WO2022135355A1 - 无机硫催化活化二氧化碳作为羰基化试剂的方法 - Google Patents
无机硫催化活化二氧化碳作为羰基化试剂的方法 Download PDFInfo
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- WO2022135355A1 WO2022135355A1 PCT/CN2021/139810 CN2021139810W WO2022135355A1 WO 2022135355 A1 WO2022135355 A1 WO 2022135355A1 CN 2021139810 W CN2021139810 W CN 2021139810W WO 2022135355 A1 WO2022135355 A1 WO 2022135355A1
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- WO
- WIPO (PCT)
- Prior art keywords
- unsubstituted
- substituted
- nmr
- group
- alkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 70
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 20
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 18
- 230000006315 carbonylation Effects 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000011593 sulfur Substances 0.000 title claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 10
- 230000003213 activating effect Effects 0.000 title abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 305
- 238000006243 chemical reaction Methods 0.000 claims description 147
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 45
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 40
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000012442 inert solvent Substances 0.000 claims description 30
- -1 NH 2 Inorganic materials 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 125000001072 heteroaryl group Chemical group 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 21
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 230000009471 action Effects 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 13
- 150000007530 organic bases Chemical class 0.000 claims description 13
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 12
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- SLYRGJDSFOCAAI-UHFFFAOYSA-N 1,3-thiazolidin-2-one Chemical class O=C1NCCS1 SLYRGJDSFOCAAI-UHFFFAOYSA-N 0.000 claims description 6
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 claims description 6
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 claims description 6
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical compound NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 239000012973 diazabicyclooctane Substances 0.000 claims description 6
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical class NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003672 ureas Chemical class 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical class O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 claims description 3
- MHBPJMUAIOKJNL-UHFFFAOYSA-N 1h-quinazoline-2-thione Chemical compound C1=CC=CC2=NC(S)=NC=C21 MHBPJMUAIOKJNL-UHFFFAOYSA-N 0.000 claims description 3
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 claims description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000001409 amidines Chemical class 0.000 claims description 3
