(E)-1,4-dichlorobut-2-ene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 80 mmol (17.4 g) of caesium carbonate are added to a solution, cooled to 0° C., of 80 mmol (10 g) of trans-1,4-dichloro-2-butene and 53.3 mmol (9.23 g) of para-bromophenol in 500 ml of acetonitrile, and then the mixture is stirred at ambient temperature for 4 days. The mixture is hydrolysed with 250 ml of a saturated aqueous solution of ammonium chloride and then extracted with ethyl acetate. The organic phases are combined and washed with a saturated aqueous solution of sodium chloride and then dried over magnesium sulphate. After evaporation, the expected product is obtained following purification by chromatography on silica gel using a 98:2 petroleum ether/ethyl acetate mixture as eluant. extracted with ethyl acetate washed with a saturated aqueous solution of sodium chloride dried over magnesium sulphate After evaporation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound was prepared according to Method GA from trans-7-(3-chloro-allyloxy)-2-methyl-benzothiazole and 1-(10,11-dihydro-5H-dibenzo[a,d]-cyclohepten-5-yl)piperazine. mp 151-152° C.; LSIMS m/z 496. The trans-7-(3-chloroallyloxy)-2-methyl-benzothiazole was prepared by Method IV with trans-1,4-dichloro-2-butene as the alkylating agent.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 130 lt of ethanol, 12.1 kg of sodium methoxide are added while cooling and stirring, followed by 26.5 kg of salicylaldehyde at 30°. Thereupon 33.3 kg of trans-1,4-dichloro-2-butene are added and the mixture heated to 68° for 4 hours. It is combined with 156 lt of toluene, 187 lt of water and 9.4 kg of 36% hydrochloric acid while keeping the temperature at about 30°. The precipitate formed is filtered off and washed with 16 lt of toluene. The filtrate is separated, the organic layer washed 3 times with 27 lt of water, evaporated, the residue distilled and the fraction boiling at 170°/0.2 mmHg collected, to yield the 2-(4-chloro-trans-2-butenyloxy)-benzaldehyde. while cooling the mixture heated to 68° for 4 hours at about 30° The precipitate formed is filtered off washed with 16 lt of toluene The filtrate is separated the organic layer washed 3 times with 27 lt of water evaporated the residue distilled the fraction boiling at 170°/0.2 mmHg collected

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 2 lt of refluxing water, 3 ml of 40% aqueous tetrabutylammonium hydroxide, 250 ml of salicylaldehyde and 280 ml of trans-1,4-dichloro-2-butene are added while vigorously stirring, followed by the dropwise addition of the solution of 83 g of sodium hydroxide in 400 ml of water at such a rate that the pH of the mixture is kept between 7 and 8 (ca 25 minutes). Thereafter the mixture is refluxed for about 6 minutes until the pH is about 7, cooled to 20° and the aqueous layer is extracted with diethyl ether. The extract is combined with the organic layer, washed with 5% aqueous sodium hydroxide, dried, evaporated, the residue distilled and the fraction boiling at 141°-147°/0.7 mmHg collected, to yield the 2-(4-chloro-trans-2-butenyloxy)-benzaldehyde. is kept between 7 and 8 (ca 25 minutes) Thereafter the mixture is refluxed for about 6 minutes until the pH is about 7 cooled to 20° the aqueous layer is extracted with diethyl ether washed with 5% aqueous sodium hydroxide dried evaporated the residue distilled the fraction boiling at 141°-147°/0.7 mmHg collected

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 1.2 lt of refluxing water, 1 ml of 40% aqueous tetrabutylammonium hydroxide, 160 g of 5-chloro-salicylaldehyde and 140 ml of trans-1,4-dichloro-2-butene are added while vigorously stirring, followed by the dropwise addition of the solution of 42 g of sodium hydroxide in 200 ml of water at such a rate that the pH of the mixture is kept between 7 and 8. Thereafter the mixture is refluxed until the pH is about 7, cooled and extracted with methylene chloride. The extract is washed with 5% aqueous sodium hydroxide, dried, evaporated and the residue heated to 30°/0.1 mmHg in order to remove the excess of 1,4-dichloro-2-butene. The residue is taken up in 1 lt of diethyl ether, the solution filtered, the filtrate evaporated and the residue recyrstallized from ethyl acetate, to yield the 5-chloro-2-(4-chloro-trans-2-butenyloxy)-benzaldehyde melting at 62°-63°. Thereafter the mixture is refluxed until the pH is about 7 cooled extracted with methylene chloride The extract is washed with 5% aqueous sodium hydroxide dried evaporated the residue heated to 30°/0.1 mmHg in order to remove the excess of 1,4-dichloro-2-butene the solution filtered the filtrate evaporated

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 125 parts of 1,4-dichlorobutene-2 and 60 parts of trimethylamine are mixed with 700 parts toluene. This mixture is allowed to react (reflux) at 110°C. for 18 hours. This mixture yields about 82% 4-chloro-2-butenyltrimethylammonium chloride. to react

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 125 parts 1,4-dichlorobutene-2 and 60 parts trimethylamine are mixed with 700 parts 2-hexanone in a stainless steel pressure reactor. The mixture is allowed to react for 5 hours at a temperature of about 75°C. to about 80°C. Next, 60 parts of water are added to the cooled reaction mixture. This mixture yields about 93.5% 4-chloro-2-butenyltrimethylammonium chloride. The 2-hexanone is removed either by vacuum distillation or separated by decantation from the reaction mixture. About 95% of the 2-hexanone is recovered for reuse. to react for 5 hours at a temperature of about 75°C. to about 80°C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 125 parts 1,4-dichlorobutene-2 and 60 parts trimethylamine are mixed with 700 parts 2-hexanone in a stainless steel pressure reactor. The mixture is allowed to react for 5 hours at a temperature of about 75°C. to about 80°C. Next, 60 parts of water are added to the cooled reaction mixture. This mixture yields about 93.5% 4-chloro-2-butenyltrimethylammonium chloride. The 2-hexanone is removed either by vacuum distillation or separated by decantation from the reaction mixture. About 95% of the 2-hexanone is recovered for reuse. to react for 5 hours at a temperature of about 75°C. to about 80°C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 60 parts trimethylamine and 125 parts 1,4-dichlorobutene-2 are mixed with 700 parts acetone in a stainless steel pressure reactor. The mixture is allowed to react for 5 hours at a temperature of about 75°C. to about 80°C. Next, 60 parts water are added to the cooled reaction mixture. This mixture yields about 96% 4-chloro-2-butenyltrimethylammonium chloride. to react for 5 hours at a temperature of about 75°C. to about 80°C

Conditions: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl acetoacetate was reacted with 1,4-dichlorobutene-2 in a manner similar to that described in Example III using a poly(oxypropylene) catalyst. For the reaction, 5.6 g potassium hydroxide and 50 mls. methylene dichloride were combined in the reaction vessel and ethyl acetoacetate (6.5 g), the poly(propylene glycol) catalyst (1.06 g) and 20 mls. methylene dichloride rapidly added with vigorous stirring. 1,4-Dibromobutene-2 (10.7 g) was then added via a solids addition funnel while maintaining the temperature at about 35° C. Seventy-four percent yield 1-carboethoxy-1-methylketo-2-vinylcyclopropane was obtained. The product had a boiling point of 58° C. at 0.85 mm Hg, refractive index (nD25) of 1.4707, and the structure was confirmed by infrared and proton nmr spectroscopy. When the process is repeated reacting 1,4-dichlorobutene-2 with phenylacetonitrile, ethyl phenylacetate and acetoacetanilide, 1-cyano-1-phenyl-2-vinylcyclopropane, 1-carboethoxy-1-phenyl-2-vinylcyclopropane, and 1-carboxanilido-1-methylketo-2-vinylcyclopropane are respectively obtained.

Conditions: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl acetoacetate was reacted with 1,4-dichlorobutene-2 in a manner similar to that described in Example III using a poly(oxypropylene) catalyst. For the reaction, 5.6 g potassium hydroxide and 50 mls. methylene dichloride were combined in the reaction vessel and ethyl acetoacetate (6.5 g), the poly(propylene glycol) catalyst (1.06 g) and 20 mls. methylene dichloride rapidly added with vigorous stirring. 1,4-Dibromobutene-2 (10.7 g) was then added via a solids addition funnel while maintaining the temperature at about 35° C. Seventy-four percent yield 1-carboethoxy-1-methylketo-2-vinylcyclopropane was obtained. The product had a boiling point of 58° C. at 0.85 mm Hg, refractive index (nD25) of 1.4707, and the structure was confirmed by infrared and proton nmr spectroscopy. When the process is repeated reacting 1,4-dichlorobutene-2 with phenylacetonitrile, ethyl phenylacetate and acetoacetanilide, 1-cyano-1-phenyl-2-vinylcyclopropane, 1-carboethoxy-1-phenyl-2-vinylcyclopropane, and 1-carboxanilido-1-methylketo-2-vinylcyclopropane are respectively obtained.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To demonstrate the versatility of the process, 16 g (0.1 mol) diethyl malonate and 62.55 g of a block copolymer of ethylene oxide and polypropylene oxide having an average molecular weight of about 13,300 (Pluronic® 127) were charged to a reactor. Methylene dichloride (100 mls.) and 11.2 g solid potassium hydroxide (90%) were added and the mixture vigorously agitated while maintaining the temperature at or below 35° C. The 1,4-dichlorobutene-2 (12.4 g; 0.1 mol) was then added over a 5 minute period. About 22% conversion to diethyl 2-vinylcyclopropane-1,1-dicarboxylate was obtained after one hour of reaction. The reaction was continued to obtain essentially complete conversion of the reactants to the desired vinylcyclopropane product. were charged to a reactor while maintaining the temperature at or below 35° C