1 0.68 mole pes mole ofthe Genzaldehee (1) ‘The proces as defined by clam 1 wherein sad 1 ‘romasting agent couple compeizes hydrogen peror He, (se amount meres ranging from OSs 12 male pet ‘ate of tbe Reomine. 7. The proces a defined by claim 1, wherein aid, bromimating apeet couple comprises sire acid, dhe mount there ranging From 0.3100 male of HINO) fee mole of the bromine. "The proces 24 defined by cin 1. whercin sad rominatng agent covple comprises an alkall metal 25 Iypochloree the amovntthereet ranging from O17 to iol per mate ofthe bromine,4,551,558 9 10 er hts snd te depts ofsmversin of ‘vanillin was HLE4% and the yield of $bromovanillin eeena is: ‘et evel conven oa 98 ‘he poets of Huampe 7 was epee, exept acne ages vance a be we epaced bt srr ane bn eal men, eae ee etna a cere tm cf taaegie ¢ wn Se rt LininSoastiOs met sce SHAT vanlncf TSH andagio Somers rive we cope [he vanila comarca a5 wee sealed ‘ae is sans edie of onveron of EXAMPLE 16 ‘The procedure of Example 7 wat sepeated. except at IN agus eon of Hen vec By "apo coven of aio 26 at ‘Sbeomovalla teluive 19 the vanilla “The procs of Example 7 war cope mH 4g FL9% were obtained, thatthe 1 hye aoe wo place yon pe ‘Sut solution containing 48% by weigh of HB (40m) Gas the sean dg comer of ERANPLE I? anil was 882% snd the yield of $-bromovaniin Enamel wa repeated, but wit the adion of Felaive othe vali converted was 3496. sae ee eee EXAMPLE? (0.050 mole) and NaNO> (001 mae. EXAMPLE 11 the scope Of the peeseat invention be limited solely by Example 7 was repeated, excep thatthe hydrogen the sonpe othe following lame perovie was replaced by HNOs (aqueous soubon cee. | Wi elm faining 4896 by wedeht of HNO DIST wole) and *? 1A. process for the preparation of & sahara sodi Site! oats ees es ae Ts eae ae of emt ot washer HG ne yl fc it @ =e aM ee aoa perslina pac by td bons Sorat 7 be wale set ea gs” ae Rc ek ty ea eres oe See Cains DXAMPLE 1s oer eee spit ger pia = anlerlar nd inte peers sobe ant a ees felaive 19 the valli converted was 94.15. Te ee ‘wherein Rand Rares defied above with les han Examgle 7 was repented. ence that tbe chloofeem — okthioestc smoon of bromine. and Cs) completing was reper by incerogy thee (50 a). (6 ‘91d bromination reaction wih brominating agent ‘Under thou condom the gree of conversion of "ple which compris (1) he ydrobromie ae Ben anil was #626 sed the ied of Sbromovanilin ered in sim the sep OP and 2) + Brome te ou Frlave (othe vanlin converted wae 81 ‘ise,Ratton etal, BENZALDEHYDES (2) App Nos 688373 QO) Fi: De 28 Dee. 22,08 FR). Fane United States Patent (3) BROMINATION OF SUBSTITUTED (9) leven: Serge Rat LaVrie, ‘eateLue Bonen SuinteFoy les ‘Lye, both of France (5) signee: Ron Pokee Seilies Chinigus, Cuts Fe (8) ig Apt Prt Dt ow 2088 anew Ags 8M 508 87 (i) Patent Number: 4,551,558 (4) Date of Patents Nov, 5, 1985 4 Beles Cited US PATENT DOCUMENTS 4320 ON Mit nen SRT Primary Examiner—Bernard Helin tug F—Bars, Do, eck Matis i ABSTRACT Subsite bromobemldeydes, eg, $bromorailn, tne faclely prepared with over avoidance of HBr by got, by () ist roninaing he coreg bennaldehydle with ales than stoichiometric amoant of ‘roan, and (i) completing si bonination reaction with a brominting couple which compris (1) the hydronic acid generated in tan the sep) nd (2) «bromide in oii,4,951,558 3 ‘sing the pair ot couple which compris the hyto- Brome acs persed daring the il veastion and a ‘once for bromide on. DETAILED DESCRIFTION OF THE INVENTION ‘Mote panicalarly secording Yo the present inveition, ‘he bromide toa oxidizer is advaatageocly any com ousd sued for sch parpose, expecially hydagen ‘eros, sd and hypackiorc toms purtiuly the frm f the alla etal Bypcbloction Although ib geerally inown tothe at to oxiize ‘bromide lows to bromine with the aid of cera ex Chet, the me ofthe HBrordier pat ffxt bromi- ‘ation of hyeroxy anor alkoxy Bearldehydes would [ve teen a cane foe concer atoot the corse oe fosidtion and/or esbsicution reactions of the saring Produces Thus the prot art teaches oxidation of te idetiyde group with hydrogen peronde acoraingt08 eset of the Beer And Wiliger type (ef ©. H. asa, Orsanie