CN1594245A - Application of ketene thioacetal derivatives as thioalcohol substituted reagent - Google Patents
Application of ketene thioacetal derivatives as thioalcohol substituted reagent Download PDFInfo
- Publication number
- CN1594245A CN1594245A CN 200410010963 CN200410010963A CN1594245A CN 1594245 A CN1594245 A CN 1594245A CN 200410010963 CN200410010963 CN 200410010963 CN 200410010963 A CN200410010963 A CN 200410010963A CN 1594245 A CN1594245 A CN 1594245A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- expression
- general formula
- reagent
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the use of ketene thioacetal derivatives in organic synthesis as thioalcohol substituted environment-friendly type organic reagent, wherein thioalcohol has strong volatility, irritation bad odor, toxicity and carcinogenic action, aiming at solving this problem, the invention employs ketene thioacetal derivatives as thioalcohol substituted reagent to realize the synthesizing of sulfur-containing compounds.
Description
Technical field:
The invention belongs to the application of organic reagent, particularly a kind of ketene thioacetal derivative is the application of environment-friendly type organic reagent in organic synthesis of mercaptan use as an alternative.
Background technology:
Mercaptan is organic reagent of using always and synthetic precursor or the intermediate that can be used as multiple organic synthesis; as: the carbonyl protective agent of carbonyl compound such as aldehyde, ketone and derivative thereof; nucleophilic reagent in Michael (Michael) addition reaction; particle dispersion agents during nano material is synthetic etc. are again the basic raw materials of numerous chemical such as synthetic drugs, agricultural chemicals, spices.
Yet, mercaptan (especially low-molecular-weight mercaptan) has very strong volatility, pungent odour and big toxicity, from the source, the sulphur source of preparation mercaptan also is the chemical with intense stimulus stink and even carcinogenesis as hydrogen sulfide, Sodium sulfhydrate, thiocarbamide and thioacetate etc.This class material has caused greatly harm to human body health and environment.With the target that is developed as of environmental friendliness chemical, some investigators once were devoted to nontoxic, the odorlessness transformation of thiol reagent.For example, adopt to increase alkyl chain length, on aromatic ring, introduce silylation and method [(1) TetradedronLett.2001,42,9207 such as mercaptan high moleculars; (2) Tetrahedron Lett.1998,39,9263; (3) Org.Lett.2003,5 (2), 101.].Adopted small molecules mercaptan or other deleterious sulfur-bearing regent but the preparation of these odorlessness thiol reagents itself is again more, failed from the original problem of source solution.Therefore, for finding corresponding odorlessness, substitute products nontoxic, inexpensive, that be convenient to transport and store, thiol reagent has important theory and practical significance.
Summary of the invention:
The objective of the invention is the problem that in application, exists at mercaptan, a kind of environment-friendly type organic reagent of alternative mercaptan is provided, adopt in present method that the preparation method is simple, productive rate is high, do not have bad smell, low-cost ketene thioacetal derivative substitutes mercaptan as organic reagent, realized the synthetic of serial sulfocompound.
Technical solution of the present invention is as follows:
Compound involved in the present invention is represented with following general formula:
Wherein, R
1Be hydrogen atom; Halogen atom such as chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Carboxyl; Formyl radical; Alkyl is C
1-C
4The acyl group of alkyl; Benzoyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The sweet-smelling formacyl of the phenyl that the alkoxyl group of alkyl replaces; Chloroformyl; Alkyl is C
1-C
4The alkoxyl group of alkyl; Alkyl is C
1-C
4The carbalkoxy of alkyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The carbalkoxy of the phenyl that the alkoxyl group of alkyl replaces; Aryl in the aryloxy is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Aryl in the aryloxy carbonyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Aryl in the arylthio is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Aryl in the arylsulfonyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; (aryl N=NAr) is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring the virtue azo-group
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Be connected with various C on basic carbonyl of amine (ammonia) and the amido
1-C
4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The amido carbonyl of the alkoxy substituted phenyl of alkyl; Be connected with chlorine, bromine, iodine, nitro, cyano group, sulfonic group, various C on the vinyl in the substituted ethylene base
1-C
4Alkyl and various C
1-C
4Aryl in the alkoxyl group of alkyl and carbalkoxy, the aryloxy carbonyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The vinyl of the alkoxy substituted phenyl of alkyl; Ethynyl; R
1As the substituting group that links to each other by carbon-carbon bond, carbon-oxygen bond, carbon-sulfur bond, carbonnitrogen bond on each segment of polymkeric substance such as each phenyl of polystyrene;
Wherein, R
2Be hydrogen atom; Halogen atom such as chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Carboxyl; Formyl radical; Alkyl is C
1-C
