A Study of the Effect of Long Chain Aliphatic Substituted Lyes on the Wettability of Certain Textiles by Phiroze Dhunjishah Shroff A THESIS Submitted to the School of Graduate Studies of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of DOCTOR of PHILOSOPHY in CHEMICAL EHGIHEERIHG Department of Chemical and Metallurgical Engineering Year 1951 ProQuest Number: 10008692 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10008692 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This w ork is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 A Study of the Effect of Long Chain Aliphatic Substituted Dyes on the Wettability of Certain Textiles ABSTRACT The possibility of using normal long chain aliphatic substituted dyes in imparting both color and water repellency to some of the common textiles was studied. The purpose of this investigation was to obtain information on the non-wetting properties of certain long chain substituted dyes. Fifteen different dyes of both the azo and triphenyl methane series were synthesized. ton and wool. The textile fibres used in this investigation were cot­ The Draves method of testing for water repellency was used. Extensive investigation was carried out with only one wetting agent and at one particular temperature* It was shown that the long aliphatic chain on the dye molecule imparted a degree of water repellency to the dyed fibres. Of the substituent groups studied the longer aliphatic chains imparted better water resistance than the shorter ones. The one or more long chain normal aliphatic substituents in the dye molecule did not alter the shade of the original unsubstituted dye except in the case of octyl rosaniline. All the dyes except the two unsubstituted dyes p-azo-N and p-azo-B, do not bleed on washing. Phiroze Dhunjishah Shroff C. C. DeWitt Major Professor ACIOJOv/IEBGl-ZEiTT M y sincerest acknowledgment is ms.de to Professor Clyde C. DeVitt for his conception of the possibilitj' of using long chain akkyl substituted dyes for imparting both color and water repellency to textile fibres, and for his kind and inspiring guidance and a.ctive interest throughout the course of this work. My thanks are also due to Dr. R m L. CxUile and Dr. H. A. Price for their keen interest and encouragement. IV TABLE OF C ONTENTS INTRODUCTION 1 Purpose and Scope 2 Classification of Dyes 12 Theory of Dyeing 13 Textile Fibres 13 PROCEDURE Application of Dyestuffs 15 Water Repellency Test on Fibres 29 TABULATED RESULTS 31 CHARTS 33 DISCUSSION OF RESULTS 35 CONCLUSIONS 40 APPENDIX ORGANIC PREPARATIONS Preparation of 2 , 4 ,6-Trihydroxyphenylalkyl Ketone 42 Preparation of Alkyl Acid Chlorides 46 Preparation of Alkylphenyl Ketone 47 Preparation of Alkyl Benzene 49 Nitration of Alkyl Benzene 51 Preparation of Alkyl Aniline 53 Diazotization of Alkyl Aniline 55 Preparation of 1-p-Bromophenyl-1-Octanone 56 Preparation of p-Octylbromobenzene 58 V Preparation of Alkyl Benzaldehyde Preparation of Alkyl Malachite Green 65 Preparation of Alkyl 68 Rosaniline 60 WETTABILITY LATA 73 SAMPLES OP LYEL PABRICS 77 BIBLIOGRAPHY 88 INTRODUCTION Dyeing is the process of coloring textile fibres or other materials more or less permanently by saturating them with a solution of the dyestuff. Apart from color, it does not impart any other specific property to the fabric. Water repellenc 3^ is required in a great variety of fabrics, and various methods of proofing have been used depending on the requirements of the fabric for the par­ ticular purpose in view* Proofing a woven fabric with a solid coating or layer of water proof material such as rubber, drying oil or synthetic resin makes the fabric completely impermeable to both water amid air as long as the covering film lasts* Such proofing is not suitable for clothing materials where ventilation is necessary but not absolute waterproofness. Impregnating a c l o s e d woven fabric with an alumi­ num soap, wax emulsion or a, product such as tYel a n f (23), gives water repellency to the fibres without filling up the spaces between them; the fabric, although not com­ pletely waterproof, will resist penetration of water, while at the same time remaining permeable to air and water vapor. Obviously, it would be advanta-geous if the water 2 proof finish and the color could be applied to the fabric in a, single step with a, single compound possessing both the properties. Long chain alkyl substituted triphenyl- methane dyes have been used succes s f u l ^ by LeYitt and Ludt (14) as collectors in the flotation of the mineral, chrysocolla. neither the use of the long chain alkyl substituted dyes either in the dyeing of textiles or in imparting water repellency to the fabric nor their pro­ perties save that of octyl malachite green and octyl rosaniline is apparent in literature. Prom. a consideration of both experimental investi­ gation and theory of surface chemistry, and commercial water proofing and dyeing practice, it is evident that a new dyestuff, particularly applicable to some of the more common fabrics such as cotton and wool, possessing water repelling properties would have widespread commer­ cial application. PURPOSE A1TD SCOPE The purpose of this investigation is to show that certain alkyl substituted azo and triphenylmethane dyestuffs impart non-wetting properties to the dyed textiles. Eormal long chain aliphatic substituted dyes of the azo and triphenylmethane series are used in this work. The chemical structure of these dyes and their interme­ diates is important. 3 The structure of the alkyl-triphenylmethene dyes is unknoim and may he a mixture such as is the commercial dyestuffs (V)* From the standpoint of non-wettability, the presence of one or more long aliphatic side chains in the dye structure should increase the water repellenc 3^. The normal long chain aliphatic substituted compounds would be expected, according to the theory of surface chemistry, to give better water repelling properties than the branched chain substituted compounds, byes without the long aliphatic chain are used as standards of compari son. The long chain aliphatic substituted azo dyes used in this investigation are identified as follows: 2,4,6trihydroxyphenylnonyl ketone azo-p-naphthalene as nonyl azo-I; 2 ,4,6 - trihydroxyphenylundecyl ketone azo-p-naph- thalene as undecyl azo-lT; 2 ,4 ,6 -trihydroxyphenylnonyl ketone azo-p-octylbenzene as .nonyl azo-O; 2,4, 6 - trihydroxy phenylundecyl ketone azo-p-octylbenzene as undecyl azo-O; 2 ,4,6 -trihydroxyphenjrlnonyl ketone azo-p-dodecylbenzene as non 3^1 a,zo-D; 2 ,4,6 -trihydroxyphen 3/lundec3rl ketone azo-p-dodecylbenzene as undecyl azo-D; p-oct 3nLx;)henylazop-naphthol as oct3nL azo-B; and p-dodecylphenylazo-pnaphthol as dodecyl azo-B, The triphenikLm ethane dyes are called oct3rl malachite green and oct3~l rosaniline. The d 3^es without the long aliphatic chain are ph.loroglucinolazo-p-naphthalene (P azc - F ), phloroglucinol azobenzene (P a z o - B ), p-naphtholazohenzene (ITazo-B), rialach.ite green hydrochloride and para rosaniline hydro­ chloride* The structural formulas of the long chain aliphatic substituted dyes are not definitely established, but from the procedures followed in synthesizing the intermediates used in their preparation, there is little doubt as to their ultimate structural characteristics. The only change in structure which is involved is the known addi­ tion of the long chain aliphatic group. In several cases, the literature afforded confirmation of the structure of the intermediates used. However, no references save one b y DeWitt and Ludt (15) has been found which indicate the actual use of the aliphatic long chain substituted inter­ mediates in the preparation of dyes. Even in the latter case, the long chain normal alkyl substituted malachite green was not used as a textile dye; it was used as a surface active agent for flotation of copper silicate. The structural formulas of the dyes are, on the basis of previously well established theoretical and practical grounds, presented as follows: C O — (CH^— CH; HO OH 2,4, 6 - trihydroxyphenylnonyl ketone azo-p-naphthalene OH A A N:N A\ DO — (CH^ — CHa t r ilnydr oxjnph. eny luncl e c7/1 ketone a z c-p - naplnth.a 1 e n e CHs— ~(ch^—CZ> OH O0-(CHa) — mHO CHa OH 2,4,2 trikydroxypkenylnonyl kstone azo-p- octyllbenzene OH CHa- (ch *)7------ N;N- GO— (CH2 )— CH- Hok^^iOH 2 ?^ ,6 - 1rib.ydr oxypb enylund ecy 1 ketone az c-p- 0 c tylt enz en e OH CHz--(CH *)„■ 2 ,4,£ N:N— DO— (CHZ) — CHa A \ trihydroxyphenvlnonyl ketone azo->o.odecykoenzene oH C H 3- DO— (CHa) — CH: mHO OH 2 ,4 ?6-trihydroxyph.enylnndecyl ketone azo-p-dodecyl"bensene 6 p- oc ty Iph enylazG-p-n aph tlio1 < ) — (CH-l-CH. p- d od ecy iph.eny 1 a z o-£ - n aph tlio1 N CCHa)- CH: (c^ — < C "^> : K (CH3\ Cl octyl malachite green CHs— (CH3)7- C NH Cl octyl rosaniline oh IM‘ *N y \ N / pii1 or o^ln c inole z o-J3 - n aph.th clene OH N ■H------ phloroglucinolazotoenzene N-M p ,-naph.th.ola.zo'benzene \ < )'N C| malachite green hydrochloride •NH C para rosaniline hydrochloride All the above dyes s,re synthesized except the malachite green hydrochloride and the para rosaniline hydrochloride The first step in the synthesis of the nonyl and undecyl azo-xT dyes is the preparation of the long chain substitvited phloroglucinol. These are then coupled vdth the diazotized £-napthylamine to form the dyes* In the case of the nonyl end undecyl azo-O dyes, octylbenzene is first prepared. This is used in a series of reactions to yet p-octylazobenzene. 