DD246990A1 - METHOD FOR PRODUCING GAMMA-CHLOROALLYL COMPOUNDS FROM POLYCHLORALKANES - Google Patents

Abstract

The invention relates to a process for the preparation of N- and S-substituted g-chloroallyl compounds from polychlorinated hydrocarbon precursors. The task is to direct the process so that the polychloroalkanes react in a one-pot reaction with N- or S-nucleophiles to g-chloroallyl compounds. The object is achieved by reacting the polychloroalkane in a water-miscible solvent with the N- or S-nucleophile and sodium hydroxide solution. The products are valuable as synthesis intermediates, building blocks for heterocycles and as precursors for pesticides.

Description

Field of application of the invention

The invention relates to a process for the preparation of -γ-chloroallyl compounds of the type of 1-N- or S-substituted 3-chloro-2-methyl-alk-2-enes and 3,3-dichloro-alk-2-enes in one Step out of saturated polychloride bonds.

Characteristic of the known technical solutions

γ-Chloroallyl compounds are prepared by known methods by substitution reactions e.g. allyl chloroallyl halides can be prepared by elimination from polychloroalkanes or by substitutional chlorination of alkenes, however, resulting in mixtures of constitutional isomers that can only be readily resolved; thus, e.g. in the chlorination of methallyl chloride or the gas phase chlorination of isobutene with a simple chlorine over other readily separable compounds, a mixture of approximately equal parts of 1,3-dichloro-2-methyl-propene and 1,3-dichloro-2-methylene-propane which is very difficult to separate owing to the boiling points lying close to each other (K. Schulz et al., DD-PS 106345, J. Prakt. Chem. 1984, 326, 433). It is also known that strong bases, such as NaOH or NaOR, of polychloroalkanes not only eliminate HCl, but also cause nucleophilic substitutions (Rogers, A.R. Nelson, J. Am. Chem. Soc. 1936, 58, 1029, RWTaft, GW Stratton, Trans, kansas, Acad. 1945, 50, 225). The disadvantage, however, is that polychloroalkanes of the 1,2,3-trichloro-2-methyl-propane or 1,2,3-trichloro-2-chloromethyl-propane type do not react with N or S nucleophiles.

Object of the invention

The object of the invention is to produce, starting from polychloroalkanes, in one step N- or S-substituted-3-chloroallyl compounds which are valuable as bifunctional synthesis intermediates, building blocks in heterocyclic chemistry and as precursors for pesticides.

Presentation of the essence of the invention

The object of the invention is to provide a process in which polychloroalkanes react with N- or S-nucleophiles in a one-pot reaction to form allyl compounds. The invention is based on the idea to ensure by the process sequence that the per se little reactive polychloroalkanes with N- or S-nucleophiles can be reacted.

The object is achieved in that a polychlorinated alkane, for example, 1,2,3-trichloro-2-methyl-propane to a solution of NaOH, water and the N- or S-nucleophile in a water-miscible solvent, preferably dimethyl sulfoxide or Methanol is added, and allowed to react the reaction solution for several hours at 50-80 ^c C. The work-up in the usual manner by separating the precipitated salt, evaporation of the solvent i. Vak, extraction with ether gives the N- or S-substituted allyl compounds

 The invention will be explained below with 2 examples:

Example 1 .

3-chloro-2-methyl-1-methylamino-prop-2-en

40 g (1 mol) of NaOH are dissolved in 50 ml of water and the solution is added together with 40 g (0.50 mol) of 40% aqueous methylamine solution in 100 ml of DMSO. 60 ml (0.48 mol) of 1,2,3-tri-chloro-2-methyl-propane is added dropwise to the mixture while stirring at room temperature just as quickly that no too vigorous reaction takes place. It will be about 4 hours:

Stirred with so much water, that separates an oil / ee phase, which separated and carefully with cooling while in concentrated. HCI is recorded. In hydrochloric acid insoluble unreacted 1,2,3-trichloro-2-methylpropane is separated and separated from the solution, the amine with sodium hydroxide solution, it is separated from the aqueous phase and i. Vak. fractionated.

Bp 52 ° C-54 ° C / 32 Torr n ° °: 1.4640 Yield: 65%

MS (7OeV): m / z = 119 (mt)

¹ H-NMR (CDCl ₃ , HMDS): 5 [ppm] = 1.28 m (-NH)

1.72; 1,742S (CD ₃ -C =)

2.27; 2.302d (CH ₃ -NH-)

3.08; 3.26 2d (-CH ₂ -)

5.87; 5.92 m (-CH =)

Example 2

S-chloro-methyl-1-phenylthio-propen-1-ene

60g (1.5mol) of powdered NaOH are added to 200ml of dry DMSO. This is allowed to stir while stirring 165.5g

(1.5 mol) of thiophenol and then 80 g (0.5 mol) of i-i-trichloro-methyl-propane. It leaves about 10 hours. stir at 90-100 ⁰ C and then cool. It is mixed with so much water that the oily phase separates well. The oily phase is separated and the aqueous extracted with ether. The combined ether extracts are dried with Na ₂ SO ₄ , the ether is i. Vak. evaporated and the residue fractionated.

Bp. 96 ° C-98 ° C / 1 Torr n ° °: 1.5800 Yield: 65%

MS (79 eV): m / z = 198 (Mt) -. ·

¹ H NMR (CDCl3 HMDS) Io [PPm] 1.73; 1,882s (-CH ₃ ) ".

3.58; 3.34 2s (-CH ₂ -).

5.68; 5.64 2m (-CH =)

7.14m (aromatic H)

Claims (2)

Invention claim: 1. A process for the preparation of N- and S-substituted-y-chloroallyl compounds from polychloroalkanes, characterized in that a polychloroalkane in a water-miscible solvent with a-N- or S-nucleophile at temperatures between 20 ⁰ C and 100 ° C is reacted, the reaction mixture is mixed with water, the mixture is extracted with an organic solvent such as ether and the end product is pared from the organic phase se. 2. The method according to item 1, characterized in that are used as the water-miscible solvent DMSO or methanol.