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United States Patent Office Patented Aug 3,832,364 United States Patent Office Patented Aug. 27, 1974. 2 zene, o-, m- and p-dichlorobenzene, anisole, methyl. 3,832,364 benzyl ether, n-propyl phenyl ether, m-ethyl-anisole, 4 AMINATION OF AROMATIC COMPOUNDS IN methyldiphenyl ether, di-p-tolyl ether, ethyl 2-cyclohexyl LIQUID HYDROGEN FLUORIDE Dale Robert Coulson, Wilmington, Del assignor to E. I. phenyl ether, n-heptyl phenyl ether, isobutyl phenyl ether, du Pont de Nemours and Company, Wilmington, Del. 5 cyclohexyl phenyl ether, n-octyl phenyl ether, n-octyl p No Drawing. Filed May 25, 1972, Ser. No. 256,770 tolyl ether, n-octyl m-tolyl ether, decyl phenyl ether, 1 Int. C. C07c87/50, 97/12 benzylethylheptyl ether, benzoic acid, p-toluic acid, p U.S. C. 260-378 26 Claims chlorobenzoic acid, phthalic acid, nitrobenzene, m-dinitro benzene, o-, m- and p-nitrotoluene, acetophenone, methyl O benzyl ketone, p-methylacetophenone, 3-phenyl-2-buta ABSTRACT OF THE DISCLOSURE none, propriophenone, 2-methyl-1-tetralone, phenyl. n Disclosed herein is a process for making aromatic butyl ketone, benzophenone, p-methylbenzophenone, di amines from benzene or substituted benzene and an o-tolyl ketone, phenyl isobutyl ketone, phenyl n-hexyl aminating agent via direct amination in liquid hydrogen ketone, phenyl n - undecyl ketone, anthraquinone, 2 - fluoride medium as solvent and catalyst. 15 methylanthraquinone, and 1-methyl-4-isopropylanthra quinone. Preferred aromatic compounds are those containing BACKGROUND OF THE INVENTION two or fewer substituents. Especially preferred com 1. Field of the Invention pounds are those containing two or fewer substituents 20 selected from halogen and alkyl of up to four carbons. This invention relates to a novel process for direct Most preferred aromatic compounds for amination are amination of benzene or substituted benzene employing benzene, toluene, and chlorobenzene. an aminating agent, and hydrogen fluoride as catalyst and It is noted that the aminating reactants set out below. solvent. for convenience into "groups' A, B, C, and D, are all 2. Description of the Prior Art 25 operable aminating agents in the novel process. This dis Heretofore, it has not been known to aminate aromatic closure in "groups' A, B, C, and D is not meant to imply hydrocarbons in the presence of hydrogen fluoride. any process distinctions based upon which group the Rather, prior art amination is known with hydroxylamine aminating reagent is chosen from. salts and molar amounts of aluminum chloride as catalyst The Aminating Reactant . (Graebe, Chem. Ber., 34, 1778 (1901) and Jaubert, 30 Compt. Rend., 132, 841 (1901)). Hydroxylamine-O-sul A. Aminating agents suitable for use in this invention fonic acid has also been investigated as an aminating include salts of hydroxylamine and N-alkyl and N,N- agent in the presence of aluminum chloride (Keller et al., dialkylhydroxylamines, the alkyl groups containing-1 to J. Am. Chem. Soc., 66, 1122 (1944); ibid., 68, 899 10 carbons, with such inorganic acids as HCl, HSO4, (1946); Kovacic et al., ibid., 83, 221 (1961); ibid., 84, HPO, and HCIO and such lower aliphatic carboxylic 759 (1962); ibid., 86, 1588 (1964)). Hydrazoic acid and acids as acetic, propionic, butyric, isobutyric, pivalic, its salts in the precence of aluminum chloride are known caproic, caprylic, etc. When N-alkyl and N,N-dialkylhy aminating agents (U.S. 1,637,661, Brit. 252,460, and droxylamines are used, the corresponding N-alkyl and Borsche et al., Chem. Ber., 82, 260 (1949)). A prior art N,N-dialkylamines are obtained. For example, reaction of attempt failed to achieve condensation of p-tolylhydroxyl 40 benzene with N - methylhydroxylamine hydrochloride amine with phenol in the presence of hydrogen fluoride, gives N-methylaniline and reaction with N,N-dimethyl Weinmayr, J. Am. Chem. Soc., 77, 1762 (1955). U.S. hydroxylamine hydrochloride gives N,N-dimethylaniline. 2,585,355 teaches introducing amino groups into aromatic Preferred aminating agents are the salts of hydroxyl compounds employing hydroxylamine and sulfuric acid. amine and those of N-alkyl and N,N-dialkylhydroxyl 45 amine with 4 or fewer carbon atoms. Especially preferred SUMMARY AND DETAILS OF THE are salts of hydroxylamine, N-methyl- and N,N-dimethyl INVENTION hydroxylamine with HCl and HSO4. Salts with such acids This invention concerns a process for making aromatic as HNO and HSOs, are not suitable since the resultant amines by the direct amination of benzene or substituted products may react with the aromatic amines formed. In benzene comprising reacting said benzene or substituted 50 addition such compounds as hydroxylamine-O-sulfonic benzene in a closed vessel with an aminating agent in the acid and its alkyl and N,N-dialkyl derivatives are suitable presence of hydrogen fluoride medium as catalyst and aminating agents. solvent. B. Primary nitroalkanes, RCHNO2, where R is hydro The Aromatic Reactant gen or alkyl of 1 to 10 carbons, are also suitable aminat Contemplated aromatic compounds used as starting re 55 ing agents since they react to form hydroxylamine in situ. actants include benzene and substituted benzene, wherein ; For example, amination of benzene, toluene and chloro the substituents are selected from one or more of halogen, benzene with nitromethane gives the corresponding pri alkyl of up to 10 carbons, cycloalkyl of 3 to 8 carbons, mary aromatic amines. Preferred nitroalkanes are aralkyl of up to 10 carbons, alkoxy and alkoxyalkyl of up CHNO, to 10 carbons, phenoxy, carboxyl, nitro, acyl and aroyl of 60 up to 12 carbons, and cycloalkylene of 3 to 5 carbon : C2HNO, n-CHNO. and n-CHNO. joining adjacent ring carbons. -- C. Aminating agents also include nitric oxide in com Aromatic compounds for amination include durene, bination with a tin-containing reducing agent. Although it toluene, isomers of xylene (o, m and p), isopropylben cannot be said with certainty, it is thought that a hy Zene, phenylcyclopropane, o-, m- and p-diethylbenzene, 65 droxylamine salt is generated by the in situ reduction of 1,2,4-trimethylbenzene, indane, 2- and 5-methylindane, the nitric oxide. It has also been found that, for example, phenylcyclopentane, n - amylbenzene, n - heptylbenzene, precursornitrosonium, in place bisulfate, of the NOHSO, nitric oxide. can . be employed as a phenylcyclohexane, diphenylmethane, 1,2-diphenylethane, Representative tin containingw 0. systems suitable as reduc 2 - isopropylindane, 4 - isopropylindane, phenylcyclohep 70 ing agents for nitric oxide include tin metal itself, stannous tane, phenylcyclooctane, Tetralin, 6 - isopropyltetralin, oxide, the stannous halides including stannous fluoride, chlorobenzene, bromobenzene, iodobenzene, fluoroben stannous chloride, stannous bromide and stannous iodide, 3,832,364 3 . 4. and other stannous salts including salts of organic and Uses for the aromatic amines made by the process of inorganic acids. Suitable organic acid ligands include this invention are well known to those skilled in the art. anions of lower alkanoic acids containing up to 8 carbon It is well known, for example, to use aromatic amines as atoms and anions of aromatic acids derived from benzene dye intermediates, antioxidants, antiozonants, corrosion in or benzene substituted with halo, lower alkyl or addi hibitors, curing agents for elastomers, intermediates to tional carboxyl groups, i.e., benzoate, p-toluate, n-toluate, surfactants, and intermediates for the preparation of iso phthalate, isophthalate and p-chlorobenzoate. Suitable in cyanates useful in the preparation of polyurethane foams organic acid ligands include sulfate, phosphate, borate and and elastomers. Polymeric isocyanates, useful as compo sulfide. Preferred reducing agents include the stannous nents of rigid foams, are based on aniline. The toluenedi halides with stannous chloride being particularly preferred. O amines serve as intermediates to the toluenediiso D. Although not preferred, lithium, sodium and potas cyanates, particularly useful for the preparation of flexible sium salts of hydrazoic acid and ammonium azide can be urethane foams. employed. Hydrogen Fluoride DESCRIPTION OF THE PREFERRED The amination reaction is normally carried out in sub 5 EMBODIMENTS stantially anhydrous hydrogen fluoride which serves as The following Examples are meant to illustrate but not catalyst and reaction medium. Although preferred, it is to limit the invention. not essential that the hydrogen fluoride be anhydrous and even commercial 48% hydrofluoric acid can be used. Example 1 20 Process Conditions A mixture of benzene (17.8 ml., 200 mmoles) and Stannous chloride (9.45 g., 50 mmoles) was charged to The reaction is normally carried out in a vessel that an 80 cc. corrosion resistant pressure bomb. The mixture is inert to hydrogen fluoride. Vessels based on nickel alloys, was cooled to about -80 C. and evacuated to remove or those lined with copper, silver or platinum are preferred. 25 air. Hydrogen fluoride (35 g.) was then added and nitric Normally, no additional solvent other than excess hy oxide was added to a pressure of 250 lbs./in2 gauge drogen fluoride is required for the reaction. It is possible, (p.S.i.g.) (about 19 mmoles NO). The bomb was heated however, to reduce the quantity of hydrogen fluoride used at 150 C. for 3 hours with shaking. The bomb was and to add additional inert solvents as desired. Suitable cooled and the hydrogen fluoride evaporated from the cosolvents include water, cyclohexane, acetic acid, hexane, 30 residue over a period of several hours under a nitrogen heptane, octane and decane, acetone, methyl ethyl ketone, stream. The residue was treated with 10% aqueous so methyl isobutyl ketone, carbon tetrachloride and chloro dium hydroxide solution to liberate the aromatic amine. form. The resulting mixture was filtered of insolubles, the pre Molar ratios of 100:1 to 1:100 of aromatic compound cipitate washed with ether and the filtrate extracted with to aminating agent are operable and the desired amine re 35 ether. The ether extracts were combined, dried over mag action products are obtained. Nevertheless, more nearly nesium sulfate, filtered and evaporated on a rotary evap equal ratios are preferred, for example, ratios of about orator.
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