SU1307771A1 - Method of extracting 3-methyl-(2e)-alkenylchloroderivatives - Google Patents

Abstract

The invention relates to halo-hydrocarbons, in particular the isolation of 3-methyl-2EZ-alkenylchloroproiodic acid.

Description

The invention relates to the field of organic chemistry, and to the separation of 3-methyl-2K-alkenyl chloro derivatives from a mixture with isomeric alkenyl chlorine derivatives.

3-MeTyl-2E | -alkenipochloro derivatives, for example, geranium-1-chloro-f-3, 7-dimethyl-2Ej, 6-octadien (I) and farnesyl-1-chloro-3,7,11-trimethyl , 6E, 10-dodecatriene (II) and their quaternary (LMFA) ammonium salts with S, K-dimethylaniline (DND), respectively, geranyl dimethylfenkpammonium chloride — HGDMFA (1a) and farnesyldimethylphenylammonium –– HII-DMF (1a) chloride and FNESyldimethylphenylammonium –– HII DMF (1a) salts and FNESyldimethylphenylammonium –– HII DMF (1a) and X-DMA (1a), and FNESyldimethylphenylammonium chloride — HII-DMFA (1a) and X-DMA (IIIa), and quaternary ammonium salts (LNA); intermediate for the synthesis of esters of geraniol and farnesol, which are pheromones attractants for various species of beetle beetle. The activity of attractants to a power measure depends on the degree of their purity. In addition, geraniol, farnesol and their esters derived from the above chlorinated compounds I (1a and H) are valuable fragrances for perfumery, the quality of which also depends on their purity.

In the fraction of chlorides C, which is the starting point for the synthesis of geraniol derivatives, there are also:. I 58.9-59.2%; bp 60-62 ° C (2 mmHg) I

I chlorine-3,7-dimethyl- 2 g, 6-octadiene (III) 1.9-2.2%; bp 58-60 ° C (2 mm Hg) i

1-chloro-2,7-dimethyl-2E 6-octadia (IV) 6.0-6.6%; bp 59 ° C (2 mm Hg).

As can be seen from “reduced boiling points, these chlorides are practically inseparable by means of rectification.

The purpose of this invention is to improve the quality and yield of target products, to simplify the process of being loaded;

1. The initial mixture, including: 120 DMF I 90.9

LMPA III and IV 9.1. Toluene20 ..

Petroleum ether (5.00 ml) 335

five

0

five

and preparation of chlorine derivatives of 3,7,11-trime-, bq, I 0-dodecatriene (farnesyl) in preparative amounts.

PRI me R 1. As the source, Part 9, co ... substances use the fraction C, g H, CI containing 79% I; 3% III and 5% IV, as well as 13% of non-primary chlorides, mainly linalyl- and terpenyl chlorides. From 200 g of the fraction (158 g or 0.92 mol I) and 133. From DMA, a mixture of DMF I, III and IV is obtained, which is extracted by war and the layers of unreacted C H, C1 and DMA are separated. The aqueous solution is washed with petroleum ether, then nascent potash to salve out DMF I, III and IV, 300 ml of toluene was added to the resulting mixture of DMF I, III and IV. For the final drying, the moisture is distilled off with an azeotrope of toluene-water under moderate vacuum and at a temperature below. 338 g of residue are obtained, which contain 282 g of DMF I, III and IV (of which 256 g or 0.87 mol of DMF I). You-, the course of 94.5% of DMF I in recalculation on I,. os.talnoe - toluene. I 20 g of the obtained residual mixture, containing 100 g of DMF I, III and IV (of which 90.9 g of DMF or 0.31 mol), are loaded into a flask, to which 500 ml of a pegro-layer is added. ether and stir for 6 hours at a temperature of 50 ° C. Then, the solution of petroleum ether, which .- contains I, III, and IV, as well as DND, is separated. The residue is washed twice with petroleum ether and cyDjaT cjocHM-argon to remove traces of the solvent. Drying is required only to refine the analysis.

82 g of HGDMFA are obtained (1a) | 99% (81.2 g or 0.277 mol of DMF I). The output of 89.4% of the original DMF I or 84.5% of the original I,.

The material balance of the process is given below. Get, g

i. HGDMA 9.9%, including:. DMF I DMF III and IV Petroleum ether.

