DD140041B1 - METHOD FOR THE PRODUCTION OF LONG-CHAINED N-ALKYLDIMETHYLMORPHOLINES - Google Patents

Description

Field of application of the invention

The invention is used in the manufacture of fungicidal crop protection agents.

Characteristic of the known technical solutions:

It is known that N-alkyl-substituted morpholines wherein the alkyl radical is straight or branched and the C atoms in the ring of morpholine are optionally substituted by methyl or other alkyl radicals having 1-2 carbon atoms are good fungicides

Own properties. Of practical importance are the iangkettigen representatives (N-alkyl = 012H ₂₅ -C ₁ SH ₃₇ ), especially for *

Control of powdery mildew fungi.

These effective compounds are obtained by dehydration of N-alkyl-N, N-bis (hydroxylalkyl) -amines. They are also * l

by N-alkylation of the corresponding morpholine or by reacting 2,2'-dichlorodialkyl ethers with alkylamines in f?

Present acid-binding agent accessible. The latter method seemed to be less suitable for technical production in general, as in the literature -. B. for the synthesis of N-n-dodecyl-2,6-dimethylmorpholine - only a yield of 63% of theory is specified, and the reaction time is about 35 hours.

Object of the invention

The aim of the invention is to develop a process for the preparation of long-chain N-alkyl-dimethylmorpholinen, which starts from available and cheap raw materials and has advantages over the known processes.

Features and features of the invention

The object according to the invention is achieved by starting from a 2,2'-dichlorodipropyl ether mixture which is obtained as an undesirable by-product in the production of propylene oxide by the "chlorohydrin process." According to the investigations carried out, it contains, in addition to the 2,2'-dichlorodiisopropyl ether 15 -20% of the isomeric 2,2'-dichloro-n-propyl-isopropyl ether The destruction of this undesired by-product has hitherto encountered great problems, so that meaningful utilization could also make a substantial contribution to environmental protection reacted in a one-step reaction with a fatty amine mixture which contains, for example, n-dodecylamine as the main constituent.To initiate the reaction and bind the resulting hydrogen chloride, potassium carbonate is added, which leads to a smoother reaction than other acid-binding agents. B. when using Soda formation is relatively often due to inhibition of the reaction of failed batches apparently due to the surface of the sodium carbonate being coated with reaction product.

CHO

r ^

CH - CH ₂ Clnn 't'

O + H ₂ HC H _{2 1} ^ i

^N CH - CH ₂ Cl. ^a r ^{+1 l}

CH ₃

 171.1 180-200

V " O ^ CH CHO CH - CH ₃ CHO ^

^H - ^C n ^H 2n + 1

η s 8: - 18 278-298

-2- 207 403

ι * ι

CH - CH ₂ Cl. CH - CH ₂

CH ₀ - CHCl CH ₉ - CH

- I I

In the process according to the invention, higher-boiling, water-immiscible alcohols (for example cyclohexanol or hexanol) are used as solvents for carrying out the reaction. As a result, the reaction time is significantly shortened, the reaction water can be removed by azeotropic distillation, and it can be achieved significantly higher yields. The progress of the reaction can be monitored by dehydration and CO ₂ evolution. The temperature should be> 150 ° C and towards the end of the reaction 160-180 ° C. The work-up of the reaction mixture can in various ways, for. B. by vacuum distillation, wherein the respective solvent is used again in the circulation. The implementation of the reaction according to the invention gives consistently good results when using a wide variety of fatty amines. After reaction times of 6-8 hours, yields between 85-95% of theory achieved. This smooth course was not to be expected since the 2,2'-dichlorodiisopropyl ether is known to be substantially less reactive than, for example, the 2,2'-dichlorodiethyl ether.

embodiments

The process according to the invention is illustrated by the following examples:

example 1

4-n-dodecyl-2,6-dimethylmorpholine

A 2 l three-necked flask equipped with stirrer, thermometer and water condenser with reflux condenser is charged with 185.34 g (1 mol) of dodecylamine, 205 g (1.2 mol) of 2,2'-dichlorodiisopropyl ether (technical grade) and 500 ml of n-hexanol, with stirring 230g finely powdered potassium carbonate added and turned on the heater. At 145-15O ⁰ C, the reaction begins with evolution of carbon dioxide and separation of water. After 30 minutes, 50% of the expected water of reaction is separated, after 6 hours. the reaction is over. It is filtered off with suction and distilled off from the filtrate, the solvent in vacuo. The mixture is then distilled under a fine vacuum to give 240 g = 85% of theory Th-4-n-dodecyl-2.6-dimethylmorpholine, bp. ₀ , i 113-116 ° C, ηρ ²⁰ 1.4558.

4-n-octyl, 4-n-decyl, 4-n-tetradecyl, 4-n-stearyl, 4-benzyl and 4-cyclohexyl-2,6-dimethylmorpholine were prepared by the same route.

Example 2

4-alkyl-2,6-dimethylmorpholine

In a stirred vessel, 855 parts of 2,2'-dichlorodiisopropyl ether and 850 parts of potassium carbonate are heated to boiling in 1670 parts of cyclohexanol; then you add relatively fast 740 TIe fatty amine mixture, which consists mainly of n-dodecylamine (70-80%), decyl and tetradecylamine and small amounts of other amines (average molecular weight about 180). The resulting reaction water is removed. When the reaction has ended after 6-8 hours, the mixture is allowed to cool to <100 ^° C. and then the amount of water required to dissolve the potassium chloride formed is added. The aqueous phase is drained off and the solvent is driven off with steam. After renewed phase separation, 1,100 parts of 4-alkyl-2,6-dimethylmorpholine mixture (4-alkyl-2,6-dimethylmorpholine content 92-95%) are obtained, which is formulated without further purification.

Example 3

4-n-dodecyl-2,6-dimethylmorpholine

92.67 g (0.5 mol) of n-dodecylamine, 102.6 g (0.6 mol) of 2,2'-dichlorodiisopropyl ether (techn.) And 88 g of anhydrous sodium carbonate are dissolved in 250 ml of cyclohexanol 8 h. heated under reflux with stirring, the resulting reaction water is azeotropically removed. After filtration, removal of the solvent by vacuum distillation and distillation of the residue in a fine vacuum, 100.6 g = 71% of theory 4-n-dodecyl-2,6-dimethylmorpholine.

Claims (1)

-1-207 403 Claim: A process for the preparation of long-chain N-Alkyldimethylmorpholinen by reacting a obtained in the production of propylene 2,2'-dichloropropyl ether mixture with fatty amines, characterized in that worked in the presence of potassium carbonate, preferably cyclohexanol used as the solvent and the resulting water of reaction is removed by azeotropic distillation ,