Rectiens 9, pages 73 49106 [1957 3 E. Leffler, Chem. en, 45, pages 285 40 10 (1909). ‘Accordingly. it would nos Bave heen eapecied that the Ipyérony and/or alkony substiuted aromatic aldehydes ‘could be bomisated comstest withthe reason mech Seam Bereot witmout concomitant onion of the enyde functions ‘Without withing te hound tony particular theory or explanation, its comer that the ever epecha- ‘tm af the nvenon proneats secant the Follow. (ag rections (a) pana tromiaton of the abstr wing + oichiemeri fs of bromine acsording the rez ‘ion scheme: ‘o) complete oeinstion of the enconverted Ide hye using the MB/osiice pits inthe ita ere the ler compris hydrogen peranide the fas tion muy be represented by the sche + Heo ‘contioned s 10 0 The overall balanced section may then be repre> seated bythe tetera A a OS ine Ey ‘The process according tthe ivestion ths mahes it to completly rominate whatuled benauise 0 fdas with bromine ano Stet ali the Bromine Compeiang the bydrobeomc acd intial reaction Dy: Prods. ‘Altiough the bromination scoring 19 the invention may be cari ont a water ancora iar, preferably 28 atecinanuciBledypans sclven. wath a8 alogeeated Tipbete Byceocurbone oe ether it © preferable, to ‘Bln the Righan sh ad rest of Sonseran 1 tury cut the resco tbe prestce of apatie ct Inorgane acid wich i inet f9 bromine oF the Gude «2 In hin stance the smouet of aid express smes 4,551,558 tered i teh ma el slp i gh sc ot ‘om of tsrganic acd at leant partially comneecs he Eyulropenporoide maybe ved. In db xe cane, tt ‘actions Thun tetroninatgn mar becerind perl nett ened | ee of 3hOs pete of Tule uniacaucrercatuieeftaas § Naepepaoue ‘Gehyscs vs coocenaratedsolonon oF HB. Ie abo The soncentation of the squeces slut of 140s Powible to employ topetber wilh the nisi aguroes employed sso no ital i slecon i ditated By {Stun an organ sofvent for beazicebyce and for pnctcal aspects which are wel Ewa t this art (CE ‘omin, which is tect ener the feacbon Coody, ample concern over nc incteaing tbe volume of he wes 2140! ‘coming scocen seating 1 the esse enced fe es 32 Soo fet tak facie, say vary seme proved Egtontecham ni sprctriictartinsmren ance tgpetine se prccrly coe at snr ont specrtictct nent sacent con ce trhar cet ons suv eseca wnchiometetmownt slclonetaty required byte enon. tama. | (ihn theta roll or rece sr mich at mos persue a wet, psec, amount Josie thelon ef ronimein he oem iyirbroms | pecieen ate wel taggin tL mole pot ‘Site the srcun: of bowie prteaty ngs tlc of bromine aa gcfey fom C0 | woke er fromasoadsriicowonepermacolteamise mil of brmiae Tae emcenuaice of he uae antraly required by ‘Seen rensctes by te rescln tchema (a, amaly. the rection reprenented by the scheme (0). umes “ppronimatly Tmo permoieetbecmine pose close Wj of a mcle of HNOs per | mole O Bry Ks {Siar wombat (rom the amount mihi epering femble, breve, to Sept apprecaly fom the from the scope of he preset invention. Srocssd stochsomety without meverbelss, depar- Impeach thi amount preferasy range (rom O81 leg fom he scope of oe lveaon Thuy beaches 12 mole per mole bromise and depends fo some | ite ar may vary fom 04 99.0.8 me o¢INOa per ‘arnt om Oe aur of the tenakinnedom and pos maleoftromine or preferably, om BS 1007 mele oF {Beecd employed: Wienan njensletionGtRsae. HINO; per mole of homie3 455) “The concentration of he aqeaees solution of wit seid employed for completing the bromioation too b Pot erteal nod may ange fom 24 Some by weight of HINO; Neventeles, is advantageous to employ con- centrated slatonn in order not to increase the veane > ‘ifthe reaction mature. Solutions containing from #510 Sosz by weight oC HNOp sfe capes eitabie Te as bean found that avaneageous 1 employ, Joly with the nitric acid, a snall amount of nitzous ‘Sead wtich ensures a prompt tating Of the Foxconn this imance, an lial etl stile (NaNO, KNOg i tied at an intene” Aw amount oa the ander of OL ‘mole of tite per tale of aldehyde H sfBcent 29 Inte the reaction. [a peseral it is umeccuaty Lo we ‘more than 2 mole of ner per mele of benzaldehyde ‘Amounts ranging fom 108 fo 0.18 made of mete pet Inole of benzaldehrde are ctpecially site, “The temperatere at whic the bromanatoe reaction is aered oot advactageooaty ranges from 07 19 100°C. 29 tod preferably from to a "Amoag the aldehyées of formula (2) which may te brominated by the proctst of the favestion, exemplary fie erates adele Cutddriybeneale ‘jie, vain ethan, ural See Geamatiryoemisnpae)Proccnehas aldehyde, vanilia and etkylvanilin provide bromabea- {aldehyer containing & bromine nen ina tewpoai= en relative tothe aldehyde group. Veraraidehye wed to prepare. Dbrome-bhydrony-Danetboryben- adehyge” and. bowanlin 10" prepare 2OrOmO-+ tmethon-S-bydreantheazsMdetyde, Th process accord Sg the tveuon pata thy male for ‘he beomination of waniin o S.romovsniin. "The present procet is aa particalany salable for ‘consinvows eperation, Tore fuer iestene the present invention and the advantages theres the fain specs examples ae given, ie being enderstood that sate are lnseded ‘oly 2 letratve ad in nowise Smite, EXAMPLE | ‘Ashydrous scec sca (20m) fltowed by vaniin (5 gj 00S male) were charged into a 100ml round les Task gin orth » wiring systen, hermeme tet.a dropping funnel and cooled witha wate bath at 30°C. Seing was begus aad then, sehen the vanian dissolved, solution of ome (48 6083 le} in scetic aid (10 ml) was added dropwise The tempera tre gradeaily mereaued to 30°C. When the bromine sion was complete, scte ek (20 al) was ad, {followed dropwise, by hydrogen peroxide at a concen ‘wabon of 30% of HzO (226 OM ele). Siring was ‘ontineed for 10 mir upon completson of the addaion tnd the terogenects reaction manture was cooled {2 130": r wat neat flgred andthe cake was watbed oa ‘he fier wisn eth aces ac (10 wl) followed by ice water (00 mal). After deving under vacwum, 8 pecduct GO mcking a 162" C was obtained, fo seb romain (C060 g) was determiond by high pees sure guid chromatography. Uncoaverted vuln (048 was determined fn the fate and the ace acid om “The degree of comverion of vanilin sy 94%, and the yield of Sbromovanilin relnive 10 the vanillin covered was 9%. 8 EXAMPLES2 AND? EXAMPLES [ALIN aqosoos solution of sift sed (100, ot. owed by asin (15.15 69. moe) were change inca 1 2%. rowed fat equipped asia Example | Siring ‘arbegun and thes bromine (98 gO mete) waradeed ‘drops #0 the vaniln suspension thas tained: the Tecperature gradually increased to X0"-C. Whe the sedition was complet an agvezes solesioe containing 1p BO by wright of HO: Cal ge. Owe) wan 25 ineroduotd inthe same manner, Upoe completion of the sddition, sienog ws contin for an adatonl mi. “The beteropeooous reaction mistere was cooled 10 29° (Ct tes the S08 pase was separate by fasion. ‘Sate che ta with wate and then ied at 60" C wade reduced pressure The fraie was extracted with ‘methylene chioride (92130 ml), The unconverted ¥an> lin a the brome i Uh sh phate sd ie Oe methylene chloride washings was detzmiaed by bish eessre guid chvomatograpiy ‘tn ths manner, 292 of vain (Le, a gree of conversion of BA7%%) and 1642 g of Sbrecaovanitin {G71 mabe), correspooaing ox ylldof th ist of theo- etic relative to the vaniin converte, were deter ined. EXAMPLE ‘Chlocofoem (110 sl) followed by vaailin (15.15 2) ‘were charge into the appara of ‘sand su. ‘ng was began. When the vail bad dhaived 2% agucous solution of Hy904(20 al wis set. Beceine (bg 0.050m0%) was thea ade dropwine to the eter: ‘Spencou mitre thes tained. The temperate grad: Uy incresed 30°C. When the adaion af Groening ‘was complete, as aqueous solution containing 30% by Weight of 1:03 42 g he, O04 anole) was charged he same mbmaer The Svomranibin which bas pee. ‘lpeaied as was formed was separaied off by flea ‘on. The gud paves ofthe frate were separaed by decantation and he aqueaus phate was extracted wi Imedhylene cMorid (3% 150 al ach tame) By employing the same peocedere as inthe previews ‘example a total 121 g oF unconverted van (cor spending to adegee coer of 7) and 3? eet which vepresem’ a yieid of 99.5% Felaive 1 the sania converted, were determined EXAMPLE 6 “The procedure st unde the tame con © oars n Example 5 ba vith ltr eat ropased by {228 agocous solution of hyrobromic acd (3 ral. tbe ‘oem of ehotoem being 100 ma