* 2 Organic Chemistry Lab Manual A. Preliminary Reactions w Experiment Colour Observe the colour of sub. Smell Note the smell of sub. Litmus test 0.1 g (or 2 dp.) sub. +2 ml water. Shake well and test soln. with litmus paper. Solubility tests 0.1 g sub, +2 mi satd. NaHCO, soln, 0.5 p sub. + 2 ml dil. HCI. Shake well. 0.5 sub. + 2m! 10 % NaOH, Shake well. Observation Yellow Dark brown Colourless Pleasant or Phenolic Aniline-like Kerosene-like irritating, Blue turns red Red turns blue Dissoves with brisk effer- vescence of CO,. Dissolves in HCI. reappears on adding 10 % NaOH dropwise Dissoves in NaOH, reprecipitates on dding con. HCI ing a strong yellow colour, which is removed by con, HCI Inference Aromatic nitro compd. quinone, diketone. Aromatic amine, phenol. Acid, aldehyde, ketone, ester, carbo- hydrate. Ester Phenol Aromatic amine, Hydrocarbon. Aromatic compd., with halogen in side chain. Acid or phenol. Amine Acid and acid chloride. Basic substance (amine). Aromatic acid, Phenol. Nitrophenol, salicylaldehyde.Ammonia gas evolved Solution turns yellow or brown when boiled Oily globules obtai- ned having aniline- like smell. when boiled Oily layer dis- appears on boiling: white ppt. obtained on acidification with con. HCI and cooling The sub. unaffected in cold and on boiling Action of con. H,SO, 0.1 g sub. + 1 ml Sub becomes black con. H,SO,. Warm with burnt sugar gently. smell. Violent reaction Soda lime test ).1 g. sub, + 1g. soda Ammonia gas lime. Heat mixture liberated strongly. Kerosene smell Phenolic smell Neutral FeCl, test 0.1 g. sub. + | ml Violct, blue or water (or alcohol if. green colour insoluble in water) Blue ppt +5 dp.* neutral FeCl,. *see Sect. H for Brown ppt prepn. Strong yellow colour «, Tollen’s reagent Ammonium salt, amide. Sugar, aliphatic aldehyde. Anilide. Ester and amide of aromatic acid Nitro compd., ketone, amine, hydrocarbon, aromatic halogen compd. Carbohydrate, polyhydric alcohol. Aliphatic or aromatic alcohol. Ammonium salt or amide. Acid. Phenolic acid, ester. Phenol Naphthyl amine, naphthol. Carboxylic acid Hydroxy acid. O.1g.sub.+2ml Black ppt. or Aldehyde. reducingTollen’s reagent. Heat in water bath bright silver mirror sugar, polyhydric phenol or other reducing agent. B. Tests for Saturation/Unsaturation 11. 0.1 g sub. + | ml ~ “water +3-4 dp. bromine water. Shake well. 12. 0.1 g. sub. + 3-4 dp. bromine in CCl, (instead of Br,/H,O, if sub. does not dissolve in water). Shake well. 13. 0.1 g. sub. + 1 ml Na,CO, soln. + 1 % KMn0O, dropwise. Yellow colour decolourised Yellow colour persists Yellow colour decolourised, ppt. formed Yellow colour decolourised Yellow colour persists Pink colour decolourised Pink colour remains Unsatd. compd. Satd. compd. Satd. compd. like amine, phenol, Unsatd. compd. Satd. compd. Unsatd. compa. easily oxidisable compd. (aldehyde) Satd. compd. C. Tests for Aliphatic / Aromatic Nature 14. Ignite 0.1 g. (2 dp). sub. in Ni spatula. 15. 