DD146591A1 - METHOD FOR THE PRODUCTION OF LENGTH-CONTAINING VICINAL BISSEKUNDAEREN OR BISTERTIAEREN DIAMINES - Google Patents

Abstract

Longer-chain vicinal bis-acidic or bertertiary diamines can be used - possibly after quaternization - as N-surfactants, extractants, sparing agents, bacteriostats or auxiliaries in the textile industry. Their erfindungsgemäaesze preparation is carried out by reaction of vicinal dihaloalkanes in which at least one halogen atom is bonded to a secondary carbon atom, with primary or secondary amines at temperatures of preferably 120 to 180 degrees C and reaction times of 5 to 15 h, optionally with the addition of a acid binding agent.

Description

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Process for the preparation of longer chain vicinal bissecondary or bis-tertiary diamines

Field of application of the invention

The invention relates to a process for the preparation of relatively long-chain vicinal diamines of the general formula

I R ₂ I N / - H H ι - Λ ¹ . I C - R ₃ . / \ N Y / '\ R ₄ R ₃ ^R 4

in which R ^ is an alkyl radical, Ro is an alkyl or aryl radical and Rp and R ^ Η-atoms or optionally also alkyl radicals. Such diamines - especially those in which at least one alkyl radical has a chain length of at least Cg - are, possibly even after quaternization, as surfactants, extractants, Sparbeizmittel, bacteriostats or as auxiliaries in the textile industry applicable.

Characteristic of the known technical solutions

It is known to react alkenes with dinitrogen tetroxide to vicinal dinitroalkanes (Houben-Weyl, Methods of Organic Chemistry, Vol. X / 1, p. 76 ff. / Wl7). These dinitro compounds can be reduced to vicinal diamines by known methods.

Furthermore, it is possible to obtain such diamines from oil-bromine-carboxylic acid esters via multi-stage syntheses (Ge Kempter, G ₀ Moser, J. prakt. Chemistry / Ä7 j-4, 104-11 679667).

In both cases vicinal primary diamines are obtained, which can be converted by alkylation into vioinale bissekundäre or bistertiary diamines.

Further, it is known to obtain primary tertiary vicinal diamines by reduction of 6-dialkylamino-oximes (J, Beger, TT. Ionion, C _e Thielemann, P _e D _o Thong, J. prakt. Chem., 220, 433 p.

These processes for the preparation of longer-chain vicinal diamines are technologically very complicated. In the reaction of alkenes with dinitrogen tetroxide, in addition to the dinitroalkanes, further compounds are formed, such as β-nitro-nitrites or β-nitro-alcohols. These compounds are thermally labile and often lead to violent decomposition of the reaction mixture.

? The production method over relatively long <C-bromo-carbonsäureester with its many synthetic steps and the step of reduction with lithium aluminum hydride a marked laboratory synthesis _e same applies to the production of the diamines on <s <- amino-oxime.

The simplest synthesis route for vicinal bis-secondary or bistatic diamines, the nucleophilic substitution on vicinal dihalogen compounds, has hitherto been carried out only on 1,2-dichloro-ethane or 1,2-dibroxn-ethane and thus yields only ethylenediamine or its N -substituted derivatives. (Houben-Weyl, Methoden der Organischen Chemie, Bd _e XI / 1, S «43 ff / Ϊ9527 'Ulimann's Sncyklopadie der technischen Chemie, 4 * Aufl., Vol. 7, S * 380 ff / 19747)«

This limitation is explained by the technical prejudice, according to which in all higher vicinal dihaloalkanes in very slow-running reactions predominantly elimination products, such as 2-halo-alk-1-ene and 1-haloalk-1 ~ ene would be formed and thus an economical justifiable

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bare production of long-chain diamines after a substitution process is not possible. Accordingly, the diamines according to the invention have hitherto not been described in the literature.

Object of the invention .

The aim of the invention is a process which makes it possible to produce longer-chain vicinal bis-secondary and bisteric diamines in a technically and economically advantageous manner.

Explanation of the essence of the invention

The object is achieved in that vicinal dihalogen compounds in which at least one of the two halogen atoms is bonded to a secondary carbon atom, at elevated temperatures with primary or secondary amines, optionally in the presence of acid-binding agent, be converted to longer chain vicinal diamines.

The reaction is preferably carried out at temperatures of 120 to 160 ⁰ C. The reaction times are between 5 and 15 hours.

After working up, the diamines formed can be obtained by distillation as free bases or by crystallization in the form of their salts, such as hydrochlorides, hydrobromides, etc.

As vicinal Dihalogenkohlenwasserstoffe 1,2-dihaloalkanes, such as 1,2-dichloro-propane, 1,2-dibromo-octane or mixtures of i-chloro-2-bromo and 1-bromo-2-chloro-decane and vicinal dihaloalkanes such as 2,3-dibromo-butane or 2 (3) -chloro-3 (2) -bromo-octane are used internally. In addition to open-chain compounds are also vicinal Dihalogencycloalkane, such as 1 ^ -Dichlor-cyclopentane or i-chloro-2-bromo-cyclooctane into consideration.

As primary amines, for example, ethylamine, n-butylamine, cyclohexylamine or aniline can be used.

- 4 - .dm

When secondary amines are _ζ β Β β dime thy lainin, DodeoyImethylamin, pyrrolidine, morpholine, N-methyl-aniline or N-alkyl -guanidines applicable "

To neutralize the hydrogen halide formed during the reaction, use is made of alkali metal or alkaline earth metal hydroxides or carbonates or an excess of the amine used for the substitution.

Execution sbei.sp le le

example 1

In an autoclave 113 g. (= 1 mol) of 1,2-dichloro-propane and 219 S (= 3 mol) of diethylamine are heated for 12 hours at 160 + 5 ⁰ C The reaction mixture is mixed with NaOH in excess and the organic Phase distilled in vacuo.

The obtained 1 _s 2-bis (diethylamino) propane boils at 78 to 86 ⁰ C under a pressure of 1.73 · 10 ^ Pa. Yield: 80 g = 43 % of theory

Purity It. GC 98 % \ n | ° 1.4368

about " C H N ° 11 ^H 26 ^N 2 gef. 70,90 14.05 15.05 186.3 '70,85 13.78 14.98 Example 2

In the manner described in Example 1, 51.2 g (= 0.25 mol) of 1,2-dibromo-propane and 63.8 g (= 0.75 mol) of piperidine reacted «After acidification of the reaction mixture, the deposited neutral substances by Ausethern removed and made the aqueous phase alkaline. The distillation of the thereby separating base fraction gives 1,2-dipiperidino-propane boiling range 110 to

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H 13 N 12.45 13 30 12.41 , 23

_ 5 - * ·

113 ^° C. at 0.67 × 10.3 Pa

Yield: 13.8 g = 26.9 % of theory

Purity It. GC 99 % \ n ^ ° 1,4858

° 13 ^H 26 ^N 2 ^over · ^{74> 25} 210.4 gef. 74.16

Example 3

According to Example 2, 84.25 S (= 0.75 mol) of 1,2-dichloro-propane are reacted with 2.25 mol of piperidine »The 1,2-dipiperidino-propane obtained has a boiling range of 129 to 133 ⁰ C at 1 , 6. 1θ3 Pa.

Yield: 70.1 g = 44.5 % d ₀ Th.

p | ° = 1.4858.

Example 4

In a 3-neck round bottom flask with stirrer, sump thermometer and reflux condenser, 45.5 g (= -0.2 mol) of a mixture of about 70% i-bromo-2-chloro-octane and about 30 % i-chlorine -2-bromo-octane with 47.8 g (= 0.55 mol) of piperidine and 21.1 g (= 0.2 mol) of anhydrous sodium carbonate heated for 12 hours at reflux. This initially sets a bottom temperature of 120 ⁰ O, which increases in the course of the reaction to 140 ⁰ C. After cooling, add 200 ml of water and acidify carefully in an ice bath with half-concentrated hydrochloric acid. As the upper, organic phase, 19.8 g of neutral substances are precipitated from the elimination products n-oct-1-ene, octa-1,3-cienes, octa-2,4-diene, 2-chloro-oct-1 -en, cis-1-chloro-oct-1-ene, trans-1-chloro-oct-i-ene, bromoctenene and unreacted starting material.

After separation of the neutral substances, the aqueous solution are made alkaline and the deposited bases are worked up by distillation to obtain 1,2-Dipiperidino-octane boiling range 160 to 166 ⁰ C at 0.2. ΛΦ Pa.

Yield: 17.9 g = 32.5% d "Th _e, relative to the dihalo compound bzvn 39.6% d.Th" ,, based on unreacted dihalo

Purity It. ' GC 98.2 % \ n | ° = 1.4800

calc. 0 H N ^G 18 ^H 36 ^W 2 Gefe 77.08 12.93 9.99 280.5 77.08 12.82 9.64 Example 5

In the apparatus of Example 4, 42.4 g (= 0.2 mol) of 1,2-dichloro-decane, 48 _S 75 S (= 0.55 mol) morpholine and 42 _S 4 g (= 0.4 mol) Sodium carbonate for 24 hours under otherwise identical conditions as in Example 4 reacted., There are at 99% conversion of 1,2-dichloro-decane 16.2 g = 26 % doTtu 1,2-dimorpholino-decane with a boiling range of 160 to 168 ⁰ C at 0.13 * 10 ³ Pa obtained. n £ ° = 1 _f 4775

calc. 0 H N O ₁₈ H ₃₆ N ₂ O ₂ gef. 69.20 11.61 8.95 312.5 69.43 11.46 8.91 Example 6

45t5 g (0.2 mol) of a mixture of about 70% 1-bromo-2-chloro-ootane and about 30% of 1-chloro-2-bromo-octane and 87.2 g (1 mol) of morpholine 8 hours autoclave heated to I50 ⁰ C and then worked up. This gives 1,2-dimorpholino-octane with a boiling point of 160 ⁰ C.

0.13 x 10 ³ Pa. 49.8 % O theory C 11 H 9 N Yield: 24.8 g = O , 56 11 , 34 10 , 84 n ° ° = 1.4790 , 52 , 31 00 about 67 O ₁₆ H ₃₂ N ₂ O ₂ Found 67 284.4 -

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¹ H-KlVIR (GCIy,., HMDS):

₃ : 0.88 t, 3H; - (CHg) ₅ -: 1.25 s (broad), 10 H; CH-N and CH ₂ Ni 1.85 - 2.75 m, 11 H; CH ₂ -O-CH ₂ : 3.40 - 3.65 m, 8 H. '

Example 7

40.6 g (= 0.15 mol) of 1,2-dibromo-octane, 54.7 g (= 0.75 mol) of n-butylamine and 26.5 g (= 0.25 mol) of sodium carbonate are prepared analogously to Example 6 implemented. -

There is obtained 1,2-di-n-butylamino-octane with a boiling range of 124 to 134 ⁰ C at 0.13 "10 ³ Pa.

Yield: 12.8 g = = 1.4484 35 % of the year. 74 C H N 20 ¹¹ D 75 90 14.15 10,95 ^C 16 ^E 36 ^N 2 , 03 13.99 10.66 256.5 calc. Found ·

Claims (1)

Invention claim. A process for the preparation of longer vicinal bissekundären or bistertiären diamines gekennz eichnet in that vicinal dihalo compounds in which at least one of the two halogen atoms is bound to a secondary carbon atom, at elevated temperatures with primary or secondary amines, optionally with the addition of acid-binding agents , be implemented.