DE2400111A1 - Amine and amide prepn. by Hofmann degradation - in presence of amine catalysts, polymn. inhibitors and opt. prim. or sec. amines - Google Patents

Abstract

In the title process amides are reacted with hypohalides in the presence of an excess of an alkaline hydroxide at least equal to 0.2 mole/amide group and cpds. of formula R1R2NK (I) (where R1 is sulphonic, sulphonate or sulphamoyl group; R2 is H, Cl, Br or an aliphatic group and X is H, Cl, or Br; NR1R2 also may be a heterocyclic ring contg. at least one sulphonyl or PO-OR3 group near the M atom and R3 is ' or alkl metal; or R1+R2 is CO-R4-CO and R4 is alkylene, R5 is H, Cl or Br and R6 is an aliphatic group) or a polymn. inhibitorsand opt. a prim. or sec. amine is added at the beginning or during the reaction. Inhibitors may also be catalysts and amines are pref. added after mixing hypohalide with amide. Thus anthranite acid is prepd. from a reaction prod. of phthalic anhydride and ammonia by reaction with naClO (javel water) in the presence of sulphamic acid and NaOH.

Description

Process for the preparation of substituted ureas The invention relates to a process for the production of substituted ureas by reaction of carboxamides with hypochlorites in the presence of bromine, iodine and / or haloamides and excess alkali hydroxide with the addition of primary or secondary amines.

Addendum to patent. ... ... (Patent application P 23 28 757.2) Subject of the main patent. ... O .. (patent application P 23 28 757.2) is a process for the preparation of amines from carboxamides by reaction with hypohalites in an aqueous medium, the carboxamide in the presence of bromine, iodine and / or haloamides of the formula where R1 denotes a sulfonic acid group, a sulfonate group, a sulfonamide group, R2 denotes a hydrogen atom, an aliphatic group, a chlorine atom or a bromine atom, X denotes a chlorine atom, a bromine atom or a hydrogen atom, R1 and R2 also together with the adjacent nitrogen atom are members of a heterocyclic group , the at least one sulfonic group or phosphonyl group of the formula which is adjacent to the nitrogen atom wherein R3 stands for a hydrogen atom or an alkali atom, contains, can denote, or R1 and R2 together also the remainder can mean where R4 is an alkylene radical, the radical or the rest R5 represents a hydrogen atom, a chlorine atom or bromine atom and R6 represents an aliphatic radical, is reacted with alkali metal hypochlorites and in the presence of an excess of more than 0.2 mol of alkali metal hydroxide, based on 1 mol of starting carboxamide and carbonamide group on the molecule.

It is from Houben-Weyl, Methods of Organic Chemistry, Volume XI / 1, Pages 854 to 862, it is known that carboxamides can be produced by Hofmann synthesis with bromine or can convert chlorine and alkali into primary amines; as a generally applicable procedure is described that you first from 1 mole of bromine and 4 moles of alkali in the form of Alkali solution produces an alkali hypbromite solution and then this to 1 mol of carboxamide allowed to act, if necessary, an excess of bromine of approx. 10 is used %.

In most cases, the Hofmann build-up is only possible with hypobromite solutions satisfactory, which are more expensive and less durable than hypochlorite solutions. For this reason alone, the technical utilization of the reaction is special To implementations with aromatic carboxamides remained limited.

It is known from German Offenlegungsschrift 2 129 200 that one arylcarboxamides with prepared from alkali or alkaline earth and halogen Reacts hypohalite in the presence of water and then the aqueous solution in one second step with amines. As the examples teach, there must be an excess of at least 3.2 moles of alkali metal hydroxide over that of the halogen in the form of hypohalite already bound hydroxide amount, based on the starting amide, can also be used. Corresponding amounts result from this comparatively honed excess Alkali salts in wastewater. As examples and equations teach, the reaction must be carried out in two partial conversions each lasting some time.

It has now been found that the process of the main patent ... ... (patent application P 23 28 757.2) on a process for the production of substituted Urea can be developed further, if one at the beginning or during the implementation adding primary or secondary amines.

The reaction can be carried out in the case of using benzamide, methylamine and sodium hypchlorite by the following Display formulas: 0 O tr is 3 NH2 + NaOCl + CH3-NH2 j C 3 + NaCl + H20 Compared to the known process and in view of the prior art relating to the production of amines using hypobromite, the process according to the invention provides substituted ureas in a simpler and more economical way in better yield and purity and enables the production of a large number of Urea with alkali hypochlorite solutions also on an industrial scale. Since the alkaline hypochlorite solution is more stable than the hypobromite solution and its content hardly decreases even after days, the process according to the invention is reliable, trouble-free and especially suitable for industrial operation. Compared to the known method that uses hypochlorite solution, it provides better overall results with regard to space-time yield and purity of the end product or lower consumption of alkali lye and improvement of the waste water and is therefore more environmentally friendly.

With regard to the German Offenlegungsschrift, the implementation times are longer not necessary before adding the amine. All of these beneficial results are in the Surprising in view of the state of the art.

Preferred carboxamides are those of the formula wherein R7 is an aliphatic radical, preferably an alkyl radical with 1 to 10 carbon atoms or an alkylene radical, alkenyl radical or alkenylene radical with 3 to 10 carbon atoms each, a cycloaliphatic radical, preferably a cyclohexyl radical, an araliphatic radical, preferably an aralkyl radical with 7 to 12 carbon atoms, a aromatic radical, preferably a phenyl radical, a benzoylphenyl radical, a phenylene radical or a naphthyl radical, a heterocyclic radical, preferably a 5- or 6-membered heterocyclic ring, which can contain one or two nitrogen atoms and to which a benzene nucleus can also be fused, and n denotes an integer, preferably 1 or 2. The aforementioned radicals and rings can also be replaced by groups and / or atoms which are inert under the reaction conditions, e.g. B. a benzene nucleus, substituting chlorine atoms, bromine atoms, iodine atoms, trichloromethyl =, trifluoromethyl groups or alkoxy groups each with 1 to 4 carbon atoms; Alkyl groups with 1 to 4 carbon atoms, benzoyl groups, sulfonic acid groups, hydroxyl groups, carbalkoxy groups with 2 to 4 carbon atoms, nitro groups.

For example, the following carboxamides are used as starting materials II suitable: the amides of isobutyric acid, caprylic acid, valeric acid, isovaleric acid, Acetic acid, propionic acid, adipic acid, glutaric acid, butyric acid, benzoic acid, phthalic acid, p-toluic acid, p-nitrobenzoic acid, phenylpropionic acid, cyclohexanecarboxylic acid, imidazole-4-carboxylic acid, Nicotinic acid, pyrazine carboxylic acid, pyridine-o-carboxylic acid, quinoline-2-carboxylic acid, Pyrrole-2-carboxylic acid, p-SulSo-benzoic acid, o-, m-, pu-methoxy-benzoic acid, o-, m-, p-Benzoylbenzoic acid, i-naphthoic acid, ß-naphthoic acid, phenylacetic acid, o-, m-, p-chloro, o-, m-, p-bromo, o-, m-, p-iodo-benzoic acid, -ethylcaproic acid.