2. Solution

including:

Petroleum

ether

3. Petroleum ether for washing (2 times 40 mp)

Total: 509

60-80 79.0 98.0

50 84.5 99.0

55 88.0 98.5

55 88.8 99.6

70 65.4 99.0

Example 7: From the hydrochlorination of myrcene C, (, H, 7C, containing 79%, 4% III and 17% non-primary chlorides, a mixture of DMF I and III is obtained according to example 1. 100 g of this mixture in toluene (contains 95.2 DMF I), a total of 127 g, is loaded into a flask, 500 ml of gasoline is added and stirred for 6 hours at 55 ° C. The solution is treated as in Example 1.

Obtain 85 g of HGDMF (I a) with a purity of 98.5% (0.837 mol of DMF D). Yield 88%.

Example 3. From 1500 g of the fraction containing 79% I (1185 g or 6.87 mol), 3% III and 5% IV, and also 13% non-primary chlorides and lOOO g DMA, receive a mixture of DMF I, III and IV according to Example 7. The last drying with toluene (distillation of moisture in an azeotrope with toluene) is carried out in a continuously operating extraction apparatus, where the further purification process is carried out. After distilling off toluene, 6 l of extraction beisin is charged into the apparatus, the mixture is stirred at 55 ° C

19 5.3 A, 7 7.0

21; 54

Total: 509

five

0

five

within 6 hours. The gasoline solution of isomeric chlorides I, III, and IV, as well as DMA, is produced continuously by the apparatus. From the solution, the solvent (extraction gasoline) is regenerated continuously and sent back to the extraction apparatus. At the end of the process, the mixture in the apparatus is cooled, the solvent is drunk. In the remainder receive,. 1798 g HGDMFA (1a) with a purity of 99.6Z (DMF I 1790.8 g or 6.1 mol). Life course 88.8% (on the source I),

Method for isolating 3-MeTHn- 2Ej-an-. Kenyl chloro derivatives, in particular, HGDMFA (1a), has advantages over the known copyright certificate in application no. 3537377/04, which is evident from the table.

The decomposition of the mixture of DMF I, III and IV at 45-55 C allows to obtain in the one-stage process HGDMF (1a-target product) with a yield of 84.5- 88.8% and purity (content of DMF I) 98.5-99.6 % Compounds 1a (and Na) obtained by this method allow to obtain attractants of the required DYMET purity. Purity increase

0

51

Attractant from 98 to 98.5% increases the pheromone-attractant efficiency up to 2 times, and up to 99.6 - already 10 times.

Example 4. The starting material used is the fraction CijHjpCl, in Kon iecTse 240 g (contains 43.5%), 11, or 104.4 g, or, 0.434 mol and 49.0% of non-primary chlorides); 3.5% 1-chloro 3,7,11-trime-, 6E, 10-dodecatriene (V) and 4.0% 1-chloro-3, 7,11-trimethyl-2Z BE, 10-dodecatriene (VI) . Add - ioT 160 g DMA, which forms 00-7 responsibly DMF II, V and VI. Petroleum ether and methanol are added to the resulting mixture, mixed and the layers are separated. The resulting methanol solution containing DMFL II, V and VI is washed with petroleum ether. In petroleum ether, unreacted ingredients, mainly non-primary chlorides and an excess of DMA, remain. Dichloroethane is then added and diluted with 40% CaCl solution to form two layers. Separated dichloroethane solution (contains DMF II, V and VI). Washed several times with 40% CaCl solution. The dichloroethane is then distilled off under reduced pressure. Get 198 T

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the residue containing 182 g of DMF II, V and VI (DMF II 155 g), the rest is dichloroethane.

100 g of DMF il, V and VI (containing 5 DMF Cu 85, h), total with dichloroethane 109 g are loaded into the flask, 500 ml of petroleum ether are added and stirred for 6 hours. After separating the solution, washing and drying with dry argon 71 g of HFDMFA (Na) t are obtained with a purity of 95% (DMF II 67.5 g or 0.19 mol). The yield equals 79.1%.

Claims (1)

The method of separation 3-methyl-23-alkenylchloro derivatives from a mixture with isomeric 2-methyl-2EZ-alkenyl and (or) 3-methyl-22-alkenylchloride derivatives by treating the mixture with dimethylaniline followed by decomposition of the mixture. Quaternary ammonium salts at elevated temperature, characterized in that, in order to improve the quality and yield of the target products and simplify the process, decomposition is carried out at 45--55 ° C, with simultaneous extraction of the isomeric chlorine derivatives by hydrocarbon organic solution 15 20 thirty tel eat