2 Coupling with the .4.6 -trihydroxyphen 3dLalkyl ketone gives the desired dyes. ITonyl and undecyl azo-D dyes are prepared by coupling 2.4. 6 - trihydroxyphenylnonyl s.nd 2,4, 6 - 1rihydr oxyph eny1undecyl ketones respectively with diazotized p-dodecylaniline. kor the octyl and dodec;- 1 azo- dyes, p-octyl and p-dodecylaniline are diazotized and coupled with p-naphthol. p-Octylbenzaldehyde is synthesized and used as a reactant for the malachite green dye. for the octyl rosaniline d y e , o-octylaniline is formed and used in an ordinary rosaniline process. The principal steps in the synthesis f©r each inter­ mediates are shown below: 2 .4 .6 -Trihydr oxypheny lalky 1 ketone c6h 3.(oh) » Eo e s ch reacti on (OE )p.CgHg.CO.R 2,4, 6 - trihydr oxyphenylalliyl ketone Alkyl b en z en e hri edel-Crafts reaction alkyl phenyl ketone ’,/oIf f -hi shn er reduction alkyl benzene 4 lkyl nitrobenzene o-r.cge 4 .kc2 c6h 5.r o-alkyl nitrobenzene ni trat'i on p-R.C 6 K 4 .EC2 p-alkyl nitrobenzene p-Alkyl azobenzene p-r.c6h 4 .ito2 p—K *c gxi4 .mip reduction p -aIky 1 ani 1 in e p-r.c 6 h 4 .it:uci diazotizati on p-alkyl azobenzene p-n-Alkyl benzaid ehyde CgHg.Br Br. CgK^. CO.R* r'rieael-Craf ts reaction 1- p -'b r om oph eny 1 - 1 alkanone Br.CgH^.K I/oif f -ICi shn er reducti on p-n-e,lkyl broiTiObenzene R.CgH^.hgBr G-rignard s3m t h e sis p-n- alJy Iph e:ry1magn e siurn b r omi d e H.CgK^.CK(OGgHg)2 ethyl or th of orniat e p-n- allyglbenzaldehyde di ethy lac eta,l K.C^E^.CHO hydrolysi s p- n- allrulb enzald ehyde 10 o-Alkyl aniline o-H.C 5 H 4 .lTO2 ------------- > reduction o-h.c^h 4 .itfi2 o-alkyl aniline In general, standard procedures for the reactions from the literature are employed. Deviations from the standard methods are made in several cases. High mole­ cular weight and high hoiling point of the compounds, ease of separation of the products, and in some cases, arbitrary choice are some of the factors that necessitate the changes. A discussion of the alternate methods used is given below. In the formation of alkyl benzene, acylation followed by reduction is employed. This procedure is preferred to that of direct alkylation using alkyl halide and benzene for the following reasons, hirst, isomerization of the aliphatic chain takes place by the latter method while acylation does not alter the chain length. Secondly, ortho and para isomers are obtained on alkylation of bromobenzene, whereas the para isomer is obtained exclusively b y the former method. In the reduction of the ketone, the Clemmensen method is rejected in favor of the more satisfactory \7olffKishner reaction. This method is employed successfully with compounds of high molecular weight where the Clemmen­ sen technique fails, presumably because of the insolubility 11 of the carbonyl compound. The reaction goes smoothly; the yield is high. The method of Bouvealt (2) as given by "/eygand (48) for the preparation of alkyl substituted aromatic alde­ hydes is not used* The more straightforward and simple method as outlined by Bachman (1) is adopted. method gives higher yields. This latter Bachman (1) suggests the preparation of a Grignard reagent which, through the for­ mation of the aldehydediethylacetal, can be converted into the aldehyde. The nitroalkylbenzenes are prepared by direct nitra­ tion. The para isomer predominates at very low tempera­ tures of reaction. At s. suitably higher temperature, equal amounts of both the ortho and para nitro compounds are formed. Physical data on heptylphenyl ketone, octylbenzene, octylbenzaldehyde, n-octyl nitro compounds and n-octjdLanilines are available and are used for identification. Por the remaining intermediates, no such data is available in the literature, and hence it is not possible to identify them. Tor the purpose of this work, elaborate methods of identification are not carried out since structure is of secondary importance to wettability properties of the final products. The procedure used for the preparation of these dyes is given in the appendix. 12 :CLASSIFICATION OF DYES As mentioned previously, dyeing is broadly defined as the art of coloring textiles and other materials* It is very difficult to give an exact definition as dyeing becomes synonymous with staining when the coloring matter is easily removed or painting when the color is applied superficially. All the dyes used in this investigation belong to two main classes, the basic dyestuffs end the azoic dyestuffs. In the basic dyes, the actual coloring prin­ ciple has a basic character owing to the presence in the dye molecule of either free amino groups or amino groups alkylated in varying degrees. The azoic dyestuffs are characterized by the presence of the azo group, -ITsiT-. ilonyl and undecyl azo-N, nonyl and undecyl azo-O, nonyl and undecyl azo-D, and octyl and dodecyl azo-B dyes are azoic dyestuffs. Octyl malachite green and octyl rosa­ niline are the basic d 3restuffs. It has been well established that the dyeing property of a dye is dependent upon its structure. Briefly, the character of the dyestuff is derived from some particular group contained in It; this particular group is called the chromophore. The chromogen is the fundamental substance containing the chromophore, and the auxochrome is some salt forming group which converts the chromogen into the dyestuff. Bor the azoic dyestuffs used in this Investi­ gation, the chromophore is the azo group, -N:-, the 3 -uxo chrome is the hydroxyl group, -OH. The chromophore in the “basic dye stuffs used herein is the para benzanoid group, the auxochrome in the alkyl malachite green dye and in the a-lkyl rosaniline dye is the alkylated amino group, -H(CH ;*)2 anc^- amido group, -HEg , respec­ tive^-. from the theories of color and constitution, it is apparent that in these particular dyestuffs» the produc­ tion of color is due to the presence of the conjugated linkages within the d 3^e molecule. The conjugated linka.ge retards the intramolecular vibrations within the aromatic nuclei and thus shifts the absorption band from the ultra­ violet region into the visible range of the spectrum. TEEOKY OP DYEIITG According to Horsfall (27), no one single theory has been generally accepted by the majority of dyers and color chemists. There are five main theories of dyeing as pointed out by Cain and Thorpe (3), the mechanical theory, the chemical theory, the solid solution theory, the colloi­ dal absorption theory and the electrical theory. Hone of these, however, give a, true scientific explanation of the nature of the dyeing process. TEXTILE PIBHES The textile fibres used in this investigation are wool 14 ,and cotton, The former is a fibre of animal origin (nitrogenous), characterized by its heing rea.dily dis­ integrated "by alkafLies, hut is more resistant towards acids. Cotton belongs to the genersJ- group of fibres of vegetable origin (non-nitrogenous). It is not attacked by alkalis, but it is readilj^ dissolved by acids* 15 PRO CIBBKE APPLICATION OP THE BYES THEE S G-en eraJ. Bi sous si on Basic d3^estuffs are used directl 3r in the dyeing of wool. Cotton is dyed after having been mordanted with tannic acid and tartar emetic, Knect (32) points out that the mechnism of dyeing of be,sic dyestuffs on wool depends upon the acid groups of the wool which combine with the color hase of the d 3< restuff to form the dyed fabric. Cotton contains no acidic groups and, therefore, it has no direct affinity for basic d 3^estuffs and requires mordanting with acidic substances % a mordant being a substance which has a chemical affinity for both fibre and dyestuff and, therefore, serves to fix the dye on the fibre. The chemistry involved in the formation of tannic acid lakes is not entirely clear, but it appears to involve first, the reaction between tannic acid and the ba.sic dye molecule and secondly, the reaction between the antimony salt and the tannic acid portion of the pigment molecule (38). The presence of the antimonjr salt is said to improve the brilliance and the physical properties of the final pigment and appreciablj?’ decreases 16 its tendency to “bleed in various vehicles. The “basic dyestuffs are not readily soluble. The dye is g e n e r a l ^ dissolved by mixing it into a paste with a 40% solution of acetic acid, and while stirring, it is diluted with boiling water. This prevents the dye from forming semi-tarry balls floating on the top of the water solution. The addition of acetic acid also helps in correcting any slight hardness of water, facilitates level dyeing, and acts as a restraining agent for the dyes which would otherwise be rapidly absorbed. The dye solution is filtered to prevent an3^ undis­ solved particles entering the dye bath, since such parti­ cles quickly attach themselves to the material being dyed and cause spots. In the dyeing of wool, the material is first worked in the cold dye. The temperature is raised to 60-70°C. The increase in temperature serves to render a more com­ plete formation of the color lake. Starting in a cold solution of dyestuff is merely a. precautionary measure to ensure the attainment of level dyeing. The process of dyeing cotton consists in first, treating the fabric with tannic s,cid upon which it is fixed by means of tartar emetic, and then, the cotton thus mordanted, is steeped into a solution of the dyestuff. “ W hittaker and Wilcock (49) report that the maximum absorp­ tion of tannic acid takes place at 40°C. The fabric is, 17 '-however, placed in the tannic acid solution at the tempe­ rature or 70°C. The higher temperature is necessary to ensure thorough penetration, otherwise, the mordant would he exhausted on the fabric surface with the result that it would only he surface dyed* Great care is excercised in the amount of tannic acid used because too little mordant does not exhaust the dye hath while excess of mordant in addition to being a waste of material causes the dyestuff to rush on the fibre thus giving uneven results. The resulting sha.de will also be dull and lifeless. The azoic colors are developed directly on the textiles. The fabric impregnated, with a second component is immersed into a bath containing a solution of the diazo salt of the first component. The naphthol or the phloroglucinol is dissolved with caustic soda since the ba.se is insoluble in water and alkaline condition is required for the coupling reaction. Gain and. Thorpe (8 ) recommend treating the fabric in lukewarm solution of the naphthol dissolved in sodium hydroxide, after which, it is wrung out and dried by means of hot air. However, it is easily oxidized and turns brown if the drying process is too prolonged or carried, out at too high a temperature. the final dye. This re stilts in duller shades of Whittaker and Wilcock (50) have shown that in the dyeing process, ^-naphtholate concentrates at the point of evaporation, thus nullifying even distribution. A modification of the above procedure is, therefore, used. The fabric is worked in the diazotized solution, after which, the excess of the solution is evenly squeezed out. The prepared fabric is steeped into the alkaline naphthol solution, worked in for several minutes, and finally, thoroughly rinsed and washed. This procedure seems to give the best results from the standpoint of economy of dye, even depth of shade end ease of manipulation. In all cases, 0.1/5 dye solution is used. Each fabric is dyed in duplicate with each dye. Application of the Basic Dyestuffs on Wool Octyl malachite green hydrochloride, octyl rosaniline hydrochloride, malachite green hydrochloride and pararosaniline hydrochloride are the four basic dyes used. One gram of each of the above dyes is separately ground to a thin paste with 2.0 ml. acid. 5u0 ml. of a 4 of solution of a.cetic of boiling water is poured over the paste. The mixture is thoroughly mixed by stirring end 48 ml. 4Of* acetic acid, is added. of The solution is made up to one liter with distilled water. The dye bath is made up with 150 ml. of the above dye solution to which is added 7.5 grams of sodium sulfate. The addition of the sodium sulfate forces the d 3restuff out ia 6f solution, thus enabling it to he depositee, on tlie fabric since the dye cannot he extracted readily by the fibre from the hath, Cain and Thorpe (10) report that the completeness of the exhaustion of the dye hath is, in general, proportional to the amount of salt added. Care should, therefore, he exercised not to add too much ss.lt, otherwise, the dyestuff nay he precipitated from its solution and cause uneveness in the dyeing. Two skeins of wool are used for each dye. The skein is entered cold into the dye hath which is then gradually heated to 9 0°C. The dye hath is maintained at the tempe­ rature and the skein worked in for 20 minutes. The skein is then washed and dried. Application of the Basic Dyestuffs on Cotton The property possessed by basic coloring matters of forming insoluble lakes with tannic acid is taken advan­ tage of in dyeing them on the cotton fibre. The mordanting hath is made with 2b to 5 percent of tannic acid on the weight of the material as suggested by Cain and Thorpe (9). dissolved in 200 ml. Two grams of tannic acid is of boiling distilled water and the whole solution is made up to one liter. The skeins of cotton are worked in 500 ml,of the mordanting solution a.t a temperature of 50°C. for 15 minutes. They are made to remain in the hath at room 20 temperature for 6 hours. 25 grams of ts.rtar ematic Is dissolved in one liter of distilled water. The fibres from the tannic acid bath are immersed, without rinsing, into y liter of the cold solution of tartar emetic. They are worked in for hour after which they are thoroughly washed and wrung out. The dye bath used for dyeing cotton is prepared identically the same as that used for the d 3reing of wool, except that HagSO^ Is not added. The mordanted cotton fibre is entered into a cold solution of the dye bath and is worked while slowly rah sing the temperature to 70°G. It is kept at this temperature for 20 minutes till all the coloring matter has been absorbed. Application of the Azoic Dyestuffs on bool and Cotton The azoic dyestuffs used in this invest!gation are nonyl and undecyl azo-INT, nonyl and undecyl azo-0, nonyl and undecyl OvZO-D, oct3^1 and dodecyl azo-B, phloroglucinolazo-p-naphthalene, phloroglucinolazobenzene and p-naphtholazobenzene. The intermediates in the synthesis of these dyes comprise of 4 amino compounds and 4 bases. The amino compounds are p-naphthalamine, p-n-octylaniline, p-n-dodecylaniline, and aniline. The bases e„re 2,4,0- trihydroxyphenylnonyl ketone, 2,4, 6 -trihydroxyphenylundecyl ketone, p-naphthol and. phloroglucinol. The amines are diazotized separately and the skeins 21 impregnated with the diazo salt and immediately developed in an alkaline solution of the selected base. The reaction between the diazo component and the base in which the two aromatic nuclei are linked through the azo grouping is called the process of coupling. The usual procedure is to stir the solution of the diazo chloride slowly into a chilled solution of the base con­ taining sufficient alkali to neutralize the organic and inorganic acids in the resulting mixture and maintain a condition of alkalinity. ho heating is required and the reaction goes to completion in a very little time. The rapidity of coupling precludes destruction of the dis.zo component. There is marked preference for para substitution although coupling will take place in the ortho position if this s„lone is available. The presence of an isomer is seldom discoverable (19). The rate of reaction increases with increasing pH because a greater proportion of the reactive phenoxide component becomes available (20). The coupling reaction is carried out in the pH range 8-9. TEE DEVELOPING BATHS Alkaline Bath Ho. 1 Using 2,4, 6 -Trihydroxyphenylnonyl Ketone 3.0 grams trihydroxyphenvInony 1 ketone 22 10.0 grams sodium hydroxide 20.0 cc. methanol 985.0 cc. distilled water The sodium hydroxide is dissolved in 100 cc. of distilled water and a solution of the 2,4, 6 -trihydroxyphenylnonyl ketone dissolved in the methanol is added. The whole is then diluted with distilled water to 1000 cc. Alkaline Bath ho. 2 Using 2 , 4 ft-Trihydroxyphenylundecyl Ketone 3.0 grams 2 ,4,6 -trihydroxyphenylundec 3rl ketone 10.0 grams sodium hydroxide 20.0 cc. methanol 985.0 cc. distilled water The developing hath is prepared identically the same a,s the one described previously. Alkaline Bath ho. 3 U sing p-ITs.phth.o1 5.0 grams p-haphthol 10.0 grams sodium hydroxide cc. distilled water 1000.0 The £~naphthol is dissolved in a solution of 200 cc. of distilled water contemning the sodium hydroxide. The solution is diluted to one liter with distilled water. 23 Alkaline Bath TTo. 4 Using Phloroglucinol 5.0 grains phloroglucinol 10.0 grams sodium hydroxide cc. distilled water 1000.0 The phloroglucinol and sodium hydroxide are dissolved in 200 cc. of distilled water and the whole made to 1000 cc. Diazotization of the Amino Compounds The formation of the azo-compound is usually quanti­ tative. A known weight of the amine is diazotized corres­ ponding to a concentration of 1.0 gram per liter of the dyestuff. Diazotization of p-ITaphth^lamine 0.7 grams p - naphthfejlamine 0.5 grains soaium nitrite 1.5 cc. hydrochloric acid (Sp. Gr. 1.19) The p-naphthalamine is added slowly with continuous stirring into the concentrated hydrochloric acid which has “been previously cooled. 