RU2002751C1 - Method of trithiabicyclooctane derivatives synthesis - Google Patents

Description

the solvent was removed in vacuo and the residue was partitioned between diethyl ether and water. The organic phase was separated, washed with water and brine, and then dried with anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain 6-iodo-1-trimethylsilylheco-1-in as a yellow oil (20.0 g).

(III) To a solution of 2-hydroxymethyl-2-n. propylpropane-1,3-diol (28.0 g) in dry pyridine (200 ml) in a nitrogen atmosphere at 0 ° C was added dropwise over 30 minutes methanesulfonyl chloride (74.0 g). The mixture was allowed to warm to room temperature. After stirring for 18 hours, the mixture was poured into water (200 ml) and extracted with chloroform (2 x 200 ml). The chloroform extracts were washed with water (2 x 100 ml), dried with anhydrous magnesium sulfate, evaporated in vacuo to give a brown solid. This material was stirred in dry diethyl ether (200 ml) to give 2-hydroxymethyl-2-n trimethanesulfonate. propylpropane-1.3-diol as a white solid (70.0 g); so pl. 103 -10 ° C.

(IV) To a solution of 2-hydroxymethyl-2-n trimethanesulfonate. propylpropane-1,3-diol (12.0 g) in dimethylformamide (100 ml) was added a solution of sodium trithiocarbonate (18.0 g) in water (25 ml). The mixture was refluxed (130 ° C) for 4 hours, then allowed to cool to room temperature. After further stirring for 18 hours, dilute sulfuric acid (50 ml) was added slowly over 30 minutes. The mixture was extracted with chloroform, the extracts were dried with anhydrous magnesium sulfate, evaporated in vacuo to give a brown liquid. Hexane (200 ml) was added, the mixture was washed with water (3 x 50 ml), dried with magnesium sulfate, evaporated to give an amber oil (6.8 g). The crude oil (6.4 g) in diethyl ether (10 ml) was added dropwise to a suspension of lithium aluminum hydride (3.0 g) in dry diethyl ether (100 ml) at a rate sufficient to maintain reflux. Upon completion of the addition, the mixture was stirred for an additional 1 hour, then water (3 ml) was carefully added. Diluted sulfuric acid (3 ml) was added, followed by water (3 ml). The mixture was filtered, the solid was washed with diethyl ether (50 ml), and the combined filtrates were dried with anhydrous magnesium sulfate and evaporated in vacuo to give 2-mercaptomethyl-2-n. propylpropane-1,3-dithiol as a pale yellow oil (5.3 g).

(V) 2-Mercaptomethyl-2-n. propylpropane-1, 3-dithiol (4.0 g) and triethylorthoformate (3.6 g) were heated under reflux with stirring in dry toluene (120

5 ml) containing Amberlust 15 (1.0 g). The mixture was cooled and filtered. The filtrates were evaporated in vacuo, and the residue was purified by chromatography on alumina (eluent mixture 1: 10 dichloromethane: hexane saturated with ammonia). Received 4 N. propyl-2,6.7-trithiabicyclo (2.2.2) octane as a colorless solid (31.1 g, mp 139 ° C).

(VI) To a solution of 4 N. propyl-2,6,7-trithia-5 bicyclo (2.2.2) octane (0.3 g) in dry tetrahydrofuran (20 ml) was added dropwise with stirring under a nitrogen atmosphere and at -70 ° C. butyllithium (1.0 ml. 1.6 M solution in hexane). The resulting solution was stirred at -70 ° C for 45 minutes, and a solution of 1-trimethylsilyl-6-iodohex-1-in (0.41 g) in dry tetrahydrofuran (10 ml) was added dropwise. The reaction mixture was stirred at -70 ° C for 2 hours, allowed to warm to 20 ° C and stirred at this temperature for 18 hours. Water was added carefully and the aqueous mixture was extracted with diethyl ether. The ether extracts were washed with water, dried with anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by chromatography on silica (eluent: dichloromethane: hexane 1g10). Received 1- (6-trimethyl-silylhex-5-ynyl) -4-n. propyl5 2,6,7-trithiabicyclo (2.2.2) octane as a pale yellow crystalline solid (0.062 g, mp 113.3 ° C).

Mass spectrum (chemical ionization): (M + 1) 359.

0 (VII) To a solution of 1- {6-trimethylsilylhex-5-ynid) -4-n. propyl-2,6,7, -tritiabicyclo (2.2.2.) octane (1.0 g) in tetrahydrofuran (50 ml) was added with stirring a solution of tetrabutylammonium fluoride (1.0 M solution

5 in tetrahydrofuran, 4.0 ml). After 40 minutes, the reaction mixture was evaporated in vacuo, water was added and the aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water, dried

Anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by chromatography on silica (eluent dichloromethane hexhexane 1:20). Received 1- (geco-5-ynyl} -4-n. Propyl-2,6,7-tritiabicyclo (2.2.2) octane

5 as a colorless solid (0.15 g, mp 88 ° C).

Mass spectrum (M + 1) 287. When using 2-hydroxymethyl-2-cyclopropylmethylpropane-1,3-diode and 2-hydroxymethyl-2-isopropylpropane-1, 3-diol as the starting compounds, as described above 1- (geco-5-ynyl) -4-cyclopropylmethyl-2,6,7-tritioabicyclo (2.2.2) octane and 1- (geco-5-ynyl) -4-isopropyl-2,6.7-tritiabicyclo, respectively, were obtained (2.2. 2) octane.

PRI me R 2. 1- {3,3-Dimethibutyl) -4-n, lropyl-2.6,7-trithiabicyclo (2.2.2) octane.

(I) Using 3,3-dimethylbutan-1-one (Aldrich) and 1 equivalent of methanesulfonyl chloride as the starting compound. By the procedure described before step (111) of Example 1, 3.3-dimethylbutylmethanesulfonate was obtained.

(I) 3,3-Dimethylbutyl iodide was obtained from 3,3-dimethylbutylmethanesulfonate according to the procedure described in step (II) of Example 1.

(Ill) Using 3,3-dimethylbutyl iodide and 4-n as starting compounds. propyl-2, b, 7-trithiabicyclo (2.2.2) octane according to the procedure described in step (VI) of Example 1. 1- (3,3-dimethylbutyl) -4-n was obtained. propyl-2,6,7-trithiabicyclo (2.2.2) octane in the form of a colorless solid (mp. 144 ° C).

Mass Spectrum (Chemical Ionization) (M + +1) 291.

Similarly, when using as starting compounds 3,3-dimethylbutyl iodide, respectively

4-isopropyl-2, b, 7-triabicyclo (2.2.2) octane or 4-cyclopropylmethyl-2,6,7-trithiabicyclo (2.2.2) octane gave 1- (3,3-dimethylbutyl) -4- isopropyl-2-6,7-trithiabicyclo (2.2.2) octane and 1- (3,3-dmme lbutyl) -4-cyclo p ro p yl-methyl-2, b, 7-t tri - thiabicyclo (2.2.2) octane.

PRI me R 3. 1- (But-3-ynyl oxymethyl} - 4-N. Propyl-2,6,7-tritiabicyclo (2.2.2) octane.

(I) 2-Mercaptomethyl-2-n. propylpropanone-1,3-dithiol (5.3 g) was obtained according to the procedure described in example 1, stage (III) and (IV).

(II) Through a suspension of paraformaldehyde (4.3 g) in but-3-yn-1-olo (10.0 g) and dry dichloromethane (30 ml) at -20 ° C, gaseous hydrogen chloride was bubbled for 30 minutes . The mixture was allowed to warm to room temperature, and then was further stirred for 18 hours. Cold water (30 ml) was added and the organic layer was separated, dried with anhydrous calcium chloride and evaporated to give but-3-ynylchloromethyl ether as an amber liquid (14.2 g).

(Iii) 2-mercaptomethyl-2-n. propylpropan-1,3-dithiol (2.3 g) and triethylorthoformate (1.74 g) in dry toluene (5 ml) containing

p-toluenesulfonic acid (5 mg) was heated with distillation of the resulting ethanol. After cooling, toluene (15 ml) was added and the mixture was washed with water (2x10 ml). Drying with anhydrous magnesium sulfate and evaporation

under vacuum gave a light yellow oil. The oil was extracted with diethyl ether (50 ml) and the extracts were evaporated in vacuo to give a solid. Purification by chromatography on alumina

(eluent 1:10 dichloromethane: hexane saturated with ammonia) gave 4-n. propyl-2,6,7-trithiabicyclo (2.2.2) octane as a white solid (0.33 g; mp 139.

Mass spectrum (chemical ionization) :( M

+1) 207.

(IV) To a solution of 4-n. propyl-2, b, 7-trithio-bicyclo (2.2.2) octane (0.1 g) in dry tetrahydrofuran (2.0 ml) was added n. -butyl lithium (0.3 ml, 1.6 M solution in hexane)

and the reaction mixture was allowed to warm to 20 ° C. Water (10 ml) was added and the resulting mixture was extracted with diethyl ether. The ether extracts were dried with anhydrous magnesium sulfate and the solvent was removed in

vacuum. The residue was purified by chromatography on alumina (eluent 1:10 dichloromethane: hexane saturated with ammonia). Received 1- (but-3-yniloxymethyl) - 4-n. propyl-2,6,7-tritibicyclo (2.2.2) octane

as a waxy solid (0.032 g).

In the table. 1 and 2 show the pesticidal activity of new and known compounds.

(56) EP No. 152229, C 07 D 493/08, 1985. EP No. 211598. C 07 D 493/08, 1987. EP No. 216624, C 07 D 493/08, 1987. EP N; 216625, C 07 D 493/08, 1987.

9200275110

The pesticidal activity of M-diminished b. T-tritibitsnyb (2.2.2) octane.

Table 1

Note: Md - Musea domestlca PX - Plutella xylostella Mp - Myzus perslcae Dl - Dlabrotlca undeclmpunctata Sg - SHopNIus granarlus Te - Trlbollum castaneum Ap - Aphis (abae Ml - Meloldogone Incognlu Ma - Macraclanta Paera mantra Paula

Table

Claims (1)

The claims METHOD FOR PRODUCING TRITIABicyclooctane derivatives of the general formula R : H2-sA-X where R Cr is a Ce-hydrocarbon non-aromatic group; A - X - Ca - Cb-alkyl. possibly substituted by Cr with a Cb-alkynyloxy group, or Cg - with Cb-alkynyl, possibly substituted with a trimethylsilyl group characterized in that the tritiabicyclooctane of the general formula R: n where R has the indicated meanings, is reacted with a compound of the general formula L - A X, where A - X has the indicated meanings; L is a leaving group. Priority by signs: 07.22.87 at R - Ca - Ce hydrocarbon non-aromatic group; A — X — Cg — Cb-alkyl substituted with Ca — Cb-alkynyloxy group, or Cg — Cb-alkynyl optionally substituted with trimethylsilyl group. 04/26/88 at R - Cr - Cb-hydrocarbon non-aromatic group; A - X - Cr - Cb-alkyl.