0.2 g. sub. + a mix. of 1 ml con. HNO, and | ml con. H,SO,. Shake well. Heat 10-15 min. ona boiling water bath. Pour it into 20 mi of cold water. Bums, sooty flame. Burns, non-- luminous flame Yellow ppt. or yellow soln. No yellow colour Aromatic compd. Aliphatic compd. Aromatic compd. Aliphatic compd.p. Test for Elements 16. Sodium fusion tests Melt a small piece of dry Na in a small fusion ube. Add 0.1 g. solid (or 3 dp. Liquid) to fusion tube. Heat gently at first, then to red-hotness. Quickly and carefully plunge red-hot end of tube into 10 ml distilled water in China dish. Stir soln. well with broken end of tube, boil and filter. Divide filtrate into 4 parts and test as follows: (a) Test for N : 1 ml fusion ext + few crystals of ferrous sulfate. Boil and cool. Add 2 ml dil. H;SO,. Blue/green ppt. or soln. indicates N. Na+C+N ——> NaCN 2NaCN + FeSO, —> Na,SO,+ Fe(CN), Fe(CN), + 4NaCN —> Na,[Fe(CN),] = sod. ferrocyanide 3Na,[Fe(CN),J+4Fe* —— Fe,[Fe(CN),}, +12 Ferrie ferrrocyanide — (Prussian blue) Fe* in the last step originates from aerial oxidation of Fe? of FeSO, soln. (on standing). Test for S: (b) Sod. nitroprusside test : To | ml fusion ext, add | ml of sod. () nitroprusside soln. Violet colour shows S. 2Na+S ——> Na,S Na,S + Na, [Fe(CN),(NO)] —> Na,{Fe(CN),(NOS)] sod. nitroprusside Violet colour Lead acetate test ; To 1 mi fusion ext, add 1 ml of lead acetate soln. Black ppt. shows S. 2Na+S —> Na,S Na,S + (CH,COO),Pb—> PbS! + 2CH,COONa : black ppt. Test for Halogens : | ml fusion ext + 1 ml dil. HNO,. Boil, then cool. Add | ml AgNO,. White ppt. (easily soluble in aq. NH,) shows Cl. Pale yellow ppt. (partially soluble in aq. NH). shows Br. Deep yellow ppt. (insoluble in ag. NH,) shows |.Na+X —— NaX Nax + AgNO, eee AgCl + 2NH, (aq) —> [Ag(NH,)9]CI white ppt. colourless soln. Note: The ext. should be boiled well with dil. HNO, (especially when Nis present) to destroy NaCN, which would interfere by forming insoluble white ppt. of AgCN with AgNO,. NaCN + HNO, —~> NaNO, +HCNT E. Tests for Functional Groups 1. Tests for Acids (a) Litmus test: 0.1 g. sub. (3 dp.) + 1 ml water. Shake wel:. Add a dp. of this soln. to blue litmus paper. If it turns red, an acid is present. (b) NaHCO, test: To 0.1 g. sub. (3 dp). add 1 ml of satd. NaHCO, soln. A brisk effervescence with the evolution of CO, (which turns lime water milky) shows an acid, RCOOH + NaHCO, —+ RCOONa+H,O + CO, f acid . sod. salt - = Ca(OH), +CO, —. Caco, | +H,0 lime water white ppt. Note: On passing carbon dioxide into lime water for a long time, the white ppt. formed initially, dissolves(due to formation of calcium bicarbonate). CaCO, + CO, +H,0 —> Ca(HCO,), colourless soin. (c) NaOH test: 0.1 sub. (3dp.)+ 1 ml of 10% NaOH soln. Shake well. All ganic acids dissolve when shaken with NaOH. On acidifying with con. HCI, the acid is precipitated, if it is insoluble in water (aromatic acid). C.H,COOH + NaOH — ©H.COONa+H,0 Benzoic acid L sod. benzoate, Hc] —. C,H,COOHL + NaCl Note: \V the given acid is soluble in Water piceipitaion will Nor take place.} c 6 (a) Esterification : 0.) g. (3dp.) sub. + | ml rectified spirit + 5 dp. con. H.SO,, Shake well and warm gently. Pour the hot mixture into 10 ml dil, Na,CO, soln. Pleasant odour (due to the formation of an ester) indicates an organic acid. RCOOH + C\H.OH H:S0, RCOOC,H,+ H,O - Ester ~ ° 7 Note: Sodium carbonate soln. will destroy the excess of sulphuric acid. (ec) Phenolphthalein (HPh) test : Dissolve 0.1 g. (3dp.) of sub. in I ml water, add a drop of HPh, then add dil. NaOH. drop by drop. Pink colour afier 2 or 3 dp. shows acid. (N , Fluorescein test : Mix 0.1 g. sub. with 0.5 g. resorcinol and 4 dp. con. H,SO, in a hard glass test tube. Heat for 3-5 mis. pour into dil. NaOH. An intense greenish-yellow fluorescence indicates a dicarboxylic acid. which.forms an inner anhydride (eg., succinic acid. phthalic acid.) co. eutais (CJT COOH SO, © Prat = | coon 7a DP ivr co CO. HO. OH HO. oO OH AiO = Ol co Re ont oxy oO 