JPS6249264B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for producing arylamines by reacting an alcohol and an amine in the presence of a phosphorus compound. It is known that phenols can be reacted with aliphatic amines to form the corresponding aniline compounds, according to Houben-Weyl, Methoden der Organitsien Chemie, Vol. 11/1, pp. 160-170. . As detailed on page 162, direct reactions are rarely carried out even with highly reactive phenols. The reaction is usually carried out in the presence of dehydrating or catalytic additives, such as hydrochlorides, sulfates, phosphates, chlorides, boric acid or iodine of the amine to be reacted. The yield and purity of the target product are unsatisfactory with this method, with reactions of resorcinol and various amines in the presence of phosphoric acid showing only 7-16% performance;
and 23% yield in case of higher excess of amine (Journal of Medicinal Chemistry 1970, 13
Vol., pp. 371 and 375). In particular, tar-like and resin-like precipitates are formed, and the formation of substituted m-phenylenediamines is a nuisance. Under certain reaction conditions, such as long reaction periods, high reaction temperatures and/or the presence of acids or salts as catalysts, the formation of this N-substituted m-phenylenediamine becomes the main reaction. According to GB 168,689, for example in the presence of a sulphite or hydrochloride salt of the amine to be reacted, both hydroxyl groups of the resorcinol react and substituted m-aminophenols are obtained only to a small extent. do not have. According to German Patent No. 14612, excess primary and secondary amines in the form of β-naphthol and hydrochloride are converted into naphthylamine during a reaction period of 7 to 12 hours at temperatures of 170 to 210° C. under pressure. However, the yields are unsatisfactory, especially on an industrial scale. This patent teaches that there is a risk of tertiary base formation due to the subsequent reaction of the formed secondary amine and unchanged naphthol at higher temperatures. This results in deterioration of the yield and purity of the target substance. It is also known in this connection that at higher temperatures dealkylation and transalkylation of the alkylamines used can occur, resulting in more highly and less alkylated amines.
That is, according to German Patent Application No. 2301203, in all known processes, even in the amination of naphthol, naphthylamine is present in the target product and therefore purification of the alkylnaphthylamine produced is necessary. be. Furthermore, on page 135 of the above-mentioned volume of the book by Houben-Weyl, it is described that N-n-butylaniline rearranges into 4-n-butylaniline even at 240 DEG C. Berichte der Deutschen Hemitschen Gesellschaft, vol. 14, p. 2343 (1881) describes how β-naphthol and excess ammonium acetate are mixed with or without the addition of glacial acetic acid from 270 to
It is stated that by reacting at 280° C., β-acetaminonaphthalene and small amounts of free amine as by-products as well as β-dinaphthylamine are obtained. In the book of Houben-Weyl (cited above, pp. 162 and 164), dehydrating salts are recommended for the reaction of naphthol, and dinaphthylamine is also formed in substantial amounts in the reaction with ammonia; It has been shown (page 165) that the prepared naphthylamine is also converted to dinaphthylamine and ammonia under similar conditions. 1- and 2-naphthylamine is produced from 1- and 2-naphthol using ammonia and calcium chloride as a catalyst, with 1,1'- or 2,2'-dinaphthylamine as a by-product. In contrast, when zinc chloride is used, these by-products are produced as the main product. German Patent No. 848196 teaches that the production of aromatic secondary amines by reacting aromatic primary amines with phenols in the presence of iodine as a catalyst requires extremely long reaction times. ing. Replacing iodine with zinc chloride or sulfuric acid can shorten the reaction time, but
A solid, unmeltable residue with very poor thermal conductivity is formed, the yield is reduced and the heat transfer deteriorates such that further condensation is no longer possible. According to the teaching of this patent specification, organic sulfonic acids, especially aromatic sulfonic acids, are added as catalysts during the condensation of phenols and aromatic primary amines. The residue produced in this case is liquid when heated. According to this reaction, in the case of naphthols, a good yield of the target substance can be obtained only in the case of β-naphthol. According to the teachings of Houben-Weyl (cited above, volume 165), the different reactions of α- and β-naphthols can also be achieved in the presence of iodine, calcium chloride or sulfonic acids as catalysts in the reaction with arylamines. Gender arises. According to U.S. Pat. No. 2,503,778, trialkyl phosphate as a catalyst in the reaction of hydroquinone with aniline can give a yield of N.N'-diphenyl-p-phenylenediamine of 73-80.5%. is known and this is shown in all its examples. According to the experiments described in U.S. Pat. No. 2,376,112, resorcinol, hydroquinone or other phenols are reacted with ammonia or amines in the presence of ammonium phosphate or ammonium arsenate for a reaction time of 12 hours or more. Yields of 22-80% are obtained. Also, Hoben-Weyl's writings (volume 134~)
136), it is known to react an aliphatic alcohol and an amine in the presence of an acid or an alkali to form the corresponding alkyl amine. As a result of this reaction, an amine mixture can be expected according to the teachings of Houben-Weyl's book. The reaction likewise depends on the mixing ratio of the reactants, the reaction conditions and, in the case of aromatic amines, on their structure. Aromatic amines can be alkylated at the core, and the temperature at which the alkyl group is transferred from the nitrogen atom to the aromatic amine core depends on the type of alcohol. Primary alcohol and aniline, 4
-nitroaniline, 4-aminophenol or 2
-The reaction with naphthylamine can be carried out to form tertiary amines. In this regard, it is stated (p. 135) that when a large amount of acid is used to accelerate the reaction, excess primary alcohol causes overalkylation to a quaternary ammonium salt. Also, the reaction between alcohols and aromatic amines in the presence of their hydrochlorides or sulfates, or in the presence of iodic acid, ammonium iodide, boron fluoride, methyl iodide, ammonium chlorozincate or alkylphenylammonium iodide Since the process does not proceed uniformly, the secondary and tertiary amines must be separated in a special manner. The inventors have determined that the general formula (in the formula, R ² and R ⁵ have the meanings given below), an alcohol represented by the general formula R ¹ -OH (in the formula, R ¹ has the meanings given below), and a catalyst of the general formula (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, an aliphatic, araliphatic or aromatic residue) , general formula (In the formula, R ¹ is a residue

[Formula] or group

[Formula] Aliphatic, alicyclic or araliphatic residue, R ² means an aromatic residue, R ¹ is a residue

When it means [Formula], R ² may further mean an aliphatic, alicyclic, or araliphatic residue, and R ³ and R ⁴ may be the same or different, and each is a hydrogen atom. , means an aliphatic residue or an alkoxy group, R ⁵ means a hydrogen atom, or when R ¹ means an aliphatic, cycloaliphatic or araliphatic residue, R ⁵ further represents an aliphatic residue or an alkoxy group; It has been found that arylamines of the formula (which may also refer to residues of the group, cycloaliphatic or araliphatic) are advantageously obtained. Furthermore, the inventors have determined that the general formula (wherein R ² means an aromatic residue), the aromatic primary amine represented by the general formula R ¹ −OH (wherein R ¹ is a residue) is

[Formula] or residue

[Formula], R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, or an alkoxy group) and the general formula as a catalyst. arylamines of the formula are advantageously obtained when reacting in the presence of a triarylphosphite of the formula (in which the individual radicals R ⁶ may be the same or different and each denote an aromatic residue) I found out. Furthermore, the inventors have determined that the general formula (wherein R ² means an aromatic residue), the aromatic primary amine represented by the general formula R ¹ −OH (wherein R ¹ is a residue

[Formula] or residue

[Formula], R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, or an alkoxy group) and the general formula as a catalyst. (In the formula, the individual groups R ⁶ may be the same or different, and each represents a hydrogen atom, an aliphatic residue, or an araliphatic residue, and one or two groups R ⁶ each represent an aromatic residue. It has been found that arylamines of the formula are advantageously obtained when reacting in the presence of a phosphorus compound (which may also represent a group). Furthermore, the inventors have determined that the general formula (In the formula, R ² means an aliphatic, alicyclic or araliphatic residue) (In the formula, R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, or an alkoxy group) and a general formula as a catalyst. (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, an aliphatic, araliphatic or aromatic residue) It has been found that arylamines of the formula are advantageously obtained. Furthermore, the inventors have determined that the general formula An aromatic amine represented by ^the general formula ^{R 1 −} Alcohol represented by OH (in the formula R ¹ means an aliphatic, alicyclic or araliphatic residue) and the general formula as a catalyst (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, an aliphatic, araliphatic or aromatic residue) It has been found that arylamines of the formula are advantageously obtained. This reaction can be expressed by the following reaction formula when resorcinol or α-naphthol and aniline are used. This reaction can be shown by the following reaction formula when ethylamine and α-naphthol are used. Furthermore, this reaction can be expressed by the following reaction formula when m-toluidine and 2-phenylethanol are used. With the process of the invention, compared to the known processes, arylamines are obtained by simple and economical means with improved yields, space-time yields and purities. The formation of tar-like or heat transfer inhibiting residues as well as the formation of N.N'-disubstituted-m-phenylenediamines are unexpectedly not observed to any significant extent. Expensive purification operations are avoided and in many cases the crude target material can be used for subsequent syntheses. Because corrosive strong acids and acid salts are not used as catalysts, the process of the present invention has greater operational safety and environmental friendliness, and equipment parts and conduits are much less subject to corrosion. Devices with linings such as lead enamel, nickel alloys, etc., which are stable to high corrosion and high temperatures, are thus saved. Compared to known processes, especially those without catalysts, very high reaction temperatures and pressures and correspondingly long heating and cooling operations, which promote resinification of the reaction mixture, are avoided. The amines can be used economically, ie in approximately stoichiometric amounts. Known methods using high reaction temperatures of at least 250°C, for example German patent no.
Compared to the operating procedure described in 848196, higher yields of the target substance are obtained despite lower temperatures. N of α- or β-naphthylamine
- Compared to the synthesis of N-alkylnaphthylamines carried out by alkylation and with regard to the high toxicity of β-naphthylamines, the process according to the invention offers greater operational safety and environmental friendliness, especially on an industrial scale, and the health of workers. There is no danger above. Compared to the synthesis of N-alkylarylamines carried out by N-alkylation of aromatic primary amines, the process of the invention is more selective and the formation of heterogeneous mixtures is essentially not observed to a moderate extent. . All these advantageous results of the method of the invention are unexpected. In view of the state of the art, low reaction rates and significantly lower yields would have been expected, especially in the case of α-naphthol and phosphorus derivatives as catalysts. Also, to obtain satisfactory results, at least substantially higher temperatures, e.g.
A reaction time of 250-300°C and at least 12 hours would have been considered necessary. Acylation products, tertiary amine bases and naphthylamines, which may be formed by the reaction of naphthol with the decomposition products of the amines used, and nuclear alkylated amines by rearrangement, unexpectedly do not occur to a significant extent. Not generated. the starting materials in stoichiometric proportions or in excess, preferably in the case of aromatic alcohols in a ratio of 1 to 3.5 mol, particularly preferably 1 to 1.8 mol, especially 1 to 1.3 mol, of starting material per mole thereof; In the case of aliphatic, cycloaliphatic or araliphatic alcohols, each mol of aliphatic, cycloaliphatic or araliphatic alcohol is preferably reacted in a proportion of 0.3 to 4 mol of starting material, particularly preferably 0.5 to 2 mol. In the case of aliphatic, cycloaliphatic or araliphatic alcohols, and in the case of the reaction of primary amines, one of the alcohols is used to obtain the secondary amine.
Preferably 1 to 4 moles of starting material per mole,
In order to obtain the tertiary amine, preferably 0.3 to 0.7 mol of starting material are used per mole of alcohol. Preferred starting materials and correspondingly preferred target materials are those in which each symbol in the formula has the following meaning. R ¹ is a residue

[Formula] or residue

[Formula] or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms;
an alkoxyalkyleneoxy group with an alkyl group having 4 carbon atoms and an alkylene group having 2 to 4 carbon atoms, 1 to 4 in each alkyl group;
dialkylamino group having 6 to 6 carbon atoms,
Aryloxy radicals having 14 carbon atoms, especially phenoxy radicals, phenoxyethoxy radicals and/or
an alkyl group having 1 to 18, preferably 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms or 7 to 12 carbon atoms, substituted several or preferably one by benzyloxy groups; means an aralkyl group having 5 carbon atoms. R ² is an unsubstituted phenyl group, or 1 or 2 alkyl groups each having 1 to 4 carbon atoms and/or 1 or 2 alkyl groups each having 1 to 4 carbon atoms in each alkyl group; a phenyl group substituted with two alkoxy groups and/or one or two dialkylamino groups and/or a phenoxy group, an unsubstituted α-naphthyl group or β-naphthyl group, or one to
1 or 2 alkyl groups having 4 carbon atoms and/or 1 in each alkyl group respectively
means an α-naphthyl group or a β-naphthyl group substituted by one or two dialkylamino groups and/or phenoxy groups having ~4 carbon atoms, and R ¹ is a residue

When it means [Formula], R ² is further 1 to 18, preferably 1
an alkyl group having ~14 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, 1 to
an alkoxyalkyleneoxy group with an alkyl group having 4 carbon atoms and an alkylene group having 2 to 4 carbon atoms, 1 to 8 in each alkyl group;
1 to 18, preferably 1 to 8 carbon atoms, substituted several or preferably one by dialkylamino, phenoxy, phenoxyethoxy and/or benzyloxy groups with 1 to 18 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms or an aralkyl group having 7 to 12 carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8, especially 1 to 4 carbon atoms, or an alkoxy group having 1 to 8, especially 1 to 4 carbon atoms. means. R ⁵ means a hydrogen atom, or R ¹ is 1 to 18
Preferably an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an alkylene group having 2 to 4 carbon atoms. alkoxyalkyleneoxy radicals with radicals, dialkylamino radicals with 1 to 4 carbon atoms in each alkyl radical, aryloxy radicals with 6 to 14 carbon atoms, especially phenoxy radicals, phenoxyethoxy radicals and (or ) alkyl radicals having 1 to 18, preferably 1 to 8 carbon atoms, or cycloalkyl radicals having 5 to 8 carbon atoms, or cycloalkyl radicals having 7 to 8 carbon atoms, substituted severally or preferably once by benzyloxy groups When denoting an aralkyl group having 12 carbon atoms, R ⁵ further represents an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms;
or an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an alkoxyalkyleneoxy group having an alkylene group having 2 to 4 carbon atoms, 1 in each alkyl group. dialkylamino radicals having ~4 carbon atoms, aryloxy radicals having 6 to 14 carbon atoms, in particular several or preferably one substituted by phenoxy, phenoxyethoxy and/or benzyloxy radicals; 1 to 18, preferably 1 to 8
an alkyl group having 5 to 5 carbon atoms;
cycloalkyl group having 8 carbon atoms or 7
It may also mean an aralkyl group having up to 12 carbon atoms. The residues mentioned can be further substituted by groups which are inert under the reaction conditions, for example alkyl groups or alkoxy groups each having 1 to 4 carbon atoms. For example, the aromatic primary amines listed below are suitable as starting materials. Aniline, methyl group, ethyl group, n at the 2-position, 3-position or 4-position
-propyl group, isopropyl group, n-butyl group,
Aniline substituted by an isobutyl group or a secondary butyl group, methoxyaniline, ethoxyaniline, n-propoxyaniline, isopropoxyaniline, n-butoxyaniline, isobutoxy substituted in the o-, m- or p-position Aniline or secondary butoxyaniline, 2-position, 3-position
or 4-position: N・N-dimethylamino group, N・N-diethylamino group, N・N-di-
m-propylamino group, N·N-diisopropylamino group, N·N-di-n-butylamino group,
Aniline substituted by N.N-diisobutylamino group or N.N-disec-butylamino group, o
-Phenoxyaniline, m-phenoxyaniline, p-phenoxyaniline, depending on the above substituents: 2/4-position, 2/5-position, 2/6-position, 2/3-position
Aniline, α-naphthylamine or β-naphthylamine disubstituted in the -, 3, 4 or 3, 5-positions. As the secondary amine, those in which the nitrogen atom of the above-mentioned primary amine is further substituted with the following group are used. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, n-pentyl group, n-
Hexyl group, n-octyl group, 2-ethylhexyl group, 1,4-dimethylpentyl group, cyclohexyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, ω-methoxy-, ω-ethoxy-, ω- n-propoxy, ω
-isopropoxy-, ω-n-butoxy-, ω-
isobutoxy- or ω-secondary butoxy-ethyl group, ω-methoxy-, ω-ethoxy-, ω-n-
propoxy-, ω-isopropoxy-, ω-n-
butoxy-, ω-isobutoxy- or ω-sec-butoxy-propyl group, ω-methoxybutyl group, ω
-Ethoxybutyl group, ω-n-propoxybutyl group, ω-isopropoxybutyl group, ω-n-butoxybutyl group, ω-isobutoxybutyl group, ω-
Secondary butoxybutyl group, ω-methoxy-, ω-ethoxy-, ω-n-propoxy-, ω-isopropoxy-, ω-n-butoxy, ω-isobutoxy- or ω-secondary butoxy-ethyleneoxy- Ethyl group and the corresponding ethyleneoxypropyl and propyleneoxyethyl groups, phenoxyethyl group, benzyloxyethyl group, and residues of the formula. −(CH ₂ ) ₃ −OC ₂ H ₄ −OCH ₂ C ₆ H ₅ , −(CH ₂ ) ₃ −
OC ₂ H ₄ −OC ₂ H ₄ C ₆ H ₅ , −(CH ₂ ) ₃ −OC ₂ H ₄ OC ₆ H ₅ ,