50 cc. of "boiling distilled water is added and the solution heated to boiling for half an hour. The clear solution of the amine hydrochloride is then chilled in an ice bath. The sodium nitrite is dis­ solved in 20 cc. of distilled water. With control of tem­ perature at 0°C. 9 the aqueous solution of sodium nitrite ■ 24' is. slowly added in. The mixture is stirred continuously. During this process, pieces of ice are added into the reaction mixture to keep it cool. The solution is allowed to stand for 5 minutes, after which, it is tested for excess of nitrous acid with starch-potassium iodide paper. Urea is added in i grara portions to the reaction mixture to destro 3r the excess of nitrous acid. Care should he taken due to the excessive foaming taking place when the urea, is added in larger quantities. After each addition of urea,, the solution is tested for nitrous acid. After all the nitrous acid is destroyed, the reaction mixture is diluted to 500 cc. with distilled water and maintained at 0°C. In this work, the above procedure is used for the diazotization of all the amines. It is, therefore, referred to from here on as the *General Pro­ cedure1 for diazotization. Application of Nonyl Azo-N Dye to Wool and Cotton 150 cc. of the reaction mixture of the diazotized p-naphthalamine is diluted with ice-cold distilled water to 530 cc. Two skeins each of wool and cotton are thoroughly worked in the cold solution of the above dye bath for 10 minutes. They are evenly squeezed out and immediately immersed into 300 cc. of the developing Bath No. 1 which is made up with. 2,4,6-trihydroxyphenylnonyl ketone. The diazotized materials are worked in this bath 25 lfor 15 minutes? after which, they are thoroughly washed and dried. This for all the dyes procedure is used in this investigation developed directly on the fibres; it is therefore referred to from hereon as the TSts.nde.rd Pro­ cedure1 for dyeing. Application of Undecyl Azo-IT Dye to Wool and Cotton 150 cc. aliquot of the diazotized p-naphthalemine reaction mixture to 570 cc. is taken and diluted with distilled water 300 cc* of the developing for developing the diazotized fibres. Bath 2To. 2 is used Wool and cotton, in duplicate, are dyed using the s t a n d a r d Procedure1. Application of Phloroglucinolazo-p-naphthalene Dye to Wool and Cotton The s t a n d a r d Procedure1 for dyeing is used. The dye bath is made with 150 cc. of the diazotized p-naphthalamine reaction mixture diluted to 350 cc. with distilled voter. The developing bath consists of 500 cc. of the alkaline Bath Bo. 4. Diazotization of p-n-Octylaniline 0.7 grams p~n-octylanili:ie 0.5 grams sodium nitrite 1.5 cc. hydrochloric acid (Sp. G-r. 1.19) The ’General Procedure’ for the diazotization is 26 ^ used* The reaction mixture is diluted to 500 cc* , of which 150 cc* portions are used in the formation of the dyes, nonyl azo-0, undecyl azo-0 and octyl azo-B. Application of Bonyl Azo-0 Bye to Wool and Cotton The developing hath is made up from 300 cc* of the . Alkaline Bath Bo. 1. 150 cc* of the diazotized p-n-octyl aniline is diluted to 430 cc* and used as the dye hath* The ’Standard Procedure’ for ds^eing is employed. Applice/fcion of Undecyl Azo-0 Bye to Wool and Cotton The dye hath is made with 150 cc. of the diazotized p-n-octjnLaniline diluted to 450 cc. with distilled water. Por developing, 300 cc. of the Alkaline Bath Bo. 2 is used. The fabrics are dyed employing the ’Standard Procedure,! Application of Octyl Azo-B Bye to Wool and Cotton The ’Standard Procedure’ for dyeing is used. Por the dye hath, 150 cc. of the diazotized reaction mixture is used. It is diluted with distilled water to 310 cc. The fabrics are developed in 300 cc. of the Alkaline Bath Bo. 3. Biazotization of p-n- Bodec 3rlaniline 0.8 grams p-n-dodecylaniline 0.6 grains sodium nitrite 1.5 cc. hydro chloric acid (Sp. Gr. 1.19) 27 p-n-Bodecylazobenzene is obtained 133* follcvi ’General Procedure’ for diazotizaticn. mixture is me.de to 500 cc. in volume. eg the The reaction ICO cc. of this solution, suitshl 3r diluted with distilled v;ater, is taken for each of the dyes, nonyl e^zo-B, undecyl azo-D and dodecyl azo-B. Application of ITonyl Azo-B Bye to v/ool and Cotton The dye is applied to the fibres using t h e .1Standard ’Procedure’. 150 cc. of the reaction mixture is diluted to 450 cc. for the dye hath solution. The developing hath consists of 300 cc. of the Alkaline Bath ITo. 1. Application of Undecyl Azo-B Bye to hocl end Cotton The ’Standard Procedure ’ for dyeing is followed. 300 cc. of the Alkaline Bath ho. 2 Is used for developing the diazotized fibres. 300 cc. of distilled water is added to ICO cc. of the diazotized mixture, and t he solution used as the d^/e bath. Application of Bodecyl Azo-B Bye to wool and. Cotton The fibres a.re immersed into a solution of ICO cc. of the diazotized reaction mixture in 170 cc. of distilled water. They are developed in the Alkaline Bath 17o. 3. ’Standard Procedure’ for dyeing is used. The 28 Diazotization of Aniline 1.0 grarir aniline 1.2 grams sodium nitrite 3.0 cc. Aydrochloric acid (Sp. Gr. 1.19) Aniline is converted to azotenzene hy following the usual ’General Procedure’ for diazotization. The total volume of the reaction mixture is made to 500 cc. Aliquot quantities of this solution is diluted to the required volume with distilled mater and applied to the fibres. Application of p-Haphtholazobenzene to Wool and Cotton 150 cc. of the azobenzene solution is diluted to 670 cc. with distilled water. The diazotized compound is applied to the fibres from this solution. 400 cc. of the Alkaline Bath. Ho. 3 is used, for developing the fibres. The operation is carried on by the ’Standard Procedure’. Application of Phloroglucinolazobenzene to Wool and Cotton Por the dye bath, 150 cc. of tie diazotized reaction mixture, to which is added 470 cc. of distilled water, is taken. The diazotized. fibres are developed in the Alkaline Bath Ho. 4. 500 cc. of the developer is used. ’Standard Procedure’ is followed for the application of the dye. 29 WATAA AAPELIAITCY TA3T Cli rIBRA3 A great variety of fabrics require waterproofing. The only final test for water repellency is by a,ctual use, since it is impossible to evaluate in the laboratory all the conditions to which the article may he subjected during its normal life of service* The braves ITethod of testing* chosen for use in this investigation* gives am approximate evaluation of actual use. The value of the test lies in the comparison of the non-wettability of the fibres dyed with a dye, with and without one or more long aliphatic chains. by these comparisons, it is shown that the long aliphatic chain on the dye molecule imparts a degree of water repellency to the dyed fibres. The water repellency of a fabric does not depend solely upon the proofing material. A great deal depends upon the material and construction of the fabric (34). Comparative results can be expected only when the test is performed on both dyed and undyed fibres of the same material and construction. There are several methods used in. testing the fibres for absorbency. braves method, which is the standard method of the American Association of Chemists and Colorists, is an elaboration and improvement of the 1Sinking Time* test method (44). It measures the time required for a standard skein to sink in a solution of a. wetting agent when the skein carrying a standard wreight 30 iLs held below the surface of a ire tv ing solution "by an anchor• As clescrit)ed by Araves end Clarbson (16), the si nicer consists of a 2 inch, length, of To, 12 copper wire bent into the form of a ho clcj the m i g h t should be 1.5 grsns. of the sinker The sinher is fastened, by a fine strong thread at a distance of 1 inch from an anchor which should weigh at least 20 grams. A 5-gram skein of 2 ply cotton yarn is folded, once to form a loop, the si nicer and anchor are attached, and the opposite end of the slcein is cut through with shears. The wetting solu­ tion in a 500 cc. graduated cylinder is brought to 25 °C. and the skein dropped in. The whole sinks to the bottom, but so long as the hank has any buoyancy, the cotton tie thread is tau^tt. The time elapsing between the entrance of the skein and the moment when the weighted skein starts to sink (when the thread between the sinker and anchor slackens), is measured with a stop watch. The procedure as described by Draves and Clarkson (16) is used with the following modification. A 2000 cc. graduated cylinder replaces the 500 cc. cylinder. at 25 °C. is used as the wetting solution. hater Lyed and undyed fibres of wool and cotton, in duplicate, are tested. average of 3 readings are taken for comparison. An 31 1ABULATBD INSULTS -Table I Long Chain Aliphatic Substituted. Dyes on Vool Dye Average Time (Sec* ) Nonyl azo-H 4851 Undecyl azo -N 4868 Nonyl azo-0 8537 Undecyl azo-0 8964 Nonyl azo-D 8653 Undecyl azc-D 9081 OctjUL azo-B 6629 Dodecyl azo-B 7200 Oc tyl malaclii t e green 5747 Octyl rosaniline 8273 Unsubstituted Dj^e on Vocl p-Azo-N 1488 p-Azo-B 2384 n-Azo-B 2802 Nalachite green 29 52 Para rosaniline 3607 B 1 anh (tindy ed f ab r