CN114213294B - Method for synthesizing disulfide compound by using basic zeolite molecular sieve as catalyst - Google Patents
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- -1 disulfide compound Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000010457 zeolite Substances 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 title claims description 35
- 239000002808 molecular sieve Substances 0.000 title abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 26
- 150000002019 disulfides Chemical class 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 44
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 23
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N gem-dimethylcyclohexane Natural products CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000005815 base catalysis Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000003818 flash chromatography Methods 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- GKQXPTHQTXCXEV-UHFFFAOYSA-N (4-chlorophenyl)methanethiol Chemical compound SCC1=CC=C(Cl)C=C1 GKQXPTHQTXCXEV-UHFFFAOYSA-N 0.000 description 1
- CLPVCAXOQZIJGW-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfanylbenzene Chemical compound C1=CC(Br)=CC=C1SC1=CC=C(Br)C=C1 CLPVCAXOQZIJGW-UHFFFAOYSA-N 0.000 description 1
- ITVKOVQVBCQQGY-UHFFFAOYSA-N 1-chloro-4-[(4-chlorophenyl)methylsulfanylmethyl]benzene Chemical compound C1=CC(Cl)=CC=C1CSCC1=CC=C(Cl)C=C1 ITVKOVQVBCQQGY-UHFFFAOYSA-N 0.000 description 1
- YYYOQURZQWIILK-UHFFFAOYSA-N 2-[(2-aminophenyl)disulfanyl]aniline Chemical compound NC1=CC=CC=C1SSC1=CC=CC=C1N YYYOQURZQWIILK-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- YOLFWWMPGNMXFI-UHFFFAOYSA-N 2-thiophen-2-yldisulfanylthiophene Chemical compound C=1C=CSC=1SSC1=CC=CS1 YOLFWWMPGNMXFI-UHFFFAOYSA-N 0.000 description 1
- CTUFQKDQCZIHMS-UHFFFAOYSA-N 4-bromo-2-phenylbenzenethiol Chemical compound SC1=CC=C(Br)C=C1C1=CC=CC=C1 CTUFQKDQCZIHMS-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- XWMWRWORUNGQNO-UHFFFAOYSA-N COC1=CC(=C(C=C1)S)C1=CC=CC=C1 Chemical compound COC1=CC(=C(C=C1)S)C1=CC=CC=C1 XWMWRWORUNGQNO-UHFFFAOYSA-N 0.000 description 1
- ODHAQPXNQDBHSH-UHFFFAOYSA-N Dicyclohexyl disulfide Chemical compound C1CCCCC1SSC1CCCCC1 ODHAQPXNQDBHSH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- HAXFWIACAGNFHA-UHFFFAOYSA-N aldrithiol Chemical compound C=1C=CC=NC=1SSC1=CC=CC=N1 HAXFWIACAGNFHA-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- OSZKBWPMEPEYFU-UHFFFAOYSA-N methyl 3-[(3-methoxy-3-oxopropyl)disulfanyl]propanoate Chemical compound COC(=O)CCSSCCC(=O)OC OSZKBWPMEPEYFU-UHFFFAOYSA-N 0.000 description 1
- LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001021 polysulfide Chemical group 0.000 description 1
- 239000005077 polysulfide Chemical group 0.000 description 1
- 150000008117 polysulfides Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 238000006456 reductive dimerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 238000006177 thiolation reaction Methods 0.000 description 1
- WZMPOCLULGAHJR-UHFFFAOYSA-N thiophen-2-ol Chemical compound OC1=CC=CS1 WZMPOCLULGAHJR-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
-
- 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
- C07D333/26—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing and synthesizing disulfide compounds by using an alkaline zeolite molecular sieve, belonging to the field of green organic fine catalytic synthesis. According to the method for synthesizing the disulfide compound by using the thiol compound as the substrate, the aromatic thiol, the aliphatic thiol and the heterocyclic thiol are subjected to self-coupling reaction under the condition of no oxidant and no metal in the nitrogen atmosphere through the solid base catalysis of the ETS-10 zeolite molecular sieve, and the sulfur hydrogen bond is activated. Finally obtaining a series of disulfide compounds. The method has simple steps, high product yield and easy separation and purification.
Description
Technical Field
The invention belongs to the field of green organic fine catalytic synthesis, and particularly relates to a method for synthesizing disulfide compounds by catalyzing mercaptan compounds with an ETS-10 zeolite molecular sieve.
Background
In natural compounds, biological agents and drugs, the sulfur-sulfur bond is a functional group which has high value and rich content, and shows excellent biological activity and reaction activity. Because of their biocompatibility, disulfide compounds have been used by drug researchers as important intermediates in the synthesis of new drugs, as well as precursors for drug delivery. In addition, the disulfide compound plays an important role in functional materials such as biological materials, biochemical sensors, rechargeable batteries, rubber vulcanization accelerators and the like.
General methods for synthesizing disulfide compounds include a thiolation method, a reductive dimerization method of a thiolate, a reductive coupling method of sulfur or polysulfide substituted alkyl halohydrocarbon, a sulfonyl chloride, and the like, and in the above-described method for synthesizing disulfide compounds, thiol is oxidized with a strong oxidizing agent to form a corresponding radical, and then disulfide compounds are formed. In industry, the production of disulfide compounds generally uses only equivalent amounts of oxidizing agents, such as NaClO or NaNO 2, for oxidative coupling reactions (j. Chem. Technology. Biotechnol.,2012,87,341-345). However, during the reaction, harmful liquid wastes are generated, which contain a large amount of salts and nitrogen oxides, so that the treatment cost increases and the environment is not friendly. Accordingly, other catalysts using oxygen as an oxidizing agent are also produced, such as metal salts K 3PO4 (Tetrahedron letters 2005,46,3583), csF (Tetrahedron letters 2003,44,6789), metal oxides CeO 2 (chem. Sci.2012,3,398), transition metals (Green chem.,2017,19,2491-2495), organic ligand catalysts (Asian j. Org. Chem.,2017,6,265-268), enzymes (Green chem.,2013,15,1490-1495), etc., but when asymmetric coupling reactions of thiols are catalyzed by these catalysts, not only yields are low, but also are not easily separable, and are liable to affect subsequent processes.
The titanosilicate molecular sieve ETS-10 is formed by bridging SiO 4 tetrahedron and TiO 6 octahedron through sharing oxygen atoms, and simultaneously has a three-dimensional pore canal structure of a three-membered ring, a five-membered ring, a seven-membered ring and a twelve-membered ring. The SiO 4 tetrahedron in the framework is electrically neutral, and the whole octahedron has 2 negative charges due to the fact that Ti is positioned in the center of the TiO 6 octahedron. This allows ETS-10 to have a stronger Lewis base. Thus, ETS-10 may be used in a base catalyzed reaction. We have found through research that the basic sites on the ETS-10 surface are capable of adsorbing and activating thiol compounds, converting them into the corresponding free radicals, and generating disulfide compounds through free radical coupling reactions.
Therefore, the invention provides a one-step method for converting the mercaptan compound into the disulfide compound by taking alkaline ETS-10 as a catalyst without using a traditional metal catalyst and a strong oxidant, and the method is high-efficiency and clean, has no byproduct generation, has high atom economy, and is easy to separate and recycle the catalyst.
Disclosure of Invention
The invention uses commercial basic ETS-10 zeolite as a catalyst, and realizes the direct conversion of the mercaptan compound into the disulfide compound in a nitrogen atmosphere under the condition of not using a strong oxidant or metal salt.
The specific synthesis method is as follows:
the preparation method comprises the steps of taking a mercaptan compound as a reaction raw material, adding a set amount of ETS-10 zeolite as a catalyst into a reaction tube, adding a solvent, reacting in a nitrogen atmosphere, centrifuging to obtain a reaction liquid, and performing column chromatography separation on the obtained liquid product after rotary evaporation to obtain the disulfide compound.
Wherein the mercaptan compound is aromatic mercaptan, heterocyclic mercaptan and aliphatic mercaptan, and the structural formulas are shown in formula I, formula II and formula III respectively:
Further, the catalyst used in the present invention is a nano ETS-10 zeolite catalyst.
Further, the organic solvent selected for the reaction is selected from one of dichloromethane, dimethyl sulfoxide and cyclohexane.
Further, the amount of the thiol organic compound to be added is 0.005 to 0.02:1 (mol/g) relative to the amount of the catalyst.
Further, the reaction temperature is 80-120 ℃ and the reaction time is 3-10 h.
Compared with the prior art, the invention has the following technical advantages
(1) Compared with the catalytic reaction system of metal salts (K 3PO4, csF) and metal oxides (CeO 2) reported in the literature, the catalytic reaction system can realize the reaction under the nitrogen atmosphere, and does not need to add an additional strong oxidant or oxygen.
(2) The invention has high tolerance of functional groups, wide substrate range, low toxicity, environmental friendliness and simple synthesis method, and the selectivity of the disulfide compounds reaches 100 percent, and the subsequent separation steps are also simple.
Drawings
FIG. 1 is a chart showing the NMR spectrum of dibenzyldisulfide 1 H of example 1
FIG. 2 is a chart showing the NMR spectrum of bis (2-aminophenyl) disulfide 1 H of example 2
FIG. 3 is a chart showing the NMR spectrum of p-toluenedisulfide 1 H of example 3
FIG. 4 is a chart showing the NMR spectrum of p-methoxydisulfide 1 H of example 4
FIG. 5 is a chart showing the NMR spectrum of p-bromophenyl sulfide 1 H of example 5
FIG. 6 is a chart of the NMR spectrum of dicyclohexyl disulfide 1 H of example 6
FIG. 7 is a chart showing the NMR spectrum of bis (2-thienyl) disulfide 1 H
FIG. 8 is a chart showing the NMR spectrum of dimethyl 3,3' -dithiodipropionate 1 H
FIG. 9 is a 1 H NMR spectrum of p-chlorobenzyl sulfide of example 9
FIG. 10 is a chart showing the NMR spectrum of bis (2-pyridyl) disulfide 1 H of example 10
Detailed Description
For a further understanding of the objects, aspects and advantages of the present invention, specific embodiments of the present invention will now be described in detail, but are not limited to the examples described below, and the reaction conditions will be changed according to the actual circumstances.
Example 1:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. After rotary evaporation, the obtained liquid phase product was subjected to flash column chromatography (volume ratio of petroleum ether and ethyl acetate as eluent: 10:1) to obtain a yellow oily substance. The yield of the product can reach 95%, and the characterization data of the product are as follows: 1 H NMR (500 MHz, chloro form-d) delta 7.25-7.12 (m, 10H), 3.50 (s, 4H).
Example 2:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of o-aminothiophenol and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The solid phase product obtained was subjected to flash column chromatography (eluting reagent petroleum ether to ethyl acetate in a volume ratio of 4:1) to give a yellow solid. The yield of the product can reach 90%, and the characterization data of the product are as follows :1H NMR(500MHz,Chloroform-d)δ7.09(ddd,J=7.6,6.1,1.8Hz,4H),6.66–6.62(m,2H),6.54–6.49(m,2H),4.26(s,4H).
Example 3:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of p-methylthiophenol and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The solid phase product obtained was subjected to flash column chromatography (volume ratio of petroleum ether to ethyl acetate as eluent: 50:1) to obtain a white solid. The yield of the product can reach 84%, and the characterization data of the product are as follows: 1 H NMR (500 mhz, chloroform-d) delta 7.30 (d, j=8.2 hz, 5H), 7.02 (d, j=7.9 hz, 5H), 2.23 (s, 6H).
Example 4:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of p-methoxyphenylthiophenol and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The solid phase product obtained was subjected to flash column chromatography (volume ratio of petroleum ether to ethyl acetate as eluent: 10:1) by rotary evaporation to give pale yellow liquid. The product yield can reach 89%, and the characterization data of the product are as follows: 1 H NMR (500 mhz, chloro-d) delta 7.32 (d, j=8.9 hz, 4H), 6.76 (d, j=8.8 hz, 4H), 3.72 (s, 6H).
Example 5:
30mg ETS-10 catalyst was weighed into the reaction tube, and then 0.22mmol of p-bromophenylthiophenol and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The solid phase product obtained was subjected to flash column chromatography (eluting with pure cyclohexane) by rotary evaporation to give a white solid. The product yield can reach 89%, and the characterization data of the product are as follows: 1 H NMR (500 MHz,Chloroform-d) delta 7.38-7.32 (m, 4H), 7.25 (d, j=8.6 hz, 4H).
Example 6:
30mg ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of cyclohexanediol and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The liquid phase product obtained was subjected to flash column chromatography (volume ratio of petroleum ether to ethyl acetate as eluent: 2:1) to obtain colorless liquid. The yield of the product can reach 89%, and the characterization data of the product are as follows :1H NMR(500 MHz,Chloroform-d)δ2.65–2.58(m,2H),2.02–1.95(m,4H),1.71(dd,J=9.4,4.6 Hz,4H),1.55(dt,J=10.3,3.4 Hz,2H),1.27–1.18(m,10H).
Example 7:
30 mg ETS-10 catalyst was weighed into the reaction tube, and then 0.2. 0.2 mmol of 2-thiophenol and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. Rotary evaporation to obtain liquid phase product, adding ethyl acetate, directly rotary evaporating to obtain product as yellow solid. The yield of the product can reach 98 percent, and the characterization data of the product are as follows :1H NMR(500 MHz,Chloroform-d)δ7.41(dd,J=5.3,1.3 Hz,2H),7.07(dd,J=3.6,1.3 Hz,2H),6.93(dd,J=5.3,3.6 Hz,2H).
Example 8:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of methyl 3-mercaptopropionate and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The liquid phase product obtained was subjected to flash column chromatography (volume ratio of petroleum ether to ethyl acetate as eluent: 50:1). The product yield can reach 82%, the obtained product is colorless oily liquid, and the characterization data of the product are as follows: 1 H NMR (500 MHz, chloro-d) delta 3.63 (s, 6H), 2.85 (s, 4H), 2.67 (s, 4H).
Example 9:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of 4-chlorobenzyl mercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The liquid phase product obtained was subjected to flash column chromatography (eluent petroleum ether and ethyl acetate in a volume ratio of 20:1) by rotary evaporation. The product yield was up to 90% and was a pale yellow oily liquid, the characterization data of the product were as follows: 1 H NMR (500 MHz, chloroform-d) delta 7.23-7.20 (m, 4H), 7.09-7.06 (m, 4H), 3.49 (s, 4H).
Example 10:
30mg of ETS-10 catalyst was weighed into the reaction tube, and then 0.2mmol of 2-mercaptopyridine and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The liquid phase product obtained was subjected to flash column chromatography (eluent petroleum ether and ethyl acetate in a volume ratio of 20:1) by rotary evaporation. The yield of the product was 92% and was a pale yellow oily liquid, and the characterization data of the product were as follows :1H NMR(500MHz,Chloroform-d)δ8.47(dd,J=4.9,2.0Hz,2H),7.55(td,J=7.7,2.0Hz,2H),7.39–7.36(m,2H),7.09(ddd,J=7.6,4.9,1.1Hz,2H).
Comparative example 1:
30mg of potassium fluoride catalyst was weighed into a reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 2:
30mg of potassium bromide catalyst was weighed into the reaction tube, followed by addition of 0.2mmol of benzylmercaptan and 1mL of cyclohexane. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 3:
30mg of potassium carbonate catalyst was weighed into a reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 4:
30mg of sodium carbonate catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 5:
30mg of sodium nitrate catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 6:
30mg of potassium nitrate catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 7:
30mg of rubidium nitrate catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 8:
30mg of cesium carbonate catalyst was weighed into a reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 9:
30mg of NaX catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
Comparative example 10:
30mg of NaY catalyst was weighed into the reaction tube, and then 0.2mmol of benzylmercaptan and 1mL of cyclohexane were added. And (3) reacting for 5 hours in a heater at 120 ℃ under the nitrogen atmosphere, and centrifuging after the experiment is finished. The obtained liquid phase was analyzed in Agilent gas chromatography to calculate the conversion of benzyl mercaptan and the selectivity of the target product.
(1) Compared with the traditional catalytic reaction system of the metal salt (K 3PO4, csF) and metal oxide (CeCO 2,Al2O3) catalytic reaction body, the invention can realize the reaction in the nitrogen atmosphere without adding additional strong oxidant
Catalyst | Conversion% | Selectivity% | |
Example 1 | ETS-10 | 95 | 100 |
Comparative example 1 | KF | 3 | 100 |
Comparative example 2 | KBr | 5 | 100 |
Comparative example 3 | K2CO3 | trace(<1%) | 100 |
Comparative example 4 | Na2CO3 | - | - |
Comparative example 5 | NaNO3 | - | - |
Comparative example 6 | KNO3 | - | - |
Comparative example 7 | RbNO3 | - | - |
Comparative example 8 | Cs2CO3 | trace(<1%) | 100 |
Comparative example 9 | NaX | 30 | 65 |
Comparative example 10 | NaY | trace | 100 |
Claims (5)
1. A method for synthesizing disulfide compounds, which is characterized by comprising the following steps: in nitrogen atmosphere, sequentially adding ETS-10 zeolite, mercaptan compounds and organic solvent into reaction equipment, reacting at a reaction temperature, centrifuging to obtain reaction liquid, and performing column chromatography separation on the obtained liquid product after rotary evaporation to obtain disulfide compounds.
2. The method for synthesizing the disulfide compound according to claim 1, wherein the structural formula of the thiol compound is shown as formula I, formula II and formula III respectively:
3. the method for synthesizing disulfide-based compounds according to claim 1, wherein the organic solvent is selected from one of dichloromethane, dimethyl sulfoxide and cyclohexane.
4. The method for synthesizing a disulfide compound according to claim 1, wherein the amount of the thiol compound to be added is 0.005 to 0.02:1 (mol/g) with respect to the amount of the catalyst.
5. The method for synthesizing disulfide compound according to claim 1, wherein the reaction temperature is 80-120 ℃ and the reaction time is 3-10 h.
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