Hypochlorites in an aqueous medium, usually in the form of corresponding aqueous, alkaline solutions, are used as further starting materials. Aqueous suspensions of 1 to 50% by weight of the starting carboxamide are advantageously used. The aqueous hypochlorite solutions generally contain from 5 to 15, preferably from 12 to -14% by weight of hypochlorite and can additionally contain from 0.2 to 2.5 mol, preferably 1 to 2.1 mol, of alkali metal hydroxide per mole of hypochlorite. In the case of an excess of more than 0.2 mol of alkali metal hydroxide, the alkali which may be contained in the catalyst or hypochlorite or bound by the catalyst is not included in the calculation. The starting mixture of the two starting materials generally contains a total of 0.9 to 1.5, preferably 0.95 to 1.1 mol of hypochlorite and expediently from a total of 0.2 to 2.5 mol, preferably 1 to 2.1 mol of alkali metal hydroxide ( not including the alkali contained in the hypochlorite), based on 1 mole of starting carboxamide and carbonamide group on the molecule. If the aqueous hypochlorite solution does not contain any free alkali metal hydroxide, then at the beginning or in the course of the reaction it is expedient to add from 0.2 to 2, preferably 1 to 2 moles of alkali metal hydroxide per mole of hypochlorite. Preferred alkali hypochlorites are the sodium or potassium salt. Possible catalysts are bromine, iodine and / or halogenamides I, generally in an amount of from 0.0001 to 0.1, preferably from 0.001 to 0.01 mol of catalyst per mol of starting carboxamide. Instead of the substances mentioned, compounds which bffllden such substances under the reaction conditions can also be used, e.g. B. bromides and iodides instead of bromine or iodine. It is expedient to choose water-soluble halides. These halides are advantageously used in the form of their alkaline earth salts and, in particular, their alkali metal salts, e.g. B. calcium bromide, calcium iodide, magnesium bromide, magnesium iodide, lithium bromide, lithium iodide and especially sodium and potassium bromide or iodide Preferred halogen amides I are those in whose formula R1 denotes a sulfonic acid group, a sulfonate residue, in particular an alkali sulfonate residue such as sodium sulfonate or potassium sulfonate, a sulfonamide group, R2 denotes a chlorine atom, a bromine atom, an alkyl radical with 1 to 4 carbon atoms or, in particular, a hydrogen atom, X denotes a bromine atom, a chlorine atom or, expediently, a hydrogen atom, R1 and R2 also together with the neighboring nitrogen atom are members of a heterocyclic, 5- or 6-membered ring, the at least one sulfonic group or phosphonyl group of the formula adjacent to the nitrogen atom in which R3 represents a hydrogen atom or an alkali atom, in particular a sodium atom or potassium atom, contains, or R1 and R2 together can also denote the remainder can mean in which R4 is an alkylene radical having 2 to 4 carbon atoms, the radical or the rest R5 represents a hydrogen atom, a chlorine atom or a bromine atom, and R6 represents an alkyl radical having 1 to 4 carbon atoms, in particular the methyl group. A phenylene nucleus can also be fused to the aforementioned heterocyclic ring. Advantageously, the heterocyclic radical contains two sulfonic or phosphonic groups adjacent to the nitrogen atom or two or three sulfonamido or phosphonamido groups, especially in the same ring in the case of polynuclear heterocyclic radicals inert groups or atoms, e.g. B. chlorine atoms, bromine atoms, alkyl groups with 1 to 4 carbon atoms, the phenyl nucleus substituted carboxyl or carboxylate groups.

As catalysts zO Bo can be considered: glutaramide, adipic acid imide, Succinimide; preferably cyanuric acid, 5,5-dimethylhydantoin, trisulfamide, N-methyl- sulfamic acid, sodium trimidometaphosphate; corresponding mixtures of the aforementioned Halo genamide I; in particular, sulfamic acid and its salts are suitably alkali salts such as the sodium or potassium salt, and sulfamide, optionally in a mixture with the aforementioned haloamides I.

Preferred starting amines are those of the formula and accordingly preferred ureas as end products are those of the formula where R7 and n have the aforementioned preferred meaning, R8 and R9 can be the same or different and each is an aliphatic radical, preferably an alkyl radical with 1 to 10 carbon atoms or an alkenyl radical with 3 to 10 carbon atoms, a cycloaliphatic radical, preferably a cyclohexyl radical, an araliphatic radical Radical, preferably an aralkyl radical with 7 to 12 carbon atoms, an aromatic radical, preferably a phenyl radical or a naphthyl radical, in addition R8 can also denote a hydrogen atom or R8 and R9 together with the adjacent nitrogen atom also denote members of a 5- or 6X-membered ring can. The aforementioned radicals and rings can also be replaced by groups and / or atoms which are inert under the reaction conditions, e.g. B. a benzene nucleus substituting chlorine atoms, brsmatcme, iodine atoms, trichloromethyl groups, trifluoromethyl groups or alkoxy groups each with 1 to 4 carbon atoms, alkyl groups with 1 to 4 carbon atoms, benzoyl groups, hydroxyl groups, carbalkoxy groups with 2 to 4 carbon atoms, nitro groups. The starting amine can be added in stoichiometric amounts or in excess, preferably in an amount of 0.9 to 1.5 mol, based on the starting carboxamide, and into the starting mixture of the other reactants or to one or more of these participants or to the mixture during the reaction will. The addition is expediently carried out shortly after the starting carboxamide, water, hypochlorite, hydroxide and catalyst have been mixed, preferably 0.01 to 60, in particular 0.1 to 30 minutes after the aforementioned substances have been mixed.

For example, the following amines are suitable as starting materials IV: Ethylamine, diethylamine aniline, N-methylaniline, benzylamine, cyclohexylamine, di-tert.-butylamine, Isopropylamine, ethylaniline, diphenylamine, dimethylamine, methylamine, n-hexylamine, Diisopropylamine, toluidine, cyclopentylamine, dicyclohexylamine, -naphthylamine, ß-naphthylamine, p-carbethoxyphenylamine, piperidine, morpholine, laurylamine, stearylamine, n-butylamine, Di-n-butylamine, amylamine, diamylamine, piperazine, dimethylamine, ethanolamine, diethanolamine, Pyrrolidine, imidazolidine, propylamine, dipropylamine, sec-butylamine, tert-butylamine, Dibenzylamine, N-methyl-N-butylamine, N-methyl-N-ethylamine, mono-m, o, pchlorphenylamine, Di-m, o, p-chlorophenylamine, m, o, p-ethoxyphenylamine, di-m, o, p-ethoxyphenylamine, nitro-phenylamine, Di (nitrophenyl) amines, hexamethyleneimine, allylamine, crotylamine, n-undecen- (11) -yl- (1) -amine, Diallylamine.

It is usually used at a temperature of -10 ° C to + 1000C, preferably from 10 to 850C, in particular from 10 to 400C before adding the amine, or without pressure continuously or discontinuously under pressure. After adding the amine advantageously a reaction temperature of 40 to 100 ° C., preferably 40 to 850 cm chosen. The reaction can be carried out as follows: A mixture of starting carboxamide, Catalyst, alkali hydroxide and water becomes an aqueous solution of the hypohalite fed and the mixture for 1 to 4000 seconds at the reaction temperature held. Then the amine, optionally in the form of an expediently from 0- to 50% by weight, aqueous solution, and the mixture for one second up to one hour at the reaction temperature, optionally held with heating The end product is now processed in the usual way, eg by filtration or extraction with an organic solvent such as benzene, ethyl alcohol or chlorinated hydrocarbons such as trichlorethylene or by steam distillation, isolated. To separation and To facilitate cleaning, the end product can also be acylated, e.g. B.

with benzoyl chloride, and so brought into an easily crystallizable form will.

You can use the catalyst, advantageously in a mixture with water, also the Add the starting mixture separately or together with the hypohalite. In a preferred embodiment, at the same time the particularly simple and advantageous 3 operation of plants according to the method according to the invention is illustrated, the starting carboxamide, z. B. phthalamic acid, first from carboxylic anhydride, ammonia and optionally Alkali hydroxide is produced at a temperature of usually 20 to 800C and the reaction mixture thus formed without isolating the reaction product directly implemented as a starting material according to the process according to the invention.

The compounds preparable by the process of the invention are Fragrances and valuable raw materials for the production of dyes, pesticides and fragrances. With regard to the use, reference is made to the aforementioned laid-open specification and Ullmanns Encyklopadie der technischen Chemie, Volume 8, pages 390 to 392 and Supplementary volume, pages 213 and 215, referenced.

The parts given in the following examples are parts by weight. They relate to parts by volume like kilograms to liters. ' Example 1 5.9 Parts of acetamide are hydroxide in a solution of 2 parts and 100 parts by volume Water entered. 0.1 part of sulfamic acid is added to the suspension at 200.degree and slowly 44 parts by volume of sodium chloride solution (containing 7.5 parts of sodium hypochlorite) added with stirring. After one minute, 8.5 parts of 40% strength by weight aqueous are then added Methylamine solution, the mixture is heated to 80 ° C. for 20 minutes and evaporated. Man extracted the mixture three times with 100 parts by volume of Ethylalkoholn the dries organic phase over potassium carbonate and distilled. Bag 7.9 parts (90 ß theory) N, Ni-dimethylurea from fixed point 104 to 1050C.

Examples 2 to 6 Those listed in Table 1 are analogous to Example 1 End materials manufactured.

Table 1 CU O \ 0 Ln t O 0 \ 13 HHH a F R mmm o Starting parts starting amine parts end product Q of the Fp (0C) on S s cu game amid co s to the a, d 0 t cu n co ç PE-I 5.9 cyclohexylamine 11 OH3 82 145 co 0 4 acetamide 5.9 N-methyl-cyclo-12.5 OH3-NH-CN 73 97 to 100 Q amin pno i 5 Acetamide 5.9 Benzylamine 10.7 OH3-NH-C-NH-OH 88 87 to o = v om 6 acetamide 5.9 hexylamine 11 OH3-NH-O-NH-C6H13 86 72 to 76 mvvc) O H Ln F a) o H cm o H Eq HHHHH H o HH rl F EH f O f UX <<E < S o hE UE UU UH o pH XH XHHEX > 5 XZU mm H 0 \ a 0E Eq n tn t bo HHH <H SEEE <F: ba t 4 XH @ O a} : EO oooo I a) m A cu n »o W In Examples 2 to 6, the mixture is cooled after the reaction, filtered and the end product is dried in vacuo.

Example 7 12.1 parts of benzamide are suspended in 100 parts of water, 0.1 part of sulfamic acid is added and the mixture is made up with 0.1 part of 50% by weight Sodium hydroxide solution adjusted to pH 10. Thereafter, 44 parts by volume of sodium chloride solution are added at 20 ° C (containing 7.5 parts of sodium hypochlorite) and after one minute 11.5 parts of N-methyl-N-cyclohexylamine admitted. The suspension turns milky and turns yellow. One warms up half a Hour to 80 ° C and cools down. The final urea falls as a sand-colored precipitate on and is filtered. 16> 6 parts (71.5% of theory) of N-phenyl-N'-methyl-N'-cyclohexylurea are obtained of m.p. 195 to 1970C (methanol).

Examples 8 to 13 The end products listed in Table 2 are prepared analogously to Example 7, Table 2 Ln F. O FF rn u tn op ti d At- starting parts starting amine parts end product p of Fp (00) o cu play amid n ao n Ln t- Ln o \ 0 Clk <I) O u Eq s OD s W 00 u u- Ln Ln II 10 12.1 hexylamine 11.5 NH - NH-O6H13 78 67 to 71 uu UYUUU I. I. v O = UO = UO = U Benzylamine OV NHO? tNH0H2 U 67 to 70 k I 1 I 1 I 1 $ 0 i H 12 Benzamide 12.1 Dithylatin 8 NON 73 O2H5 0 d 4 H 4 13 Benzamide CU Dithanolamine 13.5 NHO ?? NOo) 2: oO.H220H 64 69 B n HHHH H <SS <EXHESO WBE ;; rJ ta) rI hw wp, O ~ I hz S: bl) J :: ~ I Pa N »4 tQ 4 C) XJSX 2 h ç < <>: v: om AA HH 'HHHHH Cx J CU C \ l CU N t uz currently 6I $ 1 <E <H < UE td <BN td U < bOt NN g NNN ev HHHH n AE O @ m <W az mmmm I. 0 A o H cu n Q r2 oD ffi HHHH

Claims (1)

A process for the preparation of substituted ureas according to the procedure for the preparation of amines from carboxamides by reaction with hypohalites in an aqueous medium, the carboxamide in the presence of bromine, iodine and / or halogen amides of the formula where R1 denotes a sulfonic acid group, a sulfonate group, a sulfonamide group, R2 denotes a hydrogen atom, an aliphatic group, a chlorine atom or a bromine atom, X denotes a chlorine atom, a bromine atom or a hydrogen atom, R1 and R2 also together with the neighboring nitrogen atom denotes members of a heterocyclic The radical, the at least one sulfonic group or phosphonyl group of the formula which is adjacent to the nitrogen atom wherein R3 stands for a hydrogen atom or an alkali atom, contains, can denote, or R1 and R2 together also the radical can mean where R4 is an alkylene radical, the radical or the rest R5 stands for a hydrogen atom, a chlorine atom or bromine atom and R6 stands for an aliphatic radical, with alkali metal hypochlorites and in the presence of an excess of more than 0.2 mol of alkali metal hydroxide, based on 1 mol of starting carboxamide and carbonamide group on the molecule, reacted according to the patent. ... ... (patent application P 23 28 757.2), characterized in that primary or secondary amines are added at the beginning or during the reaction.