2. Tests for Phenol: (a) Neutral Ferric chloride test : 0.1 g. (3 dp.) sub. +5 dp. neutral ferric chloride soln. Appearance of blue, violet or green colour indicates a phenol. The -colour is due to complex formation between ferric ion and phenol (or substituted phenol), Note: Prepare neutral ferric chloride soln, as follows : To | ml ierric chloride soln.. add aq. ammonia. till a permanent brown ppt. of ferric hydroxide appears. Add dil. HOAc. dropwise. till the ppt. just d ves. If solid ferric chloride is av ailable, dissolve 0.5 g in 50m! water + 2 dp. HCI. and repeat the procedure described above) o o8 Organic Chemistry Lab Manual (b) NaOH test: Shake 0.1 g (3 dp.) sub. with | ml 10% NaOH soln. The sub. dissolves and reappears on adding con. HCI, showing the presence of phenol. (This test is common for aromatic acid also.) C,H.OH + NaOH >» CoHsONa + H,0 Pel sod. phenoyide CyHsONa + HCl — > C,HsOH + NaCl Note: Phenols do not give CO, with NaHCO, soln. This test could be u (c sed to differentiate phenols from acids.) ) Phthalic anhydride test: 0.1 g (3 dp.) sub. + 0.1 g phthalic anhydride + 3 dp. con. H,SO,. Heat gently for 2-3 mts. and pour into 20 ml dil. NaOH soln. Appearance of pink colour (due to phenolphthalein) indicates monohydric phenol ; greenish yellow colour (due to fluorescein) indicates dihydric phenol (eg., resorcinol). (d) Dye test : Dissolve | ml aniline in 4 ml dil. HCI. Cool the soln, under the tap or in ice. Add Na }, soln., drop by drop, to the cold soln. To this soln. (which contains diazonium salt) add slowly 0.5 g sub. dissolved in 5 ml dil. NaOH soln, Orange dye shows phenol. scarlet or red dye coe naphthol, resorcinol, ete. CHNH, + HCL > CH.NH*CI NaNO, + HCl —. HNO, + NaCl CyH NHS Cr 8. (CQHeNT =nj cr Bel ] ‘ene diazonium chloride O-n =N—cl+ ©yo i—(©)-N=n{O)—01n P- hydroxyazobenzene (Orange dye) OH OH a-Naphthol So, Searlet-red dye(e) semi-Micro Qualitative Analysis & Libermann’s test : Mix 0.1 g sub. with 0.5 g NaNO, ina dry test tube. Heat for 2 mts. Cool. Add 5 dp. con. H,SO,. A blue or green soln. is got. Pour this into 30 ml water in a beaker. and add NaOH in excess. A red soln. obtained first : with excess NaOH, the colour changes to deep blue. Note: All phenols do not give this test.) on | SOS 3. Tests for Esters (a) (b) Hydrolysis : 0.2 g. sub. + 2 ml 10 % NaOH. Boil for 3 mts. The disappearance of pleasant odour indicates ester. CH,COOCH, + NaOH ——> CH,COONa + CH,OH Methyl acetate sod. acetate methanol Precipitation of acid : Cool the reaction mixture from above test (a), add 1 ml HCl. A white ppt. indicates aromatic ester. C,H,;COONa + HCl —=> C,H,COOH | + NaCl Benzoie acid (insoluble in Hx0 in cold) Test with phenolphthalein : 0.2 g. sub + 2 dp. phenol- phthalein + 3 dp. NaOH soln. Heat. Pink colour disappears on heating; indicates an ester. fo Initially the free NaOH gives pink colour with indicator. On heating, NaOH is used for alkaline hydrolysis of ester: hence, free indicator (colot -ss) is liberated.10 Organic Chemistry Lab Manual * 4. Tests for Aldehydes and Ketones (a) () Borsche's test: To 0.1 g sub, add 1 ml Borsche’s reagent, Boil and add con. HCl. Cool. Add 1 ml water. Yellow or orange ppt. shows aldehyde or ketone. NO, \ S=0+ HNN NO, ——> aldehyde or 2.4 - dinitrophenyl- ketone hydrazine(Borsche’s regent) NO; e e Neon : : JAN NH NO, + H,0 2.4 - dinitrophenylhydrazone (yellow/orange ppt) Phenylhydrazine test : 0.1 g sub, + 1 ml ethanol + 1 ml phenylhydrazine. Heat