CN109180607B - A kind of method that organic catalyst catalyzes carbonyl sulfide conversion to synthesize thiazidedione heterocyclic compound - Google Patents
A kind of method that organic catalyst catalyzes carbonyl sulfide conversion to synthesize thiazidedione heterocyclic compound Download PDFInfo
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000004440 column chromatography Methods 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001336 alkenes Chemical class 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- SNBXBCVVXOLOPL-UHFFFAOYSA-N 1,3-thiazine-2,4-dione Chemical class O=C1C=CSC(=O)N1 SNBXBCVVXOLOPL-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- -1 1,3-thiazine-2,4-dione class compounds Chemical class 0.000 abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003749 cleanliness Effects 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000007363 ring formation reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- YEOYYWCXWUDVCX-UHFFFAOYSA-N 2-iodobenzamide Chemical compound NC(=O)C1=CC=CC=C1I YEOYYWCXWUDVCX-UHFFFAOYSA-N 0.000 description 1
- BAEGNKLHQHKNHN-UHFFFAOYSA-N C=1C=CC=CC=1CNC1(N)CCCCC1 Chemical compound C=1C=CC=CC=1CNC1(N)CCCCC1 BAEGNKLHQHKNHN-UHFFFAOYSA-N 0.000 description 1
- RWBIPOOOLDZZBY-UHFFFAOYSA-N N1C(C=C2C(C=CC=C12)=O)=O Chemical compound N1C(C=C2C(C=CC=C12)=O)=O RWBIPOOOLDZZBY-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- IHPVFYLOGNNZLA-UHFFFAOYSA-N Phytoalexin Natural products COC1=CC=CC=C1C1OC(C=C2C(OCO2)=C2OC)=C2C(=O)C1 IHPVFYLOGNNZLA-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- PRLVTUNWOQKEAI-VKAVYKQESA-N buprofezin Chemical class O=C1N(C(C)C)\C(=N\C(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-VKAVYKQESA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- MAEPBGMZUQKSOT-UHFFFAOYSA-N n-benzyl-4-methylpenta-2,3-dienamide Chemical compound CC(C)=C=CC(=O)NCC1=CC=CC=C1 MAEPBGMZUQKSOT-UHFFFAOYSA-N 0.000 description 1
- UYBGMYUWQOMNCW-UHFFFAOYSA-N n-benzyl-4-phenylpenta-2,3-dienamide Chemical compound C=1C=CC=CC=1C(C)=C=CC(=O)NCC1=CC=CC=C1 UYBGMYUWQOMNCW-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000280 phytoalexin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XXDOCAGWDUVEAN-UHFFFAOYSA-N thiazinane-3,4-dione Chemical compound O=C1CCSNC1=O XXDOCAGWDUVEAN-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/04—1,3-Thiazines; Hydrogenated 1,3-thiazines
- C07D279/06—1,3-Thiazines; Hydrogenated 1,3-thiazines not condensed with other rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种有机催化剂催化羰基硫转化合成噻嗪二酮杂环化合物的方法，属于有机合成、农药及医药化工合成技术领域。该方法是在高压釜中加入联烯酰胺类化合物原料和溶剂，加入氮杂环卡宾、氮杂极性烯烃或其与羰基硫的加合物作为有机催化剂，通入羰基硫气体，在60～100摄氏度条件下搅拌12小时，反应结束后冷却至室温，缓慢释放未反应的羰基硫气体，抽干溶剂得粗产品，经柱层析纯化得到1,3‑噻嗪‑2,4‑二酮类化合物。本发明使用羰基硫代替传统硫源，该反应具有清洁，反应条件温和，高官能团耐受性，高转化率和立体选择性特点，在有机合成、农药及医药中具有广泛用途。The invention provides a method for synthesizing a thiazidedione heterocyclic compound by catalyzing the conversion of carbonyl sulfide with an organic catalyst, belonging to the technical fields of organic synthesis, pesticide and pharmaceutical chemical synthesis. The method is to add allenamide compound raw material and solvent into the autoclave, add nitrogen heterocyclic carbene, aza polar olefin or its adduct with carbonyl sulfide as organic catalyst, feed carbonyl sulfide gas, and at 60～ Stir at 100 degrees Celsius for 12 hours, cool to room temperature after the reaction, slowly release unreacted carbonyl sulfide gas, drain the solvent to obtain a crude product, which is purified by column chromatography to obtain 1,3-thiazine-2,4-dione class compounds. The present invention uses carbonyl sulfide instead of traditional sulfur source, and the reaction has the characteristics of cleanliness, mild reaction conditions, high functional group tolerance, high conversion rate and stereoselectivity, and has wide applications in organic synthesis, pesticides and medicine.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, pesticides and pharmaceutical chemical synthesis, and relates to a method for synthesizing a 6-alkylidene-1, 3-thiazine-2, 4-diketone compound by catalyzing and converting carbonyl sulfide and a dienamide compound to perform cyclization reaction by using an organic small molecular catalyst.
Background
Heterocyclic skeletons containing oxygen, nitrogen and sulfur heteroatoms are representative structures in many synthetic drugs, biomolecules and natural products, in particular six-membered heterocyclic thiazinone compounds, which have attracted a great deal of attention as biologically active substances and important intermediates in pharmaceutical and organic synthetic chemistry, for example thiazinanedione (N-methyl-1, 3-thiazine- [6,5-b ] indole-2, 4-dione) is a class of sulfur-containing heterocyclic phytoalexins that effectively inhibit the growth of pathogenic microorganisms. Therefore, the green and efficient construction of thiazine heterocyclic compounds has important theoretical research and practical significance.
According to the previous research reports, the construction of thiazine heterocyclic molecules is basically prepared by using thiocyanic acid, 2-mercapto aromatic acid, thiourea, carbon disulfide, sulfur powder, thioacetamide and the like as sulfur sources. Despite some advances, these reactions are mostly achieved by stoichiometric reactions and suffer from a single type (Shestakov, a.s.; prefent, m.a.; zlatovskaya, e.o.; Shikhaliev, k.s.; falalev, a.v.; sidornko, o.e. chemistry of Heterocyclic Compounds 2015,51,370.), a complex reaction route (Soliman, a.m. phoshor, Sulfur, and Silicon and the Related Elements 1994,97,1.), severe reaction conditions (Youssef, a.m.; Azab, m.e., yuref, m.m.m.modules, 17,6930.), and the like. In addition, the preparation of buprofezin compounds by using metallic nickel to catalyze the reaction of thiourea with o-iodobenzamide was also reported by K.Takagi et al in 1990 (Takagi, K.chemistry Letters 1990,19, 2205.). However, the research of constructing the thiazine heterocyclic compound by using carbonyl sulfide as a sulfur source and catalyzing the carbonyl sulfide by using an organic small molecular catalyst has not been reported so far.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for selectively preparing thiazine diketone heterocyclic compounds by catalyzing carbonyl sulfide and bisacrylamide cyclization reaction by using an organic small-molecule catalyst. The reaction raw materials and reagents are simple and easy to obtain, the applicability of the substrate is wide, the post-treatment process is simple, the target product can be obtained with high yield, high chemical selectivity and high stereoselectivity, and the atom economy is realized.
The invention takes carbonyl sulfide and dienamide derivatives as raw materials, and the thiazine diketone six-membered heterocyclic sulfide compound is synthesized by catalytic cyclization reaction under the action of an organic small molecular catalyst.
