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The polymerization and synthesis of phenyl vinyl ether and certain derivatives (part 1), and the synthesis… Harris, Gordon Richard 1949

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THE POLYMERIZATION AND SYNTHESIS OF PHENYL VINYL ETHER AND CERTAIN DERIVATIVES (Part I) and THE SYNTHESIS OF SCHIFF'S BASES FROM 2-AMINOVANILLIN (Part II) by GORDON RICHARD HARRIS A thesis submitted i n partial fulfillment of the requirements for the degree of MASTER OF ARTS in the Department of Chemistry THE UNIVERSITY OF BRITISH COLUMBIA APRIL, 1949. ABSTRACT Certain aromatically substituted phenyl vinyl ethers were prepared by means of a two-step synthesis involving f i r s t , the synthesis of the corresponding beta-chlorophenetole derivative and subsequently treating this compound with flake potassium hydroxide to y i e l d the vinyl ether. The beta-chlorophenetole derivatives prepared were: ortho-methyl-, meta-methyl-, para-methyl-, ortho-methoxy-, para-methoxy-, ortho-chloro-, and ortho-phenyl-beta-chlorophenetole. The vinyl ethers prepared were: phenyl, ortho-methyl-, meta-methyl-, and para-methyl-phenyl vinyl ether. A l l y l phenyl ether was also prepared. The polymeric properties of these ethers were investigated. 2-aminovanillin was prepared from v a n i l l i n and i t s condensations with anthranilic acid, ortho-toluidine, ortho-phenylenediamine, and ortho-aminophenol were attempted. Diagnostic derivatives of 2-aminovanillin were also prepared: 2-acetaminovanillin, 2-aminovanillin phenylhydrazone, 2-aminovanillin 2,4-dinitrophenylhydrazone. ACKNOWLEDGEMENT I would l i k e to acknowledge the invaluable guidance and assistance afforded by Dr. R. H. Clark and Dr. H. L. Holmes i n this work. A generous quantity of v a n i l l i n was received from the Howard Smith Paper Mills Limited, Cornwall, Ontario. This g i f t i s gratefully acknowledged. TABLE OF CONTENTS Page Part I: Introduction 1 A. Beta-chlorophenetole and derivatives 3 Experimental 4 B. Phenyl vinyl ether and derivatives . . . . . 6 Experimental . . . . . . . . . . . . . . . . 7 C. A l l y l phenyl ether . . . . 9 Experimental . 9 : Polymerization 9 Summary 13 Conclusions . . . 1 3 Part H i Introduction 15 Experimental 16 Summary 19 References 20 PART I: THE POLYMERIZATION AND SYNTHESIS OF PHENYL VINYL ETHER AND CERTAIN DERIVATIVES INTRODUCTION It was proposed i n this project to systematically investigate several derivatives of phenyl vinyl ether: their syntheses, polymeriz-ation, and copolymerization with butadiene. A search of the literature of a l l monomers previously copolymer-ized with butadiene revealed that although certain of the aliphatic vinyl ethers had been employed, the copolymerization of aromatic v i n y l ethers had apparently not been attempted. A report by C. S. Marvel (1) indicated that aliphatic vinyl ethers do not undergo copolymerization with butadiene, however, there was found a reference (2) which stated that methyl vinyl and divinyl ethers have been employed as constituents of copolymers. The method of preparation of phenyl vinyl ether which was developed consists of a two-step synthesis, adopted from methods described in the literature, with certain modifications applied. The f i r s t step involves the treatment of phenol with ethylene dichloride to produce^ beta-chlorophenetole. This compound i s then treated with powdered potassium hydroxide to y i e l d phenyl vinyl ether. Further investigation revealed that this method could be extended to the synthesis of other aromatically substituted vinyl ethers by the use of substituted phenols as starting materials. A number of these vinyl ethers were prepared and their polymeric properties investigated. A brief study of a l l y l phenyl ether was also undertaken since no data was available regarding i t s polymerizability. 3. A. BETA-CHLOROPHENETOLE AND DERIVATIVES The method of synthesis employed was a modification of that of Wohl and Berthold (3) which consisted of the refluxing of small equi-molecular quantities of phenol and ethylene dichloride together with sodium hydroxide and water. (fcjI50H + C1CH2CH2C1 + NaOH •* Cg H50CH2CH2C1 + NaCl + H20 It was found i n the course of the present investigation that under the above conditions considerable amounts of ethylene glycol diphenyl ether were formed. 2C5H5OH + C1CHSCH2C1 + 2NaOH - CfcH50-CH2CH2OC6H5 + 2NaCl + 2H20 It was necessary to prepare much larger quantities of the product than permitted by the original method i n order to give accurate polymerization data and so the following modified procedure was used which resulted i n somewhat higher yields than those obtained by Wohl and Berthold (3): 2 moles of phenol, 4 moles ethylene dichloride, 2.2 moles potassium hydroxide and 300 ml. of water. The excess of ethylene dichloride serves a dual role* i t reduces the formation of ethylene glycol diphenyl ether to a negligible amount and i t acts i n the role of a solvent, allow-ing the product to be washed free of unreacted phenol by means of sodium hydroxide solution. Upon refluxing for twenty^six hours the yield, after purification, was found to be 55$ of the theoretical amount. Longer refluxing periods resulted i n small increases i n the y i e l d while a 4:1 ratio of ethylene dichloride to phenol had no appreciable effect on the yi e l d . This procedure provides a convenient synthesis of beta-chlorophenetole and at the same time permits the use of a more moderate reaction temperature than the original method (3). 0 4. This method was found to be capable of further application -to the synthesis of aromatically substituted derivatives of beta-chlorophenetole i n which the corresponding substituted phenol i s used, e.g., para-cresol was used to prepare para-methyl-beta-chlorophenetole. ' p-CEg-C^^OH + C1CH2CH2C1 + KOH - p-CRg-Cg H40CH2CH2C1 + KCl + H20 Experimental Beta-chlorophenetole (I) Two moles of phenol (188 gm.), 2.2 moles potassium hydroxide (123 gm.), 4 moles ethylene dichloride (322 ml.), and 300 ml. of water were refluxed for 26 hours on a hot plate. The mixture was then cooled, the layers separated (addition of water was sometimes necessary to effect a separation), and the o i l layer washed free of phenol with hot 10$ sodium hydroxide solution. The excess ethylene dichloride was removed by d i s t i l l a t i o n and the residue was d i s t i l l e d and the fraction boiling at 200° - 225°C. was collected, yielding 180 gm. of crude beta-chlorophentole. This product was sufficiently pure to proceed directly to the production of the vinyl ether. This was found to be true for a l l beta-chlorophenetole derivatives, which were converted to the corresponding vinyl ether. That i s , the purity of the compound had l i t t l e effect on the yields of the subsequent reaction indicating that the amount of impurity was small. However the. pure product could be obtained by twice u i s t i l l i n g this crude product and collecting the fraction boiling at 219° - 220°C, yielding 170 gm. of colourless beta-chlorophenetole. Yield rartho-metbyl-beta-chlorophenetole (4) The same procedure was employed as for (I) except for the use of 2 moles of ortho-cresol (216 gm.). D i s t i l l a t i o n after washing yielded 190 gm. of crude product boiling at 227° - 237°C. Two further d i s t i l l a t i o n s yielded 174 gm. of colourless product boiling at 230°C - 231°C. Yield 50$. Meta-methyl-beta-chlorophenetole o The same procedure was employed as for (I) except for the use of 2 moles of meta-cresol (216 gm.). Di s t i l l a t i o n after washing yielded 187 gm. of crude product boiling at 230°- 238°C. Two further d i s t i l l a -tions yielded 174 gm. of colourless product boiling at 235° - 236°C. Yield 50$. Analysis. Calculated for CgR^0C1: CI, 20.79$. Found: 01,20.69$. Para-methyl-beta-chlorophenetole The same procedure was employed as for (I) except for the use of 2 moies of para-cresol (216 gm.). D i s t i l l a t i o n after washing yielded 174 gm. of crude product boiling at 220° -240°C. Two further d i s t i l l a -tions yielded 160 gm. of colourless product boiling at 236° - 237°C. and which sol i d i f i e d on cooling. Yield 46$. Crystallization from an ethyl alcohol-water mixture yielded colourless platelets, m.p. 44° - 45°C. Analysis. Calculated for. CgEjjOCl: CI, 20.79$. Found: 01,20.73$. Ortho-methoxy-beta-chlorophenetole The same procedure was employed as for (I) except for the use of 2 moles of guaiacol (248 gm.). Di s t i l l a t i o n after washing yielded 226 gm. of crude product boiling at 240° - 260°C. Two further d i s t i l l a -ations yielded 206 gm. of colourless product boiling at 254° 7 255°C. and which sol i d i f i e d on cooling. Yield 55$. Crystallization from an ethyl alcohol-water mixture yielded colourless needles, m.p. 40° - 41°C. Analysis. Calculated for C 9H 1 ; L0 2C1: 61,19J.04$% Found: Cl,18.90£. ^ A l l melting points are corrected and taken on a Fisher S c i e n t i f i c Co. hot stage melting point apparatus. 6. Para-methoxy-beta-chlorophenetole The same procedure was employed as for (I) except for the use of 2 moles of hydroquinone monomethyl ether (248 gm.). D i s t i l l a t i o n after washing yielded 222 gm. of crude product boiling at 265° - 270°C. Two further d i s t i l l a t i o n s yielded 205 gm. of colourless product boiling at 286° - 287°C. and which s o l i d i f i e d on cooling. Yield 55$. C r y s t a l l i z -ation from an ethyl alcohol-water mixture yielded colourless platelets, m.p. 49° - 50°C. Analysis. Calculated for CgHj^OgCl: Cl,1904$. t Found: CI, 18.90$. Ortho-chloro-beta-chlorophenetole (5) The same procedure was employed as for (I) except for the use of 2 moles of ortho-chlorophenol (257 gm.). Di s t i l l a t i o n after washing yielded 224 gm. of crude product boiling at 255° - 256°C. Two further d i s t i l l a t i o n s yielded 212 gm. of colourless, product boiling at 251° - . 252°C. Analysis. Calculated for CgHgOCl8: 01,57.10$. Found: 01,37.06$. Ortho-phenyl-beta-chlorophenetole (6) The same procedure was employed as for (1) except for the use of 1 mole of ortho-phenylphenol (170 gm.). D i s t i l l a t i o n after washing yielded 98 gm. of crude product boiling at 300° - 317°C. and which solid-i f i e d on cooling. Two crystallizations from an ethyl alcohol-water mixture yielded 78 gm. colourless product boiling at 315° - 317°C. and m.p. 54° -55°C. Yield 35$. B. PHENYL VINYL ETHER AND DERIVATIVES The synthesis of these compounds was accomplished essentially by the method of Lauer and Spielman (7) which consists of twice d i s t i l l -ing beta-chlorophenetole or i t s derivatives from finely powdered potassium hydroxide. 7. C6H50CH2CH2C1 + KOH - CgH5OCH=CH2 + KC1 + H20 or p-CH3-C6H40CH2CH2Cl + KOH - p-CH3-Cg H4OCH=CH2 + KC1 + H20 The action of the a l k a l i on glass i s too severe under the conditions of temperature required for this reaction and i t was necessary to secure some type of vessel which would be alkali-resistant. Satis-factory results were obtained by the use of a cyli n d r i c a l stainless steel vessel equipped with a thermometer and a stainless steel d i s t i l l i n g neck connected to a water-cooled Leibig condenser. Two prolonged d i s t i l l a t i o n s from this vessel over a Bunsen flame gave yields up to 65% of the theoretical, which were considerably higher than those reported by Lauer and Speilman (7). It was found that not a l l of the derivatives of beta-chlorophen-etole which were synthesized could be converted to the corresponding vinyl ether by this method. Ortho-phenyl-beta-chlorophenetole decomposed and ortho-methoxy-beta-chlorophenetole produced a low boiling liquid which could not be identified as ortho-anethoxyphenyl vinyl ether. The conversion of a l l of the beta-chlorophenetole derivatives to the corresponding vinyl ethers was not completed. Experimental Phenyl Viavl Ether (II) One hundred grams of pure (I) and 100 gm. of finely powdered, flake potassium hydroxide were placed i n the stainless steel vessel previously'described. Heat was gently applied and the temperature maintained at about 150°C. for two hours without allowing d i s t i l l a t i o n to take place. T One hundred grams of crude (I) as previously described may be used producing only slightly lower yields. This applies to a l l derivatives of (I) which were converted to the corresponding . vinyl ether. 8: The temperature was then raised u n t i l d i s t i l l a t i o n occurred. At the point when chlorine i s f i r s t detected i n the d i s t i l l a t e (Beilstein Test) the temperature i s lowered and refluxing allowed to take place for about fifteen minutes. D i s t i l l a t i o n was recommenced and about 80 gm. of d i s t i l l a t e collected, including the water formed i n the reaction. To the freshly cleansed, steel d i s t i l l i n g flask i s added the entire d i s t i l l a t e along with 80 gm. of powdered, flake potassium hydroxide and the entire process repeated. The f i n a l d i s t i l l a t e was extracted with ether, the layers separated and the ether removed by d i s t i l l a t i o n . Three d i s t i l l a t i o n s yielded 42 gm. to 46 gm. of colourless phenyl vinyl ether boiling at 155° - 156°C. Yield 55 - 60$. Ortho-methyl-phenyl Vinyl Ether The same procedure was employed as for (II) except for the use of 100 gm. of orth-methyl-beta-chlorophenetole. After two d i s t i l l a t i o n s from powdered potassium hydroxide and three fractional d i s t i l l a t i o n s , 47 gm. of colourless product was obtained boiling at 168° - 169°C. Yield 60$. Meta-methyl-phenyl Vinyl Ether The same procedure was employed as for (II) except for the use of 100 gm. of meta-methyl-beta-chlorophenetole. After treatment as above the f i n a l yield was 44 gm. of colourless product boiling at l?-3° - 174°C. Yield 56$. Para-methyl-phenyl Vinyl Ether The same procedure was employed as for (II) except for the use of 100 gm. of para-methyl-beta-chlorophenetole. After treatment as.above the f i n a l yield was 44 gm. of colourless product boiling at 176° - 177°C. Yield S6$. 9. C. ALLYL PHENYL ETHER This compound, the closest homologue of phenyl vinyl ether, was the most obvious aliphatic variation of the original substance. Experimental A l l y l Phenyl Ether (8) One hundred and eighty-eight gm. of phenol, 242 gm. of a l l y l bromide, 280 gm. of potassium carbonate, and 300 gm. of acetone were heated under reflux on a hot plate for eight hours. The residue was washed free of phenol with 10$ sodium hydroxide, the aceton removed by d i s t i l l a t i o n and the residue d i s t i l l e d . The fraction boiling at 190° - 200°C. was collected. Redistillation resulted i n an 86$ y i e l d of a l l y l phenyl ether boiling at 191° - 192°C. A l l y l phenyl ether undergoes a rearrangement to ortho-allyl phenol ( 9 ) when subjected to heat. The inhibitive effect of phenols on emulsion polymerization made i t essential that there should be no phenols present i n the system. After the above preparation the a l l y l phenyl ether was further purified by several washings with cold sodium hydroxide solu-tion and f i n a l l y d i s t i l l e d under vacuum. Tests showed no phenols present in the product used for polymerization. POLYMERIZATION With regard to the polymerization of the vinyl ethers i t was decided that, i n addition to the Mutual Formula, the Redox System should also be employed and i n some cases both of these with and without butadiene. Also non-aqueous systems were u t i l i z e d with a l l y l phenyl ether. The recipes used herein are as follows unless otherwise statedt 10. I. Mutual Formula (a) H20 180 parts (b( RRC Soap Flakes 5 « (c) DD Mercaptan 0.4-0.5 " (d K 3S 20 a 0.3 " r 7 (e) Butadiene 75 " (f) Monomer 25 " II. Redox System (10) (a) H20 200 parts (b) Na 4P 207.10H 20 1.25 " (c) Je(NH 4) 2(S0 4) 2.6H 20 1.25 " (d) RRC Soap Flakes 5.0 " (e) Benzoyl peroxide 0.5 " (f) Butadiene 70.0 " (g) Monomer 50.0 " The soap was dissolved i n the water at 60°C. followed by Na4P207,10H20 and Fe(NH 4) 2(S0 4) 2.6H 20 and the whole allowed to stand 15 minutes, cooled to 25°C, the monomer added in which i s dissolved the peroxide, and f i n a l l y the butadiene. A l l polymerizations and copolymerizations were carried out at 45°C. and 10 R.P.M. i n the mechanical bottle copolymerizer. Phenyl Vinyl Ether The similarity of the structure of this compound to styrene was the i n i t i a l factor i n instigating work along the present lines. Although phenyl vinyl ether differs structurally from styrene by only an oxygen atom in an ether linkage, i t i s in no way similar i n polymeric properties. It was found that phenyl vinyl ether produced only low-grade polymers in both emulsion and non-aqueous systems. (a) Mutual Formula - After 48 hours rotation the latex yielded no coagulant and a l l of the monomer was recovered by steam d i s t i l l a t i o n of the latex. (b) Mutual Formula with Butadiene - After 48 hours i t was observed that there was remaining two distinct l i q u i d layers i n the bottle, indicating 11. immiscibility. This run was followed by a similar one i n which the soap and catalyst concentrations were doubled. After 48 hours rotation the emulsion was observed to be a homogeneous mixture. This showed some promise, however upon steam d i s t i l l a t i o n of the latex practically a l l of the monomer was recovered and apparently no copolymerization had occurred. The effect of the change of formula was merely a solubilization effect. (c) Redox System - Upon coagulation with isopropyl alcohol after 48 hours rotation, the latex yielded a soft, j e l l y - l i k e substance with no consistency and no elastic qualities. (d) Redox System with Butadiene - After 66 hours there s t i l l remained two layers i n the emulsion and a large amount of unpolymerized butadiene. From this i t would appear that phenyl vinyl ether inhibited the formation of polybutadiene. Steam d i s t i l l a t i o n of the latex recovered a l l of the monomer, indicating no copolymerization. Ortho-me'thyl-phenyl Vinyl Ether (a) Mutual Formula with Butadiene - After 66 hours of rotation the latex appeared very viscous and contained coagulable material on the addition of isopropyl alcohol. However, steam d i s t i l l a t i o n of the latex recovered a l l of the monomer. Thus the coagulant was merely polybutadiene which was calculated to be 83.5$ converted. The above was repeated for the meta and para isomers with similar results and further work on copolymerization was abandoned. A l l y l Phenyl Ether (a) Mutual Formual - After 48 hours of rotation i t was observed that the soap had darkened considerably and upon coagulation with isopropyl alcohol the latex yielded a soft, j e l l y - l i k e substance with no consistency and no elastic qualities. 12. (b) Mutual Formual with Butadiene - After 48 hours of rotation, steam d i s t i l l a t i o n of the latex recovered most of the monomer. However, calcu-lations showed that up to 2% of the monomer had entered the copolymer. This would indicate that this ethylenic double bond i s slightly more reactive than the one in the vinyl ethers. (c) Redox System - After 48 hours of rotation and coagulation with isopropyl alcohol the latex yielded a polymer similar to the one obtained by the Mutual Formula. (d) Redox System with Butadiene - After 75 hours of rotation, coagulation of the latex with isopropyl alcohol yielded a brown-coloured polymer possess-ing a slight resilience when dry. Even under these drastic conditions there s t i l l remained much unreacted butadiene, indicating further that:this type of compound tends to inhibit the formation of polybutadiene. (e) Non-aqueous Systems - Polymerization of a l l y l phenyl ether i n non-aqueous mediums u t i l i z i n g a metallic chloride catalyst was also attempted; A l l y l phenyl ether (12.5 gm.), benzene (60 ml.), and aluminum chloride ( l gm.), after 40 hours of rotation yielded a pink-coloured, low molecular weight, solid polymer i n the form of a powder with no elastic properties. A l l y l phenyl ether (12.5 gm.), benzene (100 ml.), butadiene (57.5 gm.), aluminum chloride (1 gm.), and DD mercaptan (0.25 ml.), yielded a considerable amount of brown, solid polymer possessing no elastic prop-erties. Considerable butadiene entered the polymer as indicated by the reduced pressure in the bottle. 13 SUMMARY 1. An improved method of synthesis of aromatically substituted phenyl vinyl ethers.was developed. The method involved the preparation and decomposition of the corresponding beta-chlorophenetole derivative. Several of these latter derivatives are unlisted in the chemical l i t e r -ature . 2. Phenyl vinyl ether, with several of i t s derivatives, and a l l y l phenyl ether were prepared for purposes of polymerization. 3. The vinyl ethers were found to be extremely inert to emulsion polymerization and copolymerization. 4. Phenyl vinyl ether was found to inhibit the polymerization of butadiene while ortho-methyl-phenyl vinyl ether did not. 5. A l l y l phenyl ether appeared to copolymerize in emulsion to a slight extent. CONCLUSIONS 1. The method of synthesis of the beta-chlorophentole derivatives, while not resulting i n high yields, offers a convenient method capable of producing appreciable quantities of pure product. Several of these derivatives were obtained which are not l i s t e d in.the chemical l i t e r -ature . 2. The decomposition of the beta-chlorophenetole derivatives was effected with yields improved over those cited in the literature for a similar method, 5. Possibly the phenyl vinyl ether undergoes a rearrangement, similar to that of a l l y l phenyl ether, to produce ortho-vinyl phenol. Although an elevated temperature (200°C) i s required for the a l l y l i c rearrangement 14. the prolonged heating (48 hours) at the lower temperature may result in.a small amount of rearrangement of the phenyl vinyl ether. The inhibitive effect of very small concentrations of phenols would then account for the observed inhibitive effect of phenyl vinyl ether on the polymerization of butadiene. This supposition i s supported by the fact that ortho-methyl-phenyl vinyl ether, i n which the ortho position i s substituted, did not inhibit the polymerization of butadiene. Presumably i t could not undergo a rearrangement to the ortho position. 15, PART II: SYNTHESIS OF SCHIFF'S BASES FROM 2-AMINOVANILLIN INTRODUCTION ' As a portion of a project undertaken to synthesize dyestuffs derived from v a n i l l i n , i t was proposed to prepare azomethine dyes analogous to-certain ones cited in the chemical literature (11, 12, 13). In general, these dyes are prepared by condensing an ortho-substituted, aromatic amine and an ortho-substituted aromatic aldehyde resulting i n the azomethine derivative, commonly known as a Setoff's base. The ortho substituted groups being, for example, -QH, _SH, -NHg or -COOH, i*e., groups capable of combining with a metal. The resulting product i s treated simultaneously or subsequently with a reagent that supplies a metal suqh as the zinc acetate or chromic oxide (13). e.g. ortho-hydroxybenzaldehyde (salicaldehyde) + ortho-aminophenol + a heavy bivalent metal -* *C= N ^ / ^ M= heavy bivalent metal (12) am n It was thus necessary to prepare a derivative of v a n i l l i n containing a group in the ortho position which was capable of combining with a metal and 2-aminovanillin was chosen since 2-nitrovanillin was available from another project. The former compound was then condensed with certain ortho-substituted amines for the purpose of forming the corresponding azomethine derivatives. In addition several new diagnostic derivatives of 2-aminovanillin were prepared and their melting points recorded'. Work was not advanced to the stage of the formation of the metallic compounds. 16. Experimental Vanillin Acetate (14) The v a n i l l i n acetate was prepared by treating a potassium hydroxide solution of v a n i l l i n with acetic anhydride. One hundred grams of v a n i l l i n was dissolved i n 657 mis. of IN. potassium hydroxide under an atmosphere of burner gas. A solution of 65 mis. of acetic anhydride i n 50 mis. of ether was added dropwise to the mechanically stirred solu-tion. Heat was evolved and as the reaction proceeded the reddish-brown colour of the original solution gradually disappeared, and white crystals of v a n i l l i n acetate formed i n the mixture. The solid material was collected on a Buchner funnel, washed with cold water and dried. A y i e l d of 95$ was realized which, after one crystallization from aqueous alcohol gave colourless long crystals which melted at 81° (corr.). Pschorr and Summuleanu report a melting point of 77° for this compound. 2-Nitrovanillin Acetate (14) V a n i l l i n acetate was nitrated i n a 500 cc. three neck flask, equipped with a mechanical s t i r r e r . Twenty grams of v a n i l l i n acetate was added portion-wise to 80 mis. of fuming n i t r i c acid which was kept at a temperature from 0° - 4°. The v a n i l l i n acetate slowly dissolved with the formation of a dark red solution. After the addition of the v a n i l l i n acetate was complete the reaction mixture was poured alowly into a mixture of ice and water. The resulting yellow crystals were collected on a Buchner. Recrystallization of the crude nitration product gave 17.3 grams (78$) of the nitro-derivative, melting at 83° - 85°. Pschorr reports a melting of 85° - 87° for the pure nitro-derivative (14). 2-Nitrovanillin Saponification of the 2-nitrovanillin acetate was accomplished by suspending 20 grams of the acetate i n 200 mis. of water under an atmosphere of burner gas. Twenty-five mis. of 33% sodium hydroxide solution was added dropwise. The temperature of the well stirred solution was maintained at 60° throughout the addition of the sodium hydroxide. As the saponification proceeded, the reaction mixture acquired a deep red colour. When the reaction was complete the mixture was cooled and cautiously acidified with hydrochloric acid. The crude product which weighed 1*5,6 grams (95$) was crystallized from water. The melting point of the pure substance was 137°. 2-aminovanillin (III)(15) Dissolve 300 gm. of ferrous sulphate in 250 ml. of water, heat to 90° and precipitate with an excess of ammonia (600 mis.). Add,in small portions,an ammonia solution of 25 gm. of 2-nitrovanillin to the hot solution and heat to boiling for fifteen minutes. Cool the mixture and slowly acidify with dilute H 2S0 4. F i l t e r the 2-aminovanillin which precipitates and crystallize from benzene. Yield 86$ of the theoretical, m.p. 129° - 130°C. 2-acetaminovanillin (15) Dissolve 0.2 gm. of III i n 2 ml. of 6N NaOH and add acetic anhydride dropwise, with shaking and cooling, u n t i l a precipitate forms. F i l t e r and recrystallize from an ethyl-alcohol water mixture, m.p. 96° -97°C. 2-aminovanillin Phenylhydrazone In a test tube add 0.25 ml. of phenylhydrazine to 2.5 ml. of water and add glac i a l acetic acid drop by drop u n t i l the phenylhydrazine just dissolves. Then add 0.2 gm. of III and shake vigorously. The phenyl-hydrazone separates almost immediately. F i l t e r and crystallize from an 18.