CN1313461C - Process for synthesizing dithio ketene condensate in aqueous medium - Google Patents

Process for synthesizing dithio ketene condensate in aqueous medium Download PDF

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CN1313461C
CN1313461C CNB2005100169379A CN200510016937A CN1313461C CN 1313461 C CN1313461 C CN 1313461C CN B2005100169379 A CNB2005100169379 A CN B2005100169379A CN 200510016937 A CN200510016937 A CN 200510016937A CN 1313461 C CN1313461 C CN 1313461C
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CN1721419A (en
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董德文
欧阳艳
刘群
于海丰
梁永久
张前
王芒
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Northeast Normal University
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Abstract

The present invention relates to a method for synthesizing dithio-ketene condensed compounds in aqueous media, which belongs to an organic synthesis method, particularly to an environment protecting synthesis method for synthesizing dithio-ketene condensed compounds in aqueous media. Aiming at the problem of using organic media in the method for synthesizing dithio-ketene condensed compounds, the present invention adopts water as reaction media, and organic compounds with active methylene groups react with carbon bisulfide and halogenated hydrocarbon by using inorganic alkali for deprotonation under the catalytic action of quaternary ammonium salt to synthesize the dithio-ketene condensed compounds in one step with high yield. The present invention makes no use of organic solvents, and has the characteristics of environmental protection, few synthesis steps, easy obtainment of raw materials, low price, moderate reaction condition, simple operation and easy technicalization and industrialization.

Description

The synthetic method of dithio keteal compounds in a kind of water medium
Technical field:
The invention belongs to methodology of organic synthesis, particularly a kind of environment-friendly type synthetic method of in water medium, synthesizing the dithio keteal compounds.
Background technology:
Dithio keteal compounds three ten years in the past, have especially obtained to use widely in carbocyclic ring, heterogeneous ring compound synthetic in organic synthesis as the multi-functional organic synthesis intermediate of a class.From at present existing document, the existing synthetic method of this compounds mainly is to adopt the compound with active methylene radical, at N, dinethylformamide, methyl-sulphoxide, in the organic mediums such as butanone, deprotonation under the effect of Different Alkali, with the dithiocarbonic anhydride effect, further obtain with halohydrocarbons reaction.[(a)Dieter，R.K.Tetrahedron，1986，42，3029；(b)Junjappa，H.；Ila，H.；Asokan，C.V.Tetrahedron，1990，46，5423]
Along with in the worldwide to the pay attention to day by day of environmental problem, especially the birth in succession of new ideas such as the nineties Sustainable development in last century, Green Chemistry, traditional organic chemical reagent and related process are being faced with the serious challenge of chemical reagent and chemical process greenization.As everyone knows, many employing organic solvents are reaction medium in most chemical reaction processes, all more or less human body health and environment are caused certain harm inevitably.For this reason, existing both at home and abroad increasing scientist has begun specific aim research, solvent-free reaction, and environmental friendliness WATER AS FLOW MEDIUM, ionic liquid etc. become research focus in recent years in succession.Yet, the environment-friendly type synthetic method of not seeing relevant dithio keteal compounds so far.
Summary of the invention:
The objective of the invention is at the problem of using organic medium in the dithio keteal compounds synthetic method, provide a kind of in water medium the environment-friendly type synthetic method of dithio keteal compounds.
Technical solution of the present invention is as follows:
The reaction equation of synthetic dithio keteal compounds (II) involved in the present invention is represented with following general formula:
Wherein, reaction raw materials (I) is for having the organic compound of active methylene radical:
(1) non-annularity beta-dicarbonyl compound
R 1And R 2Between dotted line be blank, R 1For: acyl group: CH 3CO-, CH 2CH 3CO-, PhCO-, 2-FPhCO-, 3-FPhCO-, 4-FPhCO-, 2-ClPhCO-, 3-ClPhCO-, 4-ClPhCO-, 2-BrPhCO-, 3-BrPhCO-, 4-BrPhCO-, 2-CH 3PhCO-, 3-CH 3PhCO-, 4-CH 3PhCO-, 2-CH 2CH 3PhCO-, 3-CH 2CH 3PhCO-, 4-CH 2CH 3PhCO-, 2-CH 3OPhCO-, 3-CH 3OPhCO-, 4-CH 3OPhCO-, 2-CH 2CH 3OPhCO-, 3-CH 2CH 3OPhCO-, 4-CH 2CH 3OPhCO-; Ester group :-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOPh ,-COOCH 2Ph; Thioester substrate :-COSCH 3,-COSCH 2CH 3,-COSCH 2CH 2CH 3,-COSCH 2CH 2CH 2CH 3,-COSPh ,-COSCH 2Ph; Amide group: CONH 2,-CONHCH 3,-CONHCH 2CH 3,-CONHCH 2CH 2CH 3,-CONHCH 2CH 2CH 2CH 3,-CONHCH 2Ph ,-CON (CH 3) 2, PhNHCO-, 4-FPhNHCO-, 4-ClPhNHCO-, 4-BrPhNHCO-, 4-NO 2PhNHCO-, 4-CH 3PhNHCO-, 4-CH 3OPhNHCO-;
R 2For: acyl group: CH 3CO-, CH 2CH 3CO-, PhCO-, 2-FPhCO-, 3-FPhCO-, 4-FPhCO-, 2-ClPhCO-, 3-ClPhCO-, 4-ClPhCO-, 2-BrPhCO-, 3-BrPhCO-, 4-BrPhCO-, 2-CH 3PhCO-, 3-CH 3PhCO-, 4-CH 3PhCO-, 2-CH 2CH 3PhCO-, 3-CH 2CH 3PhCO-, 4-CH 2CH 3PhCO-, 2-CH 3OPhCO-, 3-CH 3OPhCO-, 4-CH 3OPhCO-, 2-CH 2CH 3OPhCO-, 3-CH 2CH 3OPhCO-, 4-CH 2CH 3OPhCO-; Ester group :-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOPh ,-COOCH 2Ph; Thioester substrate :-COSCH 3,-COSCH 2CH 3,-COSCH 2CH 2CH 3,-COSCH 2CH 2CH 2CH 3,-COSPh ,-COSCH 2Ph; Amide group: CONH 2,-CONHCH 3,-CONHCH 2CH 3,-CONHCH 2CH 2CH 3,-CONHCH 2CH 2CH 2CH 3,-CONHCH 2Ph ,-CON (CH 3) 2, PhNHCO-, 4-FPhNHCO-, 4-ClPhNHCO-, 4-BrPhNHCO-, 4-NO 2PhNHCO-, 4-CH 3PhNHCO-, 4-CH 3OPhNHCO-;
(2) ring-type beta-dicarbonyl compound
(a) R 1--R 2For-CO (CH 2) nCO-, wherein n is that 2,3,4 ring-type beta-dicarbonyl compound and the hydrogen atom on each methylene radical on the segment thereof are one or more by methyl substituted derivative;
(b) R 1--R 2For-COOCH 2OOC-,-CONHCCH 2NHOC-,-COSCH 2The ring-type beta-dicarbonyl compound of SOC-and one or two hydrogen atom of the methylene radical on the segment thereof are by methyl substituted derivative;
(3) contain the open chain compound (R that strong electron-withdrawing group is rolled into a ball 1And R 2Between dotted line be blank)
R 1For nitro, benzene sulfuryl, to toluene sulfuryl, cyano group;
R 2Be hydrogen; Cyano group; Alkyl :-CF 3,-Ph, 2-FPh-, 3-FPh-, 4-FPh-, 2-ClPh-, 3-ClPh-, 4-ClPh-, 2-BrPh-, 3-BrPh-, 4-BrPh-, 2-CH 3Ph-, 3-CH 3Ph-, 4-CH 3Ph-, 2-CH 2CH 3Ph-, 3-CH 2CH 3Ph-, 4-CH 2CH 3Ph-, 2-CH 3OPh-, 3-CH 3OPh-, 4-CH 3OPh-, 2-CH 2CH 3OPh-, 3-CH 2CH 3OPh-, 4-CH 2CH 3OPh-; Acyl group: CH 3CO-, CH 2CH 3CO-, PhCO-, 2-FPhCO-, 3-FPhCO-, 4-FPhCO-, 2-ClPhCO-, 3-ClPhCO-, 4-ClPhCO-, 2-BrPhCO-, 3-BrPhCO-, 4-BrPhCO-, 2-CH 3PhCO-, 3-CH 3PhCO-, 4-CH 3PhCO-, 2-CH 2CH 3PhCO-, 3-CH 2CH 3PhCO-, 4-CH 2CH 3PhCO-, 2-CH 3OPhCO-, 3-CH 3OPhCO-, 4-CH 3OPhCO-, 2-CH 2CH 3OPhCO-, 3-CH 2CH 3OPhCO-, 4-CH 2CH 3OPhCO-; Ester group :-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOPh ,-COOCH 2Ph; Thioester substrate :-COSCH 3,-COSCH 2CH 3,-COSCH 2CH 2CH 3,-COSCH 2CH 2CH 2CH 3,-COSPh ,-COSCH 2Ph; Amide group: CONH 2,-CONHCH 3,-CONHCH 2CH 3,-CONHCH 2CH 2CH 3,-CONHCH 2CH 2CH 2CH 3,-CONHCH 2Ph ,-CON (CH 3) 2, PhNHCO-, 4-FPhNHCO-, 4-ClPhNHCO-, 4-BrPhNHCO-, 4-NO 2PhNHCO-, 4-CH 3PhNHCO-, 4-CH 3OPhNHCO-;
Solvent for use is in the reaction: water.
Used alkali is in the reaction: yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, sodium phosphate, potassiumphosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, Potassium monofluoride, sodium hydroxide, potassium hydroxide.
Catalyst system therefor is in the reaction: Tetrabutyl amonium bromide, etamon chloride, tetrabutylammonium iodide, tetraethylammonium bromide, 4-butyl ammonium hydrogen sulfate, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, 2-hydroxypropyl sulfuric acid tetrabutylammonium, methyl trioctylphosphine ammonium chloride.
Used halohydrocarbon is in the reaction: (1) single halohydrocarbon XR 3: ICH 3X (CH 2) nCH 3, wherein X is a chlorine or bromine, n is 1 to 16 natural number; RCH 2X, wherein X is a chlorine or bromine, R is-Ph 2-FPh-, 3-FPh-, 4-FPh-, 2-ClPh-, 3-ClPh-, 4-ClPh-, 2-BrPh-, 3-BrPh-, 4-BrPh-, 2-CH 3Ph-, 3-CH 3Ph-, 4-CH 3Ph-, 2-CH 2CH 3Ph-, 3-CH 2CH 3Ph-, 4-CH 2CH 3Ph-, 2-CH 3OPh-, 3-CH 3OPh-, 4-CH 3OPh-, 2-CH 2CH 3OPh-, 3-CH 2CH 3OPh-, 4-CH 2CH 3OPh-, 2-NO 2Ph, 3-NO 2Ph, 4-NO 2Ph, 4-(CH 3) 3CPh-, 4-CNPh, PhCO-, CH 3CO-, CH 3OOC-, CH 2CH 3OOC-; (2) dihalo hydrocarbon XR 3R 3X:1,2-ethylene dichloride, 1,3-propylene dichloride, 1,4-dichlorobutane, glycol dibromide, 1,3-dibromopropane, 1,4-dibromobutane.
With a kind of reaction raw materials (I) of representing in a certain amount of above-mentioned reaction expression, 2.0 above-mentioned a kind of alkali of～5.0 moles of multiples, 0.01 above-mentioned a kind of catalyzer of～1 mole of multiple, add in the water of 20～500 moles of multiples, stirred 10 minutes～5 hours down at-10 ℃～40 ℃, add 1.2～2.5 moles of multiple dithiocarbonic anhydride, continue to stir 30 minutes～10 hours, single halohydrocarbon or 1.0～1.5 moles of multiple dihalo hydrocarbon of adding 2.0～2.5 moles of multiples again continue stirring and got dithio keteal compounds (II) in 1～10 hour.Productive rate is looked differential responses between 70-100%, sees the embodiment in the embodiment for details.
Positively effect of the present invention is: the environment-friendly type synthetic method that provides a kind of and abandoned the use of organic solvent, synthesizes the dithio keteal compounds in water-bearing media.This method synthesis step few (step), raw material is easy to get, and is cheap, and the reaction conditions gentleness is simple to operate, is easy to technology, industrialization.
Embodiment:
Embodiment 1
In the 50mL round-bottomed flask, add methyl ethyl diketone (10mmol, 1.0mL), salt of wormwood (30mmol, 4.14g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 15ml water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, adds 1, and (11mmol 1.11mL), continues to stir 6 hours the 3-dibromopropane, reacts completely to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.01g, productive rate 93%.
Embodiment 2
In the 50mL round-bottomed flask, add methyl ethyl diketone (10mmol, 1.0mL), salt of wormwood (30mmol, 4.14g), tetraethyl-chlorine bromine ammonium (TEBA) (0.8mmol, 0.17g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.63mL), continues to stir 6 hours, reacts completely to add monobromethane to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.24g, productive rate 97%.
Embodiment 3
In the 50mL round-bottomed flask, add methyl ethyl diketone (10mmol, 1.0mL), salt of wormwood (30mmol, 4.14g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 15ml water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, adds n-butyl bromide (22mmol), continues to stir 6 hours, reacts completely to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.78g, productive rate 97%.
Embodiment 4
In the 50mL round-bottomed flask, add methyl aceto acetate (10mmol, 1.26mL), salt of wormwood (30mmol, 4.14g), cetyl trimethylammonium bromide (CTAB) (0.8mmol, 0.29g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, adds 1, and (11mmol 1.30mL), continues to stir 6 hours the 4-dibromobutane, reacts completely to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.31g, productive rate 89%.
Embodiment 5
In the 50mL round-bottomed flask, add diethyl malonate (10mmol, 1.52mL), yellow soda ash (30mmol, 3.18g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 15ml water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 2.53mL), continues to stir 6 hours, reacts completely to add benzyl chloride to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 4.08g, productive rate 98%.
Figure C20051001693700101
Embodiment 6
In the 50mL round-bottomed flask, add diethyl malonate (10mmol, 1.52mL), yellow soda ash (30mmol, 3.18g), tetraethyl-chlorine bromine ammonium (TEBA) (0.8mmol, 0.17g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.37mL), continues to stir 6 hours, reacts completely to add methyl iodide to add dithiocarbonic anhydride.Use CH 2Cl 2Extraction, washing, drying steams CH 2Cl 2, get light yellow liquid product 2.56g, productive rate 97%.
Embodiment 7
In the 50mL round-bottomed flask, add N-(4-chloro-phenyl-)-3-carbonyl butyramide (10mmol, 2.12g), salt of wormwood (30mmol, 4.14g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.86mL), continues to stir 4 hours, reacts completely to add allyl bromide 98 to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 3.54g, productive rate 96%.
Embodiment 8
In the 50mL round-bottomed flask, add N-(2-p-methoxy-phenyl)-3-carbonyl butyramide (10mmol, 2.07g), yellow soda ash (30mmol, 3.18g), tetraethyl-chlorine bromine ammonium (TEBA) (0.8mmol, 0.17g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (11mmol 0.95mL), continues to stir 4 hours, reacts completely to add glycol dibromide to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 3.00g, productive rate 97%.
Figure C20051001693700111
Embodiment 9
In the 50mL round-bottomed flask, add N-(2-p-methoxy-phenyl)-3-carbonyl butyramide (10mmol, 2.07g), yellow soda ash (30mmol, 3.18g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 2.53mL), continues to stir 4 hours, reacts completely to add benzyl chloride to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 3.56g, productive rate 99%.
Figure C20051001693700112
Embodiment 10
In the 50mL round-bottomed flask, add N-phenyl-3-carbonyl butyramide (10mmol, 1.91g), salt of wormwood (30mmol, 4.14g), cetyl trimethylammonium bromide (CTAB) (0.8mmol, 0.29g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, adds 1, and (11mmol 1.11mL), continues to stir 6 hours the 3-dibromopropane, reacts completely to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.86g, productive rate 98%.
Figure C20051001693700113
Embodiment 11
In the 50mL round-bottomed flask, add N-phenyl-3-carbonyl butyramide (10mmol, 1.91g), salt of wormwood (30mmol, 4.14g), tetraethylammonium bromide (TEBA) (0.8mmol, 0.17g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.37mL), continues to stir 4 hours, reacts completely to add methyl iodide to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.70g, productive rate 96%.
Figure C20051001693700121
Embodiment 12
In the 50mL round-bottomed flask, add N-(2, the 4-3,5-dimethylphenyl)-3-carbonyl butyramide (10mmol, 2.05g), salt of wormwood (30mmol, 4.14g), tetraethyl-chlorine bromine ammonium (TEBA) (0.8mmol, 0.17g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.63mL), continues to stir 4 hours, reacts completely to add monobromethane to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 3.21g, productive rate 95%.
Figure C20051001693700122
Embodiment 13
In the 50mL round-bottomed flask, add N-(2, the 4-3,5-dimethylphenyl)-3-carbonyl butyramide (10mmol, 2.05g), salt of wormwood (30mmol, 4.14g), cetyl trimethylammonium bromide (CTAB) (0.8mmol, 0.29g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (11mmol 0.95ml), continues to stir 5 hours, reacts completely to add glycol dibromide to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.98g, productive rate 97%.
Figure C20051001693700123
Embodiment 14
In the 50mL round-bottomed flask, add N-(4-chloro-phenyl-)-3-carbonyl butyramide (10mmol, 2.12g), salt of wormwood (30mmol, 4.14g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 20mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 2.53mL), continues to stir 4 hours, reacts completely to add benzyl chloride to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 4.57g, productive rate 98%.
Embodiment 15
In the 50mL round-bottomed flask, add malonyl-aniline (10mmol, 2.54g), salt of wormwood (30mmol, 1.20g), cetyl trimethylammonium bromide (CTAB) (0.4mmol, 0.15g), 10mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, adds 1, and (11mmol 1.11mL), continues to stir 6 hours the 3-dibromopropane, reacts completely to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 3.66g, productive rate 99%.
Figure C20051001693700132
Embodiment 16
In the 50mL round-bottomed flask, add Nitromethane 99Min. (10mmol, 0.54mL), potassium hydrogen phosphate (30mmol, 6.36g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.63mL), continues to stir 3 hours, reacts completely to add monobromethane to add dithiocarbonic anhydride.Use CH 2Cl 2Extraction, washing, drying steams CH 2Cl 2, get light yellow liquid product 1.74g, productive rate 90%
Embodiment 17
In the 50mL round-bottomed flask, add propane dinitrile (10mmol, 0.661g), triethylamine (30mmol, 4.18mL), cetyl trimethylammonium bromide (CTAB) (0.8mmol, 0.29g), 15mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, and (22mmol 1.37mL), continues to stir 4 hours, reacts completely to add methyl iodide to add dithiocarbonic anhydride.Use CH 2Cl 2Extraction, washing, drying steams CH 2Cl 2, get light yellow liquid product 1.80g, productive rate 88%.
Embodiment 18
In the 50mL round-bottomed flask, add 1-phenyl-1, the 3-dimethyl diketone (10mmol, 1.62g), salt of wormwood (30mmol, 4.14g), Tetrabutyl amonium bromide (TBAB) (0.8mmol, 0.26g), 25mL water.Stirring at room 1 hour, (15mmol 0.90mL), stirs after 2 hours, adds 1, and (11mmol 1.11mL), continues to stir 6 hours the 3-dibromopropane, reacts completely to add dithiocarbonic anhydride.Suction filtration, washing gets light yellow solid product 2.63g, productive rate 95%.

Claims (1)

1, the synthetic method of the dithio keteal compounds in a kind of water medium, it is characterized in that adopting water is reaction medium, by the organic compound with active methylene radical (I) under quaternary ammonium salt catalysis, through the mineral alkali deprotonation, react with dithiocarbonic anhydride, halohydrocarbon, one-step synthesis dithio keteal compounds (II), formula as follows:
Wherein, reaction raw materials (I) is for having the organic compound of active methylene radical:
(1) non-annularity beta-dicarbonyl compound
R 1And R 2Between dotted line be blank, R 1For: acyl group: CH 3CO-, CH 2CH 3CO-, PhCO-, 2-FPhCO-, 3-FPhCO-, 4-FPhCO-, 2-ClPhCO-, 3-ClPhCO-, 4-ClPhCO-, 2-BrPhCO-, 3-BrPhCO-, 4-BrPhCO-, 2-CH 3PhCO-, 3-CH 3PhCO-, 4-CH 3PhCO-, 2-CH 2CH 3PhCO-, 3-CH 2CH 3PhCO-, 4-CH 2CH 3PhCO-, 2-CH 3OPhCO-, 3-CH 3OPhCO-, 4-CH 3OPhCO-, 2-CH 2CH 3OPhCO-, 3-CH 2CH 3OPhCO-, 4-CH 2CH 3OPhCO-; Ester group :-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOPh ,-COOCH 2Ph; Thioester substrate :-COSCH 3,-COSCH 2CH 3,-COSCH 2CH 2CH 3,-COSCH 2CH 2CH 2CH 3,-COSPh ,-COSCH 2Ph; Amide group: CONH 2,-CONHCH 3,-CONHCH 2CH 3,-CONHCH 2CH 2CH 3,-CONHCH 2CH 2CH 2CH 3,-CONHCH 2Ph ,-CON (CH 3) 2, PhNHCO-, 4-FPhNHCO-, 4-ClPhNHCO-, 4-BrPhNHCO-, 4-NO 2PhNHCO-, 4-CH 3PhNHCO-, 4-CH 3OPhNHCO-;
R 2For: acyl group: CH 3CO-, CH 2CH 3CO-, PhCO-, 2-FPhCO-, 3-FPhCO-, 4-FPhCO-, 2-ClPhCO-, 3-ClPhCO-, 4-ClPhCO-, 2-BrPhCO-, 3-BrPhCO-, 4-BrPhCO-, 2-CH 3PhCO-, 3-CH 3PhCO-, 4-CH 3PhCO-, 2-CH 2CH 3PhCO-, 3-CH 2CH 3PhCO-, 4-CH 2CH 3PhCO-, 2-CH 3OPhCO-, 3-CH 3OPhCO-, 4-CH 3OPhCO-, 2-CH 2CH 3OPhCO-, 3-CH 2CH 3OPhCO-, 4-CH 2CH 3OPhCO-; Ester group :-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOPh ,-COOCH 2Ph; Thioester substrate :-COSCH 3,-COSCH 2CH 3,-COSCH 2CH 2CH 3,-COSCH 2CH 2CH 2CH 3,-COSPh ,-COSCH 2Ph; Amide group: CONH 2,-CONHCH 3,-CONHCH 2CH 3,-CONHCH 2CH 2CH 3,-CONHCH 2CH 2CH 2CH 3,-CONHCH 2Ph ,-CON (CH 3) 2, PhNHCO-, 4-FPhNHCO-, 4-ClPhNHCO-, 4-BrPhNHCO-, 4-NO 2PhNHCO-, 4-CH 3PhNHCO-, 4-CH 3OPhNHCO-;
(2) ring-type beta-dicarbonyl compound
(a) R 1--R 2For-CO (CH 2) nCO-, wherein n is that 2,3,4 ring-type beta-dicarbonyl compound and the hydrogen atom on each methylene radical on the segment thereof are one or more by methyl substituted derivative;
(b) R 1--R 2For-COOCH 2OOC-,-CONHCCH 2NHOC-,-COSCH 2The ring-type beta-dicarbonyl compound of SOC-and one or two hydrogen atom of the methylene radical on the segment thereof are by methyl substituted derivative;
(3) contain the open chain compound that strong electron-withdrawing group is rolled into a ball
R 1And R 2Between dotted line be blank;
R 1For nitro, benzene sulfuryl, to toluene sulfuryl, cyano group;
R 2Be hydrogen; Cyano group; Alkyl :-CF 3,-Ph, 2-FPh-, 3-FPh-, 4-FPh-, 2-ClPh-, 3-ClPh-, 4-ClPh-, 2-BrPh-, 3-BrPh-, 4-BrPh-, 2-CH 3Ph-, 3-CH 3Ph-, 4-CH 3Ph-, 2-CH 2CH 3Ph-, 3-CH 2CH 3Ph-, 4-CH 2CH 3Ph-, 2-CH 3OPh-, 3-CH 3OPh-, 4-CH 3OPh-, 2-CH 2CH 3OPh-, 3-CH 2CH 3OPh-, 4-CH 2CH 3OPh-; Acyl group: CH 3CO-, CH 2CH 3CO-, PhCO-, 2-FPhCO-, 3-FPhCO-, 4-FPhCO-, 2-ClPhCO-, 3-ClPhCO-, 4-ClPhCO-, 2-BrPhCO-, 3-BrPhCO-, 4-BrPhCO-, 2-CH 3PhCO-, 3-CH 3PhCO-, 4-CH 3PhCO-, 2-CH 2CH 3PhCO-, 3-CH 2CH 3PhCO-, 4-CH 2CH 3PhCO-, 2-CH 3OPhCO-, 3-CH 3OPhCO-, 4-CH 3OPhCO-, 2-CH 2CH 3OPhCO-, 3-CH 2CH 3OPhCO-, 4-CH 2CH 3OPhCO-; Ester group :-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOPh ,-COOCH 2Ph; Thioester substrate :-COSCH 3,-COSCH 2CH 3,-COSCH 2CH 2CH 3,-COSCH 2CH 2CH 2CH 3,-COSPh ,-COSCH 2Ph; Amide group: CONH 2,-CONHCH 3,-CONHCH 2CH 3,-CONHCH 2CH 2CH 3,-CONHCH 2CH 2CH 2CH 3,-CONHCH 2Ph ,-CON (CH 3) 2, PhNHCO-, 4-FPhNHCO-, 4-ClPhNHCO-, 4-BrPhNHCO-, 4-NO 2PhNHCO-, 4-CH 3PhNHCO-, 4-CH 3OPhNHCO-;
Solvent for use is in the reaction: water;
Used alkali is in the reaction: yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, sodium phosphate, potassiumphosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, Potassium monofluoride, sodium hydroxide, potassium hydroxide;
Catalyst system therefor is in the reaction: Tetrabutyl amonium bromide, etamon chloride, tetrabutylammonium iodide, tetraethylammonium bromide, 4-butyl ammonium hydrogen sulfate, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, 2-hydroxypropyl sulfuric acid tetrabutylammonium, methyl trioctylphosphine ammonium chloride;
Used halohydrocarbon is in the reaction: (1) single halohydrocarbon XR 3: ICH 3X (CH 2) nCH 3, wherein X is a chlorine or bromine, n is 1 to 16 natural number; RCH 2X, wherein X is a chlorine or bromine, R is-Ph 2-FPh-, 3-FPh-, 4-FPh-, 2-ClPh-, 3-ClPh-, 4-ClPh-, 2-BrPh-, 3-BrPh-, 4-BrPh-, 2-CH 3Ph-, 3-CH 3Ph-, 4-CH 3Ph-, 2-CH 2CH 3Ph-, 3-CH 2CH 3Ph-, 4-CH 2CH 3Ph-, 2-CH 3OPh-, 3-CH 3OPh-, 4-CH 3OPh-, 2-CH 2CH 3OPh-, 3-CH 2CH 3OPh-, 4-CH 2CH 3OPh-, 2-NO 2Ph, 3-NO 2Ph, 4-NO 2Ph, 4-(CH 3) 3CPh-, 4-CNPh, PhCO-, CH 3CO-, CH 3OOC-, CH 2CH 3OOC-; (2) dihalo hydrocarbon XR 3R 3X:1,2-ethylene dichloride, 1,3-propylene dichloride, 1,4-dichlorobutane, glycol dibromide, 1,3-dibromopropane, 1,4-dibromobutane;
Press following formula, with a certain amount of organic compound of as above mentioning with active methylene radical (I), 2.0～5.0 moles of multiple alkali, 0.01 the catalyzer of～1 mole of multiple, add in the water of 20～500 moles of multiples, stirred 10 minutes～5 hours down at-10 ℃～40 ℃, add 1.2～2.5 moles of multiple dithiocarbonic anhydride, continue to stir 30 minutes～10 hours, single halohydrocarbon or 1.0～1.5 moles of multiple dihalo hydrocarbon of adding 2.0～2.5 moles of multiples again, continue to stir 1～10 hour, get corresponding dithio keteal compounds (II), productive rate is 70-100%.
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