The technical scheme of the invention is as follows:
a method for synthesizing thiazine diketone heterocyclic compound by catalyzing carbonyl sulfide conversion with organic catalyst comprises the following steps: adding a dienamide compound and a solvent into an autoclave, adding an N-heterocyclic carbene carbonyl sulfide adduct or an N-heterocyclic olefin carbonyl sulfide adduct as an organic catalyst, introducing carbonyl sulfide gas, stirring at 60-100 ℃ for 12 hours, cooling to room temperature after the reaction is finished, slowly releasing unreacted carbonyl sulfide gas, pumping out the solvent to obtain a crude product, and purifying by column chromatography to obtain a 1, 3-thiazine-2, 4-diketone compound; the reaction is shown as follows:
wherein R is1Is phenyl, methyl, ethyl, isopropyl, n-hexyl, cyclopentyl or cyclohexyl;
R2is hydrogen, methyl, ethyl or phenyl;
R3is benzyl, n-butyl, isopropyl, cyclohexyl, allyl or tosylmethyl.
The structural formula of the organic catalyst is as follows:
n-heterocyclic carbene carbonyl sulfide adduct:
azacycloolefm carbonyl sulfide adduct:
wherein R is4And R5Is methyl, isopropyl, tert-butyl, phenyl, 2,4, 6-trimethylphenyl or 2, 6-diisopropylphenyl, R4And R5The same or different;
R6and R7Is hydrogen, methyl, ethyl or isopropyl, R6And R7The same or different;
R8is methyl, ethyl, isopropyl, n-butyl or benzyl; n is 1 or 2;
further, the nitrogen heterocyclic carbene carbonyl sulfide adduct has a structural formula as follows a-f:
the structural formula of the azacyclo-olefin carbonyl sulfide adduct is as follows g-j:
the molar ratio of the organic catalyst to the bisacrylamide compound is 1: 20.
The solvent is dichloromethane, tetrahydrofuran, toluene, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane or acetonitrile.
The reaction pressure is 0.1-1.0 MPa, and the high-pressure kettle is an intermittent high-pressure reaction kettle or a continuous high-pressure reaction kettle.
The eluent of the column chromatography is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of the n-hexane to the ethyl acetate is 5: 1.
The invention has the beneficial effects that: the method adopts the organic micromolecular catalyst to catalyze the cyclization reaction of the carbonyl sulfide and the dienamide derivative, and has the characteristics of mild reaction conditions, safe and simple experimental operation, low toxicity of reaction substrates, environmental friendliness and the like. The reaction raw materials and reagents are simple and easy to obtain, the substrate applicability is wide, the post-treatment process is simple, the target product can be obtained with high yield, high chemical selectivity and high stereoselectivity, the atom economy is realized, and the method has potential application prospects in chemical production of thiazine ketone series pesticides, medicines and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the method of carrying out the present invention and the substrate to which the present invention is applied are not limited thereto.
Example 1
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-benzyl-4-methylpenta-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release the unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 96%.
The structural characterization data of the resulting product are shown below:
1H NMR(500MHz,CDCl3)δ7.44(d,J＝7.0Hz,2H),7.28(dt,J＝16.6,4.7Hz,3H),6.37(s,1H),5.18(s,2H),2.79–2.56(m,1H),1.24(d,J＝6.9Hz,6H).13C NMR(126MHz,CDCl3)δ165.2,164.0,160.0,136.3,129.3,128.6,127.9,113.4,44.7,35.4,21.8.HRMS(ESI):calcd for C14H15NO2S:262.0896[M+H]+.Found:262.0897[M+H]+.IR vC＝O:1689,1651cm-1(vs).
example 2
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-benzyl-4-methylhexane-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 99%.
The structural characterization data of the resulting product are shown below:
1H NMR(400MHz,CDCl3)δ7.51–7.39(m,2H),7.28(dq,J＝14.2,7.0Hz,3H),6.35(s,1H),5.17(s,2H),2.54–2.37(m,1H),1.67–1.46(m,2H),1.21(d,J＝6.9Hz,3H),0.91(t,J＝7.4Hz,3H).13C NMR(101MHz,CDCl3)δ165.2,163.8,159.0,136.2,129.3,128.5,127.9,114.2,44.7,42.8,28.9,19.7,11.7.HRMS(ESI):calcd for C15H17NO2S:276.1053[M+H]+.Found:276.1051[M+H]+.IR vC＝O:1684,1652cm-1(vs).
example 3
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-benzyl-3-cyclohexylidenediamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, the heating and stirring were stopped, the mixture was cooled to room temperature, and unreacted carbonyl sulfide was slowly released. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 87%.
The structural characterization data of the resulting product are shown below:
1H NMR(400MHz,CDCl3)δ7.50(d,J＝6.8Hz,2H),7.41–7.26(m,3H),6.41(s,1H),5.23(s,2H),2.37(m,J＝11.0Hz,1H),1.91(m,J＝17.7,9.9Hz,4H),1.77(d,J＝12.6Hz,1H),1.49–1.17(m,5H).13C NMR(101MHz,CDCl3)δ165.2,163.9,158.9,136.2,129.2,128.4,127.8,113.4,44.9,44.5,32.1,25.9,25.4.HRMS(ESI):calcd for C17H19NO2S:302.1209[M+H]+.Found:302.1211[M+H]+.IR vC＝O:1683,1651cm-1(vs).
example 4
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-benzyl-4, 5-dimethylhex-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, heating and stirring were stopped, and cooling was carried out to room temperature to slowly release unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 93%.
The structural characterization data of the resulting product are shown below:
1H NMR(400MHz,CDCl3)δ7.36(d,J＝7.0Hz,2H),7.29–7.09(m,3H),6.25(s,1H),5.08(s,2H),2.30–2.04(m,1H),1.73–1.57(m,1H),1.09(d,J＝7.0Hz,3H),0.84(t,J＝6.6Hz,6H).13C NMR(101MHz,CDCl3)δ165.1,163.7,158.8,136.2,129.2,128.4,127.8,114.5,48.1,44.6,32.6,21.1,19.5,17.0.HRMS(ESI):calcd for C12H15NO2S:290.1209[M+H]+.Found:290.1207[M+H]+.IR vC＝O:1686,1647cm-1(vs).
example 5
A20 ml autoclave was charged with a stirrer, 0.5 mmol of 4-ethyl-N- (prop-2-yn-1-yl) hex-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, stirred at 60 ℃ for 12 hours, then the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release the unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 97%.
The structural characterization data of the resulting product are shown below:
1H NMR(400MHz,CDCl3)δ6.39(s,1H),4.76(d,J＝2.3Hz,2H),2.40–2.14(m,2H),1.73–1.61(m,2H),1.55(tt,J＝14.5,7.4Hz,2H),0.93(t,J＝7.4Hz,6H).13C NMR(101MHz,CDCl3)δ164.3,162.4,157.9,115.0,77.5,71.1,51.0,30.5,27.2,27.0,11.7.HRMS(ESI):calcd for C12H15NO2S:238.0896[M+H]+.Found:235.0895[M+H]+.IR vC＝O:1695,1651cm-1(vs).
example 6
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-benzyl-4-phenylpentane-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, heating and stirring were stopped, and cooling was carried out to room temperature to slowly release unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 98%.
The structural characterization data of the resulting product are shown below:
1H NMR(400MHz,CDCl3)δ7.42(d,J＝7.1Hz,2H),7.35–7.13(m,8H),6.43(s,1H),5.12(s,2H),3.79(q,J＝7.0Hz,1H),1.55(d,J＝7.2Hz,3H).13C NMR(101MHz,CDCl3)δ164.8,163.7,157.6,140.2,136.1,129.2,129.0,128.4,127.9,127.8,127.5,114.4,45.5,44.6,19.6.HRMS(ESI):calcd for C19H25NO2S:332.1679[M+H]+.Found:332.1680[M+H]+.IR vC＝O:1682,1651cm-1(vs).
example 7
A20 ml autoclave was charged with a stirrer, 0.5 mmol of 4-phenyl N- (tosylmethyl) penta-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 98%.
The structural characterization data of the resulting product are shown below:
1H NMR(500MHz,CDCl3)δ7.77(d,J＝8.3Hz,2H),7.37(t,J＝7.3Hz,2H),7.32(dd,J＝7.5,3.8Hz,3H),7.24–7.20(m,2H),6.45(s,2H),5.42(s,1H),3.87(q,J＝7.0Hz,3H),2.44(s,2H),1.63(d,J＝7.1Hz,3H).13C NMR(126MHz,CDCl3)δ164.1,162.2,158.8,145.5,139.9,136.2,130.0,129.3,128.7,128.3,127.6,113.9,60.4,45.8,21.8,19.8.HRMS(ESI):calcd for C20H19NO4S2:402.0828[M+H]+.Found:402.0847[M+H]+.IR vC＝O:1698,1658cm-1(vs).
example 8
A20 ml autoclave was charged with a stirrer, 0.5 mmol of 4-phenyl-N- (tosylmethyl) but-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of acetonitrile, and after stirring at 60 ℃ for 12 hours, the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 98%.
The structural characterization data of the resulting product are shown below:
1H NMR(500MHz,CDCl3)δ7.77(d,J＝8.3Hz,2H),7.44–7.28(m,5H),7.24–7.14(m,2H),6.34(s,1H),5.43(s,2H),3.78(s,2H),2.44(s,3H).13C NMR(126MHz,CDCl3)δ164.0,161.9,153.7,145.5,136.3,134.0,130.0,129.3,129.3,128.7,128.3,115.4,60.4,42.2,21.9.HRMS(ESI):calcd for C19H17NO4S2:388.0672[M+H]+.Found:388.0667[M+H]+.IR vC＝O:1698,1656cm-1(vs).
example 9
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-butyl-4-methylpent-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of dimethyl sulfoxide, and after stirring at 100 ℃ for 12 hours, the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release the unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 94%.
The structural characterization data of the resulting product are shown below:
1H NMR(500MHz,CDCl3)δ6.35(s,1H),4.07–3.85(m,2H),2.78–2.62(m,1H),1.59(dt,J＝15.3,7.6Hz,2H),1.36(dq,J＝14.8,7.4Hz,2H),1.26(d,J＝6.9Hz,6H),0.94(t,J＝7.4Hz,3H).13C NMR(126MHz,CDCl3)δ165.0,164.1,159.7,113.3,41.8,35.4,29.8,29.8,21.8,20.3,13.8.HRMS(ESI):calcd for C11H17NO2S:228.1053[M+H]+.Found:228.1051[M+H]+.IR vC＝O:1689,1655cm-1(vs).
example 10
A20 ml autoclave was charged with a stirrer, 0.5 mmol of N-cyclohexyl-4-methylpenta-2, 3-dienamide, 0.025 mmol of THPE-COS (j), and 1 ml of dimethyl sulfoxide, and after stirring at 100 ℃ for 12 hours, the heating and stirring were stopped, and the mixture was cooled to room temperature to slowly release the unreacted carbonyl sulfide. The reaction solution in the reaction kettle was dissolved in 2 ml of dichloromethane and transferred to a 50 ml round bottom single neck flask, the reaction kettle was flushed with (3 × 2 ml) dichloromethane, and the solvent was removed in vacuo to give the crude product. The crude product is separated and purified by column chromatography (developing solvent: petroleum ether/ethyl acetate 5: 1). The yield was 98%.
1H NMR(400MHz,CDCl3)δ6.30(s,1H),4.85(tt,J＝12.2,3.7Hz,1H),2.67(hept,J＝6.8Hz,1H),2.33(qd,J＝12.3,3.3Hz,2H),1.87–1.78(m,2H),1.63(dd,J＝7.7,3.6Hz,3H),1.45–1.27(m,3H),1.25(d,J＝6.9Hz,6H).13C NMR(101MHz,CDCl3)δ165.1,164.8,159.6,113.6,55.7,35.1,28.7,26.4,25.3,21.6.HRMS(ESI):calcd for C13H19NO2S:254.1209[M+H]+.Found:254.1213[M+H]+.IR vC＝O:1687,1651cm-1(vs).
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