六氯-1，3-丁二烯

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A flame dried 250 ml Schlenk flask containing TBF (20 ml) was cooled to −78° C. and n-butyl lithium (20 ml of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes hexachlorobutadiene (1.88 ml, 12.0 mmol) was added dropwise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C., and dimethylaminodimethylchlorosilane (3.6 ml, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis(dimethylaminodimethylsilyl)-butadiyne. The TBF was removed in vacuo, and the mixture was taken up in a minimum amount of pentane and filtered. The pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne. A flame dried 250 ml Schlenk flask containing TBF (20 ml) After completion of addition the cold bath was removed The resulting 1,4-dilithio-1,3-butadiyne was used without further purification was then recooled to −78° C. The flask was removed from the cold bath the reaction mixture stirred at room temperature for 16 hours The TBF was removed in vacuo filtered The pentane was removed in vacuo

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A flame dried 250 ml Schlenk flask containing TBF (20 ml) was cooled to −78° C. and n-butyl lithium (20 ml of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes hexachlorobutadiene (1.88 ml, 12.0 mmol) was added dropwise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C., and dimethylaminodimethylchlorosilane (3.6 ml, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis(dimethylaminodimethylsilyl)-butadiyne. The TBF was removed in vacuo, and the mixture was taken up in a minimum amount of pentane and filtered. The pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne. A flame dried 250 ml Schlenk flask containing TBF (20 ml) After completion of addition the cold bath was removed The resulting 1,4-dilithio-1,3-butadiyne was used without further purification was then recooled to −78° C. The flask was removed from the cold bath the reaction mixture stirred at room temperature for 16 hours The TBF was removed in vacuo filtered The pentane was removed in vacuo

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Synthesis of 1,4-bis(dimethylaminodimethylsilyl)butadiyne—A flame dried 250 mL Schlenk flask containing diethyl ether (20 mL) was cooled to −78° C. and n-butyl lithium (20 mL of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes, hexachlorobutadiene (1.88 mL, 12.0 mmol) was added drop wise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C. and dimethylaminodimethylchlorosilane (3.6 mL, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time, 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis(dimethylaminodimethylsilyl)butadiyne 206. Diethyl ether was removed in vacuo, and the mixture taken up in a minimum amount of pentane and filtered. Pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne 206 as a viscous red liquid. IR (cm−1) 2074 (s), (—C≡C—C≡C—). 1H NMR (ppm) 2.44 (s), (N(CH3)2), 0.20 (s), (Si(CH3)2). 13C NMR 87.6, 84.4, (—C≡C—C≡C—) 37.7, (N(CH3)2), −1.2, (Si(CH3)2). flame dried 250 mL Schlenk flask containing diethyl ether (20 mL) After several minutes After completion of addition the cold bath was removed The resulting 1,4-dilithio-1,3-butadiyne was used without further purification was then recooled to −78° C. The flask was removed from the cold bath the reaction mixture stirred at room temperature for 16 hours Diethyl ether was removed in vacuo filtered Pentane was removed in vacuo

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A flame dried 250 ml Schlenk flask containing TBF (20 ml) was cooled to −78° C. and n-butyl lithium (20 ml of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes hexachlorobutadiene (1.88 ml, 12.0 mmol) was added dropwise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C., and dimethylaminodimethylchlorosilane (3.6 ml, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis(dimethylaminodimethylsilyl)butadiyne. The TBF was removed in vacuo, and the mixture was taken up in a minimum amount of pentane and filtered. The pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne. A flame dried 250 ml Schlenk flask containing TBF (20 ml) After completion of addition the cold bath was removed The resulting 1,4-dilithio-1,3-butadiyne was used without further purification was then recooled to −78° C. The flask was removed from the cold bath the reaction mixture stirred at room temperature for 16 hours The TBF was removed in vacuo filtered The pentane was removed in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The present invention is directed to a process for the preparation of of Z-1,1,1,4,4,4-hexafluoro-2-butene from 2,3-dichloro-1,3-butadiene. The process of the present invention includes the sequential steps initiating with initiating the reaction of chlorine with 2,3-dichloro-1,3-butadiene to obtain 1,2,2,3,3,4 hexachlorobutane followed by contacting the 1,2,2,3,3,4 hexachlorobutane with tetrabutyl ammonium chloride in a basic aqueous solution to produce 1,2,3,4-tetrachlorobuta-1,3-diene. Chlorine is added to the 1,2,3,4-tetrachlorobuta-1,3-diene to obtain 1,1,2,2,3,3,4,4 octachlorabutane followed by contacting the 1,1,2,2,3,3,4,4 octachlorobutane with tetrabutyl ammonium chloride in a basic aqueous solution to produce 1,1,2,3,4,4-hexachlorobuta-1,3-diene. Hydrogen fluoride is chlorinated and combined with the 1,1,2,3,4,4-hexachlorobuta-1,3-diene to provide E- or Z-1326mxz (1,1,1,4,4,4-hexafluoro-2-chloro-2-butene). Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene is reacted with an aqueous solution of an alkali metal hydroxide and an alkali metal halide in the presence of a quaternary alkylammonium salt having alkyl groups of from four to twelve carbon atoms and mixtures thereof, to produce a mixture including hexafluoro-2-butyne. The final step is hydrogenating hexafluoro-2-butyne to 1,1,1,4,4,4 hexafluro-2-butene. to obtain 1,1,2,2,3,3,4,4 octachlorabutane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The present invention is directed to a process for the preparation of of Z-1,1,1,4,4,4-hexafluoro-2-butene from 2,3-dichloro-1,3-butadiene. The process of the present invention includes the sequential steps initiating with initiating the reaction of chlorine with 2,3-dichloro-1,3-butadiene to obtain 1,2,2,3,3,4 hexachlorobutane followed by contacting the 1,2,2,3,3,4 hexachlorobutane with tetrabutyl ammonium chloride in a basic aqueous solution to produce 1,2,3,4-tetrachlorobuta-1,3-diene. Chlorine is added to the 1,2,3,4-tetrachlorobuta-1,3-diene to obtain 1,1,2,2,3,3,4,4 octachlorabutane followed by contacting the 1,1,2,2,3,3,4,4 octachlorobutane with tetrabutyl ammonium chloride in a basic aqueous solution to produce 1,1,2,3,4,4-hexachlorobuta-1,3-diene. Hydrogen fluoride is chlorinated and combined with the 1,1,2,3,4,4-hexachlorobuta-1,3-diene to provide E- or Z-1326mxz (1,1,1,4,4,4-hexafluoro-2-chloro-2-butene). Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene is reacted with an aqueous solution of an alkali metal hydroxide and an alkali metal halide in the presence of a quaternary alkylammonium salt having alkyl groups of from four to twelve carbon atoms and mixtures thereof, to produce a mixture including hexafluoro-2-butyne. The final step is hydrogenating hexafluoro-2-butyne to 1,1,1,4,4,4 hexafluro-2-butene. to obtain 1,1,2,2,3,3,4,4 octachlorabutane

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A flame dried 250 ml Schlenk flask containing TBF (20 ml) was cooled to −78° C. and n-butyl lithium (20 ml of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes hexachlorobutadiene (1.88 ml, 12.0 mmol) was added dropwise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C., and dimethylaminodimethylchlorosilane (3.6 ml, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis(dimethylaminodimethylsilyl)-butadiyne. The TBF was removed in vacuo, and the mixture was taken up in a minimum amount of pentane and filtered. The pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne. A flame dried 250 ml Schlenk flask containing TBF (20 ml) After completion of addition the cold bath was removed The resulting 1,4-dilithio-1,3-butadiyne was used without further purification was then recooled to −78° C. The flask was removed from the cold bath the reaction mixture stirred at room temperature for 16 hours The TBF was removed in vacuo filtered The pentane was removed in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Tetrachlorocyclobutenone, required as a starting material, is obtained with high yields and conversions by a not yet published process from hexachlorocyclobutene and a mixture of sulphuric acid and sulphur trioxide at elevated temperatures, e.g., by reaction of 1 mol hexachlorocyclobutene with approximately 1 mol each of sulphuric acid and sulphur trioxide at a temperature of 80° C. within 5 hours. Hexachlorocyclobutene can be obtained from hexachloro-1,3-butadiene in yields of near 100% of theory (DE-OS No. 26 18 557), corresponding to U.S. Pat. No. 4,115,460), for example by rectifying commercial hexachlorobutadiene at a pressure of from 2 to 100 mm Hg with a reflux ratio of from 300:1 to 600:1, subjecting hexachlorobutadiene remaining in the bottoms to a heat treatment at from 150° to 200° C. and then returning it to the rectifying column together with fresh commercial hexachlorobutadiene while withdrawing the product rich in hexachlorocyclobutene over the top. A suitable starting material is not only pure tetrachlorocyclobutenone but also crude tetrachlorocyclobutenone which may, for example, contain hexachlorobutadiene and hexachlorocyclobutene originating from its process of manufacture. is obtained with high yields

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Tetrachlorocyclobutenone, required as a starting material, is obtained with high yields and conversions by a not yet published process from hexachlorocyclobutene and a mixture of sulphuric acid and sulphur trioxide at elevated temperatures, e.g., by reaction of 1 mol hexachlorocyclobutene with approximately 1 mol each of sulphuric acid and sulphur trioxide at a temperature of 80° C. within 5 hours. Hexachlorocyclobutene can be obtained from hexachloro-1,3-butadiene in yields of near 100% of theory (DE-OS No. 26 18 557), corresponding to U.S. Pat. No. 4,115,460), for example by rectifying commercial hexachlorobutadiene at a pressure of from 2 to 100 mm Hg with a reflux ratio of from 300:1 to 600:1, subjecting hexachlorobutadiene remaining in the bottoms to a heat treatment at from 150° to 200° C. and then returning it to the rectifying column together with fresh commercial hexachlorobutadiene while withdrawing the product rich in hexachlorocyclobutene over the top. A suitable starting material is not only pure tetrachlorocyclobutenone but also crude tetrachlorocyclobutenone which may, for example, contain hexachlorobutadiene and hexachlorocyclobutene originating from its process of manufacture. is obtained with high yields

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A flame dried 250 ml Schlenk flask containing THF (20 ml) was cooled to −78°C. and n-butyl lithium (20 ml of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes hexachlorobutadiene (1.88 ml, 12.0 mmol) was added dropwise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C., and dimethylaminodimethylchlorosilane (3.6 ml, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis-(dimethylaminodimethylsilyl)-butadiyne. The THF was removed in vacuo, and the mixture was taken up in a minimum amount of pentane and filtered. The pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne. A flame dried 250 ml Schlenk flask containing THF (20 ml) After completion of addition the cold bath was removed The resulting 1,4-dilithio-1,3-butadiyne was used without further purification was then recooled to −78° C. The flask was removed from the cold bath the reaction mixture stirred at room temperature for 16 hours The THF was removed in vacuo filtered The pentane was removed in vacuo

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 1 liter flask, a mixture of 78 g of concentrated sulphuric acid and 78.5 g of phosphorus pentoxide was poured onto 100 g of 96% pure hexachlorocyclobutene [96 g (0.368 mole) of hexachlorocyclobutene; remainder hexachloro-1,3-butadiene], with stirring (molar ratio of hexachlorocyclobutene:sulphuric acid:phosphorus pentoxide=1:2:1). The mixture was heated at 100° C. for 3 hours. After cooling, the reaction mixture was poured onto ice, the organic phase was then separated immediately from the aqueous phase and the latter was extracted three times with petroleum ether. The petroleum ether solution and the organic phase were combined and dried with sodium sulphate, the petroleum ether was distilled under normal pressure and the residue was subjected to fractional distillation under 35 mbars. 43.6 g of tetrachlorocyclobutenone, 14.3 g of hexachlorocyclobutene and 3.6 g of hexachloro-1,3-butadiene were obtained. The selectivity of the reaction was 69.0% of theory with a conversion of 85% of theory. After cooling the reaction mixture was poured onto ice the organic phase was then separated immediately from the aqueous phase the latter was extracted three times with petroleum ether dried with sodium sulphate the petroleum ether was distilled under normal pressure the residue was subjected to fractional distillation under 35 mbars

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 500 cc flask, 143.4 g of 21.4% strength fuming sulphuric acid (oleum) were poured onto 209.8 of 95.3% pure hexachlorocyclobutene [199.9 g (0.766 mole) of hexachlorocyclobutene; remainder hexachloro-1,3-butadiene], with stirring (molar ratio of hexachlorocyclobutene:sulphuric acid:sulphur trioxide=1:1.5:0.5). The mixture was heated at 80° C. for 5 hours. After cooling, the reaction product was poured slowly into a mixture of ice and sodium chloride, with vigorous stirring, and the organic phase was then separated immediately from the aqueous phase. A mixture of 83.2 g of tetrachlorocyclobutenone, 58.9 g of hexachlorocyclobutene and 8.6 g of hexachloro-1,3-butadiene was obtained. The selectivity of the reaction was thus 75% of theory with a conversion of 71% of theory. After cooling the organic phase was then separated immediately from the aqueous phase A mixture of 83.2 g of tetrachlorocyclobutenone, 58.9 g of hexachlorocyclobutene