-ethyl alcohol-water mixture. This results i n small, colourless needles, m.p. 163° - 165°C. • 2-aminovanillin 2, 4-dinitrophenylhydrazone In a test tube a mixture of 0.15 gm. of 2,4-dinitrophenylhyrazone, 0.2 gm. of III, and 10 ml. of 25% ethyl alcohol i s brought to the boiling point on a steam bath. At this point 0.2 ml. of concentrated hydro-chloric acid i s added and the mixture boiled under reflux for five minutes. Allow the mixture to cool to room temperature and f i l t e r the deep red crystals. Crystallize from 25% alcohol. Deep red needles result which decompose at 250° - 251°C. Condensation of 2-aminovanillin (III) and Anthranilic Acid (IV) (a) Dissolve 0.5 gm. (0.003 moles) of III and 0.82 gm. (0.006 moles) of IV in 10 ml. of 95% ethyl alcohol and heat under reflux for two hours. The solution turned a dichromate orange almost immediately upon dissolving in the alcohol. After the refluxing period a small amount of the alcohol was removed by d i s t i l l a t i o n and upon cooling a small amount of colourless needles separated which were identified as urireacted anthranilic acid.. This would indicate that an equimolecular ratio of III and IV would be sufficient for reaction. Removal of a further amount of alcohol yielded a deep red o i l which so l i d i f i e d into a bright orange solid upon cooling and scratching. Crystallizations from an ethyl alcohol-water mixture and benzene yielded an amorphous orange solid which decomposed above 200°C. (b) Mix intimately 0.5 gm. (0.003 moles) of III and 0.41 gm. (0.003 moles) of IV and heat on a hot plate, bringing the temperature slowly up to 170°C. This treatment resulted i n a bright orange melt which after crystallizations, as in part (a) above, yielded an orange 19. solid which likewise decomposed above 200°C. Condensation of 2-aminovanillin (III) and ortho-Toluidine (V) Mix together 0.5 gm. (0.003 moles) of III and 0.32 gm. (0.003 moles) of freshly d i s t i l l e d V and heat for one-half an.hour over a steam bath. The mixture changed to an amber colour almost, immediately upon heating. After heating, the mixture was placed i n a refrigerator for several days and there appeared a large number of centres of crystal-l i z a t i o n containing yellow needles. Recrystallization from an ethyl alcohol-water mixture yielded a bright, canary-yellow amorphous solid. Condensations of III i n alcohol solution were also attempted i n equimolecular proportions with both ortho-phenylenediamine and ortho-aminophenol. Addition of water to the alcohol solutions yielded yellow precipitates i n both cases. Attempts to crystallize the resulting products from ethyl alcohol-water mixtures resulted only i n dark-coloured solutions yielding no crystals. SUMMARY 1. 2-aminovanillin was prepared from v a n i l l i n according to published methods. 2. Two new diagnostic derivatives of 2-aminovanillin were prepared. 3. Condensations of 2-aminovanillin were effected, although the products were d i f f i c u l t to crystallize, .presumably because of their susceptibility to air oxidation. 4. Schiff's bases were obtained i n the case of anthranilic acid and ortho-toluidine. 20. REFERENCES •1. Marvel, C. S., Rubber Reserve Report, CR632, Page 54. 2. Gilman, H., "Organic Chemistry", Vol. I, John Wiley and Sons, Page 756. 3. Wohl, A. and Berthold, E., Ber., 43, 2175 (1910). 4. Clemo, G. R. and Perkin, W. H., Jr., J. Chem. Soc, 121, 642 (1922). 5. Coleman, G. H. and Stratton, G. B., U.S. 2,186,367, Jan. 9, 1940. 6. Livak, J . E., Coleman, G. H., and Moyle, C. L., U. S. 2,185,208, Jan. 2, 1940. 7. Lauer, W.M. and Spielman, N. A., J. Am. Chem. Soc, 55, 1572 (1933). 8. Claisen, L., Ann., 418, 78(1919). 9. Claisen, L., Z. Angew. Chem., 36, 478 (1923). 10. Rubber Reserve Report, CR1066, Page 10, Recipe B. 11. I. G. Farbenind. A. - G., B r i t . 480, 539, Feb. 22, 1938. 12. Schmidt, K. and Wahl, 0., U. S. 2,116,913, May 10, 1938. 13. I. G. Farbenind, A. - G. and Johnson, G. f., B r i t . 493,501, Oct. 10, 1938. 14. Pschorr, R. and Sumuleanu, C , Ber., 32, 3409 (1890). 15. Sumuleanu, C , Ann. Sc. de Univ. de Jassy, 2_, 134 (1903). 

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