in a boiling water bath for 10 mts. Yellow ppt. indicates aldehyde or ketone. Deep yellow osazone indicates aldoses (like glucose). C=0+HN—NH—CiHs — >C=N—NH—C\Hs4 + 130 (c) Phenythydrazine ~~ Phenylhydrazone (yellow ppt.) Semicarbazidg, test: 0.2g¢ sub, + a mixture of 0.2 g semicarbazide hydrochloride, 0.5 g sod. acetate and 2 ml water, Add about 1 ml of a alcohol, drop by drop, to get clear soln, Heat f@ 2 mts., cool. Colourless crystals of semicarbazone indicate aldehyde or ketone. ~~ ‘ DC++ HyN-NH—CO-NH; > >C=N=NH-CO~ NH; + H:0 (d) Semicarbazide . Semicarbazone Schiff's reagent test : (aldehydes only.) To 0.1 g sub, add 3-4 dp. Schiff's reagent. Shake well. Immediate pink or red colour shows aldehyde. (Some aliphatic ketones. like acetone. also give a pink colour, but very slowly). Schiff’s reagent js prepared from p-rosaniline hydro- chloride.” P Semi-Micro Qualitative Analysis 11 CH; c —<_ NH3'¢r The pink colour of this salt soln. in water is decolourised by passing sulphur dioxide. This decolouration results from destruction of quinonoid structure of the dye by H,SO,. Aldehyde combines with H,SO,, restores the quinonoid structure, hence pink colour. ° (e) s soln. test : (for aliphatic aldehydes only.) To 0.1 g. sub. add | ml each of Fehling’s soln. “A” and “B™. Heat to boil. A red ppt. shows aliphatic aldehyde or aldose (like glucose). 4 Fehling’s soln. “A” : Copper sulfate soln. Fehling’s soln. “B” : Alkaline sod. pot. tartrate. RCHO +2CuO ——> RCOOH +Cu,0] cuprous oxide (red ppt.) () Tollen’s reagent test : (aldehydes only). To 0.1 g sub. add 1 ml Tollen’s reagent. Heat the test tube in a water bath for 5-10 mts. Black ppt. (or bright silver mirror) indicates aldehyde or aldose (like glucose) Tollen’s reagent : Ammoniacal AgNO, soln. RCHO +2[Ag(NH3)x]OH ——> RCOONH, + 2Ag| + 3NH3 + H,0 black ppt. (g) Legals test: (for ketones only) 0.1 g. sub + 2 ml water + 5dp. sod. nitroprusside soln. + 5 dp. NaOH + 5 dp. glacial HOAc. Orange colour changes to purple, indicates ketone. 5. Tests for Carbohydrates (a) Charring test : To 0.1°g sub. in a dry test con, H,SO,- Heat gently. Charring (with burnt sug indicates carbohydrate. tube, add 5 dp. ar smell)CygHs,0,; + HxSO, —> 12C + (HySO, + 11H0) Carbohydrates lose water when heated with con. sulphuric acid. Sulphur dioxide is also evolved. C + 2H,SO, —> 2SO) t+ CO,*+ 2H,0 (b) Molisch’s test : 0.1 g sub. in 1 ml water + 1 ml alcoholic alpha-naphthol soln. Shake well. Add con. H,SO,. drop by drop, through side of test tube. The formation of deep violet ring at the junction of the two liquids, and the spreading of colour on standing, shows carbohydrate. The violet ring may be due to an unstable condensation product of alpha-naphthol with furfural (formed by the cyclodehydration of a carbohydrate with acid). (c) Osazonetest:0.1 g.sub.in3 ml water+ | ml phenylhydrazine. Heat for 5-10 mts. in a boiling water bath. Yellow crystals of osazone show monosaccharide (like glucose). CHO CH =N—NH— CoH, CHOH C =N—NH—Coh, CoHsNHNH3 (CHOH); ————$ (CHOH), CH,OH CHOH Glucose Glucosazone (yellow) (4) Refer test Nos. 4 (¢) and (f) also, for monosaccharides (like glucose) Tests for Alcohols (a) Na fest: 0.5 ml org. liquid + 1 ml benzene + small Piece of sodium, Vigorous reaction with evolution of hydrogen (pop , Sound with burning splinter) indicates alcohol. 