i c ) 147 ■'Table II Long Chain Aliphatic Substituted Lyes on Cott bye honyl azo-h Average Time 0275 Undecyl azo-h 10676 honyl azo-0 12202 Undecyl azo-0 129 48 honyl azo-D 13298 Undecyl azo-B 14592 0ct3rl azo-B 10501 Bodecyl azo-B 11919 Octyl malachite green 11277 Octyl rosaniline 15166 Unsubstituted Byes on Cotton p-Azo-N 529 5 p-Azo-B 3864 n-Azo-B 6488 Malachi t e green 7342 Bare, rosaniline 8783 B 1 ank (undyed f albr i c ) 1237 33 lOOOO T" CHART I BRAVES TEST OH *?ooo .. WOOL 0 $000 1 0 -- 1 31 < o 2 $ -6 C z> o 11 3R.COC1 + H 3P O 3 47 Procedure for the Preparation of n-Caprylyl Chloride Reactsnt s 3.0 moIs n-carrylie acid 1.2 moIs phosphorus trichloride Cs.pr; lie acid is pla.ced in s, 3-necked round-bottom flask provided with a reflux condenser, a mercury sealed stirrer and a thermometer. The phosphorus trichloride is added a.nd the mixture is heated to 40°C. It is maintained at this tempere.ture for 8 hours to permit the reaction to go to completion. After allowing to stand overnight, the lower layer of phosphorus acid is drawn off. The acid chloride is heated to 85°C until excess of phosphorus trichloride has vaporized. tion under reduced pressure. It is purified "by fractiona­ n-Caprylyl chloride, hoils at 83 °C (15mm); the yield is 9 5 percent of theoretical he.sed on the acid. PREPARATION OP ALhYXPHlUhT. KETOKK The formation of the ketone from the n-alkyl acid chloride and bezene is carried out by a Priedel-Crafts reaction. The method is similar to that described by J u , Shen and Wood (30), except that carbon disulfide is not used as the diluent. Good results are obtained without its use, as indicated by Montague (36). Excess of benzene is used a.s a diluent; it presents less difficulties in subsequent purification of the product. 48 Tlie reaction may "be represented toy the equation: ° 6 H 6 + R.COC1 AICI 3 ---------------- > C 6 H 5 .CO.H d- HC1 Tlie meciianism of tlie process includes tlie formation of a well characterized aluminum chloride complex* Procedure of Preparation of n-Heptylphenyl Ketone Beactants 1.5 mols caprylyl chloride 2.5 mols anhydrous aluminum chloride 20.0 mols toenzene Dried toenzene is placed in a 5-liter 3-necked roundtoottom flask provided with a mercury sealed stirrer, a reflux condenser, a dropping funnel and a thermometer. The solution is cooled to 10°C. with a salt-cracked-ice hath, and the aluminum chloride slowly added. perature is maintained during the reaction. This tem­ Caprylyl chloride is added from a dropping funnel over a period of two hours. The progress of the reaction can toe followed toy the evolution of hydrohloric acid. After the addition of acid chloride, the reaction mixture is kept stirred for 5 hours, while the temperature is maintained toelow 10°C. lowed to stand over night. It is packed with ice and al­ The cooled mixture is poured on cracked ice which has been acidified with hydrochloric acid and kept for 4 hours to complete hydrolysis of the aluminum chloride complex. Benzene is distilled off and the ketone is washed twice with tooiling sodium carbonate solution and then with water. The ketone is dried over 49 anhydrous sodium sulfate and fractionated# n-Heptylphenyl ketone boils at 140— 143°C. at 5 mm# pressure# The yield is 90 percent of theoretical based on caprylyl chloride# PREPARATION OF ALECYL BENZENE The reduction of the ketone to the hydrocarbon is not carried out by the Clemmensen method as described by Martin (35). In the Clemmensen technique, the zinc sur­ face is an essential factor. Tn/hen the surface of the amalgamated zinc is in poor condition, formation of an excessively large amount of a heavy, oily by-product and a negligible yield have been reported by Ludt (15). n-Heptylphenyl ketone is reduced by the modified Wolff-Kishner method proposed by Huang-Mrnlon (29). Eighty-five percent hydrazine hydrate is used as the reducing agent, and potassium hydroxide as the catalyst# The reduction is illustrated by the following equations: T51 H 2 H#HH 2 13 * KOH Ther are two principal side reactions that may take place in the above process. First, there is a possibility of the azine formation by the reaction of one molecule of hydrazone with one mole of the carbonyl compound. 50 RT R t ■" __ ^ ^ it C — 0 -*-^ ^ > C ^ ! h u H ^ ----» _ ^ > C =S1T.1T= C ^ XV The second is 4-H^O ^ R' i-l thef ursiption of a spcond.BTy P.lcohol from the ketone ? or oi the pri.me.ry alcohol from the aldehyde# The Iormer difficulty can be eliminated by the rigid exclusion of water, since the ketone can be formed onl3r by hydrolysis of the hydr&zone. sed either b y The latter may be repres­ the exclusion of water or by the addition of hydrazine, since water is necessary for the hydrolysis and the presence of hydrazine shifts the equilibrium in favor of tb e hyd raz one. It seems to be taken for granted that an alkaline catalyst is necessary to promote the reduction reaction. However, it is not clear in just which reaction a catalyst is essential. Procedure for the Prepara.tion of n-Octyl Benzene Reactants 2.00 mols n-heptylphenyl ketone 6.25 mols potassium hydroxide 275.00 cc. 85 percent hydrazine hydrate 2.000 cc. p? p 1-dihydrcxyethyl ether In a, 3-necked, 5-liter round-bottom flask provided with a partial take-off reflux condenser, mercury sealed stirrer and a thermometer are placed p? p*-dibs droxyethyl ether and potassium hydroxide. The stirrer is started, and the ketone and hydrezi e hydrate are added. The mix­ ture is refluxed for one arid one-hedf hours, after which, 51 enough, h/arazine hydre te unci, ve_ter m e removed through the partial take-off tc rsise the te. ircrc ture to 195 °G. Xt is re fluxed at tnat temperature tor 4 hours* The solution, is cooled, end diluted with 2*5 liters of voter and the hydrocarbon extracted with ether. The ether ex­ tract is washed with water till free of potassium hydrox­ ide* It is dried over anhydrous sodium sulfate and the ether eva.pora.ted* The residual hyclrc carton is fraxtion- ated under reduced pressure. 110-114°C (6mm.). Octylbenzene boils at Yield is 90 percent of theoretical based on the ketone. 1X1THAT I Oh OP ALKYL BELZLKE The usual methods for nitration cannot be used to substitute the nitro group on the aryl ring of the alkyl benzenes because of the relative reactivity of the hydro­ carbon chain. Rinkes (40), however, shows that by using fuming nitric acid at -50G , good yields are obtained. Of the total yield, he obtained 75 percent of the para and 27 percent of the ortho compound. In using this m e thod, a temuerature of 10°C to 15°C is maintained during the reaction. This increases the yi e Id of the or th o c ornp ound t o appr oxima.t ely 45 percent. The yield of the para, is 5 5 xaercent. Both ortho and para, nitro alkyl benzenes are pre­ pared. 52 The nitration reaction may be set forth, as follows: HOaN i + 0 r -g 6 H 5 -► OH | R. CgH 4 .IT;0 OH ► R.C6H 4 .H02 + H 20 Procedure for the Preparation of Octylnitrobenzene Reactants 1 mo le 250 cc, n~o ctylbenzene fuming nitric acid (sp. gr, 1,50) In a 1-liters 3-necked flask provided with a reflux condenser, a dropping funnel, a mechanical stirrer and a thermometer is placed the alkyl benzene* The flask is cooled and the temperature maintained at 10°C. Puming mitrie acid is then added drop by drop over a period of 4 hours. The mixture is kept stirred for one more hour* It is then poured on ice and a 3.1owed to settle for one and one-half hours. oil is extracted with ether and The separated from the acid solution. The product is washed with water and then with dilute sodium carbonate. Finally, it is washed with water and dried over anhydrous sodium sulfate. 0- After distillation of the ether, the combined a.nd p-octylni trobenzene mixture is subjected to frac­ tions t i c under vr. cuum, u s ing a, Todd cc lumn. Product E.P.°C. % Yield o-n-octylnitrobenzene 174-179 (10 m m . ) 40 p-n-oct 3rInitrobenzene 19 0-200 (10 mm. ) 44 53 Overall yields as given are based on the amount of alkyl benzene as starting material. REDUCTION OP ALKYL M TROBENZENE Weygand (4V) states that the tendency towards side reactions is especially prevalent during the reduction of aromatic nitro compounds when stannous chloride or zinc is used with hydrochloric acid. The use of sulfides and poly sulfides of the alkali metals and of ammonium to reduce aromatic nitro compounds to amines was first demonstrated by Zinn (51). Reduction with ammonium sulfides is generally effected by solution of the nitro compound in aqueous alcoholic ammonia and subsequent saturation with hydrogen sulfide. The course of the reduction can be represented by the following equations; 2NH3 + H2S ------- »(NH4)2S 3(NE4 )2S + N0 2 .C6 H 4 .R ---► MI 2 .C6 H 4 .R+ 6 PH 3 -4* 3S *+* 2H20 Zinn's method (51) for forming the amine is used. The procedure outlined by Hickinbottom (25) is followed. The o~ and p-octylaniline are reduced separately. Procedure for the Preparation of Octylanilines Reactants 0.75 mole nitro octylbenzene 54 117 cc* 24 % aqueous ammonia 100 cc. ethyl alcohol In a 5uu-cc. 3-necked, round-bottom flask provided with a reflux condenser and a thermometer is placed 200 cc* of alcohol in which is dissolved the octylnitrobenzene. One hundred and seventeen cc. of 24 percent aqueous ammo­ nia is added and then hydrogen sulfide is passed for 20 minutes till the solution is saturated* under reflux for 3/4 hour. cool. It is heated The solution is allowed to Saturation with hydrogen sulfide and heating under reflux is repeated twice. The solution is diluted with 1 liter of water and the oil is extracted with ether. The ether extract is washed twice with dilute acid and then with water. It is dried over anhydrous sodium sulfate, and the sulvent is removed by distillation. The o-octylaniline is fractionated under vacuo. o-Octylaniline boils at 172-17?°C at 13mm. pressure. The yield is 80 percent of theoretical based on the nitro compound. The para octyl compound is isolated as the hydrochlo­ ride salt. It is placed in a beaker and cold concentrated hydrochloric acid is slowly added under vigorous stirring, the temperature being maintained between 5-10°C* p-octylaniline hydrochloride separates as a solid. The The mixture is removed from the ice bath and allowed to stand for a couple of hours. It is washed with dry ether to 55 remove the unreacted p-octylnitrobenzene. ride salt is white. The hydrochlo­ The yield is 85 percent of theoretical based on the nitro compound. DIAZOTIZATION OP ALKYIAKELIHE The alk^laniline is diazotized and used as an aqueous solution in coupling reactions to form the dyes* Diazo- nium salts are sensitive to light and decompose in a short time even when kept at ice bath temperature. Every batch is therefore freshly prepared when required. The procedure outlined by Pieser (18) is used. The amine is dissolved in a suitable volume of water contain­ ing three equivalents of hydrochloric acid. The solution is cooled well in ice, and an aqueous solution of sodium nitrite is added in slight excess. The amine hydrochlo­ ride dissolves in the process to give a clear solution of the more soluble diazonium salt. One equivalent of hydrochloric acid is bound by the amine and provides the anion of the reaction product; a second reacts with the sodium nitrite to liberate nitrous acid; and the third maintains a proper condition of acidity required to sta­ bilize the diazonium salt solution by inhibiting second­ ary changes. The excess nitrous acid formed by the sodium nitrite is removed by the addition of urea. The process of diazotization in aqueous solution can 56 be summarized, as follows: K.C 6 H 4 .HH2 + 3HC1 UaN02 in HgO * R.C 6 H 4 *N:N.C 1 + NaCI at e°c +HC1 + H2 O The exact mode of formation is not known* A possible route is through, the N-nitroso derivative as follows* R.C 6 H^. N.H A Cl HONO --------- ► R.CgHa.R.NsO A H H Cl' t H H — -* r .Cg H^. n s n .o h I H ci -H2 0 rR.CeH^.Sm] Gl~ The detailed method for the preparation of p-octylbenzenediazonium chloride and p-dodecylbenzenediazonium chloride from the respective amines is given in the chapter on procedure. PREPARATION OE 1-p-BROMGPHENYL- 1-OCTANOHE The formation of the ketone from the n-caprylic acid chloride and bromobenzene is carried out by a EriedelCrafts reaction. The bromine molecule on the phenyl rad­ ical is a predominantly para influencing group in acylation reactions. It is therefore assumed that the para compound was the product. This assumption is amply justified. Schweitzer (42) and Schopff (41) reacted acetyl chloride with bromobenzene in the presence of aluminum chloride and 57 obtained p-bromoacetophenone. Hale and Thorp (23) per­ formed the reaction using the Perrier (3 7 ) modification of the Priedel-Crafts reaction and obtained the same re­ sults. ludefind and Heid (31) also obtained the para compound by reacting the bromobenzene and acetyl chloride in the presence of aluminum chloride. Propionyl chloride and bromobenzene in the presence of aluminum chloride were reacted by Collet (12) who reported p-bromopropiophenone. Cone and Long (13) reported the reaction of bromobenzene with benzoyl chloride in the presence of aluminum chloride with the production of p-bromobenzophenone. The method as described by Schweitzer (42) is, in general, followed. diluent. Carbon disulfide is not used as a Excess of bromobenzene is used as it presents less difficulties in purification. The reaction may be represented by the equation: C 5 H 5 .Br -h B.C0C1 -----------> Br.C 6 H 4 C0.R -H HC1 Procedure for the Preparation of 1-p-Bromophenyl-l-octanone Reactants 1.5 mols caprylyl chloride 2.5 mols anhydrous aluminum 20.0 mols bromobenzene chloride Dried, freshly distilled bromobenzene is placed in a 5 -liter, 3 -necked, round-bottom flask provided with a mercury sealed stirrer, a reflux condenser, a dropping funnel and a thermometer. The flask is cooled in a salt- 58 cracked-ice bath, to -o°C and the aluminum chloride is slowly added under vigorous stirring. is not allowed to rise above 0°C. The temperature After all the alumi­ num chloride has been added, the temperature is allowed to rise to 20°C at which it is maintained during the reac­ tion. The caprylyl chloride is then added from a drop­ ping funnel over a period of one hour. After the addition of acid chloride, the mixture is maintained at 20°C for 5 hours with continuous stirring. allowed to remain overnight. It is packed in ice and The mixture is well cooled and slowly poured on cracked ice which has been acidified with hydrochloric acid. It is allowed to stand for 6 hours to complete the hydrolysis of the aluminum chloride complex. The oily layer is separated, and the bromobenzene is distilled off under vacuum. The ketone is washed with water and dried over anhydrous sodium sulfate. The mix­ ture is separated and after addition of Drierite, it is allowed to stand overnight. of water. This removes the last traces The resulting product is subjected as such to reduction to give p-octyTbromobenzene. PBEPARAT ION OP p«-OCTY JJEROMOBE NZEHE The reduction of l-p-oromophenyl-l-octanone is c a r ­ ried out with hydrazine hydrate and potassium hydroxide, according to the method outlined by Huang Minion (29). 59 Great care is taken to insure the complete absence of water as it causes side reactions. Procedure for the Preparation of p-Octylbromobenzene Reactants 1.4 mols 1-p-bromophenyl-l- octanone 4.5 mols potassium hydroxide 225 cc 85 percent hydrazine hydrate 2000 cc diethylene glycol In a 3-necked, 5-liter, round-bottom flask provided with a partial take off reflux condenser, a mercury sealed stirrer and a thermometer are placed 2000cc. of diethyl­ ene glycol and the potassium hydroxide. The mixture is stirred and the ketone and hydrazine hydrate are intro­ duced. The mixture is refluxed for one and one-half hours and then enough water and excess hydrazine hydrate are distilled over to raise the temperature to 190°C, at which temperature r e f l u x m g is continued for 4 hours longer. The solution is cooled and diluted with 2.5 liters of water and the oil extracted with ether. The other extract is washed with water till free of potassium hydroxide. It is dried over anhydrous sodium sulfate and the ether evaporated. The residual hydrocarbon is fractionated under reduced pressure. 13b-144°C (2mm.). p-Octylbromooenzene boils at Yield is 87 percent of theoretical based on the acid chloride. 60 P R E P A R A T I O N OF A L K Y L B E E Z A L B L H Y I E V a r i o u s m e t h o d s for the p r e p a ration of aromatic a l d e h y d e s are o u t lined b y F e r g u s o n (!*/)♦ Of these m e t h ­ ods on l y r e l a t i v e l y f e w can be applied to the alkylb e n z e n e s w i t h o u t d e s t r o y i n g the alkyl substituents. m e t h o d as outlined b y B o u v e a l t The (2) for p r e p a r i n g the a l k y l b e n z a l d e h y d e was first tried. I n B o u v e a l t *s ^2 ) method, the alkyl benzene is sub­ j e c t e d to a F r i e d e l - C r a f t s reaction w i t h ethyloxalyl chl o r i d e to f o r m e t h y l - p ~ a l k y l ^ h e n y l g l y o x y l a t e . This p l a c e s the s u bstituent in the desired p a r a position. The p r o d u c t is saponi f i e d w i t h caustic and acid i f i e d w i t h dilute h y d r o c h l o r i c acid to give p-alk y l p h e n y l g l y o x y l i c acid. The a c i d is m i x e d w i t h freshly d i stilled aniline w h e r e u p o n the a r y l i m i n o derivative is obtained. On h e a t ­ ing, it is con v e r t e d to the S c h i i f ’s base. base on h y d r o l y s i s w i t h dilute sulfuric acid gives the aldehyde. The The S c h i f f ’s steps are repres e n t e d in the f o l l o w i n g schemes C 6 H 5 . R + C I . C O . C O . O C 2 H 5 — * p-R. C5H4.CO.CO. OC2H5 ■+■H C 1 e thy 1-p-a Iky Ipheny lg ly oxy la t e NaOH ______________ -— > p - R . C 6 H 4 . C O . C O . O N a + C2H5 O H s od ium- p- a Iky lph e ny lg ly oxy la t e HC1 » p-R.CbH4.CO.COOH p- a l k y l p h e n y l g l y o x y l i c a c i d 61 CeHgHEs p-R.C6 H 4 .C.C00 H ft 4- H2 0 n.c 6h 5 arylimino derivative heat P-R.C6H 4 .CH:K.C6H 6 + COg Schiff *s base hydrolysis ► p-r.c 6h 4 .cho + c 6 h 5 he 2 sulfuric acid p-alkylbenzaldehyde The disadvantages of this process are numerous* The preparation is quite involved, and due to the numerous steps in the synthesis, the yields are expected to be low* The product from the Priedel-Crafts reaction cannot be purified by distillation as some decomposition occur even under vacuum. Purification of the p-alkylphenylglyoxylic acid by distillation under reduced pressure gives consi­ derable decomposition. Reduced distillation of the Schiff1s base is also found to result in serious loss by decompo­ sition. In the formation of the Shiff's base and its hydrolysis to the aldehyde, several by-products are formed. A dark green tarry mass is isolated. It is presumably the reaction product of aniline and p-alkylbenzaldehyde, bis (p-amino-phenyl )-p-n-alkyIphenylmethane, which is oxidized in air to a green dye. An alternate method of preparing the alkylbenzaldehyde, through the p-alkylbenzyl alcohol intermediate was then tried. In this method, benzyl alcohol and caprylyl 62 chloride are subjected to a Priedel— Grafts reaction with aluminum chloride. The pure ketone, p— octanoylbenzyl alcohol is obtained. pressure. Boiling point is 141°C. at 3 mm. The ketone is reduced by the Wolff-Klshner method using hydrazine hydrate and potassium hydroxide. p-n-Octylbenzyl alcohol boils at 118°C. (6 mm). The alkylbenzyl alcohol is treated with hypochlorite of lime at 40°C. to convert it to the aldehyde. Very poor yields are obtained at this stage. The above procedure is rejected in favor of the method as outlined by Bachman (1). In this process, p-n-octylphenylmagnesium bromide is first prepared. It is treated with ethyl orthoformate and refluxed for 6-8 hours to form p-n-octylbenzaldehyde acetal. If this period of heating is materially decreased, a sudden exothermic reaction occurs when the ether is removed and the yield may be seriously reduced. The acetal is hydro­ lyzed by sulfuric acid and the p-n-octylbenzaldehyde obtained is extracted with ether. The reactions are illustrated by the following equations: dry > CsHl7*CJ6H^.MgBr ether p-octylphenyhnagnesium bromide ch(oc 2 h 5 )5 p-n-octylbenzald ehyde diethyl acetal 63 H 2S04 ------------- > CgH^.CgE^.CHO + 2C2H 5 .0H p-n-octylbenzaldehyde Procedure for the Preparation of p-n— Octylbenzaldehyde reactants 0*77 mole 1*00 mole 25 gnu 500 cc* p—n— octylbromobenzene ethyl orthoformate magnesium turnings dry ether In a 2-liter, 3-necked, round-bottom flask fitted with a liquid-sealed mechanical stirrer, a 250-cc* dropping funnel, and a reflux condenser to which is attached a calcium chloride tube, are placed 25 g* of magnesium turnings, 100 cc* of dry ether, and a small crystal of iodine* Stirring is started and 50 g. of p-n-octylbromobenzene is added. The mixture shows a light red color. Ten cc. of dry ether, 2 cc. of dry ethyl bromide, a small quantity of magnesium powder, and a small grain of iodine are placed in a test tube. As soon as the iodine is decolorized, the contents of the test tube are poured into the main reaction mixture. This is necessary in order to initiate the main reaction. As soon as the mixture turns light yellow, which indicates that the x main reaction has started, 200 cc. of dry ether is added and then, more slowly, a solution of 219 g. of p-octylbromobenzene dissolved in 200 cc. of dry ether. The 64 reaction mixture is maintained at room temperature and all the alkyl halide added within a period of 1 hour. The solution is refluxed gently for another 2 hours to complete the reaction. The heat is removed, the flask cooled to below 50°C and 14b g. of ethyl orthoformate is added during the course of 15 to 20 minutes. 8 hours. The mixture is refluxed for Ether is distilled off completely, and the re­ action mixture is cooled and transferred to a 4-liter beaker equipped with a mechanical stirrer and a thermo­ meter. It is treated carefully with 750 cc, of chilled 6 percent hydrochloric acid. The contents of the flask are kept cold by the occasional addition of ice while the acid is being introduced. As soon as all the solid has dissolved, the upper oily layer of alky lb enzald ehyde acetal is separated. The oil is placed in a 2-liter, 3-necked, roundbottom flask provided with a mechanical stirrer, a reflux condenser and a thermometer. A solution of 100 g. of concentrated sulfuric acid in 700 cc. of water is added, and the mixture refluxed for 4 hours to complete the hydrolysis. It is cooled and the oil extracted with ether. The ether extract is washed with dilute sodium carbonate and then with water. The ether is distilled off and a solution of 100 g. (1 mole) of sodium bisulfite in 200 cc. of water is added. The mixture is shaken in a mechanical 65 shaker for 2 hours. The oily layer remaining undissolved in the "bisulfite solution is principally p-n-octylphenol. The solid is separated from the oil by filtration and washed with dry ether. The bisulfite product is refluxed for 1 hour with a suspension of 80 g. of sodium bicarbonate in 200 cc. of water. The upper layer is separated, dried with 20 g. of anhydrous sodium sulfate and distilled under vacuo. p-Octylbenzaldehyde: boiling point 175-190°C (10 mm.). Yield is 70 percent based on the amount of alkyl bromo­ benzene as starting material. PREPARATION OP AIZYL MALACHITE GREEN Malachite green is usually prepared by condensing the aldehyde with dime thy lani line to obtain the leuco base. On oxidation the leuco-base is converted to the carbinol compound or the dye base. It is treated with hydrochloric acid when 1 molecule of water is eliminated and the hydrochloride of the dye is formed. The above reactions are represented by the equations: CHO / \ !M c 1 H leuco-base 66 c OH N s ^ ~ ' dye base H Cl N Cch 3). C dye hydrochloride In preparing the octyl malachite green, p-cctylbenzaldehyde is reacted with dimethylaniline to form p-octyIpheny1-bis (p-dime thy lami nophenyl) methane* The formation of the leuco-base is carried out according to the procedure of Cain and Thorpe (5). The leuco-base is oxidized to form the dye base with lead peroxide* For this reaction, better results are obtained by using the method outlined by Weygand (46). The recovery of the dye is difficult due to the length of the alkyl chain which causes a decrease in solubility of the dye. When filter­ ing the oxidized dye from the lead peroxide precipitate, it is essential that the precipitate be washed free of dye, Procedure for the Preparation of p-n-Octyl Malachite 67 Green Hydrochloride Reactants O .1 mole 22.0 gm. 25.5 gm. p-n-octylbenzaldehyde dimethylanili ne concentrated hydrochloric acid The reactants are placed in a 5ou-cc. round-bottom flask equipped with a reflux condenser and a thermometer, and heated at 100°C for 24 hours. After refluxing, the mixture is made alkaline and steam distilled to remove the unreacted dimethylaniline. After the steam distil­ lation, the reaction products are poured into 60o cc. of water. A thick oily material separates on standing and is removed. This leuco-base is of honey-like color and consistency. Procedure for the Oxidation of the Leuco-Base Reactants 0.09 mole, (approx.) alkyl leuco-base 21.6 gm. lead peroxide 182 cc. water 363 cc. hot normal hydrochloric acid The leuco-base is dissolved in the hot normal hydro­ chloric acid, diluted to 1 liter and allowed to cool. The lead peroxide is suspended in water and added over a period of b minutes to the solution containing the leuco base, with constant shaking. It is heaxed for 1 hour at 68 100 C. The solid material is filtered with suction from the solution. The unchanged lead peroxide remaining on the filter is washed with two 2 o-cc. portions of ethanol in order to recover the undissolved dye. combined with the filtrate. The wash is The total filtrate is heated to "boiling and some sodium sulfate is added to precipi­ tate the dissolved lead. The mixture is cooled and fil­ tered to separate the lead sulfate precipitate. The filtrate is made alkaline with caustic solution and heated to boiling in order to precipitate the color base. On cooling, it is filtered off, washed and dried. It is d i s s o l v e d in benzene and dr y h y d r o c h l o r i c acid gas is p a s s e d t h r o u g h the solution until the dye is c o m ­ p l e t e l y p r e c i p i t a t e d as a dark, tarry mass. The b e nzene is d e c a n t e d off a n d the solid product is recovered. y i e l d is 47 percent benzaldehyde. The of theoretical as b a s e d on the octyl­ The pr o d u c t is a green dye. PREPARATION OP OCTYL ROSANILINE HYDROCHLORIDE The f o r m a t i o n of para-rosaniline h y d r o c h l o r i d e is s c h e m a t i c a l l y r e p r e s e n t e d as follows: ch3 o IMH^ + HaP 69 NHx. / \ NHj, / \ ■x c C.HO I H V > » , leuco-base NH * HjNl NH oh dye case NH — ---------- C para-rosaniline hydrochloride Cain and Thorpe (4) have indicated that, in order that oases may be usedin the preparation of the