4The acyl group of alkyl; Benzoyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The sweet-smelling formacyl of the phenyl that the alkoxyl group of alkyl replaces; Chloroformyl; Alkyl is C
1-C
4The alkoxyl group of alkyl; Alkyl is C
1-C
4The carbalkoxy of alkyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The carbalkoxy of the phenyl that the alkoxyl group of alkyl replaces; Aryl in the aryloxy is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Aryl in the aryloxy carbonyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Aryl in the arylthio is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Aryl in the arylsulfonyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; (aryl N=NAr) is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring the virtue azo-group
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The phenyl that the alkoxyl group of alkyl replaces; Be connected with various C on basic carbonyl of amine (ammonia) and the amido
1-C
4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The amido carbonyl of the alkoxy substituted phenyl of alkyl; Be connected with chlorine, bromine, iodine, nitro, cyano group, sulfonic group, various C on the vinyl in the substituted ethylene base
1-C
4Alkyl and various C
1-C
4Aryl in the alkoxyl group of alkyl and carbalkoxy, the aryloxy carbonyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, hydroxyl, amino, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The vinyl of the alkoxy substituted phenyl of alkyl; Ethynyl; R
1As the substituting group that links to each other by carbon-carbon bond, carbon-oxygen bond, carbon-sulfur bond, carbonnitrogen bond on each segment of polymkeric substance such as each phenyl of polystyrene;
Z is nitrogen, oxygen, sulphur atom and sulfoxide group (SO), sulfuryl (SO
2), imino-(NH);
R
3Be various C
1-C
6Alkyl; The aryl of benzyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl;
R
4Be various C
1-C
6Alkyl; The aryl of benzyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl;
R
1And R
2Between dotted line represent various keys connect relation as: R
1, R
2Be (CH
2)
n, (n=1,2,3,4); N=1,2,3,4 o'clock, the hydrogen atom on each methylene radical of segmental can be replaced by following atom or group respectively, as: chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Hydroxyl; Amino; Sulfydryl; Carboxyl; Various C
1-C
6The carbalkoxy of alkyl; Various C
1-C
6Alkyl; Various C
1-C
6The alkoxyl group of alkyl; Various C
1-C
6The alkylthio of alkyl; The aryl of benzyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl;
R
1And R
2Between dotted line represent various keys connect relation as: R
1, R
2Be CH
2OC (CH
3)
2OCH
2, CH
2NHC (CH
3)
2NHCH
2, CH
2SC (CH
3)
2SCH
2
R
3And R
4Between dotted line represent various keys connect relation as: R
1, R
2Be (CH
2)
n, (n=1,2,3,4); N=1,2,3,4 o'clock, the hydrogen atom on each methylene radical of segmental can be replaced by following atom or group respectively, as: chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Hydroxyl; Amino; Sulfydryl; Carboxyl; Various C
1-C
6The carbalkoxy of alkyl; Various C
1-C
6Alkyl; Various C
1-C
6The alkoxyl group of alkyl; Various C
1-C
6The alkylthio of alkyl; The aryl of benzyl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl; Aryl is phenyl and is connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on phenyl ring
1-C
4Alkyl, C
1-C
4The carbalkoxy of alkyl, and C
1-C
4The alkoxy substituted phenyl of alkyl;
When Z is nitrogen-atoms, R
4Be various C
1-C
6Alkyl.
One, with the compound of general formula (1) expression Thioacetalization Reactions as thioalcohol substituted reagent and carbonyl compound, acetal/ketone, hydrazone, oxime, osazone, enamine
Solvent for use is in the reaction: halogenated hydrocarbon: as chloroform, methylene dichloride, ethylene dichloride, tetracol phenixin; C
1-C
6The ethers of alkyl: as methyl ethyl ether, ether, n-butyl ether, tetrahydrofuran (THF), dioxane; C
1-C
6The ester class of alkyl: as ethyl acetate, n-butyl acetate; C
1-C
6The alcohols of alkyl: as methyl alcohol, ethanol, propyl carbinol, ethylene glycol; Amides: as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Methyl-sulphoxide; Hydro carbons: as other organic solvents commonly used such as sherwood oil, hexanaphthene, octane, benzene, oil of mirbane and picture acetonitrile, Nitromethane 99Min., acetone.
Catalyst system therefor is in the reaction: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and mineral acid commonly used; Formic acid, acetate, C
1-C
6Organic monoprotic acid, C
2-C
6Organic dibasic acid, C
4-C
6Organic ternary acid, C
5-C
6Organic tetraprotic acid; Phenylformic acid, toluylic acid, C
1-C
6The aromatic acid of alkyl; Lanthanum trichloride, silicon chlorides, aluminum chloride, Cerium II Chloride, iron(ic) chloride; Transition metal oxide with Louis (Lewis) acid effect; Have the transition metal halide of Louis (Lewis) acid effect and have the transistion metal compound that Louis (Lewis) acid acts on; Polyacid such as phospho-molybdic acid, phospho-wolframic acid and have the tart poly-metal deoxide; Molecular sieve, diatomite, silica gel; Halogenation oxygen is Phosphorus as phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride; Halogenation oxygen is Phosphorus as phosphorus oxychloride; Sulfur oxychloride, nitrogen-chlorosuccinimide, nitrogen-bromo-succinimide; Hydrogenchloride, boron trifluoride ethyl ether complex, trimethylchlorosilane; Phosphoric acid salt or ester; Phenylsulfonic acid and salt thereof; Iodine.
As above mention a certain amount of a kind of compound or more than one mixtures of adding in single or the mixed solvent to certain, add aldehyde, ketone, acetal, ketal, hydrazone, oxime, osazone or the olefinic amine compound of its equimolar amount with the compound of general formula (1) expression with general formula (1) expression.Control reaction temperature is at-20-120 ℃, stir add down 1.0-100 doubly mole such as phosphorus tribromide or above-mentioned certain catalyzer.Finish, controlled temperature-20-120 ℃ continue down to stir 10 minutes-40 hours the mercaptal or the thioketones that contracts.Productive rate is looked differential responses between 45-100%, sees the embodiment in the embodiment for details.
Two, use the compound of general formula (1) expression as thioalcohol substituted reagent and Alpha-hydroxy aldehyde/ketone and alpha-halogen aldehyde/reactive ketone
Solvent for use is in the reaction: halogenated hydrocarbon: as chloroform, methylene dichloride, ethylene dichloride, tetracol phenixin; C
1-C
6The ethers of alkyl: as methyl ethyl ether, ether, n-butyl ether, tetrahydrofuran (THF), dioxane; C
1-C
6The ester class of alkyl: as ethyl acetate, n-butyl acetate; C
1-C
6The alcohols of alkyl: as methyl alcohol, ethanol, propyl carbinol, ethylene glycol; Amides: as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Methyl-sulphoxide; Hydro carbons: as other organic solvents commonly used such as sherwood oil, hexanaphthene, octane, benzene, oil of mirbane and picture acetonitrile, Nitromethane 99Min., acetone.
Catalyst system therefor in the reaction: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and mineral acid commonly used; Formic acid, acetate, C
1-C
6Organic monoprotic acid, C
2-C
6Organic dibasic acid, C
4-C
6Organic ternary acid, C
5-C
6Organic tetraprotic acid; Phenylformic acid, toluylic acid, C
1-C
6The aromatic acid of alkyl; Lanthanum trichloride, silicon chlorides, aluminum chloride, Cerium II Chloride, iron(ic) chloride, Potassium monofluoride and have the transition metal oxide of Louis (Lewis) acid effect; Have the transition metal halide of Louis (Lewis) acid effect and have the transistion metal compound that Louis (Lewis) acid acts on; Phospho-molybdic acid, phospho-wolframic acid and have the tart poly-metal deoxide; Molecular sieve, diatomite, silica gel; Halogenation oxygen is Phosphorus as phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride; Halogenation oxygen is Phosphorus as phosphorus oxychloride; Sulfur oxychloride, nitrogen-chlorosuccinimide, nitrogen-bromo-succinimide; Hydrogenchloride, boron trifluoride ethyl ether complex, trimethylchlorosilane; Natural phosphate or ester; Phenylsulfonic acid and salt thereof; Iodine.
As above mention a certain amount of a kind of compound or more than one mixtures of adding in single or the mixed solvent to certain with the compound of general formula (1) expression with general formula (1) expression.Add equimolar halogenated ketone compounds or hydroxyketone compounds.Controlled temperature is at-20-120 ℃, stir add down 0.1-100 doubly mole such as phosphorus tribromide or above-mentioned certain catalyzer.Finish, controlled temperature-20-120 ℃ continue down to stir 0.5-40 hour the thiophene vinyl compound.Productive rate is looked differential responses at 40-98%, sees the embodiment in the embodiment for details.
Three, with general formula (1) expression compound as thioalcohol substituted reagent and α, the Michael reaction of beta-unsaturated carbonyl compound
Solvent for use is in the reaction: halogenated hydrocarbon: as chloroform, methylene dichloride, ethylene dichloride, tetracol phenixin; C
1-C
6The ethers of alkyl: as methyl ethyl ether, ether, n-butyl ether, tetrahydrofuran (THF), dioxane; C
1-C
6The ester class of alkyl: as ethyl acetate, n-butyl acetate; C
1-C
6The alcohols of alkyl: as methyl alcohol, ethanol, propyl carbinol, ethylene glycol; Amides: as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Methyl-sulphoxide; Hydro carbons: as sherwood oil, hexanaphthene, octane, benzene, oil of mirbane and picture acetonitrile, Nitromethane 99Min., acetone etc. and other organic solvent commonly used.
Catalyst system therefor in the reaction: an acidic catalyst: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and mineral acid commonly used; Formic acid, acetate, C
1-C
6Organic monoprotic acid, C
2-C
6Organic dibasic acid, C
4-C
6Organic ternary acid, C
5-C
6Organic tetraprotic acid; Phenylformic acid, toluylic acid, C
1-C
6The aromatic acid of alkyl; Lanthanum trichloride, silicon chlorides, aluminum chloride, Cerium II Chloride, iron(ic) chloride, Potassium monofluoride and have the transition metal oxide of Louis (Lewis) acid effect; Have the transition metal halide of Louis (Lewis) acid effect and have the transistion metal compound that Louis (Lewis) acid acts on; Phospho-molybdic acid, phospho-wolframic acid and have the tart poly-metal deoxide; Molecular sieve, diatomite, silica gel; Halogenation oxygen is Phosphorus as phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride; Halogenation oxygen is Phosphorus as phosphorus oxychloride; Sulfur oxychloride, nitrogen-chlorosuccinimide, nitrogen-bromo-succinimide; Hydrogenchloride, boron trifluoride ethyl ether complex, trimethylchlorosilane; Natural phosphate or ester; Phenylsulfonic acid and salt thereof; Iodine.Basic catalyst: pure salt such as sodium methylate, sodium ethylate, sodium tert-butoxide, potassium tert.-butoxide, tert-pentanol sodium, tert-pentanol potassium; Yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, pyridine, triethylamine, sodium amide, lithium diisopropyl amido, sodium hydroxide, potassium hydroxide, sodium hydride and other alkali commonly used.
To certain as above mention in single or the mixed solvent add a certain amount of with general formula (1) expression a kind of compound or more than one with the mixture of the compound of general formula (1) expression, add equimolar certain α, beta-unsaturated carbonyl compound.Stir and add doubly above-mentioned certain catalyzer of mole of 0.1-100 down.Finish, controlled temperature-78-120 ℃ continue down to stir 10-100 hour product.Productive rate is looked differential responses at 50-100%, sees the embodiment in the embodiment for details.
Four, use the nucleophilic addition of the compound of general formula (1) expression as thioalcohol substituted reagent and carbon-carbon triple bond, carbon nitrogen three key, carbon-carbon double bond, the two keys of nitrogen nitrogen, carbon-to-nitrogen double bon, the two keys of carbon oxygen, the two keys of carbon sulphur, oxyethane and derivative, ethylenimine and derivative thereof, cyclopropane and derivative thereof
Solvent for use is in the reaction: halogenated hydrocarbon: as chloroform, methylene dichloride, ethylene dichloride, tetracol phenixin; C
1-C
6The ethers of alkyl: as methyl ethyl ether, ether, n-butyl ether, tetrahydrofuran (THF), dioxane; C
1-C
6The ester class of alkyl: as ethyl acetate, n-butyl acetate; C
1-C
6The alcohols of alkyl: as methyl alcohol, ethanol, propyl carbinol, ethylene glycol; Amides: as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Methyl-sulphoxide; Hydro carbons: as other organic solvents commonly used such as sherwood oil, hexanaphthene, octane, benzene, oil of mirbane and picture acetonitrile, Nitromethane 99Min., acetone.
Used catalyzer in the reaction: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and mineral acid commonly used; Formic acid, acetate, C
1-C
6Organic monoprotic acid, C
2-C
6Organic dibasic acid, C
4-C
6Organic ternary acid, C
5-C
6Organic tetraprotic acid; Phenylformic acid, toluylic acid, C
1-C
6The aromatic acid of alkyl; Lanthanum trichloride, silicon chlorides, aluminum chloride, Cerium II Chloride, iron(ic) chloride, Potassium monofluoride and have the transition metal oxide of Louis (Lewis) acid effect; Have the transition metal halide of Louis (Lewis) acid effect and have the transistion metal compound that Louis (Lewis) acid acts on; Phospho-molybdic acid, phospho-wolframic acid and have the tart poly-metal deoxide; Molecular sieve, diatomite, silica gel; Halogenation oxygen is Phosphorus as phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride; Halogenation oxygen is Phosphorus as phosphorus oxychloride; Sulfur oxychloride, nitrogen-chlorosuccinimide, nitrogen-bromo-succinimide; Hydrogenchloride, boron trifluoride ethyl ether complex, trimethylchlorosilane; Natural phosphate or ester; Phenylsulfonic acid and salt thereof; Iodine; Copper, silver, ruthenium, palladium, rhodium and compound thereof.
As above mention a certain amount of a kind of compound or more than one mixtures with the compound of general formula (1) expression with general formula (1) expression of adding in single or the mixed solvent to certain, stirring adds doubly above-mentioned certain catalyzer of mole of 0.1-100 down.Stir after 30-100 minute and to add a kind of in the equimolar compound that contains carbon-carbon triple bond, carbon nitrogen three key, carbon-carbon double bond, the two keys of nitrogen nitrogen, carbon-to-nitrogen double bon, the two keys of carbon oxygen, the two keys of carbon sulphur.Finish, the continuation down that refluxes is stirred and was got product in 2-10 hour.Productive rate is looked differential responses at 50-95%.
Five, with the reaction of the compound of general formula (1) expression as thioalcohol substituted reagent and halohydrocarbon, acyl chlorides, acid anhydrides, ester
Solvent for use is in the reaction: C
1-C
6The ethers of alkyl: as methyl ethyl ether, ether, n-butyl ether, tetrahydrofuran (THF), dioxane; Hydro carbons: as sherwood oil, hexanaphthene, octane, benzene, oil of mirbane and picture acetonitrile, Nitromethane 99Min., acetone etc. and other organic solvent commonly used.
With the halohydrocarbons reaction catalyst system therefor: pure salt such as sodium methylate, sodium ethylate, sodium tert-butoxide, potassium tert.-butoxide, tert-pentanol sodium, tert-pentanol potassium; Butyllithium, lithium diisopropyl amido, sodium hydroxide, potassium hydroxide, sodium hydride and other alkali commonly used.
React catalyst system therefor with acyl chlorides, acid anhydrides, ester: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and mineral acid commonly used; Lanthanum trichloride, silicon chlorides, aluminum chloride, Cerium II Chloride, iron(ic) chloride, Potassium monofluoride and have the transition metal oxide of Louis (Lewis) acid effect; Have the transition metal halide of Louis (Lewis) acid effect and have the transistion metal compound that Louis (Lewis) acid acts on; Phospho-molybdic acid, phospho-wolframic acid and have the tart poly-metal deoxide; Molecular sieve, diatomite, silica gel; Halogenation oxygen is Phosphorus as phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride; Halogenation oxygen is Phosphorus as phosphorus oxychloride; Sulfur oxychloride, nitrogen-chlorosuccinimide, nitrogen-bromo-succinimide; Hydrogenchloride, boron trifluoride ethyl ether complex, trimethylchlorosilane; Natural phosphate or ester; Phenylsulfonic acid and salt thereof; Iodine.
As above mention in single or the mixed solvent to certain and to add a certain amount of a kind of compound or more than one mixtures, add a kind of in equimolar halohydrocarbon, acyl chlorides, acid anhydrides, the ester cpds with the compound of general formula (1) expression with general formula (1) expression.Stir and add doubly above-mentioned certain catalyzer of mole of 0.1-100 down.Finish, controlled temperature-78-120 ℃ continue down to stir 5 hours-100 hours product.Productive rate is looked differential responses at 50-100%, sees the embodiment in the embodiment for details.
Positively effect of the present invention is: the environment-friendly type organic reagent that a kind of alternative poisonous thiol reagent is provided, abandoned the use of poisonous thiol reagent in traditional organic chemistry chemical industry, the ketene thioacetal derivative as thioalcohol substituted reagent compare with traditional thiol reagent be easy to preparation, cheap, be convenient to transportation and storage, easy to use, free from extraneous odour, be easy to industrialization.
Embodiment:
Embodiment 1:
In flask at the bottom of 50 milliliters of gardens, add 0.648 gram (2 mmole) 2-(1,3 inferior third disulfide group) methylene radical-methyl-butyrate-3-ketone and 2 mmole phenyl aldehydes, then, add 10 milliliters of ethanol, stir, add 0.712 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the phenyl aldehyde disappearance, and decompression steams ethanol, column chromatography, get white solid 2-phenyl-[1,3] dithiane, productive rate: 84.1%.React formula as follows:
Embodiment 2:
In flask at the bottom of 50 milliliters of gardens, add 0.404 gram (2 mmole) 3-(1, the inferior ethylene dithiol base of 2-) methylene radical-2,4-diacetylmethane and 0.302 gram (2 mmole) 4-nitrobenzaldehyde then, add 10 ml methanol, stir, add 0.712 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the 4-nitrobenzaldehyde and disappears, decompression steams methyl alcohol, and column chromatography gets white solid and gets 2-(4-nitrophenyl)-[1,3] two thiophene pentanes, 0.380 gram, productive rate 83.5%.React formula as follows:
Embodiment 3
In flask at the bottom of 50 milliliters of gardens, add 0.432 gram (2 mmole) 3-(1, inferior third disulfide group of 3-) methylene radical-2, the 4-diacetylmethane, 0.212 gram (2 mmole) phenyl aldehyde and 0.240 gram (2 mmole) methyl phenyl ketone add 10 ml methanol then, stir, add 0.5 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitoring reaction 3 hours, decompression steams methyl alcohol, column chromatography, get white solid 2-phenyl-[1,3] dithiane 0.383 gram, productive rate 91.3% has reclaimed methyl phenyl ketone 0.218 gram (95%) simultaneously.React formula as follows:
Embodiment 4:
In flask at the bottom of 50 milliliters of gardens, add 0.441 gram (2 mmole) 1-(1, inferior third disulfide group of 3-) methylene radical-acetone and 0.272 gram (2 mmole) 4-methoxybenzaldehyde, add 10 milliliters of ethanol then, stir, add 0.712 milliliter of concentrated hydrochloric acid again, reflux, TLC monitors to the 4-methoxybenzaldehyde and disappears, decompression steams ethanol, and column chromatography gets white solid and gets 2-(4-p-methoxy-phenyl)-[1,3] dithiane 0.394 gram, productive rate 86.3%.React formula as follows:
Embodiment 5:
In flask at the bottom of 50 milliliters of gardens, add 0.432 gram (2 mmole) 3-(1, inferior third disulfide group of 3-) methylene radical-2,4-diacetylmethane and 0.240 gram (2 mmole) methyl phenyl ketone add 10 ml methanol then, stir, add 0.5 milliliter of Witco 1298 Soft Acid again, reflux, TLC monitors to the methyl phenyl ketone disappearance, and decompression steams methyl alcohol, column chromatography, get white solid and get 2-methyl-2-phenyl-[1,3] dithiane 0.383 gram, productive rate 90.3%.React formula as follows:
Embodiment 6:
In flask at the bottom of 50 milliliters of gardens, add 0.690 gram (3 mmole) 2-(1,4 Aden's disulfide group) methylene radical-ethyl butyrate-3-ketone and 0.240 gram (2 mmole) 4-tolyl aldehyde, then, add 10 milliliters of ethanol, stir, add 0.712 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the disappearance of 4-tolyl aldehyde, and decompression steams ethanol, column chromatography, get white solid 2-(4-aminomethyl phenyl)-[1,3] two sulphur heptane, productive rate 51.6%.React formula as follows:
Embodiment 7:
In flask at the bottom of 50 milliliters of gardens, add 0.434 gram (2 mmole) 2-(1,3 inferior third disulfide group) methylene radical-butyramide-3-ketone and 0.281 gram (2 mmole) 4-chlorobenzaldehyde, then, add 10 ml methanol, stir, add 0.5 milliliter of 98% vitriol oil again, reflux, TLC monitors to the disappearance of 4-nitrobenzaldehyde, and decompression steams methyl alcohol, column chromatography, get white solid 2-(4-chloro-phenyl-)-[1,3] dithiane 0.382 gram, productive rate 80.2%.React formula as follows:
Embodiment 8:
In flask at the bottom of 50 milliliters of gardens, add 2 mmole 2-(1,3 inferior third disulfide group) methylene radical-butyric acid-3-ketone and 2 mmole pimelinketone phenylhydrazones, add 10 ml methanol then, stir, add 0.3 milliliter of boron trifluoride-diethyl ether solution again, reflux, TLC monitors to the pimelinketone phenylhydrazone and disappears, decompression steams methyl alcohol, column chromatography gets white solid product, productive rate 87.2%.React formula as follows:
Embodiment 9:
In flask at the bottom of 50 milliliters of gardens, add 2 mmole 1-(1, inferior third disulfide group of 3-) methylene radical-acetone and 2 mmole benzaldoximes, add 10 milliliters of ethanol then, stir, add 0.3 milliliter of sulfur oxychloride again, reflux, TLC monitors to benzaldoxime and disappears, decompression steams ethanol, column chromatography gets white solid product, productive rate 91.6%.React formula as follows:
Embodiment 10:
In 50 milliliters of round-bottomed flasks, add 0.628 gram (2 mmole) 1,1-two benzylthio-s-butylene-3-ketone and 0.302 gram (2 mmole) piperonylaldehyde.Add 0.2 milliliter of phosphorus oxychloride of 10 milliliters of ethanol and tetrahydrofuran (THF) mixed solvent (volume ratio=2: 3) then, stir, TLC monitors to the piperonylaldehyde disappearance, and column chromatography gets white solid, productive rate 92.1%.React formula as follows:
Embodiment 11:
In 50 milliliters of round-bottomed flasks, add 0.380 gram (2 mmole) 1,1-diethyl sulfenyl-2-butylene-3-ketone and 0.192 gram (2 mmole) furtural add 10 milliliters of ethanol and 0.400 gram (3 mmole) aluminum trichloride (anhydrous) then, stir, TLC monitors to furtural and disappears, column chromatography gets colourless liquid, productive rate 72.3%.React formula as follows:
Embodiment 12:
In 50 milliliters of round-bottomed flasks, add 0.432 gram (2 mmole) 3-[1,3] two thiophenes-2-subunit-2, the alpha-brominated ethyl ketone of running quickly of 4-diacetylmethane and 2 mmoles then, adds 10 ml methanol, stir, add 0.8 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to halogenated ketone and disappears, decompression steams methyl alcohol, column chromatography gets white solid, productive rate 75.6%.React formula as follows:
Embodiment 13:
In 50 milliliters of round-bottomed flasks, add 0.404 gram (2 mmole)) 3-(1, the inferior ethylene dithiol base of 2-) methylene radical-2,4-diacetylmethane and the alpha-brominated methyl phenyl ketone of 2 mmoles then, add 10 ml methanol, stir, add 0.8 milliliter of Acetyl Chloride 98Min., reflux, TLC monitors to the halogenated ketone disappearance, and decompression steams methyl alcohol, column chromatography, get white solid 2-phenyl-5,6-dihydro-1,4-thiophene alkene, productive rate 73.5%.React formula as follows:
Embodiment 14:
In 50 milliliters of round-bottomed flasks, add 2 mmole 2-(1,3 inferior third disulfide group) methylene radical-methyl-butyrate-3-ketone and the alpha-brominated methyl phenyl ketone of 2 mmoles, then, add 10 ml methanol, stir, add 0.8 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the halogenated ketone disappearance, and decompression steams methyl alcohol, column chromatography, get white solid 2-phenyl-6,7-dihydro-5H-dithiene, productive rate 70.6%.React formula as follows:
Embodiment 15:
In 50 milliliters of round-bottomed flasks, add 2 mmole 2-(1,3 inferior third disulfide group) methylene radical-methyl-butyrate-3-ketone and 2 mmole st-yraxes, then, add 10 ml methanol, stir, add 0.8 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the st-yrax disappearance, and decompression steams methyl alcohol, column chromatography, get white solid product, productive rate 71.8%.React formula as follows:
Embodiment 16:
In 50 milliliters of round-bottomed flasks, add 0.436 gram (2 mmole) 2-(1, the inferior ethylene dithiol base of 2-) methylene radical-butyric acid-3-ketone and 2 mmole st-yraxes.Then, add 10 ml methanol, stir, add 0.8 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the st-yrax disappearance, and decompression steams methyl alcohol, and column chromatography gets white solid, productive rate 73.5%.React formula as follows:
Embodiment 17:
In 50 milliliters of round-bottomed flasks, add 2 mmole 2-(two benzylthio-s) methylene radical-butyric acid-3-ketone and 2 mmole cyclonenes.Then, add 10 ml methanol, stir, add 0.8 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the cyclonene disappearance, and decompression steams methyl alcohol, and column chromatography gets colorless liquid product, productive rate 80.1%.React formula as follows:
Embodiment 18:
In 50 milliliters of round-bottomed flasks, add 0.628 gram, 2 mmoles) 1,1-two benzylthio-s-butylene-3-ketone and the following cinnamophenone of 2 mmoles.Add 10 ml methanol then, stir, add 0.8 milliliter of Acetyl Chloride 98Min. again, reflux, TLC monitors to the cinnamophenone disappearance, and decompression steams methyl alcohol, and column chromatography gets white solid, productive rate 83.1%.React formula as follows:
Embodiment 19:
In 50 milliliters of round-bottomed flasks, add 2 mmoles 1,1-diethyl sulfenyl-butylene-3-ketone and the following cinnamophenone of 2 mmoles.Add then then, add 10 ml methanol and small amount of hydrochloric acid, stir, TLC monitors to the cinnamophenone disappearance, and column chromatography gets white solid, productive rate 80.6%.React formula as follows:
Embodiment 20:
In 50 milliliters of round-bottomed flasks, add 2 mmole N-phenyl-2-(diethyl sulfenyl)-methylene radical-butyramide-3-ketone and 2 mmole cinnamophenones.Add 1 mmole sodium hydroxide again, add 10 milliliters of ethanol then, stir, TLC monitors to the cinnamophenone disappearance, and column chromatography gets white solid, productive rate 88.4%.React formula as follows:
Embodiment 21:
In 50 milliliters of round-bottomed flasks, add 0.628 gram (2 mmole) 4,4-two benzylthio-s-3-alkene-2-butanone and 2 mmole phenylacetylenes, add 10 milliliters, the alcohol sodium alcohol solution that under agitation adds 2 milliliter of 1 mmole/milliliter, TLC are monitored to phenylacetylene disappearance, column chromatography, get white solid, productive rate 62.2%.React formula as follows:
Embodiment 22:
In 50 milliliters of round-bottomed flasks, add 2 mmole N-o-tolyl-2-(two benzylthio-s)-methylene radical-butyramide-3-ketone and the alpha-brominated methyl phenyl ketones of 2 mmoles, add 1 mmole sodium hydroxide again, add 10 milliliters of ethanol then, stir, the TLC monitoring disappears column chromatography to alpha-brominated methyl phenyl ketone, get colorless liquid product, productive rate 96.4%.React formula as follows:
Embodiment 23:
In 50 milliliters of round-bottomed flasks, add 0.628 gram (2 mmole) 1,1-two benzylthio-s-butylene-3-ketone and 10 milliliters of methylene dichloride drip 2 Acetyl Chloride 98Min.s, stirred 3 hours, TLC monitoring 4,4-two benzylthio-s-3-alkene-2-butanone disappears, and then adds 3 mmole Acetyl Chloride 98Min.s, stirred 15 minutes, column chromatography gets colorless liquid product, productive rate 74.6%.React formula as follows:
Embodiment 24:
In 50 milliliters of round-bottomed flasks, add 2 mmoles 1,1-two benzylthio-s-butylene-3-ketone, 10 milliliters of methylene dichloride, 5 mmole sodium ethylates and 4 mmole butyl bromides stirred 3 hours, TLC monitoring 4, and 4-two benzylthio-s-3-alkene-2-butanone disappears, column chromatography gets product liquid, productive rate 84.5%.React formula as follows:
Embodiment 25:
In 50 milliliters of round-bottomed flasks, add 2 mmole N-phenyl-2-(diethyl sulfenyl)-methylene radical-butyramide-3-ketone and 2 mmole oxyethane, add 1 mmole sodium hydroxide again, add 10 milliliters of ethanol then, stir, TLC monitors to 2-diethyl sulfenyl-2 '-methyl-alpha.-acetylacetanilide disappearance, column chromatography, get colorless liquid product, productive rate 76.3%.React formula as follows:
Claims (6)
1. the ketene thioacetal derivative application of environment-friendly type organic reagent in organic synthesis of mercaptan use as an alternative with general formula (1) expression.
2. described with the application of environment-friendly type organic reagent in organic synthesis used of mercaptan as an alternative of general formula (1) expression ketene thioacetal derivative according to claim 1, it is characterized in that described organic synthesis is with the compound of general formula (1) the expression Thioacetalization Reactions as thioalcohol substituted reagent and carbonyl compound, acetal/ketone, hydrazone, oxime, osazone, enamine.
3. according to the described ketene thioacetal derivative application of environment-friendly type organic reagent in organic synthesis of mercaptan use as an alternative of claim 1, it is characterized in that described organic synthesis is to use the compound of general formula (1) expression as thioalcohol substituted reagent and Alpha-hydroxy aldehyde/ketone and alpha-halogen aldehyde/reactive ketone with general formula (1) expression.
4. according to the described ketene thioacetal derivative application of environment-friendly type organic reagent in organic synthesis of mercaptan use as an alternative of claim 1 with general formula (1) expression, it is characterized in that described organic synthesis is to use the compound of general formula (1) expression as thioalcohol substituted reagent and α, the Michael reaction of beta-unsaturated carbonyl compound.
5. according to the described ketene thioacetal derivative application of environment-friendly type organic reagent in organic synthesis of mercaptan use as an alternative of claim 1, it is characterized in that described organic synthesis is to use the nucleophilic addition of the compound of general formula (1) expression as thioalcohol substituted reagent and carbon-carbon triple bond, carbon nitrogen three key, carbon-carbon double bond, the two keys of nitrogen nitrogen, carbon-to-nitrogen double bon, the two keys of carbon oxygen, carbon sulphur pair keys, oxyethane and derivative, ethylenimine and derivative thereof, cyclopropane and derivative thereof with general formula (1) expression.
6. according to the application of environment-friendly type organic reagent in organic synthesis used of mercaptan as an alternative of the described ketene thioacetal derivative with general formula (1) expression of claim 1, it is characterized in that described organic synthesis is with the reaction as thioalcohol substituted reagent and halohydrocarbon, acyl chlorides, acid anhydrides, ester of the compound of general formula (1) expression.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410010963 CN1594245A (en) | 2004-06-24 | 2004-06-24 | Application of ketene thioacetal derivatives as thioalcohol substituted reagent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410010963 CN1594245A (en) | 2004-06-24 | 2004-06-24 | Application of ketene thioacetal derivatives as thioalcohol substituted reagent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1594245A true CN1594245A (en) | 2005-03-16 |
Family
ID=34662655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410010963 Pending CN1594245A (en) | 2004-06-24 | 2004-06-24 | Application of ketene thioacetal derivatives as thioalcohol substituted reagent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1594245A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978167A (en) * | 2020-07-22 | 2020-11-24 | 广东石油化工学院 | One-step synthesis method of polysubstituted cyclohex-2-enone |
-
2004
- 2004-06-24 CN CN 200410010963 patent/CN1594245A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978167A (en) * | 2020-07-22 | 2020-11-24 | 广东石油化工学院 | One-step synthesis method of polysubstituted cyclohex-2-enone |
| CN111978167B (en) * | 2020-07-22 | 2021-03-23 | 广东石油化工学院 | One-step synthesis method of polysubstituted cyclohex-2-enone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nguyen | Recent advances in organic reactions involving elemental sulfur | |
| Lu et al. | Transition metal-free direct trifluoromethylthiolation of indoles using trifluoromethanesulfonyl chloride in the presence of triphenylphosphine | |
| KR20100124233A (en) | Method for preparing sulfone or sulfoxide compound | |
| DE502006007977D1 (en) | RUBBER MIXTURE AND TIRES | |
| CN100336812C (en) | Method for synthesizing organic sulfur compound under condition without solvent | |
| Rostami et al. | Ligand-free Cu-catalyzed odorless synthesis of unsymmetrical sulfides through cross-coupling reaction of aryl/benzyl/alkyl halides with an aryl boronic acid/S 8 system as a thiolating agent in PEG | |
| CN108569942A (en) | A kind of preparation method of α-trifluoromethylthio substituted acetophenone class compound | |
| CN108440375B (en) | Catalytic oxidation synthesis method of 3-mercaptoindole compound with disulfide as sulfur source | |
| CN1594245A (en) | Application of ketene thioacetal derivatives as thioalcohol substituted reagent | |
| CN1117743C (en) | Process for producing 5-hydroxybenzo [b] thiophene-3-carboxylic acid derivatives | |
| Liu et al. | Novel synthesis of benzothiazole by self-redox tandem reaction of disulfide with aldehyde | |
| Lin et al. | Copper-catalyzed cycloaddition of heterobicyclic alkenes with diaryl disulfides to synthesize dihydrobenzo [b] thiophene derivatives | |
| CN1082955C (en) | Process for preparing 3 -(1 -hydroxyphenyl -1 -alkoximinomethyl) dioxazines | |
| CN1266147C (en) | Synthesis for organic sulfur compound in hydrous medium | |
| CN108586312B (en) | Green sulfuration method of indole compound by using triphosgene as reducing agent | |
| Safaei-Ghomi et al. | The reaction of carbon disulphide with α-haloketones and primary amines in the presence of potassium iodide as catalyst | |
| Abbasi et al. | One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea | |
| CN106518634A (en) | Preparing method of photocatalytic alpha-diketone compound | |
| CN1422857A (en) | Dithio keteal derivatives and synthesis method thereof, and their use for thio ketal ization and mercaptal ization reaction | |
| CN1651408A (en) | Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate | |
| CN109422732B (en) | Preparation method of 1,2,4, 5-tetrasubstituted imidazole | |
| JP4041881B2 (en) | Novel N-thio-substituted heterocyclic compound and method for producing the same | |
| CN116768852A (en) | Preparation method of benzo [ b ] selenophene derivative | |
| Toyota et al. | Silica gel-assisted synthesis of benzo [b] thiophenes from o-(alkylsulfanyl)(ethynyl) benzenes | |
| JP2004196730A (en) | Novel n-sulfenylpyrrole compound and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |