DE1265742B - Process for the preparation of 1,4-bis- (monoalkylamino) -trans-butenen- (2) - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WJLW PATENT OFFICE

EDITORIAL

Int. Cl .:

C 07c

German KI .: 12 ο - 19/03

Number:
File number:
Registration date:
Display day:

1265 742
F47760IVb / 12o
November 25, 1965
April 11, 1968

It is known that in the implementation of 1,4-dichlorobutene- (2) long-chain with primary aliphatic amines through polyalkylation as the main product tertiary polyamines arise and that here the corresponding secondary diamines only in an extraordinary way low yield (J. Amer. Chem. Soc, 73 [1951], pp. 2118 to 2121). Furthermore, in US Pat. No. 2,038,593 describes that 1,4-dichlorobutene- (2) under the action of amines polymerized to brown, solid resins.

Surprisingly, it has now been found that 1,4-bis (monoalkylamino) -trans-butene- (2) of the general Formula. .

R-NH-CH ₂ -CH = CH-CH ₂ -Nh-R

wherein R represents an optionally substituted alkyl group, characterized obtained in good yield, that l, 4-dichloro-trans-butene (2) with at least 6-fold molar amount of a primary aliphatic amine are reacted at temperatures between 20 and 150 ⁰ C.

The primary aliphatic amines are, in particular, amines with 1 to 12 carbon atoms and preferably those with 3 to 6 carbon atoms. The amines can also be replaced by hydroxy, lower alkoxy or aryl groups may be substituted.

In the reaction, a molar ratio of 1,4-dichlorobutene- (2) to amine of 1: 8 to 1:40 applied. The amine used in excess also serves as a solvent. The reaction can also be carried out in the presence of aromatic solvents such as benzene or Toluene.

The process is preferably carried out at a temperature between 40 and 9O ⁰ C.

The process according to the invention is expediently carried out by adding 1,4-dichloro-transbutene- (2) to the amine heated to the reaction temperature slowly metered in and when the addition is complete, the reaction mixture continues for some time Maintains reaction temperature. The slow addition of dichlorobutene is particularly advantageous when one works at the lower limit of the specified molar ratio. After distilling off the excess primary amine, the residue is treated with aqueous alkali, whereupon the deposited The product is separated off and purified in the usual way.

The compounds obtained according to the process are valuable intermediates. For example, the products of the process can be converted into N, N'-dialkyl-substituted tetramethylene diamines by hydrogenation. The diamines obtained according to the process for the production of
1,4-bis (monoalkylamino) trans-butenes- (2)

Applicant:

Farbwerke Hoechst Aktiengesellschaft
formerly Master Lucius & Brüning,
6000 Frankfurt

Named as inventor:

Dr. Gerhard Werner, 6238 Hofheim, Germany

can also be used as an amine component in the production of high molecular weight Mannich bases will.

example 1

In a vessel equipped with a stirrer, dropping funnel and reflux condenser, three-necked flask, 1600 g (22 mol) of n-butylamine are charged and heated to reflux (78 ⁰ C). At this temperature, 125 g (1 mol) of 1,4-dichloro-trans-butene (2) are then added dropwise over the course of 2 hours with stirring. After the addition has ended, the reaction mixture is allowed to stir under reflux for a further hour. After the excess butylamine has been distilled off, the remaining salt is dissolved in 150 ml of water. To the resulting aqueous solution are added 50 g within 15 minutes 240 ° / ₀ aqueous potassium hydroxide solution. The deposited amine is separated off, dried over solid potassium hydroxide and then fractionally distilled in vacuo. This gives 166 gl, 4-bis (n-butylamino) -transbutene- (2), which corresponds to a yield of 84% of theory. Bp ₄ : 120 ° C; Neutralization Equivalent: Calculated 99, found 97.8.

For further characterization, the compound obtained can be converted into the corresponding putrescin derivative as follows to be transferred:

70 g of 4-bis (n-butylamino) -trans-butene (2) are dissolved in 200 ml of methanol and treated with 3 g of Raney nickel catalyst at 100 ^° C. and a hydrogen pressure of 30 atm until the calculated Amount of hydrogen hydrogenated. After the Raney nickel has been filtered off, the methanol is distilled off and the reaction product is then fractionally distilled. Here are 62 gl, 4-bis (n-butylamino) -

809 538/550

butene isolated. Bp ₃ : 110 ° C; Neutralization Equivalent: Calculated 100, Found 100.2.

Example 2

In the manner described in Example 1, 125 g (1 mol) of 1,4-dichloro-trans-butene (2) are reacted with 2000 g (27.4 mol) of isobutylamine at reflux temperature (68 ° C.), whereupon the reaction mixture, as described there, is worked up. 160 g of 1,4-bis (isobutylamino) trans-butene (2) are obtained, which corresponds to a yield of 81% of theory. Bp ₃ : 92 to 94 ° C; Neutralization equivalent: Calculated 99, found 100.

Example 3

According to the method described in Example 1, 55 g (0.44 mol) of 1,4-dichloro-trans-butene (2) are reacted with 415 g (7 mol) of n-propylamine at reflux temperature (47 to 50 ° C), whereupon the reaction mixture is worked up in the manner described there a °. This gives 56 g of 4-bis- (n-propylamino) -trans-butene (2), corresponding to a yield of 75% of theory. Bp ₄ : 88 ° C; Neutralization equivalent: calculated 85, found 84.

Example 4

According to the method described in Example 1, 60 g (0.48 mol) of 1,4-dichloro-trans-butene (2) are reacted with 800 g (7.5 mol) of benzylamine at 7O ⁰ C,

whereupon the reaction mixture is worked up in the manner described there. This gives gl, 4-bis (benzylamino) trans-butene (2), corresponding to a yield of 77% of theory. Kp _3: 164 ^Q C. Neutralization equivalent: calculated 133, found 133. ■

Claims (3)

Patent claims: 1. Process for the preparation of 1,4-bis- (monoalkylamino) -trans-butenes- (2) the general formula R-NH-CH ₂ -CH = CH-CH ₂ -NH-R wherein R is an optionally substituted alkyl group means, characterized in that one l, 4-dichloro-trans-butene (2) with at least 6 times the molar amount of a primary aliphatic amine at temperatures between 20 and 150 ° C. 2. The method according to claim 1, characterized in that one l, 4-dichloro-trans-butene (2) and Reacts amine in a molar ratio between 1: 8 and 1:40. 3. The method according to claim 1 and 2, characterized in that the reaction is carried out at a Temperature between 40 and 90 ° C performs. Considered publications:
British Patent No. 595 540. 809 538/550 t. 68 © Bundesdruckerei Berlin