【formula】

[Formula] -(CH ₂ ) ₃ - OC ₆ H ₅ , -(CH ₂ ) ₃ -OCH ₂ CH ₂ C ₆ H ₅ and dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n -butyl-,
di-isobutyl- or di-sec-butyl-amino-
ω-propyl groups and the corresponding ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, pentyl groups substituted in the ω-position by the aforementioned dialkylamino groups
(2) group, pentyl-(3) group, n-hexyl group or 3.
3-dimethylbutyl-(1) group, and a residue of the formula:

【formula】

【formula】

Mixtures of the abovementioned amines can likewise be used. For example, the following aliphatic, cycloaliphatic or araliphatic primary amines are suitable as starting materials.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl −
or 1,4-dimethylpentylamine, cyclohexyl-, cyclooctyl-, benzyl-, phenylethyl-, phenylpropyl- or phenylbutylamine, ω-methoxy-, ω-ethoxy-, ω-n-propoxy-, ω- Isopropoxy, ω-n-butoxy, ω-isobutoxy, ω
-Second-butoxy- or ω-tertiary-butoxyethylamine, ω-methoxy-, ω-ethoxy-, ω-n
-propoxy-, ω-isopropoxy-, ω-n
-butoxy-, ω-isobutoxy-, ω-secondary butoxy- or ω-tertiary butoxypropylamine,
ω-methoxybutylamine, ω-ethoxybutylamine, ω-n-propoxybutylamine, ω-
Isopropoxybutylamine, ω-n-butoxybutylamine, ω-isobutoxybutylamine,
ω-Secondary butoxybutylamine, ω-tertiary butoxybutylamine, ω-methoxy-, ω-ethoxy-, ω-n-propoxy-, ω-isopropoxy-, ω-n-butoxy-, ω-isobutoxy-,
ω-sec-butoxy- or ω-tert-butoxy-ethyleneoxy-ethylamine, and the corresponding ethyleneoxypropylamine and propyleneoxyethylamine, and primary amines having a residue of the formula: −(CH ₂ ) ₃ −OC ₂ H ₄ −OCH ₂ C ₆ H ₅ , −(CH ₂ ) ₃ −
OC ₂ H ₄ OC ₂ H ₄ C ₆ H ₅ , −(CH ₂ ) ₃ −OC ₂ H ₄ −OC ₆ H ₅ ,

【formula】

[Formula] -(CH ₂ ) ₃ - OC ₆ H ₅ , -(CH ₂ ) ₃ -OCH ₂ CH ₂ C ₆ H ₅ and dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n -butyl-,
diisobutyl- or disec-butylamino-ω-propylamine and the corresponding ethyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, butyl-, pentyl-, pentyl-(2)-, pentyl-(3)-, n-hexyl- or 3,3-dimethylbutyl-(1)-amine, and amines having a residue of the formula:

【formula】

【formula】

【formula】

Mixtures of the above-mentioned amines may also be used. Resorcinol, hydroquinone and naphthols such as those listed below are used as starting materials. Methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl- or sec-butyl-α-naphthol and -β-naphthol, in which the alkyl substituent is 3-
4-position, 5-position, 6-position, 7-position, 8-position, or 2-position or 1-position, preferably 2-position,
-, 4- or 5-position, α- and β- with one additional hydroxyl group in the above position
Corresponding methyl-, ethyl-, n- of naphthol
Propyl, isopropyl, n-butyl, isobutyl or secondary butyl ether, 3,4-
Methyl group, ethyl group, n-
α- and β-naphthols disubstituted with propyl, isopropyl, n-butyl, isobutyl or sec-butyl groups, the corresponding trihydroxynaphthalenes, of which the hydroxyl groups in two of the above positions are etherified with an alkyl group of Naphthols, and preferably α- and β-naphthols. For example, the following aliphatic, cycloaliphatic or araliphatic alcohols are used as starting materials.
Methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, secondary butyl-, n-pentyl-, n-hexyl-, n-octyl-, 2-ethylhexyl- or 1.4 -dimethylpentyl-alcohol, cyclohexyl-, cyclooctyl-, benzyl-, phenylethyl-, phenylpropyl- or phenylbutyl-alcohol, ω-methoxy-, ω-ethoxy-, ω-n-propoxy-, ω-isopropoxy- , ω-n-butoxy-, ω-isobutoxy- or ω-secondary butoxy-ethyl alcohol, ω-methoxy-, ω-ethoxy-, ω-n-propoxy-, ω-isopropoxy-, ω-n-butoxy -, ω-isobutoxy- or ω-secondary butoxy-
Propyl alcohol, ω-methoxybutyl-, ω
-ethoxybutyl-, ω-n-propoxybutyl-, ω-isopropoxybutyl-, ω-n-butoxybutyl-, ω-isobutoxybutyl- or ω
-Second-butoxybutyl-alcohol, ω-methoxy-, ω-ethoxy-, ω-n-propoxy-,
ω-isopropoxy-, ω-n-butoxy-, ω
-isobutoxy- or ω-secondary butoxy-ethyleneoxy-ethyl alcohol and the corresponding ω-alkoxyethyleneoxypropyl alcohol and ω-alkoxypropyleneoxyethyl alcohol and alcohols having groups of the formula. −(CH ₂ ) ₃ −OC ₂ H ₄ −OCH ₂ C ₆ H ₅ , −(CH ₂ ) ₃ −
OC ₂ H ₄ −OC ₂ H ₄ C ₆ H ₅ , −(CH ₂ ) ₃ −OC ₂ H ₄ −
_{OC6H5 ,}

【formula】

[Formula] -(CH ₂ ) ₃ - OCH ₂ CH ₂ C ₆ H ₅ , -(CH ₂ ) ₃ -OC ₆ H ₅ and dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n -butyl-,
diisobutyl- or disec-butylamino-ω-propyl alcohol, as well as ethyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, pentyl-, substituted in the ω-position by the aforementioned dialkylamino groups; Pentyl (2)
-, pentyl-(3)-, n-hexyl- or 3.3
-dimethylbutyl-(1)-alcohol, and R ⁴
Alcohol that has the meaning of the following formula.

【formula】

【formula】

Mixtures of the alcohols mentioned above may also be used. This reaction is generally carried out at 150-260°C, preferably at 175-260°C.
It is carried out continuously or discontinuously at a temperature of 235 DEG C., especially from 200 DEG to 230 DEG C., at normal pressure or under pressure. Particular preference is given to carrying out the reaction without additional organic solvents, but if appropriate organic solvents are used which are inert under the reaction conditions, preferably solvents which are immiscible or poorly miscible with water. Particularly advantageous solvents are
For example: Aromatic hydrocarbons such as toluene, ethylbenzole, o-, m- or p-xylol, isopropylbenzole or methylnaphthalene, ethers such as ethylpropyl ether, diisobutyl ether, methyl-tert-butyl ether, n-butyl ethyl ether, di-n -butyl ether, diisoamyl ether, diisopropyl ether, anisole,
phenetol, cyclohexyl methyl ether or diethyl ether, aliphatic or cycloaliphatic hydrocarbons such as heptane, nonane, o-, m- or p-cymol, benzine fractions with a boiling range of 70 to 190°C, cyclohexane, methylcyclohexane,
Decalin, hexane, ligroin, 2, 2, 4-
Trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane or octane, and mixtures thereof. The solvent is preferably used in an amount of 400 to 10,000% by weight, in particular 500 to 3,000% by weight, based on the starting materials. It is particularly advantageous to use the catalyst in an amount of 0.001 to 0.5 mol, preferably 0.005 to 0.1 mol of phosphorus compound per starting material. A preferred catalyst is
In the formula, the individual radicals R ⁶ may be the same or different, each being an unsubstituted phenyl or naphthyl group, or one or two alkyl groups each having 1 to 4 carbon atoms and/or 1 or 2 each with 1 to 4 carbon atoms
It means a phenyl group or naphthyl group substituted with alkoxy groups, a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. As the catalyst, for example, the following can be used. Tri-(2,6-dimethyl)-phenyl phosphite, tri-(2-methoxy)-phenyl phosphite, preferably tri-o-tolyl phosphite, tri-m-tolyl phosphite or tri-p
- tolyl phosphite, tri-o-xylyl phosphite, tri-m-xylyl phosphite or tri-p-xylyl phosphite, in which the ester group is in the m-position relative to one of the two methyl groups. tri-α-naphthyl phosphite, tri-β-naphthyl phosphite and especially triphenyl phosphite, trimethyl-, triethyl-, tri-n-propyl-, tri-isopropyl-, tri- n-butyl-, tri-isobutyl-, tri-sec-butyl-, tri-n-pentyl-, tri-n-heptyl-, trioctyl-, tri-n-hexyl-, tristearyl- or tridodecyl phosphite, dimethyl- , diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, disec-butyl, di-n-pentyl, di-n-heptyl, dioctyl, di-n -hexyl-, distearyl- or didodecyl-phosphite, methyl phosphite, ethyl phosphite, propyl phosphite, isopropyl phosphite, butyl phosphite, isobutyl phosphite, secondary butyl phosphite, n-pentyl, n-heptyl -, octyl- or n-hexyl phosphite, stearyl phosphite, dodecyl phosphite, phosphorous acid, tribenzyl-, triphenylethyl- or triphenylpropyl-phosphite, dibenzyl-, diphenylethyl- or diphenylpropyl-phosphite, benzyl phosphite. ate, phenylethyl phosphite, phenylpropyl phosphite, di-(2,6-dimethyl)-phenyl phosphite, di-(2-methoxy)-phenyl phosphite, di-o-tolyl phosphite, Di-m-tolyl phosphite, di-
p-Tolyl phosphite, di-o-xylyl phosphite, di-m-xylyl phosphite or di-p-xylyl phosphite, in which the ester group is in the m-position relative to one of the two methyl groups. di-alpha-naphthyl phosphite, di-beta-naphthyl phosphite, diphenyl phosphite, 2,6-dimethylphenyl phosphite, 2-methoxyphenyl phosphite, o - tolyl phosphite, m-tolyl phosphite, p-tolyl phosphite, o-xylyl phosphite, m-xylyl phosphite or p
-xylyl phosphites (in this case it is particularly advantageous for the ester group to be in the m-position relative to one of the two methyl groups), α-naphthyl phosphites, β-naphthyl phosphites, phenyl phosphites, and corresponding phosphites containing the three residues mentioned above and differing in whole or in part, such as phenyl dimethyl phosphite, methyl ethyl phosphite, methyl ethyl propyl phosphite, diphenyl butyl phosphite, phenyl Diethyl phosphite, ethyl phenyl phosphite, butylphenyl phosphite or benzyl diethyl phosphite. Preferred catalysts are: tri-n-butyl phosphite, tribenzyl phosphite,
Phosphous acid, dibutyl phosphite, diisopropyl phosphite, dibenzyl phosphite, triisopropyl phosphite, distearyl phosphite, didodecyl phosphite, triphenyl phosphite, tritolyl phosphite, tricylyl phosphite, trinaphthyl phosphite ,
Tri-n-hexyl phosphite, diphenyl phosphite, di-n-hexyl phosphite and benzylethyl phosphite. This reaction can be carried out as follows. The mixture of catalyst, starting materials and optionally solvent is heated, usually for 1 to 30 hours, particularly preferably for 1 hour.
~20 hours, preferably 4 to 20 hours in the case of naphthylamine, especially 9 to 12 hours, in other cases 1
~12 hours, preferably 1 to 8 hours, especially 2 to 4 hours,
Maintain at reaction temperature. Particularly preferably, the reaction temperature is maintained until no more water can be distilled off. The target substance is then isolated from the mixture by conventional methods such as distillation. If it is necessary to remove most of the starting naphthol from the α- or β-naphthylamine formed, 1 to 10% by weight to remove the naphthol.
Washing of the oily crude naphthylamine phase is preferably carried out using a dilute caustic soda solution of . The arylamine produced by the method of the present invention contains plant protection agents, optical brighteners, etc., aminocoumarin derivatives, and dyes, particularly xanthene, pyronine, rhodamine, and oxazine, as well as azo and triphenylmethane dyes. and is a valuable intermediate for the production of diphenylmethane-based dyes. Regarding applications, see the above-mentioned publications, Urmans Entiklopedii der Technicien Chemie, Vol. 12, pp. 623-633, Vol. 17, pp. 674-680.
Page, Kirkoo Osmer, Encyclopedia of Chemical Technology, Volume 2, 213~
224 pages (1963), Vol. 20, pp. 701-732 (1969),
and Fuencataraman, The Chemistry of Synthetic Soybeans, vol. (Academic Press, New York, 1952).
It is described on pages 1074, 1094 and 1097. Parts in the following examples are parts by weight. Example 1 3-Hydroxy-diphenylamine: 250 parts of resorcin, 250 parts of aniline and 4 parts of triphenyl phosphate are mixed and heated to 120<0>C to form a homogeneous melt. Dehydration begins when the internal temperature reaches 195°C after 60 minutes. Raise internal temperature up to 235℃ within 3 hours. After this time, 41 parts of water are distilled off and the reaction is complete. The excess aniline and resorcin still present are removed under vacuum and the 3-hydroxy-diphenylamine is distilled at 215° C. and 12 mm Hg.
402 parts of 3-hydroxy-diphenylamine with a melting point of 76 DEG -79 DEG C. are obtained, corresponding to a yield of 96% of theory. Example 2 3-Hydroxy-4'-methyl-diphenylamine: 250 parts of resorcin, 268 parts of p-toluidine and 8 parts of triphenyl phosphate are mixed and heated to 120 DEG C. to form a homogeneous melt.
Dehydration begins when the internal temperature reaches 205°C. Raise the internal temperature to 235°C within 4 hours. After this time, no more condensation of water takes place in the extra-system water remover. A total of 41 parts of water is distilled off. The excess p-toluidine and resorcinol still present are distilled off under vacuum and the 3-hydroxy-4'-
Distillation of methyl-diphenylamine at a distillation temperature of 185°C and 2 mmHg yields 3-hydroxy 4'-methyl-diphenylamine with a melting point of 86-90°C.
420 parts were obtained, corresponding to a yield of 93% of theory. Example 3 4-Hydroxy-diphenylamine: 250 parts of hydroquinone, 220 parts of aniline and 10 parts of triphenyl phosphate are mixed and 180 parts of triphenyl phosphate are mixed.
Make a homogeneous melt by heating to °C.
Dehydration begins at an internal temperature of 198℃, and after 5 hours it reaches 235℃.
Finish at °C. A total of 41 parts of water is removed from the system.
After distilling off excess aniline and hydroquinone, 4-hydroxy-diphenylamine was distilled off at a distillation temperature of 215°C and a vacuum of 12 mmHg, yielding 382 parts of 4-hydroxy-diphenylamine with a melting point of 66-68°C, which corresponds to a yield of 91% of theory. Example 4 3-Hydroxy-2'-methyl-diphenylamine: 700 parts of resorcin, 700 parts of o-toluidine and 15 parts of triphenyl phosphate are mixed and heated to 120°C to form a melt. Internal temperature is 205℃
Once this temperature is reached, dehydration begins and the internal temperature increases to 230°C within 4 hours. After this time, 115 parts of water are distilled off and the reaction is complete. The excess o-toluidine and resorcinol still present are removed in vacuo and the 3-hydroxy-2'-methyl-diphenylamine is then distilled at a distillation temperature of 185° C./3 mmHg, yielding the target product 1190 with n ²⁵ _D = 1.6455. 94% of theory, corresponding to a yield of 94% of theory. Example 5 3-Hydroxy-4'-methoxy-diphenylamine: In the same manner as in Example 1, 220 parts of resorcin, p
- from 300 parts of anisidine and 5 parts of triphenyl phosphate, 3-hydroxy-
385 parts (90% of theory) of 4'-methoxydiphenylamine are obtained. Example 6 3-Hydroxy-N-naphthyl-aniline: 220 parts of resorcin, α
- From 286 parts of naphthylamine and 8 parts of triphenyl phosphate, 3
411 parts of -hydroxy-N-naphthyl-aniline (86% of theory) are obtained. Example 7 N-phenyl-α-naphthylamine: 144 parts of α-naphthol, 150 parts of aniline and 5 parts of triphenyl phosphate are mixed and first
Heat to 180℃. The reaction begins with dehydration.
Water is separated using an external water system remover, and the aniline that comes out is returned. The temperature is increased to 210° C. within 4 hours and the dehydration is completed after a further 4 hours at a temperature of 212° C. (18 parts of H ₂ O). The reaction mixture was cooled to 150°C,
After distilling off excess aniline in vacuum,
At a vacuum of 5 mmHg and a boiling point of 202-203°C,
208 parts of N-phenyl-α-naphthylamine with a melting point of 55-58° C. are obtained, corresponding to a yield of 95% of theory. Example 8 N-3-methylphenyl-α-naphthylamine: 216 parts of α-naphthol, 214 parts of m-toluidine and 10 parts of triphenyl phosphate are mixed and the reaction is carried out in the same manner as in Example 7. The reaction is terminated after 27 parts of water is removed from the system. After distilling off the excess m-toluidine, 330 parts of N-m-tolyl-α-naphthylamine are obtained at a boiling point of 203 DEG-206 DEG C./5 mm Hg, corresponding to a yield of 94% of theory. Example 9 N-2,4-dimethylphenyl-α-naphthylamine: 216 parts of α-naphthol, 242 parts of 2,4-dimethylaniline and 10 parts of triphenyl phosphate were mixed and the reaction was carried out as in Example 7. go to
The highest reaction temperature is 220°C. After 27 parts of water was removed from the system, the reaction was completed (after 8 hours). 215~
At a boiling point of 218 DEG C./5 mm Hg, 355 parts of N-2.4-dimethylphenyl-.alpha.-naphthylamine with a melting point of 52 DEG-54 DEG C. are obtained. This corresponds to a yield of 95% of theory. Example 10 N-3,5-dimethylphenyl-α-naphthylamine: In the same manner as in Example 9, 216 parts of α-naphthol and 242 parts of 3,5-dimethylaniline were reacted with 10 parts of triphenyl phosphate. 350 parts of N-3.5-dimethylphenyl-α-naphthylamine with a boiling point of 215 DEG-216 DEG C./5 mm Hg are obtained, corresponding to a yield of 94% of theory. Example 11 N-p-ethoxyphenyl-α-naphthylamine: 288 parts α-naphthol, 411 parts p-phenetidine and 10 parts triphenyl phosphate are mixed and heated to 220°C. Dehydration begins at this temperature. When the reaction temperature was increased to 250℃ over 8 hours,
The reaction is completed and 36 parts of water is removed from the system. After removing excess p-phenetidine, N-p-ethoxyphenyl-α-naphthylamine was added to 233-235
Distillation at a boiling temperature of °C/5 mmHg yields 510 parts of the target material with a melting point of 73-75 °C. This corresponds to a yield of 97% of theory. Example 12 1,1'-dinaphthylamine: 144 parts of α-naphthol, 143 parts of α-naphthylamine
and 15 parts of triphenyl phosphate,
Then heat to 220℃. Dehydration begins at this temperature and ends at an internal temperature of 250°C. 18 parts of water is removed from the system in 10 hours. After distilling off excess α-naphthol and α-naphthylamine, 5 mm
Hg and temperature of 256-257℃, melting point 97-102
250 parts of 1.1'-dinaphthylamine are obtained. This corresponds to a yield of 93% of theory. Example 13 N-phenyl-β-naphthylamine: 270 parts of β-naphthol, 175 parts of aniline and 5 parts of triphenyl phosphate were mixed and 130 parts of
Melt at °C. The reaction begins with dehydration at an internal temperature of 190°C. After 2.5 hours internal temperature is 235
℃ is reached and 34 parts of water are distilled off. 230℃/
At a distillation temperature of 15 mm Hg, 398 parts of N-phenyl-β-naphthylamine with a melting point of 100-102° C. are distilled. This corresponds to a yield of 97% of theory. Example 14 1,2'-dinaphthylamine: 144 parts of β-naphthol, 143 parts of α-naphthylamine
and 10 parts of triphenyl phosphate,
Produces a homogeneous melt with an internal temperature of 120 °C. 230
Dehydration starts from an internal temperature of ℃, and after 3 hours it reaches 250℃.
C. and 18 parts of water are distilled off. At a distillation temperature of 239℃/0.1mmHg, the melting point
258 parts of 1,2'-dinaphthylamine are obtained at a temperature of 106 DEG -108 DEG C. This corresponds to a yield of 96% of theory. Example 15 3-Hydroxy-diphenylamine: Analogously to Example 1, 380 parts of 3-hydroxy-diphenylamine having a melting point of 75-79°C ( 90% of the theoretical value) is obtained. Example 16 3-Hydroxy-diphenylamine: Similarly to Example 1, 3-hydroxy-diphenylamine with a melting point of 74-78°C is prepared from 250 parts of resorcin, 250 parts of aniline and 10 parts of tri-3,4-dimethylphenyl phosphate. 382 parts of diphenylamine (91 parts theoretical)
%) is obtained. Example 17 N-phenyl-α-naphthylamine: 288 parts of α-naphthol, 205 parts of aniline and 10 parts of tributyl phosphate are mixed and first
Heat to 196°C. The reaction begins with dehydration.
Water is removed using an external water remover, and the aniline that comes out is returned. Internal temperature increased to 235℃ over 8 hours
The dehydration ends after the water is raised to 33 parts (33 parts of water). The reaction mixture is cooled to 150° C. and excess aniline and α-naphthol are distilled off in vacuo. Then at a vacuum of 5 mmHg and a boiling point of 202-203 °C,
400 parts of N-phenyl-.alpha.-naphthylamine with a melting point of 55 DEG -58 DEG C. are obtained, corresponding to a yield of 91% of theory. Example 18 N-3-methylphenyl-α-naphthylamine: 216 parts of α-naphthol, 214 parts of m-toluidine and 10 parts of tributyl phosphate are mixed and the reaction is carried out in the same manner as in Example 1. The reaction is terminated after 24 parts of water is removed from the system. After distilling off the excess m-toluidine, 309 parts of N-m-tolyl-α-naphthylamine are obtained at a boiling point of 203 DEG-206 DEG C./5 mm Hg, corresponding to a yield of 88% of theory. Example 19 N-phenyl-α-naphthylamine: 288 parts α-naphthol, 205 parts aniline and 10 parts diphenyl phosphate were mixed and heated to 197°C.
Heat until. At this temperature dehydration begins, and
Finishes at an internal temperature of 235°C. 31 parts of water is removed from the system in 8 hours. After distilling off excess α-naphthol and aniline, at a boiling point of 202-204°C/5 mmHg, N-phenyl-α-
372 parts of naphthylamine were obtained, which is above the theoretical value.
This corresponds to a yield of 85%. Example 20 N-phenyl-α-naphthylamine: 288 parts α-naphthol, 205 parts aniline and 10 parts diethyl phosphite are mixed and heated to 196°C. At this temperature dehydration begins, and
Finishes at an internal temperature of 234°C. 27 parts of water is removed from the system in 8 hours. After distilling off excess α-naphthol and aniline, at 5 mmHg and a boiling temperature of 203-205°C, 330 parts of N-phenyl-α-naphthylamine with a melting point of 54-58°C are obtained, which is 75% of the theoretical value. This corresponds to a yield of Example 21 3-Hydroxy-2'-methyl-diphenylamine: 250 parts of resorcin, 300 parts of o-toluidine and 10 parts of tributyl phosphite are mixed and heated to 120 DEG C. to form a melt. Dehydration begins when the internal temperature reaches 190℃, and the internal temperature is reduced within 5 hours.
Raise to 230℃. After this time, 41 parts of water are distilled off and the reaction is complete. The excess o-toluidine and resorcinol still present are removed in vacuo and the 3-hydroxy-2'-methyl-diphenylamine is then distilled at a distillation temperature of 185° C./3 mm Hg, yielding the desired product 420 with n ²⁵ _D = 1.6455. 93% of theory, corresponding to a yield of 93% of theory. Example 22 3-Hydroxy-2'-methyl-diphenylamine: 250 parts of resorcin, 300 parts of o-toluidine and 10 parts of diphenyl phosphate are mixed and heated to 120°C to form a melt. Dehydration begins when the internal temperature reaches 196℃, and the internal temperature is reduced within 5 hours.
Raise to 230℃. After this time, 41 parts of water are distilled off and the reaction is complete. The excess o-toluidine and resorcinol still present are removed in vacuo and the 3-hydroxy-2'-methyl-diphenylamine is then distilled at a distillation temperature of 185° C./3 mm Hg, yielding the desired product 416 with n ²⁵ _D = 1.6455. 92% of theory, corresponding to a yield of 92% of theory. Example 23 3-Hydroxy-2'-methyl-diphenylamine: 250 parts of resorcin, 300 parts of o-toluidine and 10 parts of diethyl phosphite were mixed and heated to 193°C.
Heat to. Dehydration begins at this temperature and the internal temperature increases to 230°C within 5 hours. After this time, 41 parts of water are distilled off and the reaction is complete. Excess o-toluidine and resorcinol still present are removed in vacuo and then 3-hydroxy-
2'-methyl-diphenylamine at 185℃/3mmHg
Distillation at a distillation temperature of gives 407 parts of the target substance with n ²⁵ _D =1.6455, corresponding to a yield of 90% of theory. Example 24 N-phenyl-β-naphthylamine: 288 parts of β-naphthol, 250 parts of aniline and 9 parts of tributyl phosphate were mixed and heated to 130°C.
to melt. The reaction begins with dehydration at an internal temperature of 190°C. Internal temperature is 235℃ after 5 hours
is reached and 34 parts of water are distilled off. 230℃/15
At a distillation temperature of mmHg, N with a melting point of 100-102℃
412 parts of -phenyl-β-naphthylamine are obtained. This corresponds to a yield of 94% of theory. Example 25 N-phenyl-β-naphthylamine: 288 parts of β-naphthol, 220 parts of aniline and 6 parts of diphenyl phosphate were mixed and heated to 130°C.
to melt. The reaction begins with dehydration at an internal temperature of 190°C. Internal temperature is 235℃ after 5 hours
is reached and 36 parts of water are distilled off. 230℃/15
When distilled at a distillation temperature of mmHg, the melting point is 100~
416 parts of N-phenyl-β-naphthylamine at 102° C. are obtained. This corresponds to a yield of 95% of theory. Example 26 N-p-ethoxyphenyl-α-naphthylamine: 288 parts α-naphthol, 411 parts p-phenetidine and 8 parts tribenzyl phosphate are mixed and heated to 218°C. Dehydration begins at this temperature. The reaction is completed by increasing the reaction temperature to 250° C. over 10 hours, and 36 parts of water is removed from the system.
After removing excess p-phenetidine, N-p
-ethoxyphenyl-α-naphthylamine 233
Distillation at a boiling temperature of ~235°C/5 mmHg yields 479 parts of the target material with a melting point of 72-75°C.
This corresponds to a yield of 91% of theory. Example 27 N-phenyl-β-naphthylamine: 288 parts β-naphthol, 220 parts aniline and 5 parts phosphorous acid are mixed and heated to 173°C. Dehydration begins at this temperature. The reaction temperature was increased over 4 hours.
Upon increasing the temperature to 230°C, the reaction is complete and 36 parts of water are removed from the system. Example 8 shows the subsequent finishing treatment.
412 parts of N-phenyl-.beta.-naphthylamine having a melting point of 100-102 DEG C. are obtained, corresponding to a yield of 94% of theory. Example 28 3-Hydroxy-2'-methyl-diphenylamine: 250 parts of resorcinol, 300 parts of o-toluidine and 2.5 parts of phosphorous acid are mixed. Dehydration begins at an internal temperature of 192°C and increases the internal temperature to 240°C within 4 hours. After this time, 40 parts of water are distilled off and the reaction is complete. The excess o-toluidine and resorcinol still present are removed in vacuo and the 3-hydroxy-2'-methyl-diphenylamine is then distilled at a distillation temperature of 185° C./3 mm Hg, yielding 407 parts of the desired product with n ²⁵ _D 1.6455. was obtained, corresponding to a yield of 90% of theory. Example 29 N-phenyl-α-naphthylamine: 288 parts α-naphthol, 205 parts aniline and 15 parts benzylethyl phosphite were mixed and
Heat to 200℃. Dehydration begins at this temperature,
and ends at an internal temperature of 235°C. water every 5 hours
33 parts are removed from the system. After distilling off excess α-naphthol and aniline, 202-204℃/5mm
At the boiling point of Hg, 381 parts of N-phenyl-α-naphthylamine with a melting point of 55-58° C. are obtained, corresponding to a yield of 87% of theory. Example 30 N-phenyl-α-naphthylamine: 288 parts α-naphthol, 205 parts aniline and 10 parts dibenzyl phosphate were mixed and heated to 195°C.
Heat until. At this temperature dehydration begins, and
Finishes at an internal temperature of 235°C. 33 parts of water is removed from the system in 4 hours. After distilling off excess α-naphthol and aniline, at a boiling point of 202-204°C/5 mmHg, N-phenyl-α-
374 parts of naphthylamine were obtained, which is above the theoretical value.
This corresponds to a yield of 85%. Example 31 N-Methyl-β-naphthylamine: 288 parts of β-naphthol, 3 parts of triphenyl phosphate and 80 parts of methylamine gas are heated to 200° C. for 10 hours with stirring in a pressurized autoclave. The pressure is 40 atmospheres. After cooling, water is added to the two-phase mixture, stirred at 70℃ for 30 minutes, and the lower oil phase is separated and distilled, resulting in a boiling point of 165-166℃/12mmHg.
305 parts of N-methyl-β-naphthylamine are obtained. This corresponds to a yield of 97% of theory. Example 32 N-ethyl-β-naphthylamine: 288 parts of β-naphthol, 6.6 parts of triphenyl phosphate and 115 parts of ethylamine gas are heated to 230° C. for 10 hours in a pressurized autoclave. The pressure is 35 atmospheres. Add the mixture to 2000 parts of water,
and stir for 30 minutes at 70-80°C. When the lower oil phase is separated and distilled, the boiling point is 119-120℃/0.1mmHg
328 parts of N-ethyl-β-naphthylamine were obtained, corresponding to a yield of 96% of theory. Example 33 N-ethyl-α-naphthylamine: 288 parts of α-naphthol, 10 parts of triphenyl phosphate and 100 parts of ethylamine gas are heated to 240° C. for 20 hours with stirring. After cooling the mixture,
First, 2.5% by weight caustic soda aqueous solution at 70℃ for 20 minutes.
Stir with 1000 parts. The separated organic phase is washed with 200 parts of water at 30°C, separated again and distilled to give N-ethyl-α with a boiling point of 119-120°C/0.1 mmHg.
308 parts of naphthylamine are obtained, corresponding to a yield of 90% of theory. Example 34 N-Butyl-α-naphthylamine: 288 parts of α-naphthol, 10 parts of triphenyl phosphate and 160 parts of n-butylamine are heated to 220° C. for 20 hours with stirring in a pressurized autoclave. Subsequent work-up as in Example 33 gives 346 parts of N-n-butyl-α-naphthylamine with a boiling point of 160-162°C/18 mmHg, corresponding to a yield of 87% of theory. . Example 35 2-Methyl-N-ethyl-α-naphthylamine: 316 parts of 2-methyl-α-naphthol, 10 parts of triphenyl phosphate and 115 parts of ethylamine gas
A portion is heated to 230° C. for 20 hours in a pressurized autoclave. When the subsequent finishing treatment was carried out in the same manner as in Example 33, the boiling point was 120-125°C/0.3 mmHg (n ²⁵ _D =
315 parts of 2-methyl-N-ethyl-α-naphthylamine (1.6145) are obtained, corresponding to a yield of 85% of theory. Example 36 2-Phenylethyl-naphthylamine: 288 parts of β-naphthol, 9 parts of triphenyl phosphate and 270 parts of 2-phenylethylamine are heated to 180° C. with stirring. Dehydration begins at this temperature and ends after 5 hours at an internal temperature of 240°C. 36 parts of water are collected in an extra-aqueous remover. After removing excess β-naphthol and amine in vacuo, 2-phenylethyl-naphthylamine was removed.
When distilled at a boiling temperature of 230-231°C/5 mmHg, 2-phenylethyl-naphthylamine 479
97% of theory, corresponding to a yield of 97% of theory. Example 37 2-[N-(2″-ethylhexoxy)-3′-propyl]-naphthylamine: 288 parts of β-naphthol, 9 parts of triphenyl phosphate and 410 parts of 3-(2′-ethylhexoxy)-propylamine. Heat to 180° C. with stirring. Dehydration begins at this temperature and ends after 8 hours at an internal temperature of 230° C. after 36 parts of water have been removed from the system.
Excess β-naphthol and amine were distilled off in vacuo and then 2-[N-(2″-ethylhexoxy)-
3'-propyl]-naphthylamine at 220-221℃/
Distillation at a boiling temperature of 3 mmHg gives 588 parts of the target material, corresponding to a yield of 94% of theory. Example 38 2-Tridecyl-naphthylamine: 288 parts of β-naphthol, 9 parts of triphenyl phosphate and 418 parts of tridecylamine are mixed with stirring.
Heat to 175°C. At this temperature dehydration begins and 230
The process is terminated after 36 parts of water have been removed from the system after 10 hours at an internal temperature of °C. Excess β-naphthol and amine are distilled off in vacuo, then 2-tridecyl-
Distillation of naphthylamine at a boiling temperature of 225° C./3 mm Hg yields 630 parts of the desired product, corresponding to a yield of 97% of theory. Example 39 1-N-Cyclohexyl-naphthylamine: 144 parts of α-naphthol, 10 parts of triphenyl phosphate and 120 parts of cyclohexylamine are heated to 250° C. in a stirred autoclave. After a reaction time of 20 hours, the autoclave is cooled and depressurized. Excess α-naphthol and amine are distilled off in vacuo, then 1-N-cyclohexyl-
Distillation of naphthylamine at a boiling temperature of 166° C./2 mm Hg gives 191 parts of the target product, corresponding to a yield of 85% of theory. Example 40 N-ethyl-α-naphthylamine: 288 parts of α-naphthol, 10 parts of tributyl phosphite and 110 parts of ethylamine gas are stirred.
Heat to 240°C for 20 hours. After cooling and depressurizing the autoclave, the mixture was first incubated at 70°C for 20 min.
Stir with 1000 parts by weight of aqueous caustic soda solution.
The separated organic phase is washed with 2000 parts of water at 30°C, separated and distilled, resulting in a boiling point of 119-120°C/0.1
290 parts of N-ethyl-α-naphthylamine are obtained, corresponding to a yield of 85% of theory. Example 41 N-ethyl-β-naphthylamine: 288 parts of β-naphthol, 6 parts of diphenyl phosphate and 115 parts of ethylamine gas are heated to 230° C. for 10 hours in a pressurized autoclave. The pressure is 35 atmospheres. The mixture is added to 2000 parts of water and stirred for 30 minutes at 70-80°C. Separation and distillation of the lower oil phase gives 314 parts of N-ethyl-β-naphthylamine with a boiling point of 119-120° C./0.1 mm Hg, corresponding to a yield of 92% of theory. Example 42 N-ethyl-β-naphthylamine: 288 parts of β-naphthol, 5 parts of tribenzyl phosphate and 115 parts of ethylamine gas are heated to 230° C. for 10 hours in a pressurized autoclave. The pressure is 35 atmospheres. Add the mixture to 2000 parts of water,
and stir for 30 minutes at 70-80°C. When the lower oil phase is separated and distilled, the boiling point is 119-120℃/0.1mmHg
321 parts of N-ethyl-β-naphthylamine were obtained, corresponding to a yield of 94% of theory. Example 43 1-N-Cyclohexyl-naphthylamine: 144 parts of α-naphthol, 6 parts of phosphorous acid and 120 parts of cyclohexylamine are heated to 250° C. in a stirred autoclave. After a reaction time of 20 hours, the autoclave is cooled and depressurized. Excess α-naphthol and amine were distilled off in vacuo, followed by distillation at a boiling temperature of 166°C/2 mmHg, yielding 184 parts of the desired product, which was below the theoretical value of 82
% yield. Example 44 2-(N-2'-ethylhexyl)-naphthylamine: 288 parts of β-naphthol, 290 parts of 2-ethylhexylamine and 8 parts of triphenyl phosphate are heated to 160° C. with stirring. Dehydration begins at this temperature and ends after 5 hours at an internal temperature of 210°C. 36 parts of water remain in the off-water stripper. Excess β
- Distillation of naphthol and amine in vacuo followed by distillation of 2-(N-2'-ethylhexyl)-naphthylamine at a boiling temperature of 180-183°C/2 mmHg yields 485 parts of the target substance, which is the theoretical value. This corresponds to a yield of 95%. Example 45 N-(2-phenylethyl)-m-toluidine: 260 parts of phenylethyl alcohol, 428 parts of m-toluidine and 20 parts of triphenyl phosphate were mixed and heated at 210°C while removing water from the system.
Heat to temperature. Dehydration begins at this temperature, and 8
Raise the internal temperature to 236°C in time. After this time the dehydration ends (36 parts of water). After distilling off the excess alcohol and amine, N-(2-phenylethyl)-m-toluidine was distilled at a boiling temperature of 167°C/5 mmHg to yield 402 parts of N-(2-phenylethyl)-m-toluidine (theoretical value). 90%)
is obtained. Example 46 N-(2'-phenylethyl)-4-methoxy-aniline: 244 parts of phenylethyl alcohol, 450 parts of p-anisidine and 30 parts of triphenyl phosphate are mixed and first removed while removing water from the system. 210℃
Heat to temperature. Dehydration begins at this temperature,
Increase internal temperature to 250°C for 8 hours. After this time the dehydration ends (36 parts of water). Finishing is carried out by vacuum distillation. After distilling off excess alcohol and amine, N-(2'-phenylethyl)-4-methoxy-aniline was heated at 187-190℃/5
When distilled at a boiling temperature of mmHg, N-(2'-
372 parts (89% of theory) of (phenylethyl)-4-methoxy-aniline are obtained. Example 47 N-(2'-phenylethyl)-1-naphthylamine: 122 parts of phenylethyl alcohol, 250 parts of α-naphthylamine and 10 parts of triphenyl phosphate.
Mix the parts and heat to a temperature of 210 °C. Dehydration begins at this temperature, increasing the internal temperature to 245 in 12 hours.
Dehydration is completed when heated to ℃ (33 parts of water). After removing excess amine and alcohol, N-
(2'-phenylethyl)-1-naphthylamine
When distilled at 225-230℃/5mmHg, N-
(2'-phenylethyl)-1-naphthylamine 210
(85% of the theoretical value) is obtained. Example 48 N-benzyl-aniline: 200 parts of aniline, 108 parts of benzyl alcohol and 10 parts of triphenyl phosphate are heated to 240° C. for 20 hours in a stirred autoclave. The autoclave was then depressurized and the reaction water produced,
Excess aniline and unreacted alcohol are distilled off in vacuo. Distillation at a boiling temperature of 125 DEG C./0.2 mm Hg gives 165 parts of N-benzyl-aniline, corresponding to a yield of 90% of theory. Example 49 N-benzyl-4-methoxy-aniline: 369 parts of p-anisidine was dissolved in benzyl alcohol.
First heat to 177° C. with 162 parts and 15 parts of triphenyl phosphate. Dehydration begins at this temperature, and after 5 hours and an internal temperature of 231° C., the condensation is completed and 27 parts of water are removed from the system. Excess p-anisidine and excess benzyl alcohol are distilled off in vacuo and distilled at 190°C/5 mmHg to give N
265 parts of -benzyl-4-methoxyaniline are obtained, corresponding to a yield of 83% of theory. Example 50 N-(n-butyl)-m-toluidine: 214 parts of m-toluidine, 75 parts of n-butanol and 10 parts of triphenyl phosphate are heated to 230° C. for 10 hours in a stirred autoclave. The autoclave is then depressurized and the reaction water produced, excess m-toluidine and unreacted butanol are distilled off in vacuo. When distilled at a boiling temperature of 65-70℃/0.2mmHg, N-(n-butyl)-
130 parts of m-toluidine were obtained, which exceeds the theoretical value.
This corresponds to a yield of 80%. Example 51 N-(β-diethylaminoethyl)-aniline: 93 parts of aniline, 2-diethylaminoethanol
180 parts and 10 parts of triphenyl phosphate are heated to 210° C. for 20 hours in a stirred autoclave. The autoclave is then depressurized and the reaction water produced, excess aniline and unreacted amino alcohol are distilled off in vacuo. 185-187℃/15
When distilled at a boiling temperature of mmHg, N-(β-
144 parts of (diethylaminoethyl)-aniline are obtained, corresponding to a yield of 75% of theory. Example 52 N.N'-di-(2-phenylethyl)-m-toluidine: 488 parts of phenylethyl alcohol, 214 parts of m-toluidine and 20 parts of triphenyl phosphate are brought to an internal temperature of 211° C. with stirring. Heat. Dehydration begins at this temperature, with a reaction time of 15 hours and
Dehydration ends after an internal temperature of 242°C. Excess alcohol and unreacted amine are removed in vacuo. When distilled at a boiling temperature of 230-232°C/5 mmHg, N.N-di-(2-phenylethyl)-
410 parts of m-toluidine were obtained, which exceeds the theoretical value.
This corresponds to a yield of 65%. Example 53 N-(2-phenoxyethyl)-m-toluidine: 138 parts phenyl glycol, 214 parts m-toluidine
and 15 parts of triphenyl phosphate are mixed under stirring and first heated to an internal temperature of 200°C. Dehydration begins at this temperature and the mixture is
Heat to internal temperature of 223°C. water during this time
18 parts are distilled off and the condensation is complete. Then, excess starting material was distilled off and the temperature was reduced to 186-192℃/5mmHg.
Distillation at a boiling temperature of gives 198 parts of N-(2-phenoxyethyl)-m-toluidine,
This corresponds to a yield of 87% of theory. Example 54 N-(2-butoxyethyl)-aniline: 200 parts of aniline, 118 parts of butyl glycol and 10 parts of triphenyl phosphate were mixed under stirring,
It is then heated to 230° C. for 20 hours in a stirred autoclave. Then, the pressure of the autoclave is released, and the generated reaction water, excess aniline, and unreacted alcohol are distilled off. Distillation at a boiling temperature of 122 DEG C./5 mm Hg gives 143 parts of N-(2-butoxyethyl)-aniline, corresponding to a yield of 74% of theory. Example 55 N-ethyl-N-phenylethyl-aniline: 182 parts of N-ethylaniline, 244 parts of phenylethyl alcohol and 20 parts of triphenyl phosphate
parts are mixed under stirring, and first the internal temperature is 206℃.
Heat until. At this temperature dehydration begins and the mixture is heated to an internal temperature of 243° C. in 20 hours. During this time 25 parts of water are distilled off and the condensation is complete. Excess ethylaniline and unreacted alcohol were then distilled off at a boiling temperature of 160°C/5 mmHg, yielding 274 parts of N-ethyl-N-phenylethyl-aniline, which was higher than the theoretical value.
This corresponds to a yield of 81%. Example 56 N-ethyl-N-butyl-aniline: 182 parts of N-ethylaniline, 150 parts of n-butanol
1 part and 10 parts of triphenyl phosphate are heated to 230° C. for 20 hours in a stirred autoclave. Then, the autoclave is depressurized, and the generated reaction water, unreacted ethylaniline, and excess alcohol are distilled off. When distilled at a boiling temperature of 88-91°C/5 mmHg, N-ethyl-N-butyl-
183 parts of aniline were obtained, corresponding to a yield of 69% of theory. Example 57 N-cyclohexyl-m-toluidine: 200 parts of cyclohexanol, 214 parts of m-toluidine
1 part and 10 parts of triphenyl phosphate are heated to 230° C. for 20 hours in a stirred autoclave. The autoclave is then depressurized and the reaction water produced, excess toluidine and excess alcohol are distilled off. Distillation at a boiling temperature of 165-170 DEG C./15 mm Hg gives 227 parts of N-cyclohexyl-m-toluidine, corresponding to a yield of 60% of theory. Example 58 N-ethyl-aniline: 200 parts of aniline, 50 parts of ethyl alcohol and 10 parts of triphenyl phosphate are heated to 250° C. for 10 hours in a stirred autoclave. The autoclave is then depressurized and the reaction water produced, excess aniline and unreacted alcohol are distilled off in vacuo. Distillation at a boiling temperature of 205 DEG C./760 mm Hg gives 110 parts of N-ethylaniline, corresponding to a yield of 83% of theory. Example 59 N-ethyl-N-(2-N'.N'-dimethylaminoethyl)-aniline: 182 parts of N-ethylaniline, 150 parts of N.N-(dimethyl)-ethanolamine and 10 parts of triphenyl phosphate. 20 parts in a stirred autoclave.
Heat to 230°C for an hour. The autoclave is then depressurized and the reaction water produced, unreacted ethylaniline and excess alcohol are distilled off in vacuo. Distillation at a boiling temperature of 115°C/5 mmHg gives 207 parts of N-ethyl-N-(2-N'·N'-dimethylaminoethyl)-aniline, corresponding to a yield of 72% of theory. do. Example 60 N-ethyl-N-benzyl-aniline: 182 parts of N-ethylaniline, 70 parts of benzyl alcohol and 10 parts of triphenyl phosphate are mixed with stirring and first heated to an internal temperature of 184°C. At this temperature dehydration begins and the mixture is heated to an internal temperature of 210° C. during 8 hours, during which time 25 parts of water are distilled off and the condensation is complete. Then, excess ethylaniline and unreacted benzyl alcohol are distilled off. When distilled at a boiling temperature of 140-144°C/5 mmHg, N-ethyl-N-
276 parts of benzyl-aniline are obtained, corresponding to a yield of 87% of theory. Example 61 N-(2-phenoxyethyl)-m-toluidine: 138 parts phenyl glycol, 214 parts m-toluidine
and 15 parts of diphenyl phosphate were mixed with stirring and the reaction was carried out in the same manner as in Example 53.
At a boiling temperature of 192℃/5mmHg, N-(2-
193 parts of (phenoxyethyl)-m-toluidine are obtained, corresponding to a yield of 85% of theory. Example 62 N-(2-phenoxyethyl)-m-toluidine: 138 parts phenyl glycol, 214 parts m-toluidine
and 20 parts of tributyl phosphate are mixed under stirring and heated to an internal temperature of 210°C. At this temperature dehydration begins and the mixture is heated to an internal temperature of 235° C. in 15 hours. During this time 18 parts of water are distilled off and the condensation is complete. 186-192℃/5
When distilled at a boiling temperature of mmHg, N-(2-
182 parts of (phenoxyethyl)-m-toluidine are obtained, corresponding to a yield of 80% of theory.

Claims (1)

[Claims] 1. General formula (in the formula, R ² and R ⁵ have the meanings given below), an alcohol represented by the general formula R ¹ -OH (in the formula, R ¹ has the meanings given below), and a catalyst of the general formula (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, aliphatic, araliphatic or aromatic residue) A general formula characterized by (In the formula, R ¹ is a residue [formula] or a residue [formula] is an aliphatic, alicyclic, or araliphatic residue, R ² is an aromatic residue, and R ¹ is a residue [formula] , R ² may further mean an aliphatic, alicyclic, or araliphatic residue, and R ³ and R ⁴ may be the same or different, and each represents a hydrogen atom, an aliphatic residue, or an aliphatic residue. residue or alkoxy group, R ⁵ is a hydrogen atom, or R ¹ is an aliphatic, cycloaliphatic or araliphatic residue, R ⁵ further represents an aliphatic, cycloaliphatic or araliphatic residue. A method for producing an arylamine represented by (which may be a cyclic or aromatic aliphatic residue). 2 General formula (wherein R ² means an aromatic residue), the aromatic primary amine represented by the general formula R ¹ −OH (wherein R ¹ means a residue [formula] or a residue [formula], and R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, or an alkoxy group) and the general formula as a catalyst. Claim 1, characterized in that the reaction is carried out in the presence of a triarylphosphite represented by the formula (in the formula, the individual groups R ⁶ may be the same or different and each represents an aromatic residue). The method described in section. 3 General formula (wherein R ² means an aromatic residue), the aromatic primary amine represented by the general formula R ¹ −OH (wherein R ¹ means a residue [formula] or a residue [formula], and R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, or an alkoxy group) and the general formula as a catalyst. (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, an aliphatic or araliphatic residue, and one or two groups R ⁶ each represent an aromatic residue. The method according to claim 1, characterized in that the reaction is carried out in the presence of a phosphorus compound represented by 4 General formula (In the formula, R ² means an aliphatic, alicyclic or araliphatic residue) (In the formula, R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, or an alkoxy group) and a general formula as a catalyst. (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, aliphatic, araliphatic or aromatic residue) A method according to claim 1, characterized in that: 5 General formula An aromatic amine represented by ^the general formula ^{R 1 −} Alcohol represented by OH (in the formula R ¹ means an aliphatic, alicyclic or araliphatic residue) and the general formula as a catalyst (In the formula, the individual groups R ⁶ may be the same or different and each represents a hydrogen atom, aliphatic, araliphatic or aromatic residue) A method according to claim 1, characterized in that: