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United States Patent (19) 11, 3,965, 182 Worrel (45) June 22, 1976

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United States Patent (19) 11, 3,965, 182 Worrel (45) June 22, 1976 United States Patent (19) 11, 3,965, 182 Worrel (45) June 22, 1976 54 PREPARATION OF ANILINE FROM 3,565,940 2197 Brown et al.................... 252/438 x PHENOL AND AMMONA 75) Inventor: Calvin J. Worrel, Detroit, Mich. a. Primary Examiner-Lewis Gotts 73 Assignee: Ethyl Corporation, Richmond, Va. Assistant Examiner-S. P. Williams (22 Filed: Oct. 2, 1969 Attorney, Agent, or Firm-Donald L. Johnson; Robert A. Linn; Joseph D. Odenweller (21) Appl. No.: 863,349 52) U.S. Cl................................. 260/578; 260/247; 260/293.72; 260/326.15; 260/346.2 R; 57 ABSTRACT 260/570 R; 260/576; 260/577 57 51) Int. Cl.................... C07C 87,152; C07C 87,156; C07C 87/62; Co7C 87/64 Aromatic amines are made by reacting a phenol with 58 Field of Search................ 260/578,581,585 B. aluminum nitride and either ammonia or a primary or 252,438 secondary amine at temperatures from 200-600°C. For example, 2,6-dimethyl-phenol reacts with alumi 56 References Cited num nitride and ammonia to yield 2,6-dimethylaniline. UNITED STATES PATENTS 2,000,410 5/1935 Morrett et al....................... 2601581 7 Claims, No Drawings 3,965, 182 1. 2 ran, 6-hydroxythionaphthene, 7-hydroxyindole, 4 PREPARATION OF ANILINE FROM PHENOL AND hydroxyisoindole, and the like. Phenols obtained by AMMONIA inserting a hydroxyl radical in the remaining aromatic nuclei will be apparent from the foregoing. BACKGROUND The process is also applicable to aryl hydroxy com The conversion of hydroxy aromatic compounds, pounds having more than one hydroxyl radical bonded referred to collectively as phenols, to the correspond to a nuclear aromatic carbon atom, For example, the ing aromatic amines has been accomplished in the past process can be applied to such polyhydroxy aromatics by such means as the Bucherer reaction, in which phe as hydroquinones, recorcinols, catechols, 1,3-dihy nols are reacted with a bisulfite salt and ammonia. In 10 droxy naphthalenes, pyrogallols, phloroglucinols, and British Pat. No. 619,877, certain phenols were con the like. verted to aromatic amines by reaction with ammonia Substituents other than hydroxyl groups may be pre and ammonium chloride. However, in some cases the sent in the aromatic compounds as long as they do not desired aromatic amine is not readily available from interfere with the course of the reaction. That is to say, prior methods. For example, 2,6-dimethylaniline can 15 the other substituents should be relatively inert to alu not readily be made by reduction of the corresponding minum nitride, ammonia, primary or secondary nitro derivative because the nitro derivative is not amines. For example, any of the previously-listed aro readily available. Also, even the reaction described in matics may be substituted in a variety of positions with the above British patent gives but trace amounts of alkyl radicals aralkyl radicals, cycloalkyl radicals, chlo 2,6-dimethylaniline when applied to 2,6-dimethyl 20 rine, bromine, iodine, fluorine, nitro groups, and the phenol. - , like. A few representative examples of these using the simpler aromatic structures are p-chlorophenol, p SUMMARY nitrophenol, 6-bromo-o-naphthol, 6-chloro-7-hydroxy It has not been discovered that aromatic amines can coumarone, 2-acetoxy-7-hydroxy-indolenine, 3-n- be prepared by reacting a phenol with aluminum ni 25 dodecyl-7-hydroxy-benzisoxazole, 4-nitro-8-hydroxy tride and ammonia or a primary or secondary amine at 1,2-benzopyran, 7-sec-octadecyl-8-hydroxy-isocouma rin, and the like. temperatures in the range of from about 200-600°C. The reaction proceeds very well when the hydroxy DESCRIPTION OF THE PREFERRED aromatic is a hydroxy-substituted mononuclear aro EMBODIMENTS 30 matic. As previously stated, these phenol type materials A preferred embodiment of this invention is a pro can be substituted with other groups as long as they do cess comprising reacting a phenol with aluminum ni not interfere with the course of the reaction. A pre tride and a nitrogen compound selected from the group ferred class of such mononuclear hydroxy aromatics consisting of ammonia and amines having at least one are those having the formula: hydrogen atom bonded to the amine nitrogen atom in a 35 temperature range of from about 200-600°C. The phenol reactants may be in general any aromatic compound having a hydroxyl radical bonded to a ben (R)-3- (OH) zene ring. The remainder of the molecule can be any thing as long as it does not interfere with the process. 40 I For example, the aryl portion of the molecule may be a di- or tri-nuclear aromatic radical or, for that matter, it whereinn is an integer from 0-3, m is an integer from can contain even more aryl groups. The aryl portion of 1-3, and R is selected from the group consisting of the phenol may be fused to other cyclic systems includ alkyl radicals containing from 1-20 carbon atoms, aral ing heterocyclic systems such as cyclic systems contain 45 kyl radicals containing from 7–20 carbon atoms, aryl ing oxygen, nitrogen and sulfur. For example, the phe radicals containing from 6–20 carbon atoms, and cy nols can be any of the isomeric hydroxy-substituted cloalkyl radicals containing from 6–20 carbon atoms. derivatives obtained by substituting a hydroxy group Some examples of these are: phenol, catechol, recor into an aromatic nucleus of benzene, naphthalene, cinol, pyrogallol, phluoroglucinol, hydroquinone, 3,5- anthracene, phenanthrene, indene, isoindene, benzofu 50 di-tert-butylphenol, 2,6-di-tert-butylhydroquinone, 3 ran, isobenzofuran, thionaphthene, indole, isoindole, methyl catechol, p-cresol, m-cresol, p-eicosylphenol, indolenine, 2-isobenzazole, 1,2-benzodiazole, 1,3-ben 2,4-didodecylphenol, 2,4-dicyclohexylphenol, p zo-diazole, indiazine, 1,3-benzoisodiazole, 1,2,3-ben phenylphenol, p-(o-naphthyl)phenol, m-(2,4-di-sec zotriazole, benzisoxazole, benzoxadiazole, 1,2-benzo heptylphenyl)phenol, p-cyclohexylphenol, 3-cyclooc pyran, 1,4-benzopyran, 1,2-benzopyrone, quinoline, 55 tylphenol, p-(4-sec-dodecylcyclohexyl)phenol, 2,4,6- isoquinoline, 1,3-benzodiazine, 1,2-benzisoxazine, ace tri-methyl phluoroglucinol, m-sec-eicosylphenol, p-(4- naphthene, fluorene, dibenzopyrrole, xanthene, thian tert-tridecylbenzyl)phenol, 4-(3,5-di-sec-heptylcy threne, phenothiazine, phenoxazine, naphthacene, clohexyl)phenol, 4-phenylphenol, 4-(a-naphthyl) phe chrysene, pyrene, triphenylene, and the like, wherein nol, and 2-sec-eicosylhydroquinone. the hydroxyl group is bonded to a nuclear carbon atom. 60 The advantages of the process over the prior art The following serve to further illustrate the phenol methods display themselves to a greater extent when reactants obtained by inserting a hydroxyl group in a the hydroxy aromatic is a mononuclear phenol in which few of the above aromatic nuclei. These include phe at least one position ortho to the phenolic hydroxyl nol, a-naphthol, g-naphthol, 9-hydroxyanthracene, radical is substituted with a radical selected from the a-hydroxyanthracene, g-hydroxyanthracene, 2 65 group consisting of alkyl radicals containing from 1-20 hydroxyphenanthrene, 3-hydroxyphenanthrene, 7 carbon atoms, aryl radicals containing from 620 car hydroxyindene, 7-hydroxyisoindene, 7-hydroxyben bon atoms, cycloalkyl radicals containing from 6-20 zofuran, 4-hydroxybenzofuran, 5-hydroxyisobenzofu carbon atoms and aralkyl radicals containing from 3,965, 182 3 4 7-20 carbon atoms. These are phenols having the for 6(cy-methylbenzyl)-o-cresol, mula: 2,4-di-methyl-6-(2,3-benzobenzyl)phenol, 203-tert-butyl-5-isopropylbenzyl)phenol, OH 2,6-dicyclooctylphenol, Ra 5 2,6-dibornylphenol, 2,6-dicyclohexylphenol, 2,6-dieicosylphenol, 6-sec-eicosyl-o-cresol, 2,4-dimethyl-6-docosylphenol, O 6-phenyl-o-cresol, 2,4-dimethyl-6-(4-tetradecylphenyl)phenol, wherein p is an integer from 0-2, R and Ra are selected 2-ethyl-6-(3,5-diheptylphenyl)-p-cresol, and the like. from the group consisting of alkyl radicals containing Another reactant in the process is either ammonia or from I-20 carbon atoms, aralkyl radicals containing an amine having at least one hydrogen atom bonded to. from 7-20 carbon atoms, aryl radicals containing from 15 the amine nitrogen atom. These are generally referred 6–20 carbon atoms and cycloalkyl radicals containing to as primary or secondary amines. Examples of these from 6–20 carbon atoms. Some further examples of amines are dimethyl amine, methylamine, ethylamine, these phenolic starting materials are: o-sec-butylphenol, diethyl amine, n-propyl amine, aniline, o-naphthyl 2,5-dimethylphenol, 20 amine, piperidine, morpholine, diethanol amine, etha o-cresol, nol amine, n-dodecyl amine, 2-docosyl amine, n-tria o-ethylphenol, contyl amine, 1-pentacontyl amine, and the like. Poly 2,4,6-tri-sec-butylphenol, amines and polyalkylene amines are also useful. Exam 2,4-dimethylphenol, ples of these amines are N,N-dimethyl-1,3-propanedia 2-(cy-methylbenzyl)phenol, 25 mine, ethylene diamine, 1,6-hexane diamine, diethyl 2-cyclohexyl-p-cresol, ene triamine, triethylene tetraamine, tetraethylene 2-cyclooctylphenol, pentamine, and the like. When amines having multiple 2(3,5-di-tert-butyl-cyclohexyl)-4-sec-eicosylphenol, NH or NH groups available are used the process can 2-sec-eicosylphenol, be carried out in a manner to utilize more than one of 2-(cy-methyl-4-dodecylbenzyl)phenol, 30 the available amine groups. For example, the reaction 2-phenylphenol, of phenol, aluminum nitride and ethylene diamine can 2-naphthylphenol, be carried out to form N,N'-diphenyl ethylene diamine. 2(4-tetradecylphenyl)phenol, Likewise, 1,6-hexane diamine will form N,N'-diphenyl 2C3,5-di-sec-heptylphenyl)phenol, 1,6-hexane diamine. Likewise, tetraethylene pent 2-tert-octadecylphenol, 35 amine will form a mixture in which the terminal nitro 2-isopropylphenol, gen atoms are substituted with a phenyl radical.
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