- 150000002357 guanidines Chemical class 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000008624 imidazolidinones Chemical class 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- BXQNSPXDWSNUKE-UHFFFAOYSA-N 1,3-benzothiazole 1-oxide Chemical class C1=CC=C2S(=O)C=NC2=C1 BXQNSPXDWSNUKE-UHFFFAOYSA-N 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- UCSVJZQSZZAKLD-UHFFFAOYSA-N ethyl azide Chemical compound CCN=[N+]=[N-] UCSVJZQSZZAKLD-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 62
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 245
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 126
- 238000004440 column chromatography Methods 0.000 description 126
- 238000000926 separation method Methods 0.000 description 125
- 239000002904 solvent Substances 0.000 description 115
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 105
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 81
- 239000000741 silica gel Substances 0.000 description 81
- 229910002027 silica gel Inorganic materials 0.000 description 81
- 238000011068 loading method Methods 0.000 description 75
- 239000003208 petroleum Substances 0.000 description 63
- 238000012856 packing Methods 0.000 description 61
- 239000007787 solid Substances 0.000 description 61
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 54
- 239000002585 base Substances 0.000 description 49
- 238000012512 characterization method Methods 0.000 description 39
- 238000001914 filtration Methods 0.000 description 35
- 238000001035 drying Methods 0.000 description 34
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 21
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical class C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 description 18
- 239000012265 solid product Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000003480 eluent Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 238000010828 elution Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000003810 ethyl acetate extraction Methods 0.000 description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 3
- KEZZFJQCDUJFJY-UHFFFAOYSA-N 6-(trifluoromethyl)-3h-1,3-benzothiazol-2-one Chemical compound C1=C(C(F)(F)F)C=C2SC(O)=NC2=C1 KEZZFJQCDUJFJY-UHFFFAOYSA-N 0.000 description 3
- HECJMTPEVWQFCY-UHFFFAOYSA-N 6-bromo-3h-1,3-benzothiazol-2-one Chemical compound BrC1=CC=C2NC(=O)SC2=C1 HECJMTPEVWQFCY-UHFFFAOYSA-N 0.000 description 3
- PUQHEPFUBPHTCG-UHFFFAOYSA-N 6-chloro-3h-1,3-benzothiazol-2-one Chemical compound C1=C(Cl)C=C2SC(O)=NC2=C1 PUQHEPFUBPHTCG-UHFFFAOYSA-N 0.000 description 3
- NMPYQLRSABFZAG-UHFFFAOYSA-N 6-methoxy-3h-1,3-benzothiazol-2-one Chemical compound COC1=CC=C2NC(=O)SC2=C1 NMPYQLRSABFZAG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- NOVHYVKPKWACML-UHFFFAOYSA-N 5-chloro-3h-1,3-benzothiazol-2-one Chemical compound ClC1=CC=C2SC(O)=NC2=C1 NOVHYVKPKWACML-UHFFFAOYSA-N 0.000 description 2
- CHCYXBPFWCRKIT-UHFFFAOYSA-N 5-methyl-3h-1,3-benzothiazol-2-one Chemical compound CC1=CC=C2SC(=O)NC2=C1 CHCYXBPFWCRKIT-UHFFFAOYSA-N 0.000 description 2
- ARILQDNHZGKJBK-UHFFFAOYSA-N 5-phenyl-1,3-oxazolidin-2-one Chemical compound O1C(=O)NCC1C1=CC=CC=C1 ARILQDNHZGKJBK-UHFFFAOYSA-N 0.000 description 2
- ZJFQBNCCRYZGSL-UHFFFAOYSA-N 6-methyl-3h-1,3-benzothiazol-2-one Chemical compound CC1=CC=C2N=C(O)SC2=C1 ZJFQBNCCRYZGSL-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QIOZLISABUUKJY-UHFFFAOYSA-N Thiobenzamide Chemical compound NC(=S)C1=CC=CC=C1 QIOZLISABUUKJY-UHFFFAOYSA-N 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OJOCOYHQMZNMPK-ICFOKQHNSA-N (4Z)-4-benzylidene-1-butyl-3-thia-1-azaspiro[4.5]decan-2-one Chemical compound CCCCN(C1(CCCCC1)/C(\S1)=C/C2=CC=CC=C2)C1=O OJOCOYHQMZNMPK-ICFOKQHNSA-N 0.000 description 1
- OJOFMLDBXPDXLQ-SECBINFHSA-N (4r)-4-benzyl-1,3-oxazolidin-2-one Chemical compound C1OC(=O)N[C@@H]1CC1=CC=CC=C1 OJOFMLDBXPDXLQ-SECBINFHSA-N 0.000 description 1
- YBUPWRYTXGAWJX-RXMQYKEDSA-N (4s)-4-propan-2-yl-1,3-oxazolidin-2-one Chemical compound CC(C)[C@H]1COC(=O)N1 YBUPWRYTXGAWJX-RXMQYKEDSA-N 0.000 description 1
- TYAJTZCIKXEDQY-LGMDPLHJSA-N (5Z)-3-benzyl-5-benzylidene-4,4-dimethyl-1,3-thiazolidin-2-one Chemical compound CC(C)(/C(\S1)=C/C2=CC=CC=C2)N(CC2=CC=CC=C2)C1=O TYAJTZCIKXEDQY-LGMDPLHJSA-N 0.000 description 1
- CSLWGKVWROUDQS-RAXLEYEMSA-N (5Z)-3-butyl-4,4-dimethyl-5-(pyridin-3-ylmethylidene)-1,3-thiazolidin-2-one Chemical compound CCCCN(C(C)(C)/C(\S1)=C/C2=CC=CN=C2)C1=O CSLWGKVWROUDQS-RAXLEYEMSA-N 0.000 description 1
- MVXQWXQCTYINQM-BENRWUELSA-N (5Z)-3-butyl-4,4-dimethyl-5-(thiophen-2-ylmethylidene)-1,3-thiazolidin-2-one Chemical compound CCCCN(C(C)(C)/C(\S1)=C/C2=CC=CS2)C1=O MVXQWXQCTYINQM-BENRWUELSA-N 0.000 description 1
- CLYCTCJSZAWJON-QINSGFPZSA-N (5Z)-3-butyl-4,4-dimethyl-5-[(4-methylphenyl)methylidene]-1,3-thiazolidin-2-one Chemical compound CCCCN(C(C)(C)/C(\S1)=C/C2=CC=C(C)C=C2)C1=O CLYCTCJSZAWJON-QINSGFPZSA-N 0.000 description 1
- CALYGGNWGOSIHQ-KAMYIIQDSA-N (5Z)-3-butyl-5-[(4-chlorophenyl)methylidene]-4,4-dimethyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(C)(C)/C(\S1)=C/C(C=C2)=CC=C2Cl)C1=O CALYGGNWGOSIHQ-KAMYIIQDSA-N 0.000 description 1
- CKBDDWKSDTZEND-QINSGFPZSA-N (5Z)-3-butyl-5-[(4-methoxyphenyl)methylidene]-4,4-dimethyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(C)(C)/C(\S1)=C/C(C=C2)=CC=C2OC)C1=O CKBDDWKSDTZEND-QINSGFPZSA-N 0.000 description 1
- YJICWTLICMCHPZ-SILNSSARSA-N (5Z)-4-benzyl-5-benzylidene-3-butyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(CC1=CC=CC=C1)/C(\S1)=C/C2=CC=CC=C2)C1=O YJICWTLICMCHPZ-SILNSSARSA-N 0.000 description 1
- YXQFEHCIKYXFLM-KAMYIIQDSA-N (5Z)-5-[(4-bromophenyl)methylidene]-3-butyl-4,4-dimethyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(C)(C)/C(\S1)=C/C(C=C2)=CC=C2Br)C1=O YXQFEHCIKYXFLM-KAMYIIQDSA-N 0.000 description 1
- XTGGMEUMUWJEPV-PEZBUJJGSA-N (5Z)-5-benzylidene-3-butyl-4,4-diethyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(CC)(CC)/C(\S1)=C/C2=CC=CC=C2)C1=O XTGGMEUMUWJEPV-PEZBUJJGSA-N 0.000 description 1
- UXEFXPZOSVAYHK-OWBHPGMISA-N (5Z)-5-benzylidene-3-butyl-4,4-dimethyl-1,3-thiazolidin-2-one Chemical compound C(/C1=CC=CC=C1)=C/1\C(N(C(S\1)=O)CCCC)(C)C UXEFXPZOSVAYHK-OWBHPGMISA-N 0.000 description 1
- UDRJZLGDSJOYQJ-JXAWBTAJSA-N (5Z)-5-benzylidene-3-butyl-4-(4-chlorophenyl)-1,3-thiazolidin-2-one Chemical compound CCCCN(C(/C(\S1)=C/C2=CC=CC=C2)C(C=C2)=CC=C2Cl)C1=O UDRJZLGDSJOYQJ-JXAWBTAJSA-N 0.000 description 1