2ROH +2Na ——> 2RONa+H,t __ sleohot Sod, alkoxide — (b) Eee O.1 g. sub. + 1 ml acetic anhydride +3 dp. con. H:50,. Heat for 2-3 mts., ¢ into 2 i wiaCO, ae cool, pour into 20 ml dilSemi-Micro Qualitative Analysis 13 ROH + (CH;CO);0 —> CH,COOR + CH,;COOH alkyl acetate HOAc is neutralised by Na,CO; soln TEST FOR N COMPOUNDS Note: Do the following tests, only if N had been detected in Na fusion test.) 7. Tests for Amines (a) Solubility test : 0.1 g. sub. + 1 ml dil HCl. Shake well. If the sub. is soluble and gets reprecipitated on adding NaOH, an amine is indicated. +.,- NaOH CoHsNH3 + HC] —> C,HsNHiCI> ——>+C,HsNH2 + NaCl + H,0 aniline aniline aniline hydrochloride (regenerated) (b) Carbylamine test : 0.1 g. sub. + 3 dp. chloroform + 2 ml alc. KOH. Shake well. Warm gently. Offensive smell of isocyanide indicates primary amine (e.g., aniline) C,H.NH, + CHCI, + 3KOH — C,H,NC + 3KCI+ 3.0 (c) Dve test : Dissolve 0.1 g. org. compd. in 3 ml dil. HCl. Cool (in tap or ice), add 1 ml sod. nitrite (0.5 g. / H,O) soln. A scarlet red dye indicates a primary amine. NCI NaNO, B= naphthol a aad “Noon aniline benzene diazonium chloride Scarlet - red dye (d) Acenvlation : 0.1 g. sub. + | ml glacial HOAc + 0.5 ml acetic anhydride. Heat gently for 3-5 mts. pour into 20 ml water in a beaker. White crystals indicate primary amine. (CH3CO),0 CoHsNH3 + CH;COOH ————+ = C,H;NHCOCH; +H,0 aniline acetanilide(ec) Liberman’ test; Dissolve 0.1 g. sub, in 3 ml ethyl aleol, 1" add | ml con, HCI. Cool (in tap or i dd 1 ml Nano, soln. Add 3 ml ether, shake well and separate ether layer and evaporate it carefully, Add 5 dp. phenol to the residue, Warm, cool, and 5 dp. con, sulphuric acid. Pour the product into 20 ml of dil NaOH soln. First a red and then a blue soln, indicates a secondary amine. CyHsNHCH + HONO —+ CyHs —N— CH N- meth Nitrous acid N25 one N - Nitrosamine (Quaternary salt test: 0.1 g. sub. + 1 ml CH,I soln, Shake well. Heat gently, allow to stand for 2-5 mts. white crystaline solid (quaternary salt) indicates tertiary amine, (CH,), N+ CH, — (CH), N° Quaternary salt 8. Tests for Amides (a) NaOH test: 0.1 g. sub. + 2 ml 10% NaOH soln. Heat strongly. Smell of NH, indicates amide. Heat till no more NH, is evolved. Add 5 dp. con. HCl. White ppt. indicates aromatic amide; no ppt. indicates aliphatic amide. CHsCONH, + NaOH — C,H,COONa “SS C,H COOH! + NaOH Benzamide + NH; (White ppt CHjCONH, + NaQH —+ CH;COONa UL cH,COOH+NaOH acetamide +NH; (soluble, no ppt.) (b) Urea nitrate test: 0.1 g. sub. + 1 ml H,O + 1 ml con. HNO,. Shake well. White ppt. shows a diamide (like urea). NH2CONH, + HNO; —> CO(NH;),. HNO;! urea urca nitrate (c) Urea oxalate test: Shake 0.1 g. sub. with 3 ml satd H,C,O, soln. White ppt. shows a diamide. 2CO(NH2)2 + H3C:0; —> [CO (NHg)2}2. H2C2044 urea, urea oxalate oSemi-Micro Qualitative Analysis 15 (d) Biuret test: Heat 0.2 g. sub. strongly in a dry test tube till no more NH, is evolved. Cool. Add | ml H,O and 5 dp. cuSO, soln.and 3 dp. NaOH soln. Violet colour shows diamide. NH-CONH; + NH;CONH; —> NH2-CO-NH-CO~-NH2+NH3 Biuret | NaoH. cus0, violet colour 9, Tests for Nitro group (a) Mulliken and Barkers test : Dissolve 0.1 g. sub. in 2ml ethanol. Add 0.5 g. NH,CI and 0.5 g. zine dust. Heat for 2 mis. Allow to stand for 3 mts. Filter. Divide the filtrate into two parts. apa 2N'NH,CI ‘ A CoHsNO. ————> CgHsNO ——> C,HsNHOH Nitrosobenzene Phenyl hydroxylamine (i) To one part. add 2 ml Tollen’s reagent. Heat in water bath. Black ppt. or bright Ag mirror indicates nitro group. CyHsNHOH + 2[Ag (NHs)2] OH —> C,HsNO + 2Ag| + 4NI (ii) To other