CN112174793B - Method and ligand for breaking C-S bond of alpha-thioaryl ethanone compound - Google Patents
Method and ligand for breaking C-S bond of alpha-thioaryl ethanone compound Download PDFInfo
- Publication number
- CN112174793B CN112174793B CN202011099051.6A CN202011099051A CN112174793B CN 112174793 B CN112174793 B CN 112174793B CN 202011099051 A CN202011099051 A CN 202011099051A CN 112174793 B CN112174793 B CN 112174793B
- Authority
- CN
- China
- Prior art keywords
- compound
- ligand
- bond
- formula
- thioarylethanone
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a ligand for breaking a C-S bond of an alpha-thioaryl ethanone compound, which comprises the steps of preparing the alpha-thioaryl ethanone compound, pinacol ester diboron and MX 2 The ligand, alkali and methanol are put into an organic solvent to react at 25-65 ℃, and the C-S bond in the alpha-thioaryl ethyl ketone compound is broken. The method adopts chloride of transition metal cobalt or nickel as a catalyst, adopts ADI as a ligand, adopts the combination of the pinacol ester diboron and methanol as a reducing agent, and breaks C-S bonds mildly under an alkaline condition.
Description
Technical Field
The invention relates to a method for breaking a C-S bond, in particular to a method for breaking a C-S bond of an alpha-thioaryl ethanone compound and a ligand.
Background
With the advance of human industrialization, the demand of fossil energy such as petroleum and coal is increasing, and the trace sulfur element contained in the fossil energy brings a series of serious air pollution problems, and acid rain is one of the expression forms. Therefore, the research on the C-S bond cleavage reaction has very important value for petrochemical industry, automobile industry and even the whole human society.
The traditional desulfurization method generally adopts a catalytic oxidation mode, but the desulfurization process has the problems of complex process, more byproducts, low desulfurization rate, large pollution and the like. The C-S bond reduction and breakage reaction catalyzed by the transition metal is one of feasible alternative methods, but because the sulfur element has stronger coordination capacity with the transition metal, the sulfur element has certain toxic action on a metal catalyst in the catalytic reaction. Therefore, it is important to develop efficient C-S bond cleavage reaction.
The alpha-thioaryl ethanone compound is an important intermediate in organic synthesis and is widely applied to a series of conversion reactions. Because of the poisoning property of sulfur element to the metal catalyst, the application of sulfur element in synthetic chemistry of alpha-thioacetophenone is limited.
At present, only one method is available for the C-S bond cleavage reaction of the alpha-thioacetophenone, and the route is as follows:
and breaking the C-S bond by using metallic zinc powder and saturated ammonium chloride as reducing agents. However, this method requires 60 times equivalent of activated zinc powder, large amount of ammonium chloride solution and tetrahydrofuran solvent, high cost and large amount of solid waste, and the severe reaction conditions have great limitation on the tolerance of the functional group of the substrate.
Disclosure of Invention
The invention aims to provide a method and a ligand for breaking a C-S bond of an alpha-thioaryl ethyl ketone compound, solves the problems of high cost and limited substrate of the existing C-S bond breaking method of the alpha-thioaryl ethyl ketone compound, can efficiently break the C-S bond of the alpha-thioaryl ethyl ketone compound, and has wide applicable substrate range.
In order to achieve the above object, the present invention provides a method for cleaving a C-S bond of an α -thioarylethanone compound, the method comprising: adding or not adding methanol into an alpha-thioaryl ethanone compound shown in a formula 1, diboron pinacol ester and a catalyst, adding alkali into an organic solvent, reacting at 25-65 ℃, and breaking a C-S bond in the alpha-thioaryl ethanone compound; the organic solvent is selected from one or more than two of tetrahydrofuran, dichloromethane, toluene and dioxane; the alkali is selected from NaOtBu and K 2 CO 3 、KOH、K 3 PO 4 Any one or more than two of NaOH, gaO and CsOH.
Wherein Y is selected from-S-),
Wherein Ar is selected from aromatic rings;
wherein R is 1 And R 2 Each independently selected from C 1 -C 5 Saturated alkanes of (a);
wherein R is 3 Selected from aromatic rings or C 1 -C 5 Saturated alkanes of (a);
the catalyst is selected from a metal compound MX 2 And a ligand; wherein M is selected from Co or Ni; x is selected from Cl; the ligand has the structure shown in formula 3:
wherein R is 4 、R 5 、R 6 、R 7 、R 8 And R 9 Each independently selected from C 1 -C 4 Of an alkane. C 1 -C 4 The alkane of (a) is selected from saturated alkanes including: any one of methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl and tert-butyl.
Preferably, the ligand has the structure shown in formula 4:
wherein R is 4 、R 5 、R 6 And R 7 Each independently selected from methyl, ethyl, n-propyl or isopropyl.
Preferably, the Ar is selected from a six-membered aromatic ring, a five-membered aromatic ring or a poly-aromatic ring.
Preferably, said Ar is selected from a substituted or unsubstituted benzene ring, thiophene, furan, pyrrole, biphenyl, naphthalene or anthracene; the substituted group is selected from an electron donating group or an electron withdrawing group, the electron donating group is selected from methyl, methoxy or methylthio, and the electron withdrawing group is selected from halogen, sulfonyl and trifluoromethyl.
Preferably, said R is 3 Selected from methyl, ethyl, and substituted or unsubstituted benzene, naphthalene or anthracene; the substituted group is selected from electron donating group or electron withdrawing group, and the electron donating group is selected from methyl or methoxyAnd the electron-withdrawing group is selected from halogen.
Preferably, the molar ratio of the diboron pinacol ester and the alpha-thioarylethanone compound is greater than or equal to 1:1, the usage amount of the diboron pinacol ester and the methanol is (1-1.1): (0-2); the alpha-thioaryl ethanone compound and MX 2 In a molar ratio of 1: (0.001-0.05), MX 2 And ligand in a molar ratio of 1:1; the base is reacted with MX 2 The molar ratio of (2) to (3): 1. the molar ratio of the diboron pinacol ester and the alpha-thioaryl ethanone compound cannot be lower than 1:1, otherwise the yield is reduced. The more catalyst, the faster the reaction but the higher the cost, the catalyst amount of the present invention can be reduced to 0.2mol% without affecting the reaction yield. The alkali is used as an activating agent of the catalyst, and the dosage of the alkali is controlled to be MX 2 2 to 3 times of the amount of the catalyst, in order to sufficiently activate the catalyst, but not too basic to cause side reactions of enol interconversion, resulting in failure to cleave the C — S bond, thereby decreasing the yield.
Another objective of the present invention is to provide a novel ligand, which has the structure shown in formula 4:
wherein R is 4 、R 5 、R 6 、R 7 、R 8 And R 9 Each independently selected from C 1 -C 4 Of (a) an alkane. C 1 -C 4 The alkane of (a) is selected from saturated alkanes including: any one of methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl and tert-butyl.
Preferably, the novel ligand has the structure shown in formula 5:
wherein R is 4 、R 5 、R 6 And R 7 Each independently selected from methyl, ethyl, n-propyl or isopropyl。
Preferably, the ligand has the structure shown in formula 5 or 6:
it is another object of the present invention to provide a method for preparing a novel ligand, which comprises:
wherein Z is selected from halogen; r 4 、R 5 、R 6 、R 7 、R 8 And R 9 Each independently selected from C 1 -C 4 Of an alkane. C 1 -C 4 The alkane of (a) is selected from saturated alkanes including: any one of methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl and tert-butyl.
2-halogenated benzene alkyl ketone compound with the structure shown as the formula S1, 2-amino benzene alkyl ketone compound with the structure shown as the formula S2 and Pd 2 (dba) 3 The xanthphos ligand and alkali are put into an organic solvent, and are heated, refluxed and stirred to react under the condition of inert gas, so as to obtain a compound with a structure shown as a formula S3; wherein the base is selected from K 2 CO 3 Or/and Na 2 CO 3 。
And (2) putting a compound with a structure shown as a formula S3, an aniline compound with a structure shown as a formula 7, an aniline compound with a structure shown as a formula 8 and p-toluenesulfonic acid or p-toluenesulfonic acid monohydrate into an organic solvent, and heating, refluxing and stirring for reaction to obtain the ligand with a structure shown as a formula 3.
Wherein the organic solvent is one or more than two of tetrahydrofuran, dichloromethane, toluene and dioxane.
Preferably, pd 2 (dba) 3 The molar weight of the compound is 1 percent of that of the 2-halogenated benzene alkyl ketone compound with the structure shown in the formula S1 or the 2-amino benzene alkyl ketone compound with the structure shown in the formula S2; of said xantphos ligandMolar weight of Pd 2 (dba) 3 2 times the molar amount of (a); the dosage of the alkali is 2equiv of a 2-halogenated benzene ketone compound with a structure shown as a formula S1 or a 2-aminobenzene ketone compound with a structure shown as a formula S2.
Preferably, the molar weight ratio of the 2-halogenated benzene ketone compound with the structure shown in the formula S1 to the 2-amino benzene ketone compound with the structure shown in the formula S2 is 1:1.
the method and the ligand for breaking the C-S bond of the alpha-thioaryl ethanone compound solve the problems of high cost and limited substrate of the existing method for breaking the C-S bond of the alpha-thioaryl ethanone compound, and have the following advantages:
according to the method, chloride of transition metal cobalt or nickel is used as a catalyst, ADI is used as a ligand, the pinacol ester diborate or the combination of the pinacol ester diborate and methanol is used as a reducing agent, and the C-S bond is mildly broken under an alkaline condition.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for breaking a C-S bond of an alpha-thioaryl ethanone compound comprises the following synthetic route:
the specific operation steps are as follows:
CoCl was added to a dry reaction tube at 25 deg.C 2 (0.05mmol)、ADI Me (0.05 mmol), alpha-Phenylthioacetophenone (1 a) (1 mmol), pinacol, diboronAlcohol esters (B) 2 pin 2 1 mmol), tetrahydrofuran (THF, 1 mL) and methanol (2 mmol), finally sodium tert-butoxide (NaOtBu, 0.15 mmol) was added, followed by stirring at 65 ℃ for 1h and column chromatography to give acetophenone (1 b) as a colorless oil in 97% yield.
The nuclear magnetic characterization data of acetophenone are:
1 H NMR(CDCl 3 ,400MHz):δ8.00-7.94(m,2H),7.60-7.54(m,1H),7.51-7.44(m,2H),2.62(s,3H)。
the nuclear magnetic characterization data of thiophenol is:
1 H NMR(CDCl 3 ,400MHz):δ6.91-7.40(m,5H),3.42(br,1H)。
wherein, ligand ADI Me The preparation method comprises the following steps:
pd is sequentially added into a dry reaction tube at room temperature under the condition of nitrogen 2 (dba) 3 (0.1 mmol), xantphos (0.2 mmol), 2-bromoacetophenone S1a (10 mmol), 2-aminoacetophenone S2b (10 mmol), dioxane (25 mL) and K 2 CO 3 (20 mmol). Then the mixture is heated and stirred under reflux for 12 hours, and the product S3a is obtained by column chromatography separation and is light yellow solid with the yield of 92 percent.
S3 (10 mmol), an aromatic amine (25 mmol) and p-toluenesulfonic acid monohydrate (pTsOH-H) were added sequentially to a dry reaction flask at room temperature 2 O) (1 mmol) and toluene, heating and refluxing for 48 hours, cooling to room temperature, and separating by column chromatography to obtain ligand ADI Me Yield 82% as a yellow solid, melting point 65-66 ℃.
The nuclear magnetic characterization data of the product S3a are:
1 H NMR(CDCl 3 ,400MHz):δ7.82(d,J＝8.0Hz,2H),7.53(d,J＝8.0Hz,2H),7.40-7.32(m,2H),6.98-6.91(m,2H),2.63(s,6H)。
ligand ADI Me The nuclear magnetic characterization data of (A) is:
1 H NMR(CDCl 3 ,400MHz):δ12.00(br,1H),7.70(d,J＝8.0Hz,2H),7.42-7.35(m,2H),7.35-7.27(m,2H),7.02-6.95(m,2H),6.91-6.84(m,4H),6.83-6.74(m,2H),2.04(s,6H),1.81(s,12H)。
examples 2 to 3
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as in example 1, except that: respectively using ADI Et 、ADI iPr Replacement of ADI Me The yields of acetophenone were 81% and 53%, respectively.
ADI Et And ADI iPr With ligands ADI Me The preparation process of (A) is substantially the same, ADI Et And ADI iPr Also all are yellow solids, the melting points are 68-69 ℃, 73-74 ℃ respectively, and the yields are 80% and 71% respectively.
ADI Et The nuclear magnetic characterization data of (A) is:
1 H NMR(CDCl 3 ,400MHz):δ12.12(br,1H),7.73(d,J＝8.0Hz,2H),7.44-7.35(m,2H),7.33-7.25(m,2H),7.00-6.93(m,2H),6.90-6.82(m,4H),6.79-6.73(m,2H),2.82(t,J＝7.2Hz,8H),2.05(s,6H),1.22(d,J＝7.2Hz,12H)。
ADI iPr the nuclear magnetic characterization data of (A) is:
1 H NMR(CDCl 3 ,400MHz):δ12.01(br,1H),7.69(d,J＝8.0Hz,2H),7.42-7.33(m,2H),7.30-7.24(m,2H),6.99-6.91(m,2H),6.88-6.82(m,4H),6.77-6.70(m,2H),2.91-8.82(m,4H),2.02(s,6H),1.81(s,12H)；1.18(d,J＝7.2Hz,24H)。
examples 4 to 5
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: examples 4 to 5 each using NiCl 2 、FeCl 2 Replacement ofCoCl 2 The yields of acetophenone were 80% and 59%, respectively.
Examples 6 to 11
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: examples 6 to 11 each use K 2 CO 3 、KOH、K 3 PO 4 NaOH, gaOH and CsOH replace NaOtBu, and the yields of acetophenone are 56%, 82%, 33%, 72%, 77% and 80% respectively.
Examples 12 to 14
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as in example 1, except that: examples 12-14 respectively use DCM, toluene, dioxane instead of THF, acetophenone yield was 45%, 33%, 77%.
Example 15
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the reaction temperature was 25 ℃ and the yield of acetophenone was 72%.
Example 16
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: without MeOH, the acetophenone yield was 55%.
Example 17
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioarylethanone compound was alpha- (phenylthio) -4-methoxyacetophenone (2 a) to give 4-methoxyacetophenone (2 b) as a white solid in 96% yield.
The nuclear magnetism characterization data of the 4-methoxyacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.94(d,J＝8.8Hz,2H),6.94(d,J＝8.8Hz,2H),3.87(s,3H),2.56(s,3H)。
example 18
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioarylethanone compound was alpha- (phenylthio) -3-methoxyacetophenone (3 a) to give 3-methoxyacetophenone (3 b) as a colorless oil with a yield of 97%.
The nuclear magnetism characterization data of the 3-methoxyacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.56-7.52(m,1H),7.51-7.47(m,1H),7.40-7.34(m,1H),7.14-7.09(m,1H),3.86(s,3H),2.60(s,3H)。
example 19
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioarylethanone compound was alpha- (phenylthio) -2-methoxyacetophenone (4 a) to give 2-methoxyacetophenone (4 b) as a colorless oil in 95% yield.
The nuclear magnetism characterization data of the 2-methoxyacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.74(dd,J＝7.6,1.8Hz,1H),7.50-7.43(m,1H),7.03-6.94(m,2H),3.91(s,3H),2.62(s,3H)。
example 20
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4-methylacetophenone (5 a) to give 2-methylacetophenone (5 b) as a colorless oil in 96% yield.
The nuclear magnetic characterization data of the 2-methylacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.86(d,J＝8.2Hz,2H),7.26(d,J＝8.2Hz,2H),2.58(s,3H),2.41(s,3H)。
example 21
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4-phenylacetophenone (6 a) to give 4-biphenylethanone (6 b) as a white solid in 99% yield.
The nuclear magnetic characterization data of the 4-diphenylethanone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ8.04(d,J＝8.4Hz,2H),7.69(d,J＝8.4Hz,2H),7.66-7.61(m,2H),7.51-7.45(m,2H),7.43-7.38(m,1H),2.65(s,3H)。
example 22
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4- (methylthio) acetophenone (7 a) to give 4- (methylthio) acetophenone (7 b) as a white solid in 96% yield.
The nuclear magnetic characterization data of the 4- (methylthio) acetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.87(d,J＝8.2Hz,2H),7.27(d,J＝8.2Hz,2H),2.57(s,3H),2.53(s,3H)。
example 23
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4- (methylsulfonyl) acetophenone (8 a) to give 4- (methylsulfonyl) acetophenone (8 b) as a colorless oil in 92% yield.
The nuclear magnetic characterization data of the 4- (methylsulfonyl) acetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ8.14(d,J＝8.6Hz,2H),8.06(d,J＝8.6Hz,2H),3.09(s,3H),2.68(s,3H)。
example 24
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4-fluoroacetophenone (9 a) to give 4-fluoroacetophenone (9 b) as a colourless oil in 92% yield.
The nuclear magnetic characterization data of the 4-fluoroacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ8.02-7.96(m,2H),7.17-7.10(m,2H),2.60(s,3H)。
example 25
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioaryl ethanone compound was α - (phenylthio) -4-chloroacetophenone (10 a), giving 4-chloroacetophenone (10 b) as a colorless oil in 96% yield.
The nuclear magnetic characterization data of the 4-chloroacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.90(d,J＝8.6Hz,2H),7.44(d,J＝8.6Hz,2H),2.60(s,3H)。
example 26
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4-bromoacetophenone (11 a) to give 4-bromoacetophenone (11 b) as a white solid in 87% yield.
The nuclear magnetism characterization data of the 4-bromoacetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.82(d,J＝8.6Hz,2H),7.61(d,J＝8.6Hz,2H),2.59(s,3H)。
example 27
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -4-trifluoromethylacetophenone (12 a) to give 4-trifluoromethylacetophenone (12 b) as a yellow oil in 88% yield.
The nuclear magnetic characterization data of the 4-trifluoromethyl acetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ8.07(d,J＝8.2Hz,2H),7.74(d,J＝8.2Hz,2H),2.65(s,3H)。
example 28
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -3, 4-dimethoxyacetophenone (13 a) to give 3, 4-dimethoxyacetophenone (13 b) as a pale yellow solid with a yield of 98%.
The nuclear magnetism characterization data of the 3, 4-dimethoxy acetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.59(dd,J＝8.4,2.0,Hz,1H),7.53(d,J＝2.0Hz,1H),6.90(d,J＝8.4Hz,1H),3.96(s,3H),3.95(s,3H),2.58(s,3H)。
example 29
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -2-acetonaphthone (14 a) giving 2-acetonaphthone (14 b) as a white solid with a yield of 96%.
The nuclear magnetism characterization data of the 2-acetophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ8.47(s,1H),8.03(dd,J＝8.6,1.8,Hz,1H),7.96(d,J＝8.0Hz,1H),7.91-7.85(m,2H),7.64-7.52(m,2H),2.73(s,3H)。
example 30
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as in example 1, except that: the α -thioarylethanone compound was α - (phenylthio) -1-acetonaphthone (15 a) to give 1-acetonaphthone (15 b) as a pale yellow oil in 89% yield.
The nuclear magnetism characterization data of the 1-acetonaphthone is as follows:
1 H NMR(CDCl 3 ,400MHz):δ8.75(d,J＝8.4Hz,1H),8.00(d,J＝8.4Hz,1H),7.94(d,J＝7.2Hz,1H),7.88(d,J＝8.2Hz,1H),7.64-7.57(m,1H),7.56-7.47(m,2H),2.75(s,3H)。
example 31
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (phenylthio) -2-thiopheneacetone (16 a), and 2-thiopheneacetone (16 b) is obtained and is bright yellow oily, and the yield is 87%.
The nuclear magnetic characterization data of the 2-thienylethanone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.71(dd,J＝3.8,1.0Hz,1H),7.64(dd,J＝5.0,1.0,Hz,1H),7.16-7.11(m,1H),2.58(s,3H)。
example 32
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (p-tolyl thio) -4-methoxy acetophenone (17 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in 97% yield according to the nuclear magnetic data in example 15.
Example 33
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (p-methoxyphenylthio) -4-methoxyacetophenone (18 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in a yield of 95% according to the same nuclear magnetic data as in example 15.
Example 34
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (o-methoxyphenyl thio) -4-methoxyacetophenone (19 a), B 2 pin 2 The amount was 1equiv, to give 4-methoxyacetophenone (2 b) as a colorless oil in 94% yield% NMR data as in example 15.
Example 35
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (m-methoxyphenylthio) -4-methoxyacetophenone (20 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in a yield of 95% according to the same nuclear magnetic data as in example 15.
Example 36
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (p-chlorophenylthio) -4-methoxyacetophenone (21 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in a yield of 96% according to the nuclear magnetic data of example 15.
Example 37
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as in example 1, except that: the alpha-thioaryl ethanone compound is alpha- (2-naphthylthio) -4-methoxyacetophenone (22 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in a yield of 98% according to the nuclear magnetic data of example 15.
Example 38
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha-benzenesulfonyl-4-methoxyacetophenone (23 a), B 2 pin 2 The amount used was 1equiv. To give 4-methoxyacetophenone (2 b) as a colorless oil in 94% yield according to the NMR data in example 15.
Example 39
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha-p-toluenesulfonyl-4-methoxyacetophenone (24 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in 92% yield according to the nuclear magnetic data of example 15.
Example 40
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha-phenylsulfonyl-4-methoxy acetophenone (25 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in 92% yield with the same nuclear magnetic data as in example 15.
Example 41
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha-methylthio-4-methoxyacetophenone (26)a)，B 2 pin 2 The amount used was 1equiv. To give 4-methoxyacetophenone (2 b) as a colorless oil in 93% yield according to the nuclear magnetic data as in example 15.
Example 42
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as in example 1, except that: the alpha-thioaryl ethanone compound is alpha-methylsulfonyl-4-methoxy acetophenone (27 a), B 2 pin 2 The amount used was 1equiv, and 4-methoxyacetophenone (2 b) was obtained as a colorless oil in 94% yield according to the NMR data of example 15.
Example 43
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha-methylsulfonyl-4-methoxy acetophenone (28 a), B 2 pin 2 The amount used was 1equiv. To give 4-methoxyacetophenone (2 b) as a colorless oil in 91% yield according to the nuclear magnetic data as in example 15.
Example 44
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: the alpha-thioaryl ethanone compound is alpha-phenylthio-4-methyl propiophenone (29 a), B 2 pin 2 The amount used was 1equiv, and 4-methylpropiophenone (29 b) was obtained as a colorless oil with a yield of 92%.
The nuclear magnetic characterization data of the 4-methyl propiophenone are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.87(d,J＝8.2Hz,2H),7.25(d,J＝8.2Hz,2H),2.98(q,J＝7.2Hz,2H),2.41(s,3H),1.22(t,J＝7.2Hz,3H)。
example 45
A method for cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 17, except that: the reaction amount is gram level, the dosage of the alpha- (phenylthio) -4-methoxyacetophenone (2 a) is (25.83g, 100mmol), B 2 pin 2 The dosage is 100mmol 2 0.1mmol of ADI Me 0.1mmol, naOtBu 0.3mmol, methanol 200mmol, and THF 10mL, 4-methoxyacetophenone (2 b) and thiophenol were obtained, with a yield of 4-methoxyacetophenone of 99% and a yield of thiophenol of 95%.
Comparative example 1
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: without ADI addition Me The yield of acetophenone was 8%.
Comparative example 2
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as described in example 1, except that: by using PDI-CoCl 2 Replacement of ADI Me And CoCl 2 The yield of acetophenone was 22%.
Comparative example 3
A method of cleaving a C-S bond of an α -thioarylethanone compound, substantially as in example 1, except that: without NaOtBu, the yield of acetophenone was 0.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A method for breaking a C-S bond of an α -thioarylethanone compound, the method comprising: adding or not adding methanol into an alpha-thioaryl ethanone compound shown in a formula 1, diboron pinacol ester and a catalyst, adding alkali into an organic solvent, reacting at 25-65 ℃, and breaking a C-S bond in the alpha-thioaryl ethanone compound; the organic solvent is selected from one or more than two of tetrahydrofuran, dichloromethane, toluene and dioxane; the alkali is selected from NaOtBu and K 2 CO 3 、KOH、K 3 PO 4 Any one or more than two of NaOH and CsOH;
wherein Y is selected from-S-),
Wherein Ar is selected from aromatic rings;
wherein R is 1 And R 2 Each independently selected from C 1 -C 5 Saturated alkanes of (1);
wherein R is 3 Selected from aromatic rings or C 1 -C 5 Saturated alkanes of (a);
the catalyst is a metal compound MX 2 And a ligand; wherein M is selected from Co or Ni; x is selected from Cl; the ligand has the structure shown in formula 3:
wherein R is 4 、R 5 、R 6 、R 7 、R 8 And R 9 Each independently selected from C 1 -C 4 Of (a) an alkane.
2. The method for breaking the C-S bond of an α -thioarylethanone compound according to claim 1, wherein the ligand has the structure shown in formula 4:
wherein R is 4 、R 5 、R 6 And R 7 Each independently selected from methyl, ethyl, n-propyl or isopropyl.
3. The method for breaking the C-S bond of an α -thioarylethanone compound according to claim 1, characterized in that the Ar is selected from a six-membered aromatic ring, a five-membered aromatic ring or a poly-aromatic ring.
4. The method for cleaving a-thioarylethanone compound C-S bond according to claim 3, wherein the Ar is selected from a substituted or unsubstituted benzene ring, thiophene, furan, pyrrole, biphenyl, naphthalene or anthracene; the substituted group is selected from an electron donating group or an electron withdrawing group, the electron donating group is selected from methyl, methoxy or methylthio, and the electron withdrawing group is selected from halogen, sulfonyl and trifluoromethyl.
5. The method for breaking the C-S bond of an α -thioarylethanone compound of claim 1, wherein R is 3 Selected from methyl, ethyl, and substituted or unsubstituted benzene, naphthalene or anthracene; the substituted group is selected from an electron donating group or an electron withdrawing group, the electron donating group is selected from methyl or methoxy, and the electron withdrawing group is selected from halogen.
6. The method for breaking the C-S bond of an α -thioarylethanone compound of claim 1, wherein the molar ratio of the pinacol ester of diboronic acid to the α -thioarylethanone compound is greater than or equal to 1:1, the pinacol ester of diboronic acid and methanolThe dosage of (1-1.1): (0-2); the alpha-thioaryl ethanone compound and MX 2 In a molar ratio of 1: (0.001-0.05), MX 2 And ligand in a molar ratio of 1:1; the base is reacted with MX 2 The molar ratio of (2) to (3): 1.
7. a ligand, wherein the ligand has the structure of formula 4:
wherein R is 4 、R 5 、R 6 、R 7 、R 8 And R 9 Each independently selected from C 1 -C 4 Of an alkane.
8. The ligand of claim 7, wherein the ligand has the structure of formula 5:
wherein R is 4 、R 5 、R 6 And R 7 Each independently selected from methyl, ethyl, n-propyl or isopropyl.
9. The ligand of claim 8, wherein the ligand has the structure of formula 5 or 6:
10. a method for preparing a ligand, the method comprising:
wherein Z is selected from halogen; r 4 、R 5 、R 6 、R 7 、R 8 And R 9 Each independently selected from C 1 -C 4 An alkane of (a);
2-halogenated benzene alkyl ketone compound with the structure shown as the formula S1, 2-amino benzene alkyl ketone compound with the structure shown as the formula S2 and Pd 2 (dba) 3 The xanthphos ligand and alkali are put into an organic solvent, and are heated, refluxed and stirred to react under the condition of inert gas, so as to obtain a compound with a structure shown as a formula S3; wherein the base is selected from K 2 CO 3 Or/and Na 2 CO 3 ；
Placing a compound with a structure shown in a formula S3, an aniline compound with a structure shown in a formula 7, an aniline compound with a structure shown in a formula 8 and p-toluenesulfonic acid or p-toluenesulfonic acid monohydrate in an organic solvent, and heating, refluxing and stirring for reaction to obtain a ligand with a structure shown in a formula 3;
wherein the organic solvent is one or more than two of tetrahydrofuran, dichloromethane, toluene and dioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011099051.6A CN112174793B (en) | 2020-10-14 | 2020-10-14 | Method and ligand for breaking C-S bond of alpha-thioaryl ethanone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011099051.6A CN112174793B (en) | 2020-10-14 | 2020-10-14 | Method and ligand for breaking C-S bond of alpha-thioaryl ethanone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112174793A CN112174793A (en) | 2021-01-05 |
| CN112174793B true CN112174793B (en) | 2023-03-28 |
Family
ID=73950117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011099051.6A Active CN112174793B (en) | 2020-10-14 | 2020-10-14 | Method and ligand for breaking C-S bond of alpha-thioaryl ethanone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112174793B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263538A (en) * | 1998-04-16 | 2000-08-16 | 三井化学株式会社 | Catalyst for olefin polymerization and method of polymerizing olefin |
| CN101812002A (en) * | 2010-04-16 | 2010-08-25 | 山东新华制药股份有限公司 | Synthesizing process of 4-methoxy-alpha-[(3-methoxyphenyl)sulfo]-acetophenone |
| CN102321199A (en) * | 2011-06-15 | 2012-01-18 | 北京理工大学 | Schiff base rare-earth catalyst, preparation method and application |
-
2020
- 2020-10-14 CN CN202011099051.6A patent/CN112174793B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263538A (en) * | 1998-04-16 | 2000-08-16 | 三井化学株式会社 | Catalyst for olefin polymerization and method of polymerizing olefin |
| CN101812002A (en) * | 2010-04-16 | 2010-08-25 | 山东新华制药股份有限公司 | Synthesizing process of 4-methoxy-alpha-[(3-methoxyphenyl)sulfo]-acetophenone |
| CN102321199A (en) * | 2011-06-15 | 2012-01-18 | 北京理工大学 | Schiff base rare-earth catalyst, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Acridine-based ligands from cobalt(II) mediated rearrangement of diphenylamine-based starting materials;Stuart J. Malthus等;《Supram olecular Chemistr y》;20161231;第28卷;第98-107页 * |
| Bis(imino)diphenylamido rare-earth metal dialkyl complexes: synthesis, structure, and catalytic activity in living ring-opening ε -caprolactone polymerization and copolymerization with γ-butyrolactone;Gaixia Du等;《Dalton Trans.》;20131231;第42卷;第1278-1286页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112174793A (en) | 2021-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | A mild and efficient copper-catalyzed coupling of aryl iodides and thiols using an oxime–phosphine oxide ligand | |
| Zeng et al. | Facile synthesis of benzofurans via copper-catalyzed aerobic oxidative cyclization of phenols and alkynes | |
| Zong et al. | Efficient C S Cross‐Coupling of Thiols with Aryl Iodides Catalyzed by Cu (OAc) 2· H2O and 2, 2′‐Biimidazole | |
| BR112017009205B1 (en) | method for preparing biphenylamines from azobenzenes by ruthenium catalysis | |
| CN112174793B (en) | Method and ligand for breaking C-S bond of alpha-thioaryl ethanone compound | |
| CN102503872A (en) | Method for preparing isothiocyanate | |
| CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
| KR101787211B1 (en) | a new palladium catalyst, method for its preparation and its use | |
| CN110423217A (en) | A kind of preparation method of conjugated enynes compound | |
| CN110054593A (en) | A method of synthesis 1,3,5- pyrrolotriazine derivatives | |
| CN111978219B (en) | Method for synthesizing diaryl thioether compound by manganese-oxygen molecular sieve doped with copper catalyst | |
| CN111253305A (en) | Alkenyl or alkylation reaction method of alkyl substituted azaarene | |
| CN109096162A (en) | A kind of nucleophilic addition method of the scandium catalysis mercaptan to o-quinone methides | |
| CN1332944C (en) | Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate | |
| CN114213298B (en) | Method for preparing thiosulfonate compound by directly oxidizing thiophenol | |
| CN115490650B (en) | Synthesis method of morpholine benzoate compound | |
| CN103145643B (en) | Aminothiazole compound dehydration and alkylation method | |
| CN109265409B (en) | Synthesis method of 2-substituted benzoxazole, 2-substituted benzothiazole and derivatives thereof | |
| CN107188837B (en) | A kind of synthetic method of α-acyl group high allyl thio-ether type compounds | |
| IE831130L (en) | Cyclic and acyclic polydentate chelating ligands¹as catalysts in nucleophilic substitutions | |
| US5214192A (en) | Process for preparing iodoarene compounds | |
| Ali et al. | Metal-free thiolation of sulfonyl hydrazone with thiophenol: synthesis of 4-thio-chroman and diarylmethyl thioethers | |
| CN108147936A (en) | A kind of cobalt manganese base composite oxidate catalytic alcohol is oxidized to the synthetic method of aldehydes or ketones | |
| KR101220154B1 (en) | Novel heterocyclic compound derivatives catalyzed by iron and its preparation method | |
| US20100274058A1 (en) | Process for Preparation of 2-[Vinyl (Hetero) Arylsulphonyl] Ethanol Derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |