CN115557983A - Organic silanol compound containing S-S bond and preparation method thereof - Google Patents
Organic silanol compound containing S-S bond and preparation method thereof Download PDFInfo
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- CN115557983A CN115557983A CN202211049449.8A CN202211049449A CN115557983A CN 115557983 A CN115557983 A CN 115557983A CN 202211049449 A CN202211049449 A CN 202211049449A CN 115557983 A CN115557983 A CN 115557983A
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- -1 silanol compound Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZWVGKXJRDIGWOB-UHFFFAOYSA-N FC=1C=C(C=CC=1)[SiH2]C1=CC(=CC=C1)F Chemical compound FC=1C=C(C=CC=1)[SiH2]C1=CC(=CC=C1)F ZWVGKXJRDIGWOB-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- QGMWYDSWNVASNC-UHFFFAOYSA-N (3-methoxyphenyl)-methylsilane Chemical compound [SiH2](C1=CC(OC)=CC=C1)C QGMWYDSWNVASNC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- QMGLMTJGVIVJKI-UHFFFAOYSA-N FC1=CC=C(C=C1)[SiH2]C1=CC=C(C=C1)F Chemical compound FC1=CC=C(C=C1)[SiH2]C1=CC=C(C=C1)F QMGLMTJGVIVJKI-UHFFFAOYSA-N 0.000 claims description 3
- FPBAHVJHTGZVOD-UHFFFAOYSA-N bis(3-methylphenyl)silane Chemical compound CC1=CC=CC([SiH2]C=2C=C(C)C=CC=2)=C1 FPBAHVJHTGZVOD-UHFFFAOYSA-N 0.000 claims description 3
- HLZHPXIBIOSNTF-UHFFFAOYSA-N bis(4-chlorophenyl)silane Chemical compound ClC1=CC=C(C=C1)[SiH2]C1=CC=C(C=C1)Cl HLZHPXIBIOSNTF-UHFFFAOYSA-N 0.000 claims description 3
- IPCJGHRRIQJAOP-UHFFFAOYSA-N bis(4-methylphenyl)silane Chemical compound C1=CC(C)=CC=C1[SiH2]C1=CC=C(C)C=C1 IPCJGHRRIQJAOP-UHFFFAOYSA-N 0.000 claims description 3
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 3
- ARMSVFMKIGKSKP-UHFFFAOYSA-N methyl-(4-methylphenyl)silane Chemical compound C[SiH2]C1=CC=C(C)C=C1 ARMSVFMKIGKSKP-UHFFFAOYSA-N 0.000 claims description 3
- WVHAIMKMNMGHMX-UHFFFAOYSA-N (4-fluorophenyl)-methylsilane Chemical compound FC1=CC=C(C=C1)[SiH2]C WVHAIMKMNMGHMX-UHFFFAOYSA-N 0.000 claims description 2
- BUFTWZHWOSHTOG-UHFFFAOYSA-N (4-methoxyphenyl)-methylsilane Chemical compound COc1ccc([SiH2]C)cc1 BUFTWZHWOSHTOG-UHFFFAOYSA-N 0.000 claims description 2
- MURXHNFHBQTMGX-UHFFFAOYSA-N C1=C(C=CC2=CC=CC=C12)[SiH2]C1=CC2=CC=CC=C2C=C1 Chemical compound C1=C(C=CC2=CC=CC=C12)[SiH2]C1=CC2=CC=CC=C2C=C1 MURXHNFHBQTMGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- GQPOYOSSLOMQKB-UHFFFAOYSA-N [SiH2](C1=CC=CC(OC)=C1)C1=CC(OC)=CC=C1 Chemical compound [SiH2](C1=CC=CC(OC)=C1)C1=CC(OC)=CC=C1 GQPOYOSSLOMQKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000000034 method Methods 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000003818 flash chromatography Methods 0.000 description 8
- 238000004896 high resolution mass spectrometry Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 150000004819 silanols Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910017489 Cu I Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to an organic silanol compound containing an S-S bond and a preparation method thereof, belonging to the technical field of organic compounds. The structural formula of the organic silanol compound containing the S-S bond is shown as
Wherein R is 1 And R 2 Independently selected from alkyl, unsubstituted or substituted aryl; when R is 1 And R 2 When all are selected from aryl, R 1 And R 2 The same is true. The preparation method is that under the action of a copper salt catalyst,
and
Description
Technical Field
The invention belongs to the technical field of organic compounds, and particularly relates to an organic silanol compound containing an S-S bond and a preparation method thereof.
Background
The organic silanol is an important organic silicon compound and an important component for synthesizing a silicon polymer material, and in addition, the silanol is widely used as a synthesis intermediate of a drug and a bioactive molecule, an anionic bond catalyst, a guide group and the like. In view of the importance of silanol compounds, selective and mild synthesis of silanol compounds is of high interest.
Silanol structures are widely found in material molecules and drugs, with a representative structural formula as follows:
currently, the synthesis of silanols involves mainly the hydrolysis of chlorosilanes and alkoxysilanes, or the oxidation from the corresponding hydrosilanes. Although the above synthesis methods are widely applied, they all have obvious disadvantages, such as the use of expensive metal catalysis, a large amount of by-products, harsh reaction conditions, low safety, etc. In recent years, various robust green catalysts are also developed to synthesize silanol, and effective ligands are designed to improve selectivity; the N-hydroxyphthalimide is used as a hydrogen atom transfer mediator to improve the yield; reactions that hydrolyze under visible light catalysis to give silanols have also been developed; silanol synthesis also extends to biocatalysis. Although the above strategies have been greatly improved, they are mainly based on the corresponding silicon-containing compounds, so that the range of substrates is limited and the diversity of functional groups is also lacking. Therefore, it is important to find suitable silicon-containing substrates and reaction conditions for synthesizing silanol compounds.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems of substrate limitation, harsh reaction conditions and the like in the preparation process of the organic silicon alcohol compound in the prior art.
In order to solve the technical problems, the invention provides an organic silanol compound containing an S-S bond and a preparation method thereof.
The first purpose of the invention is to provide an organic silanol compound containing an S-S bond, which has a structure shown in a formula (III):
wherein R is 1 And R 2 Independently selected from alkyl, unsubstituted or substituted aryl; when R is 1 And R 2 When all are selected from aryl, R 1 And R 2 The same is true.
In one embodiment of the present invention, the substituent group in the substituted aryl group is one or more of alkyl, alkoxy, and halogen.
The second purpose of the invention is to provide a preparation method of the organic silanol compound containing the S-S bond, which comprises the following steps that under the action of a copper salt catalyst, the silacyclobutane with the structure of the formula (I) and the sulfur source with the structure of the formula (II) react in a solvent to obtain the organic silanol compound containing the S-S bond shown in the structure of the formula (III);
wherein, the structural general formulas of the formulas (I), (II) and (III) are as follows,
wherein R is 1 And R 2 Independently selected from alkyl, substituted or unsubstituted aryl; when R is 1 And R 2 When all are selected from aryl, R 1 And R 2 The same is true.
In one embodiment of the invention, the silacyclobutane is one or more of 1,1-diphenylsilane, 1,1-di-p-tolylsilane, 1,1-bis (3-methoxyphenyl) silane, 1,1-bis (4-fluorophenyl) silane, 1,1-bis (4-chlorophenyl) silane, 1,1-bis (3-fluorophenyl) silane, 1,1-bis (3-fluorophenyl) silane, 1,1-di-m-tolylsilane, 1,1-bis (naphthalen-2-yl) silane, 1- (4-methoxyphenyl) -1-methylsilane, 1- (4-fluorophenyl) -1-methylsilane, 1-methyl-1- (p-tolyl) silane, and 1- (3-methoxyphenyl) -1-methylsilane.
In one embodiment of the present invention, the copper salt catalyst is one or more of cuprous chloride, tetraacetonitrileconium hexafluorophosphate, cuprous acetate, cupric acetate, cuprous iodide and cupric bromide.
In one embodiment of the invention, the molar ratio of the silacyclobutane to the sulfur source is 1.5-2:1.
in one embodiment of the present invention, the solvent is one or more of dimethylacetamide, dimethylformamide and dimethylsulfoxide.
In one embodiment of the invention, the reaction temperature is 35-45 ℃, and the reaction time is 8-14 h.
In one embodiment of the invention, the reaction is carried out under a nitrogen atmosphere.
In one embodiment of the present invention, the copper salt catalyst is used in an amount of 4mol% to 6mol% of the sulfur source.
In one embodiment of the present invention, a specific reaction scheme of the present invention:
the reaction mechanism of the present invention is as follows:
Cu I species and sulfur source (II) are subjected to oxidation addition to obtain Cu III Intermediate B, cu III Isomerization of intermediate B to C, subsequent sigma bond metathesis or intramolecular metal transfer of C with silacyclobutane (I) to provide Cu III Intermediate species D. Cu III The reductive elimination of intermediate species D occurs again to give intermediate E, and the CuI species is released. Finally, the intermediate E is further hydrolyzed to obtain the final target product (III).
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The preparation method has the advantages of simple and easily obtained raw materials, mild reaction conditions and environmental friendliness, and the yield is high by using copper salt as a catalyst in the reaction. The reaction conditions can be suitable for amplification reaction, and a foundation is laid for industrial production.
(2) The organic silanol compound provided by the invention introduces an S-S bond, provides a certain supplement for modification of silicon materials and cross chemistry of silicon and sulfur, and has important significance for the fields of organic chemistry and pharmaceutical chemistry.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
In the present invention, mol% represents a molar ratio unless otherwise specified.
Example 1
The preparation method of the (3- (tert-butyl disulfanyl) propyl) diphenyl silanol comprises the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1,1-diphenylsilane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithioperoxy acid salt) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) was added via syringe and the mixture was stirred at 40 ℃ for 12h under nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 76% yield.
The prepared compounds were tested, and the results are shown below:
infrared spectrum (neat, v, cm-1): 2961,1706,1361,1220,1115,866,700,508;
hydrogen nuclear magnetic resonance (400MHz, CDCl) 3 )δ7.67–7.62(m,4H),7.43(dt,J＝13.8,6.9Hz,6H),2.78(t,J＝7.1Hz,2H),2.54(s,1H),1.93–1.81(m,2H),1.35(s,9H),1.31–1.26(m,2H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ136.0,134.3,130.1,128.1,47.8,44.1,30.1,23.0,14.3.；
High resolution mass spectrometry (ESI): m/z calcd for:362.1194, found 362.1189.
Example 2
The preparation method of the (3- (tert-butyldisulfonyl) propyl) di-p-tolyl silanol comprises the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1,1-di-p-tolylsilane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithio-peroxonate) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) was added via syringe and the mixture was stirred at 40 ℃ for 12h under nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 70% yield.
The prepared compounds were tested, and the results are shown below:
infrared spectrum (neat, v, cm-1): 3005,1710,1358,1220,529;
hydrogen nuclear magnetic resonance spectroscopy (400MHz, CDCl) 3 )δ7.53–7.48(m,4H),7.21(d,J＝7.5Hz,4H),2.75(t,J＝7.2Hz,2H),2.38(s,6H),2.30(s,1H),1.88–1.78(m,2H),1.32(s,9H),1.25–1.19(m,2H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ140.0,134.4,132.6,128.9,47.8,44.2,30.1,23.2,21.7,14.5；
High resolution mass spectrometry (ESI): m/z calcd for:390.1507, found 390.1505.
Example 3
The preparation method of the (3- (tert-butyldisulfonyl) propyl) bis (4-fluorophenyl) silanol comprises the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1,1-bis (4-fluorophenyl) silane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithioperoxoate) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) was added via syringe and the mixture was stirred at 40 ℃ for 12h under a nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 68% yield.
The prepared compounds were tested, and the results are shown below:
infrared spectrum (neat, v, cm-1): 3005,1710,1359,1220,823,528;
hydrogen nuclear magnetic resonance (400MHz, CDCl) 3 )δ7.56(dd,J＝8.4,6.2Hz,4H),7.08(dd,J＝10.0,7.7Hz,4H),2.73(t,J＝7.0Hz,2H),2.51(s,1H),1.85–1.74(m,2H),1.30(s,9H),1.25–1.19(m,2H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )(101MHz,CDCl 3 )δ164.4(J＝248.2),136.4(J＝7.6),131.4(J＝3.7),115.4(J＝19.7),47.9,43.8,30.1,22.9,14.3；
High resolution mass spectrometry (ESI): m/z calcd for:398.1006 and found 398.1001.
Example 4
The (3- (tert-butyldisulfonyl) propyl) bis (4-chlorophenyl) silanol and the preparation method thereof specifically comprise the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1,1-bis (4-chlorophenyl) silane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithio)Peroxoate) (0.2 mmol) CuCl (5.0 mol%), anhydrous DMA (1 mL) were added via syringe and the mixture was stirred at 40 ℃ for 12h under nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 62% yield.
The prepared compounds were tested, and the results are shown below:
infrared spectrum (neat, v, cm-1): 3004,1709,1359,1220,529;
hydrogen nuclear magnetic resonance spectroscopy (400MHz, CDCl) 3 )δ7.61(dd,J＝7.8,1.7Hz,4H),7.42–7.38(m,4H),2.75(t,J＝7.1Hz,2H),2.55(s,1H),1.84(ddt,J＝11.3,8.8,6.3Hz,2H),1.31(s,9H),1.28–1.23(m,2H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ136.0,134.3,130.1,128.1,47.8,44.1,30.1,23.0,14.3；
High resolution mass spectrometry (ESI): m/z calcd for:420.0415 and found 420.0414.
Example 5
The preparation method of the (3- (tert-butyldisulfonyl) propyl) bis (3-fluorophenyl) silanol comprises the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1,1-bis (3-fluorophenyl) silane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithioperoxoate) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) was added via syringe and the mixture was stirred at 40 ℃ for 12h under a nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 57% yield.
The prepared compound was tested, and the test results are shown below:
infrared spectrum (neat, v, cm-1): 3004,1710,1420,1358,529;
hydrogen nuclear magnetic resonance (400MHz, CDCl) 3 )δ7.36(dt,J＝11.4,7.0Hz,4H),7.28–7.23(m,2H),7.10(ddq,J＝9.7,7.5,2.5,2.0Hz,2H),2.73(t,J＝7.0Hz,2H),2.69(s,1H),1.87–1.76(m,2H),1.29(s,9H),1.23(dd,J＝7.4,4.4Hz,2H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ162.8(J＝247.5),138.5(J＝3.8),130.1(J＝7.1),129.8(J＝3.0),120.6(J＝18.8),117.3(J＝20.9),47.9,43.7,30.0,22.8,13.9；
High resolution mass spectrometry (ESI): m/z calcd for:398.1006 and found 398.1000.
Example 6
The (3- (tert-butyldisulfonyl) propyl) bis (3-tolyl) silanol and the preparation method thereof specifically comprise the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1,1-di-m-tolylsilane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithio-peroxonate) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) was added via syringe and the mixture was stirred at 40 ℃ for 12h under nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 62% yield.
The prepared compounds were tested, and the results are shown below:
infrared spectrum (neat, v, cm-1): 3004,1710,1359,1220,529;
hydrogen nuclear magnetic resonance spectroscopy (400MHz, CDCl) 3 )δ7.44–7.37(m,4H),7.28(t,J＝7.3Hz,2H),7.23(d,J＝7.5Hz,2H),2.74(t,J＝7.1Hz,2H),2.35(s,6H),1.88–1.78(m,2H),1.60(s,1H),1.30(s,9H),1.25–1.21(m,2H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ137.5,136.0,134.8,131.4,130.9,128.0,47.8,44.1,30.1,23.1,21.7,14.3；
High resolution mass spectrometry (ESI): m/z calcd for:390.1507, found 390.1508.
Example 7
The (3- (tert-butyldisulfonyl) propyl) (methyl) (p-tolyl) silanol and the preparation method thereof specifically comprise the following steps:
in a glove box, an oven-dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1-methyl-1- (p-tolyl) silane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithioperoxonate) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) were added via syringe and the mixture was stirred at 40 ℃ for 12h under a nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 75% yield.
Infrared spectrum (neat, v, cm-1): 2960,1709,1360,1220,783,529,497;
hydrogen nuclear magnetic resonance spectroscopy (400MHz, CDCl) 3 )δ7.50–7.45(m,2H),7.23–7.19(m,2H),2.73(t,J＝7.2Hz,2H),2.37(s,3H),2.06(s,1H),1.81–1.71(m,2H),1.32(s,9H),0.97–0.90(m,2H),0.39(s,3H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ139.8,134.5,133.4,128.9,47.8,44.2,30.1,23.3,21.6,15.9,-1.4；
High resolution mass spectrometry (ESI): m/z calcd for:314.1194, found 314.1193.
Example 8
The (3- (tert-butyl disulfonyl) propyl) (3-methoxyphenyl) (methyl) silanol and the preparation method thereof comprise the following steps:
in a glove box, an oven dried screw cap 8mL vial equipped with a magnetic stir bar was charged with 1- (3-methoxyphenyl) -1-methylsilane (0.4 mmol), SS- (tert-butyl) benzenesulfonyl (dithio-peroxonate) (0.2 mmol) and CuCl (5.0 mol%), anhydrous DMA (1 mL) were added via syringe and the mixture was stirred at 40 ℃ for 12h under nitrogen atmosphere. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL. Times.3). Na for organic layer 2 SO 4 Dried, filtered and concentrated. The residue was purified by flash chromatography to give the product in 69% yield.
Infrared spectrum (neat, v, cm-1): 3004,1710,1358,1220,529;
hydrogen nuclear magnetic resonance spectroscopy (400MHz, CDCl) 3 )δ7.32(t,J＝7.7Hz,1H),7.18–7.08(m,2H),6.94(dd,J＝8.2,2.8Hz,1H),3.83(s,3H),2.72(t,J＝7.2Hz,2H),1.79–1.73(m,2H),1.67(s,1H),1.31(s,9H),0.98–0.92(m,2H),0.40(s,3H)；
Nuclear magnetic resonance carbon spectrum (101mhz, cdcl) 3 )δ159.2,139.7,129.4,125.6,118.7,115.3,55.3,47.9,44.1,30.1,23.2,15.8,-1.4；
High resolution mass spectrometry (ESI): m/z calcd for:330.1143 and found 330.1148.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. An organic silanol compound containing an S-S bond is characterized by having a structure shown as a formula (III):
wherein R is 1 And R 2 Independently selected from alkyl, unsubstituted or substituted aryl; when R is 1 And R 2 When all are selected from aryl, R 1 And R 2 The same is true.
2. The silanol compound having an S-S bond according to claim 1, wherein the substituent group in the substituted aryl group is one or more of an alkyl group, an alkoxy group and a halogen.
3. The preparation method of the organic silanol compound containing the S-S bond, which is characterized by comprising the following steps of reacting the silacyclobutane with the structure of the formula (I) and the sulfur source with the structure of the formula (II) in a solvent under the action of a copper salt catalyst to obtain the organic silanol compound containing the S-S bond, wherein the structure of the organic silanol compound is shown in the formula (III);
wherein, the structural general formulas of the formulas (I), (II) and (III) are as follows,
wherein R is 1 And R 2 Independently selected from alkyl, substituted or unsubstituted aryl; when R is 1 And R 2 When all are selected from aryl, R 1 And R 2 The same is true.
4. The method for producing an silanol compound having an S-S bond according to claim 3, wherein the silacyclobutane is one or more of 1,1-diphenylsilane, 1,1-di-p-tolylsilane, 1,1-bis (3-methoxyphenyl) silane, 1,1-bis (4-fluorophenyl) silane, 1,1-bis (4-chlorophenyl) silane, 1,1-bis (3-fluorophenyl) silane, 1,1-bis (3-fluorophenyl) silane, 1,1-di-m-tolylsilane, 1,1-di (naphthalen-2-yl) silane, 1- (4-methoxyphenyl) -1-methylsilane, 1- (4-fluorophenyl) -1-methylsilane, 1-methyl-1- (p-tolyl) silane, and 1- (3-methoxyphenyl) -1-methylsilane.
5. The method for producing an organic silanol compound having an S-S bond as claimed in claim 3, wherein the copper salt catalyst is one or more of cuprous chloride, tetraacetonitrileconium hexafluorophosphate, cuprous acetate, cupric acetate, cuprous iodide and cupric bromide.
6. The method for producing an organic silanol compound having an S-S bond according to claim 3, wherein the molar ratio of the silacyclobutane to the sulfur source is 1.5 to 2:1.
7. the method according to claim 3, wherein the solvent is one or more of dimethylacetamide, dimethylformamide and dimethylsulfoxide.
8. The method for producing an organic silanol compound having an S-S bond according to claim 3, wherein the reaction temperature is 35 to 45 ℃ and the reaction time is 8 to 14 hours.
9. The method for producing an organic silanol compound having an S-S bond according to claim 3, wherein the reaction is carried out under a nitrogen atmosphere.
10. The method according to claim 3, wherein the amount of the copper salt catalyst is 4mol% to 6mol% of the sulfur source.
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