DE1963609A1 - Process for the preparation of 2-carbamyl-4,5,6,7-tetrahydro-1,3-diazipins - Google Patents

Description

Our reference: O.Z. 26 531 WB / Be

6700 Ludwigshafen, December 17, 1969

Process for the preparation of 2-carbamyl-4,5,6,7-tetrahydro-

1,3-diazepines

The invention relates to a process for the preparation of 2-carbamyl-4,5,6,7-tetrahydr0-1,3-diazepines by reaction of haloacetamides with 1,4-alkylenediamines and elemental sulfur.

It has been found that 2-carbamyl-1,3-diazepines of the general formula

2 /

in which R ₁ and R _{2 can be the} same or different and each represent a hydrogen atom, an aliphatic, cycloaliphatic, araliphatic or aromatic radical, the individual radicals R can be identical or different and each represent a hydrogen atom or an aliphatic radical, above In addition, R ₁ and R ₂ together with the adjacent nitrogen atom can denote members of a heterocyclic ring, advantageously obtained when halogen acetamides of the general formula

R ₁ OH ^ iT-GC

R ₂ Y

OH η ι - G-C-X II,

in which R ₁ and R _{2 have} the aforementioned meanings, X is an Hfclögtnatom and T is a Waseeretoffatom or a halogen atom , with 1,4-dianinoalkanes of the general formula

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IW "Z ¹ Z, ^

CH - CH - CH - CH - NH ₂ III,

in which R ~ has the aforementioned meaning, and elemental Schwe fel implements.

The implementation can be used for the pail of N-diethylchloraeetamide and 1,4-diaminobutane by the following Display formula:

^H 5

N - C - CH ₂ Cl + 2 S + 2 NH ₂ -

O I

© θ

- CJ + 2 H ₂ S + ΝΗ ₂ - (CH ₂ ) ₄ -ΝΗ ₅ Cl O

The method according to the invention provides in a simple way a large number of previously unknown 2-carbamyl-4,5,6,7-tetrahydro-1,3-diazepines in good yield and purity.

Starting material II is reacted with starting material III and elemental sulfur, usually in a stoichiometric amount. However, starting material III and / or sulfur can also be used in excess, for example up to 1.5 times the excess over the stoichiometric amount, based on starting material II . Instead of the proportion of starting material III which binds the released hydrogen halide, a corresponding amount of another acid-binding agent can also be used. Suitable acid-binding agents are, for example, tertiary amines, inorganic bases such as alkali or alkaline earth oxides, hydroxides, amides, or alcoholates or salts of a weak type . polybasic acids.

Preferred haloacetamides II, 1,4-diaminoalkanes III and accordingly preferred end products I are those in which

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Formulas R ₁ and R _{2 can be} identical or different and each represent a hydrogen atom, an alkyl radical with 1 to 20, in particular 1 to 6 carbon atoms, a cycloalkyl radical with 3 to 8 carbon atoms, an aralkyl radical with 7 to 12 carbon atoms, a phenyl or naphthyl radical , the individual radicals R, can be identical or different and each stand for a hydrogen atom or an alkyl radical with 1 to 3 carbon atoms, in addition R ^ and Rg together with the adjacent nitrogen atom are members of a 5- or 6-membered, heterocyclic ring, which, in addition to the nitrogen atom, can also contain a further nitrogen atom or an oxygen atom, X stands for a chlorine atom and T stands for a hydrogen atom or a chlorine atom. The radicals mentioned and the heterocyclic ring can also be substituted by groups and / or atoms which are inert under the reaction conditions, for example by alkyl groups, alkoxy groups each having 1 to 4 carbon atoms, or by phenyl or naphthyl radicals.

For example, the following halogen acetamides are suitable as starting materials II: chloroacetamide, N-n-butyl, N-diethyl, N-methyl-N-n-propyl-, N-isobutyl-, N-cyclohexyl-, N-benzyl-, N-phenyl-, N-ß-naphthyl-, N-phenyl-N-ethyl-chloroacetamide; N-chloroacetyl-piperidine, -piperazine, -morpholine, -imidazole, -imidazolidine; analogous dichloro-, dibromo-, chlorobromo-, bromoacetamides.

As starting materials III there are e.g. 1,4-diamino-butane, -pentane, -hexane, -2-ethyl-hexane in question.

The reaction is carried out usually at a temperature between 50 and 180 ⁰ C, preferably between 80 and 15O ⁰ C, under atmospheric or superatmospheric pressure, continuously or discontinuously. It is expedient to use organic solvents which are inert under the reaction conditions, for example aromatic hydrocarbons, such as benzene, toluene or xylenes; Alkanols such as ethanol, propanol, butanol; cyclic ethers such as dioxane; preferably glycol ethers at higher temperatures, for example methyl glycol, diethyl glycol; or match «*.« Mixtures. A ratio of 3 to 10 mol of solvent per 1 ha of starting material II is preferred .

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The reaction can be carried out as follows: A mixture of starting material II and sulfur) optionally together with Solvent, the starting material III is added over the course of 1 to 3 hours at the reaction temperature. Then lets you react the mixture for 4 to 10 hours until the sulphurous water fabric development is finished. Then the end product is cooled in the usual way, e.g. by filtering the mixture the filtrate and crystallization or by distilling off the solvent and crystallization or distillation .

The new compounds which can be prepared by the process of the invention are auxiliaries for the textile industry, crop protection agents and valuable starting materials for the production of crop protection agents and textile auxiliaries. For example, they can be used to give synthetic fiber material such as polyester fiber or polyamide fiber an antistatic finish. In addition, the substances according to the invention, in an amount of 5 to 50 g / kg fiber material, using the usual finishing processes, give the finished textile material a soft or pithy feel in addition to the antistatic effect, depending on the constitution of the compound. For example, polyester piece goods can with an aqueous impregnation solution of the above concentration is impregnated at a temperature of 15 to 40 ⁰ C and dried.

The parts given in the following examples are parts by weight.

example 1

74 parts of Nn-butylchloroacetamide and 32 parts of sulfur in 600 parts of toluene are ^{heated to 105 °} C. in a stirred tank and 88 parts of 1,4-diaminobutane are slowly added over the course of 2 hours; The reaction mixture is then refluxed until the evolution of hydrogen sulfide has ended (approx. 6 to 7 hours). The toluene solution is then decanted off from the diamine hydrochloride formed and filtered. After the solvent has been distilled off, the remaining residue becomes

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distilled under reduced pressure. Bel Ep _nc = 109-111 ⁰ C are obtained 75 parts of 2- (F-Butylcarl "aiByl-) _4,5,6> 7-tetrahydrodiazepin- (1,3) with a m.p. = 26 ° C Ms 28 ⁰ C. This corresponds to a yield of 77 5 * of theory.

Example 2

If the procedure is as in Example 1 and 75 parts of H-diethylchloroacetamide are used instead of ff-butylchloroacetamide, 72 parts of 2- (N-diethylcarbamyl) 4,5,6,7-tetrahydro-1,3-diazepine are obtained with a mp = 84 ° C to 86 ⁰ C (Kp ₁ = 122-126 ° C). The yield corresponds to $ 73> of theory.

Example 3

88 parts of H-cyclohexylchloroacetamide and 32 parts of sulfur are mixed with 88 parts of 1,4-diaminobutane in 800 in a stirred tank. Parts of toluene reacted as a solvent analogously to Example 1. This gives 86 parts of 2- (FF-Cyclohexylearbamyl-) 4,5,6,7-tetrahydro-1,3-diazepin, melting at 80 ° C (Kp ₁ = 156 ⁰ C). This corresponds to a yield of 77 Ί · the theory.

Example 4

In a stirred vessel, 111 parts Hc ^ -Haphthylchloracetamid and 32 parts of sulfur in 800 parts toluene are heated to 105 ⁰ C and added thereto in 2 hours, 88 parts of 1,4-diaminobutane slowly. The reaction mixture is then refluxed until the evolution of hydrogen sulfide has ceased (approx. 8 to 10 hours). The toluene oil is then decanted from the diamine hydrochloride formed and filtered. The solvent is then distilled off from the filtrate and the residue that remains is recrystallized from cyclohexane. This gives 79 parts of 2- (F-flt-naphthylcarbamyl-) 4,5,6,7-tetrahydro-1,3-diazepin with • m.p. inta * 87 ⁰ C. The yield corresponds to 59% of theory.

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Example 5.

In a stirred kettle, 110 parts of ff- (2-methyl-4-chlorophenyl) - chloroacetamide and 32 parts of sulfur are reacted with 88 parts of 1,4-diaminobutane in 800 parts of toluene as a solvent, as in Example 4. This gives 82 parts of 2- (ür- (2 ^{f-methyl-4'-chlorophenyl} -) - carbamoyl) -4,5 "6,7-tetrahydro-1,3-diazepin with a Pp = 96 ⁰ C (from cyclohexane ). This corresponds to a yield of 62 % according to theory.

Example 6

In a stirred kettle, 110 parts of W- (2-methyl-5-chlorop, anyl) - chloroacetamide and 32 parts of sulfur are reacted with 88 parts of 1,4-dianinobutane in 800 parts of toluene as a solvent as in Example 4. HaH receives 94 parts 2- / 5- (2-methyl-5-chlorophenyl -) - carbamyl <= 74t5t6,7-tetrahydr0-1,3-diazepine with a Pp = 127 to 128 ⁰ C, corresponding to a yield of 71 # the theory.

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Claims (2)

Claims 1. Process for the production of Z- 1,3-diazepines of the general formula R H ^R 10, N - c - ο in which R ₁ and R _{2 can be} identical or different and each represent a hydrogen atom, an aliphatic, cycloaliphatic, araliphatic or aromatic radical, the individual radicals R, can be identical or different and each represent a hydrogen atom or an aliphatic radical, above In addition, R ₁ and R ₂ , together with the adjacent nitrogen atom, can denote members of a heterocyclic ring, characterized in that halogen acetamides of the general formula ^R 1 OH HI > ft f \ ΛΓ "DD · "O ~ w ^ A XXy K ₂ X in which R ₁ and R _{2 have} the abovementioned meanings, X is a halogen atom and Y is a hydrogen atom or a halogen atom , with 1,4-diaminoalkanes of the general formula ^ j ^ j
- CH - CH - CH - CH - NH ₂ III, in the R, which has the aforementioned meaning, and converts elemental sulfur. 109826/1885 - 8 - O.Z. 26 531 2. 2-carbamyl-4,5,6,7-tetrahydro-1,3-diazepines of the general formula I, in which R ₁ and R _{2 can be the} same or different and each represent a hydrogen atom, an alkyl radical with 1 to 20 carbon atoms, a cycloalkyl radical with 3 to 8 carbon atoms, an aralkyl radical with 7 to 12 carbon atoms, a phenyl or naphthyl radical, the individual R radicals can be identical or different and each represent a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, in addition R ₁ and R ₂ together with the adjacent nitrogen atom are members of a 5- or 6-membered, heterocyclic ring, which is next to the nitrogen atom may contain a further nitrogen atom or an oxygen atom. Badische Anilin- ft Soda-Fabrik 109826/1885