DE1194394B - Process for the preparation of monoalkyl ester monoamides of carbocyclic, aromatic dicarboxylic acids - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C07c

C07d

German class: 12 ο -16

1194 394
C30617IVb / 12o
3rd August 1963
June 10, 1965

According to the process of patent 1,168,413, monomethyl ester monoamides of carbocyclic, aromatic dicarboxylic acids are prepared by treating the monomethyl monophenyl esters of carbocyclic, aromatic dicarboxylic acids with ammonia or primary or secondary aliphatic, aromatic or heterocyclic mono- or diamines, preferably in equivalent amounts, in inert organic solvents, preferably aromatic hydrocarbons, at temperatures of 0 to 150 ⁰ C, preferably at 60 to 100 ° C, is reacted. These monomethyl ester monoamides of carbocyclic aromatic dicarboxylic acids can also be prepared according to patent application C 28916 IVb / 12o if, instead of the monomethyl monophenyl esters of the dicarboxylic acids mentioned, or in addition to these, the reaction with monomethyl monophenyl esters whose phenyl radicals contain one or more alkyl and / or aralkyl groups , or or and with monomethyl mononaphthyl esters.

It has now been found that monoalkyl ester monoamides of carbocyclic, aromatic dicarboxylic acids with carboxyl groups in the m or p position, especially isophthalic acid and terephthalic acid, can be obtained by reacting monomethyl monoaryl esters of carbocyclic, aromatic dicarboxylic acids with ammonia or primary or secondary aliphatic, aromatic orocyclic mono- or diamines may preferably / 12o produce 28916 IVb in equivalent amounts, in inert organic solvents, preferably aromatic hydrocarbons, at temperatures from 0 to 150 ⁰ C, particularly at 60 to 100 ⁰ C, according to patent application C when in place the monomethyl monoaryl ester of the dicarboxylic acids mentioned carries out the reaction with monoalkyl monoaryl esters whose alkyl radical is saturated straight-chain or branched and contains 2 to 5 carbon atoms and whose aryl radical is a phenyl or naphthyl radical, both of which are substituted by one or more alkyl or aralkyl groups can nen.

The monoalkyl used as starting materials are preferably prepared in such a way that dialkyl cärbocyclischer, aromatic dicarboxylic acids with the corresponding phenols or naphthols, preferably heated in equivalent amounts, in the presence of transesterification catalysts at temperatures above 16O ⁰ C while distilling off the corresponding alkanol and the alkyl -aryl ester purifies by distillation or crystallization. Unreacted dialkyl ester Process for the preparation of monoalkyl ester monoamides of carbocyclic, aromatic
Dicarboxylic acids

Addition to additional registration:
C28916IVb / 12o -
Interpretation document 1187 602

Applicant:

Chemical works in Witten
Company with limited liability,
Witten / Ruhr, Arthur-Imhausen-Str. 92 a

Named as inventor:

Dr. rer. nat. Hans-Leo Hülsmann,

Witten / Ruhr-Rüdinghausen;

Dr. rer. nat. Gustav Renckhoff, Witten / Ruhr

and the diaryl ester obtained as a by-product is returned to the transesterification stage. For the Production of the starting materials, protection is not sought in the context of this invention.

The alkyl radical of the alkyl aryl esters to be used can, for example, be ethyl, propyl, butyl or Be 2-methylpropyl.

The aryl radicals can be, for example, the phenyl radical, the isomeric cresyl radicals or xylenyl radicals, the butylphenyl, Octylphenyl, benzylphenyl or the isomeric naphthyl radicals.

As dicarboxylic acids, the monoalkyl monoaryl esters to be used are based on, for example: the iso- and terephthalic acid, the isomeric diphenyldicarboxylic acids and the mono- or disubstituted iso- and terephthalic acids in the nucleus, like 5-chloroisophthalic acid, methyl terephthalic acid, 2,5-dichloroterephthalic acid.

As amines, for. B. primary alkylamines with up to 18 carbon atoms, diamines, such as ethylenediamine, Hexamethylenediamine or xylylenediamine, or morpholine can be used.

Surprisingly, only the aryl ester group reacts with the under the reaction conditions mentioned Amine. The alkyl ester group is not

509 579/419

Claims (1)

3 4 grabbed. The yields of monoalkyl ester monoamides. The acid number is 0.5, the saponification number is 214 (they are mostly almost quantitative. The amidation is calculated as 214).
released phenol is easy to recover and again for the transesterification of a dicarboxylic acid dialkyl example 4
esters to reuse an alkyl aryl ester. S. Since there are no low-value by-products, 20.2 parts by weight of ethyl phenyl isophthalate are used the process is extremely economical. (0.075 mol) are dissolved in 100 parts by volume of xylene. Above ^{The 1} I ₂ hour that can be prepared by the process of the invention is distributed over a solution of 4.5% by weight Esteramides can be added in a manner known per se, share hexamethylenediamine (0.038 mol), for example for the production of thickening io while the xylene is boiling under reflux. To The approach is used for lubricating greases as well as basic materials for the completed addition of the amine solution Production of polycondensation products, held at 80 ° C for another 2 hours. When cooling down be turned. fall 10.0 parts by weight of colorless, crystalline N, N'-bis- (m-carboethoxybenzoyl) -hexamethylenediamine, m.p. = 137 Example 1 15 to 138 ° C, from. Another 7.3 parts by weight of the ester amide of melting point 137 to 139 ⁰ C are prepared from A solution of 14.9 parts by weight of butylphenyl of the mother liquor after distilling off the xylene terephthalate (0.05 mol) in 50 parts by volume of benzene and the phenol by recrystallization from xylene is heated to reflux temperature and a solution is obtained. The acid number of the ester amide is 1.1, the of 13.5 parts by weight of stearylamine (0.05 mol) in such a saponification number 236 (calculated 239); the nitrogen 50 parts by volume of benzene partially, content over 20 minutes is 6.1% (calculated 6.0). The yield distributed, added, the solvent continuously corresponding to 98.5% of theory, based on ester amide boils. When the addition of the amine solution is complete, the ethyl phenyl isophthalate used is added.
the batch is heated to 80 ° C. for a further 1 hour. At the Cooling the solution in an ice bath drops 14.0 weight- 25 B ice ρ ie 1 5
parts N - octadecyl - terephthalamic acid butyl ester, F. = 87 ° C, off. The end. the concentrated mother liquors in a boiling solution of 17.5 parts by weight a further 5.0 parts by weight of ethyl phenyl isophthalate (0.065 mol) in 100 volume Esteramids, F. = 86 to 87 ⁰ C, deposited. The divided benzene becomes a solution for 40 minutes Yield is 80.5% of theory. After converting 5.65 parts by weight of morpholine (0.065 mol) crystallize from butyl acetate with the addition of added dropwise. Then the solution is still The melting point of methanol is 89 ° C. The 3 hours at 8O ⁰ C kept. In the case of the distillative Acid number is 0, the saponification number is 117 (calculated 119); Work-up go after distilling off the the nitrogen content is 3.3% (calculated 3.0). Benzene 5.3 parts by weight phenol, corresponding to 84% 35 of the calculated amount, about. Then re-distill Example 2 a first run up to 196 ° C and 1 torr 13.1 parts by weight Isophthalic acid ethyl ester morpholide (corresponding to 13.5 parts by weight of ethyl phenyl isophthalate (76.5% of theory) at 196 to 200 ° C. and 1 Torr; (0.05 mol), dissolved in 50 ecm of benzene, are, as in the colorless, non-crystallizing oil.
Example 1 described, with 10.6 parts by weight of tetra to decylamine (0.05 mol) in 50 parts by volume of benzene- Example 6
set. The after distilling off the benzene and Phenol in almost quantitative yield - the solutions of 156 parts by weight of butyl Permanent N-tetradecyl-isophthalamic acid ethyl ester m-cresyl-terephthalate (0.5 mol) in 500 parts by volume melts after recrystallization from methanol at 45 xylene at 13O ⁰ C and 29 parts by weight of hexa- 56.5 to 58.0 ⁰ C. The acid number of the ester-amide is 1, methylenediamine (0.25 mol) in 100 parts by volume xylene the saponification number 139 (calculated 144); the nitrogen are combined and refluxed for 1 hour content is 3.5% (calculated 3.6). Xylene heated to boiling. After cooling down Room temperature becomes the colorless that has crystallized out Example 3 5 ° N, N '- bis - (p - carbobutoxybenzoyl) - hexamethylenediamine sucked off, digested with hot xylene and after Sucked off again after cooling to a solution of 181 parts by weight of butyl. One receives 106 ge phenyl terephthalate (0.607 mol) in 500 parts by volume parts by weight of the ester amide, corresponding to 81% of the Xylene becomes a theory solution in a nitrogen atmosphere. The melting point is after the recrystallization of 33.4 parts by weight of hexamethylenediamine 55 size from dimethylformamide at 190 to 191 ⁰ C; (0.288 mol) in 100 parts by volume of xylene at 130 ⁰ C under saponification 209 (calculated 214).
Stirring added dropwise within half an hour. To When the addition of the amine solution is complete, the patent claim becomes clear:
Solution under the reflux condenser for 1 hour Nitrogen heated to the boil. Then it is cooled down 60 Further development of the process for producing and the ester amide which has crystallized out is filtered off with suction. It position of monoalkyl ester monoamides carbo- is heated to boiling with 400 parts by volume of xylene, cyclic, aromatic dicarboxylic acids with m- cooled and vacuumed. This cleaning measure or p-position carboxyl groups, especially the is repeated once more. After drying with iso- and terephthalic acid, by reacting At 75 ° C, 133 parts by weight of N, N'-bis (p-carbo-65 monomethyl monoaryl esters of the carbocyclic, butoxybenzoyl) -hexamethylenediamine, corresponding to aromatic dicarboxylic acids with ammonia or 88.2% of theory, based on the primary or secondary aliphatic, aromatic Diamine. The melting point is 191.5 to 192.0 ⁰ C. tables or heterocyclic mono- or di- amines, preferably in equivalent amounts, in inert organic solvents, preferably aromatic hydrocarbons, at temperatures from 0 to 15O ⁰ C, especially at 60 to 100 ⁰ C, according to patent application C 28916 IVb / 12o, characterized in that instead of the mono-methyl monoaryl esters of the dicarboxylic acids mentioned carries out the reaction with monoalkyl monoaryl esters whose alkyl radical is saturated, straight-chain or branched and contains 2 to 5 carbon atoms and whose aryl radical is a phenyl or naphthyl radical, both of which are replaced by one or more alkyl and / or aralkyl groups can be substituted. 509 579/419 6.65 © Bundesdruckerei Berlin