part. add 1 ml each of Fehling’s soln. * Heat for 2mts. A red ppt. (cuprous oxide) indicates nitro compd. CiHsNHOH + 2Cu0 — C,HsNO + CuO | + H,0 red. (b) Reduction : To 0.3 g. sub. add. 5 ml con. HC] and a piece of Sn. Heat for 3-5 mts. Filter. Add KOH soln. till it becomes alkaline. An amine separates as a liquid (which may be tested by reactions under amines) : shows presence of nitro compd. SneHICl C,H.NO,— > C,H,NH, 10. Tests for Anilides (a) Carbylamine test: 0.1 g. sub. +2 ml 10 % NaOH soln. Heat for 2-3 mts. Add 2 dp. chloroform. Heat. Unpleasant smell (isocyanide) shows anilide.CgltsNHCOCH, “8 C.HsNHy + CH;COONa acetanilide aniline CotsNH + CHCl, + 3NaOH => CoHsNC + 3NaCl + 3H,0 Phenyl isocyanide (b) Bromination : Dissolve 0.1 g. sub. in 3 ml glacial HOAc. Add | ml bromine in HOAc. Shake well, pour into 10 ml water, Pale yellow ppt. indicates anilide. CH ,COOL (O)—wncoct, HEE 5 YO) nncocn, acetanilide p-bromoacctanilide (b) Dye test : Heat 0.1 g. sub. with 3 ml con. HCI for 2-3 mts. Cool the soln, (in tap or ice). Add slowly soln. of 0.5 g. sodium nitrite in water + soln. of 0.5 g. B-naphthol in 2 ml NaOH. Scarlet red dye indicates anilide. CoHsNHCOCH; + HCl —> C,HsNH, + CH,COCI OH CcHsNH; +HNO, CL oH Nsc) Pe Awitlel, Oy, SN =N O) Scarlet - red dye 11. Halogen compounds (If halogen is found in Na fusion test, do the following tests) : (a) Alcoholic AgNO, test : 0.1 g. sub. +2 mlale. AgN . Shake well. Gently warm. Formation of ppt. shows aliphatic halide or aromatic halide with halogen in side chain (eg. C\H,CH,C)). No ppt. : aromatic compd. with halogen in nucleus, (b) Anilide test : (1 pour it into 10 mi g. sub. + | ml aniline. Shake vigorously, water. White ppt. indicates acid chloride. CH;COCI + C\HNH, —_, CsHsNHCOCH;| + ¢ Acetyl chloride AcetanilideSemi-Micro Qualitative Analysis 17 12. Test for Sulphonic acid group found in Na fusion test, do the following test) :— um chloride test : Burn 0.1 g. sub. in a Ni spatula. Dissolve residue in dil. HCI, add barium chloride soln. White ppt. indicates sulphonic acid (e.g., C,H,SO,OH ~ benzene sulphonic acid): It is possible that the sulphonic acid forms, on decomposition, H,SO,, which gives a white ppt. of BaSO, with BaCl,. 13. Test for Hydrocarbons If the given unknown organic compound does not answer for any of the above functional groups, it can be considered to be a (a) Test for Aromatic hydrocarbon: Dissolve 30 mg. (or 3 drops) of the substance in | ml of chloroform. In a small dry test tube, heat a small lump of fresh anhydrous AICI, over a tiny flame, until it slowly sublimes and forms a thin coating over the sides of the tube. Now add the chloroform solution of the substance, and roll the test tube till the sublimate gets wetted completely. An intense colour (yellow or greenish blue) develops, and this colour remains unchanged fora long time. This indicates the presence of an aromatic hydrocarbon (Friedel — Crafis reaction takes place). Note: Benzene gives a deep yellow colour : naphthalene, — blue: diphenyl, — bluish - green. (b) Note: Picrate of benzene cannot be prepared; picrates of Preparation of Picrate Derivative : A picrate derivative of an aromatic hydrocarbon can be prepared as follows : To about 0.5 g. (or 10 drops) of the given substance, 0.5 P picric acid and 2 ml of rectified spirit are added, and sh: well. The picrate of the’given hydrocarbon separates out yellow solid. It is filtered, dried and the m, of Ken asa s determined. solid hydrocarbons like naphthalene. anthracene and phenanthrene can readily be preparec. For benzene and substituted benzenes, solid dinitro-derivatives can be prepared : see nitration procedure in F: 1 (c).8 Organic Chemistry Lab Manual FE. Derivatives After identifying functional group/s, confirm by Preparing solid derivative as described below -— i: Carboxylic acid (a) Anilide derivative : Mix | g. sub. with 5 mi aniline in boiliy test tube. Add a porcelain bit. fitwith air condenser and he for 30 mts. in a sand-bath. Pour hot mixture into SO ml q HCl. stir well. Allow mixture 10 stand for 10-15 minute White ppt. (anilide) Separates out. Filter, wash with co) Water. recrystallise from alcohol. C OOH + C,H;NH, ——> CoHsNHCOG,H; | + Hy nzoic acid aniline benzanilide (b) S-Ben=v1 isothiuronium derivative 10 ml 10% NaOH. and 10mloflg. chloride in NaOH. Shake well. W1 wash with cold water. : Dissolve | g. sub. i S-benzy! isothiuroniun hite ppt. obtains, Fille ~ NH Zoe RCOOH CiHs — CHy—S—c << a NH, j = | NH, le — CH,—$—c¢ a RCOO™ + HCI L Nwuy o> = QU Nitro derivative : Unsatd. acid (like cinnamic acid) can be nitrated using fuming nitric acid. Mix | g. sub. +2 mi fuming nitric acid slowly with constant stirring in dry test tube. Keep aside for 10-15 mis. Pour into 50 ml distilled Water in beaker. Yellow crystals separate out, Filter at pump, wash with water, recrystallise from alcohol, fuming (Oc ==CH= coon NO cinnamic acid P-alttecinnamig acidSemi Miero Qualitative Analysts 19 () Bromo derivative + Koy Aromatic acid (like salicyclic acid and cinnamic acid) bromo derivative can be prepared, Mix about. g. sub, with § ml Br, in glacial HOA slowly, with SONStAOE stirring, tll yellow colour develops. Shake well for 10-15 mts pour it into 50 ml water with stirring. Filter yellow crystals wash with Water, reerystallise from dil. alcohol, Ol .COOu Br [O l Bry/HOAc Salicylic acid Sym - tribromophenol 2. Phenol: (a) Bromo-derivative : [Refer (d) above] OH OH Br Br Beieay 2,4,6 - tribromophenol Br (b) Nitro derivative : Mix 1 g. sub. with 2 ml con. H,SO, warm slightly (2 mts.). Cool, add 2 ml con. HNO, drop by drop, Heat (10 mts.), pour into 20 ml water (beaker). Yellow solid shows phenolic group. Recrystallise small portion from boiling water. OH OH O.N NO, 1380, = HINO. a) — Picric acid Phenol NO, (c) Benzoyl derivative : 0.5 g. sub)+2 ml water +0.5 m| benzoy 1 chloride + 5 ml NaOH soln, Shake well. (5 mts.), pour into20 Organic Chemistry Lab Manual 20 ml water (beaker). White ppt. (benzoyl derivative of phenol). NaOH). ‘ . CHOU + CollsCOCI 10M, CyHsOCOC Hs] + HCI id 10.0.5 mlsub., add 10 ml 10% NaOH soln, (a) Acid derivative ; a : Heat for about 2-4 mts. Add con, HCI. White ppt. shows an aromatic acid. CoHsCOOCHs + NaOH ——> CoHsCOONa 4 C,H;0H sod, benzoate CoHsCOONa USS CyHsCOOH | + NaCl (b) Amide derivative ; Mix 0.5 ml sub, with 5 ml lig. NH. Shake well, and leave for 10 mts. The formation of a white ppt. shows an amide. CgHsCOOCH; + NH; —> CgHsCONH; | + CH;OH benzamide 4. Aldehydes and Ketones (a) Semicarbazone derivative + Mix 0.5 ml sub. with 0.5 g semicarbazide hydrochloride and 0.5 g. sod. acetate soln. ently for about 10 mts. and pour it into water, White als of semicarbazone is obtained. Refer Test No. 4 (¢). (b) Phenylhydrazone derivative + To 0.5 ml sub., mix | ml phenylhydrazine and | ml glacial HOAc. Heat gently for abo. 10 mts. Pour it into water. Yellow crystals show the derivative of carbonyl compounds. Refer Test No. 4 ()). (c) 2.4-dinitrophenythydrazone derivative : To 0.5 g. sub. add 1 ml Borche’s reagent and 1 ml con. HCI. Heat for about 10 mits. and pour it into water. Yellow crystals. Refer Test No. 4 (a), Sect. E. (d) Acid derivative : For aromatic aldehydes, like benzaldehyde. acid derivative can easily be prepared by oxidation. Mix Ig. sub. with 2 ml 5% Na,CO, soln. Add KMnO, soln... drop by drop, till the colour remains. Heat for about 10 mts. Add + 2Semi-Micro Qualitative Analysis 2.1 dil. sulphuric acid to the hot so sod. sulphite till the soln, be white crystals separates out, In. Then, add a strong soln. of ‘Comes colourless. On cooling, E 7 alk. KM. CoHsCHO AMOS CoH. COOH | benzaldehyde 5. Carbohydrates Phenylhydrazone derivative : Refer 4 (b) derivative. 6. Alcohols Acid derivative : Refer 4 (d) derivative. 7. Amines (a) Benzoyl derivatives : Refer 2 (c) derivative. CHsNH> + CgHsCOCI + NaOH —> CoHsNHCOC,Hs + NaCl + HO (b) Acetyl derivative : Mix 0.5 g. sub.with | ml acetic anhydride and | ml. glacial HOAc. Heat for about 10 mits. pour it into 20 ml water. White crystals. CoHsNH> + (CH3CO);0 —> C,HsNHCOCH; | + CH,;COOH acetanilide benzoic acid Acid derivative : Refer 3 (a) derivative. CgHsCONH2 + NaOH —> C,Hs;COONa + NH; benzamide sod. benzoate {Hcl CogHsCOOH + NaCl benzoic acid 9. Nitro group ‘ Reduce the nitro compounds to the corresponding amines by ‘eating with tin and HCl. Converts the amine into acetyl or benzoyl derivative. Refer 7 (a) and ()) derivative. 10. Anilides (a) Bromo derivative : Refer | (d) deriv: (O)-nacocn, Sere’. Br —{O)-nacoct, acetanilide ve.22 Organic Chemistry Lab Manual 11. Halogen compounds (a) Acid derivative : Refer 3 (a) derivative. NaOH (O) C,H,CH,CI———> C,H,CH,OH ———>_ C,H,COOH (b) Nitro derivatives : Aromatic halogen compounds (with halogen in the nucleus) can be nitrated to get nitro- derivatives Refer 2 (b) derivative. Dhucinal nnnndnnd. -£ —__Semi-Micro Qualitative a Organic Mixture dissolved in ether (NaHCO, soin, aq. layer ether layer | con. HCI. NaOH soln. acid component (regenerated) aq. layer ether layer | con. HCI. dilute HCI. phenol (regenerated) aq. layer ether layer NaOH | evaporation base neutral sub. (regenerated)Organic mixture (bulk) NaHCo, soln. aq. layer ether layer | con. HCI | evaporation acid Component - II (regenerated) Component - |rei intr ui isolvod in ether) NaOH soln a, layer ether layer | on, HCI | Cvaporation Phenol Component - I (regenerated Component - Acid separation; (Mixture Competely soluble in ether, Component is basic.) About 4-5 & of the organic mixture 1inimum amount of ether. Itis then take nd about 20 mil of dil, HClisadded, Th haken well and allowed to stand for § moved. Then about 20 ml nd the procedure is Tepeat ‘om the ether layer, The lowly by stiming with aq, Tkaline to litmus, The com (bulk) is first dissolve nina 250 ml Separating le separating funnel is st minutes, The bottom aq of dil, HCl is added to the separatin fed. All the 4g, layer are collected ge Combined aq, layers are then ne NaOH in Arops, till the solution \ponent regenerated is filtered (ifitis extracted with ether (if itis a liquid), followed by the evape ther, RNH,+HCI5 RNHi Cl RNH;Cl + NaOH = RNH, + NaCl + H,0 regenerated The ether layer from the Separating funnel, on evapora ‘omponent-II, Organic mixture (bulk) (dissolved in ether) Dil. HCl, aq. layer ether layer | aq. NOH | evaporation Base (amine) Component - Il (regenerated) Component - 1