rosaniline dyes, they must conform to certain well-defined conditions. In the first place, one of the bases must contain a paramethyl group otherwise the requisite para-methane carbon atom cannot be furnished by oxidation. Consequently, neither o- nor m-toluidme, either alone or in conjunction with aniline, can yield rosanilines on oxidation* Again 70 it is evident that 2 molecules of the bases used must have their para positions free, since it is at this point that union with the methane carbon atom takes place. Thus, p-toluidine when oxidized alone cannot yield rosaniline dyestuffs. The meta derivatives do not yield rosanilines on oxidation. Prom the above, it is clear that in order to syn­ thesize rosanilines, we must have p-toluidine and 2 moles of either aniline alone, or with substituents in the ortho position but not in the meta- or para- positions. o~Octylaniline is therefore usea together with p-toluidme and aniline for the synthesis of octyl rosaniline by the method as outlined for lineby Gain and Thorpe (6 ). produce a variety of products. xhe preparation ofrosani­ The method isknown to The procedure of Gain and Thorpe is followed up to the point of salting out the dye* Here, in place of cr^sials, an oily material forms on the surface. It is purified to obtain the pure octyl rosaniline. The percentage yield of octyl rosaniline is based on the octylaniline used in the reaction mixture. Procedure for the Preparation of Octyl Rosaniline Reactants 6.2 gm. aniline 7.1 gm. p-toluidine 71 IS •0 gm* o-octylaniline 19*0 gm. cone, hydrochloric acid All the reactants are put in a 3-necked, 500-cc. flask equipped with a mechanical stirrer and a thermo­ meter, and heated to 130°C* The rest of the reactants are then added* 3 •1 gm. aniline 3*6 gm. p-toluidine 8.0 gm. o-octylaniline 20.4 gm. nitrobenzene The flask is now proYided with a reflux condenser, the stirrer is started and the mixture is heated to 100°C* Iron powder, 1*1 grams dissolved in hydrochloric acid is added over a period of a few minutes. The condenser is removed leaving one of the flask openings open for the vaporization of water, and the mix­ ture is gradually heated to 170°C* The reflux condenser is reconnected and the heating at 170°C is continued for 6 hours* During the heating period, a red color develops in the reaction mixture* Aniline and toluidine are steam distilled from the reaction mixture. over* Unreacted octylaniline does not distil A complete separation is not made. The melt is poured with stirring into 200 cc. of boiling i^ater and 4.5 cc. of concentrated hydrochloric acid is added to obtain an acid reaction and the mixture 72 is "boiled for a few minutes* Care should he exercised during hoiling because of the tendency to foam* Twenty grams of salt is added a.nd the whole hoi led for 5 min­ utes* A black oily layer and a black aqueous layer form on standing. The aqueous layer, which is discarded, con­ tains the hydrochlorides of aniline and toluidine. The oily layer is suspended in water, treated with acid and again salted out. A black tarry mass separates. The aqueous layer is discarded. The solid is washed with water and dissolved in concentrated alcohol. The ex­ tract is evaporated down until a brown solution is left. The tarry substance which separates is washed with water and taken as the product. grams octyl rosaniline 10.2 % yield 24 The product is a red dye, soluble in concentrated ethanol or acetic acid. 73 DATA Long Chain Aliphatic Substituted Dyes on Wool Bye Time Min. Sec. Nonyl azo-N 82 76 78 85 35 37 19 52 Undecyl azo-I 79 85 87 72 27 33 140 138 144 146 07 44 16 Undecyl azo-0 145 151 150 42 37 52 Uonyl azo-D 143 149 139 33 24 41 Undecyl azo-D 148 155 150 15 26 115 109 13 38 08 56 Honyl azo - 0 Octyl azo-B 110 106 Dodecyl azo-B 12 21 01 21 123 113 19 34 54 1 22 11 120 74 Dye Time Min, Sec, Octyl Malachite green 95 47 93 92 55 28 57 132 137 144 137 42 06 22 20 18 27 30 23 17 00 05 50 100 Octyl rosaniline Unsubstituted Dyes on Wool p-Azo-U p-Azo-B 8 12 9 9 n-Azo-B Malachite 22 17 43 22 42 20 47 36 45 33 51 19 green Para rosaniline Blank (undyed fabr i c ) 45 40 38 49 14 25 33 12 53 59 65 61 52 18 42 37 2 2 2 2 26 33 19 29 75 Long Chain Aliphatic Substituted Lyes on Cotton Vye Time Min* Sec Uonyl azo-B Undecyl azo-B 156 152 22 47 174 181 39 200 41 206 02 218 213 22 Bonyl azo-D 227 235 34 31 Undecyl azo-L 246 239 52 32 Octyl azo-B 172 177 43 19 Lodecyl azo-B 195 18 202 00 Octyl Malachite green 182 187 194 23 19 08 Octyl rosaniline 254 250 35 57 p-Azo-H 82 87 94 39 23 43 p-Azo-B 64 58 69 59 42 30 Honyl azo - 0 Undecyl azo-0 12 13 Unsubstituted Lyes on Cotton Dye Time Min. Sec* n-Azo-B Malachite green Para rosaniline Blank (undyed fabric) 105 112 106 25 47 127 121 118 03 40 142 150 31 14 20 21 33 15 12 22 77 Wool Uonyl azo-H Wool ^ J : ■ . Undecyl azo-U ■■v.- ' •‘.':- * ; r ■ SIM msm Wool liisiPililliii PPMpffP »ltti*ill Uonyl azo-0 78 ^ l ■iill I mmrn Wool Undecyl azo-0 Wool Uonyl azo-D Wool Undecyl azo-D 79 Wool Octyl azo-B Wool Bodecyl azo-B Wool Octyl Malachite green 80 Wool Octyl rosaniline Wool p-Azo-N Wool p-Azo-B 81 Wool n-Azo-B Wool Malachite green Wool 82 Wool Undyed i iiiii Sulil ilia SllillliBIBSBBi Cotton Uonyl azo-U VB■ ■ Cotton Undecyl azo-N 83 Cotton Honyl azo - 0 Cotton Undecyl azo-0 Cotton Uonyl azo-D 84 Cotton Undecyl azo-D Cotton Octyl azo-B Cotton Dodecyl azo-B Cotton Octyl Mal 0.ch.ite green Cotton Octyl rosaniline Cotton Cotton p-Azo-B Cotton n- Azo-B Cotton Malachite green Cotton Para rosaniline Cotton Undyed 88 BIBLIOGRAPHY 1 ) Bachman, G. B ., ’Organic Synthesis’ collective vol. 2 p •323. 2 ) Bouveault, L. , Bull. Soc. Chim. , 1 5 , 1017, (1896 ). 3) Cain, J. C. and Thorpe, J. P., 'The Synthetic Bye­ stuff s and Intermediate Products', London, C. Griffin, p. 34, (1920). 4) I bid., p. 8 6 . 5) I b i d . , p.270. ) I b id., p.272. 7) I bid., p.318. 6 8 ) I bid., p.322. 9) I b i d . , p.323. 10 I bid., p.331. 11 Clarke, H. T. and Hartman, W. W . , ’Organic Chemistry’ collective vol. 1., p. 455, (1941). 12 Collet , A., Compt. Kend. , 126, 1577, (1898). 13 C o n e , L. H. and Long, C. P., J . Am. Chem. Soc. , 28, 518, (1906 ). 14 Be Witt , C. C. and Ludt, R. W. , "Plotation of Copper Silicate f r c m S i l i c a ” , Am. Inst. M i n i n g Met. E n g r s . , M i n i n g Eng. 1, Ho. 2., 49-51, (1949). 15 De Witt, C. C. and L u d t , B. W. , "The E l o t a t i o n of C o p ­ p e r Silicate h y A l k y l - S u b s t i t u t e d T riphenyl M e t h a n e Byes", Ph.B. Thesis, M i c h i g a n State College, (1947). 16 B raves, C. Z. and Clarksoa?,B. G. , "Hew M e t h o d s for E v a l u a t i o n of W e t t i n g Agents", Am. B y e s t u f f R e ­ porter, 20, 201, (1951). 17 P erguson, L. H. , Chem. Rev., 58, 227, (1946). 89 18) F i e s e r , M, and Fieser, L. F. , *Organic C h e m i s t r y ’ , X), C. H e a t h and Company, p. 617, (1944)# 19 Ibid., p. 626, 20 Ihid., p. 627. 21 Garner, W. , ’Textile Laboratory Manual1, The national Trade Press Ltd., London, p. 350, (1949;. 22 Gulati, K. C . , Seth, S. R. , and Venkataraman, H. , J. Chem. Soc., 1766, (1934). 23 Hale, W. J. and Thorp, L. , J. Am. Chem. Soc., 35, 267, (1913 ). 24 Helferich, B. and Schaefer, V . , ’Organic Synthesis’, Conant J. B. Ed., John Wiley and Sons, Rev; York, 9, 32, (1929). 25 Hickihbottom, W. J. , ’Reactions of Organic Compounds’, Longman Green and Company, 2 nd. Ed., p. 348. 26 Hoesch, K . , B e r . , 60, 389, (1927). 27 Horsfall, R. S. and Lawrie, L. G . , 'Dyeing of Textile Fibres’, (1927). 28 Kouben, J. and Fischer, W. , J. Prakt. Chem., 2, 123, 89, (1929). 29 Huang-Minlon, ”A Simple Modification of the Vo IffKishner Reduction” , J. Am. Chem, Soc,, 68, 2488, (1946 ). 30 Ju, T. Y . , Shen, G. and Wood, C. E . , Inst. Petr., 514, (1940). 31 Judef i n d , W. L. , and Reid, E. E. , J. Am. Chem. Soc. , 42, 1044, (1920). 32 K n e c t , Ber., p. 1556, (1888). 33 Lomax, J . , ’Textile Testing’, Longman Green and Co., London, p. 164, (1949). 34 Ibid., p. 173. 35 Martin, E. E . , ’Organic Reactions’, vol. 1., John Wiley and Sons,Hew York, p. 167, (1942). 90 (36) Montagne, P. J. , Rec. Trav. Chim. , 40, 247, (1921). (37) Perrier, G. , Ber., 33, 815 (1900). (38) Pratt, L. C. , ’Textile Chemistry*, JohnWiley Sons Inc., Hew York, p. 176, (1947). (39) Ralston, A. W. , Selby, W. M. and Pool, W. Eng. Chem., 33, 682, (1941). (40) Rinkes, I. and 0., Ind. J. ,Rec. Trav. Chim. , 63, 94, (1944). (41) Schopff, M., Ber., 24, 3766, (1891). (42) Schweitzer, R., Ber., 24, 550, (1891). (43) Skinkle, J. H., ’Textile Testing’, Chem. Publ. Co., Inc., hew York, p. 79, (1940). (44) Ihid., p. 105. (45) Thomas, C. A., et.al. , ’Anhydrous Aluminum Chloride in Organic Chemistry* , hew York, Reinhold Pub­ lishing Corp., (1941). (46) Weygand, C. , ’Organic Reactions’, hew York, Inter Science Publ., p. 133, (1945). (47) Ibid., p. 218. (48) Ibid., p. 447. (49) Whittaker, C. M. and Wilcock, C. C. , *Byeirig with Coal Tar Dyestuffs*, Bailliere, Tindall and Cox, London, p. 91, (1942). (50) Ibid., p. 180. (51) Zinn, J. Pract. Chem., 2J7, 140, (1842).