- LINBRUZFDHHMJP-SDXDJHTJSA-N (5Z)-5-benzylidene-3-butyl-4-phenyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(/C(\S1)=C/C2=CC=CC=C2)C2=CC=CC=C2)C1=O LINBRUZFDHHMJP-SDXDJHTJSA-N 0.000 description 1
- WTYRSYDMHSVZIG-SSZFMOIBSA-N (5Z)-5-benzylidene-3-butyl-4-propyl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(CCC)/C(\S1)=C/C2=CC=CC=C2)C1=O WTYRSYDMHSVZIG-SSZFMOIBSA-N 0.000 description 1
- LJYKWVBRYKGGHY-VBKFSLOCSA-N (5Z)-5-benzylidene-3-butyl-4-thiophen-3-yl-1,3-thiazolidin-2-one Chemical compound CCCCN(C(/C(\S1)=C/C2=CC=CC=C2)C2=CSC=C2)C1=O LJYKWVBRYKGGHY-VBKFSLOCSA-N 0.000 description 1
- KATLDYLSVYTLJB-NTMALXAHSA-N (5Z)-5-benzylidene-4,4-dimethyl-1,3-thiazolidin-2-one Chemical compound CC(C)(/C(\S1)=C/C2=CC=CC=C2)NC1=O KATLDYLSVYTLJB-NTMALXAHSA-N 0.000 description 1
- WIZXEPHCVRWWJI-RAXLEYEMSA-N (5Z)-5-benzylidene-4,4-dimethyl-3-propan-2-yl-1,3-thiazolidin-2-one Chemical compound CC(C)N(C(C)(C)/C(\S1)=C/C2=CC=CC=C2)C1=O WIZXEPHCVRWWJI-RAXLEYEMSA-N 0.000 description 1
- SQMGVTNHIAGTRV-QBFSEMIESA-N (5Z)-5-benzylidene-4,4-dimethyl-3-propyl-1,3-thiazolidin-2-one Chemical compound CCCN(C(C)(C)/C(\S1)=C/C2=CC=CC=C2)C1=O SQMGVTNHIAGTRV-QBFSEMIESA-N 0.000 description 1
- IDIFKESFDKLWHK-HYXAFXHYSA-N (z)-3-(5-bromofuran-2-yl)-2-cyanoprop-2-enethioamide Chemical compound NC(=S)C(\C#N)=C/C1=CC=C(Br)O1 IDIFKESFDKLWHK-HYXAFXHYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- OYELEBBISJGNHJ-UHFFFAOYSA-N 1,3-oxazinan-2-one Chemical compound O=C1NCCCO1 OYELEBBISJGNHJ-UHFFFAOYSA-N 0.000 description 1
- NSPYRFXQDUFQOM-UHFFFAOYSA-N 1-ethylimidazolidin-2-one Chemical compound CCN1CCNC1=O NSPYRFXQDUFQOM-UHFFFAOYSA-N 0.000 description 1
- COYPZADTXISTSJ-UHFFFAOYSA-N 1-methyl-1,3-diazinan-2-one Chemical compound CN1CCCNC1=O COYPZADTXISTSJ-UHFFFAOYSA-N 0.000 description 1
- VUGCBIWQHSRQBZ-UHFFFAOYSA-N 2-methylbut-3-yn-2-amine Chemical compound CC(C)(N)C#C VUGCBIWQHSRQBZ-UHFFFAOYSA-N 0.000 description 1
- VRKWIRFPHZKIJC-UHFFFAOYSA-N 3-benzyl-5-methylidene-1,3-thiazolidin-2-one Chemical compound O=C1SC(=C)CN1CC1=CC=CC=C1 VRKWIRFPHZKIJC-UHFFFAOYSA-N 0.000 description 1
- SYARCRAQWWGZKY-UHFFFAOYSA-N 4,4-dimethyl-1,3-oxazolidin-2-one Chemical compound CC1(C)COC(=O)N1 SYARCRAQWWGZKY-UHFFFAOYSA-N 0.000 description 1
- LLUBERROYPGDOF-UHFFFAOYSA-N 4,4-dimethyl-5-methylidene-1,3-thiazolidin-2-one Chemical compound CC(C)(C(S1)=C)NC1=O LLUBERROYPGDOF-UHFFFAOYSA-N 0.000 description 1
- MLAJDFOBMYBISF-UHFFFAOYSA-N 4,5-diphenylimidazolidin-2-one Chemical compound N1C(=O)NC(C=2C=CC=CC=2)C1C1=CC=CC=C1 MLAJDFOBMYBISF-UHFFFAOYSA-N 0.000 description 1
- CRHQYASHOICRND-UHFFFAOYSA-N 4-ethyl-1,3-oxazolidin-2-one Chemical compound CCC1COC(=O)N1 CRHQYASHOICRND-UHFFFAOYSA-N 0.000 description 1
- VAJFEOKPKHIPEN-UHFFFAOYSA-N 4-methyl-1,3-oxazolidin-2-one Chemical compound CC1COC(=O)N1 VAJFEOKPKHIPEN-UHFFFAOYSA-N 0.000 description 1
- MAIYZXCYLAJOFK-UHFFFAOYSA-N 4-methyl-3h-1,3-benzothiazol-2-one Chemical compound CC1=CC=CC2=C1N=C(O)S2 MAIYZXCYLAJOFK-UHFFFAOYSA-N 0.000 description 1
- DWEQVNFWAKJCEY-UHFFFAOYSA-N 4-methylimidazolidin-2-one Chemical compound CC1CNC(=O)N1 DWEQVNFWAKJCEY-UHFFFAOYSA-N 0.000 description 1
- QDMNNMIOWVJVLY-UHFFFAOYSA-N 4-phenyl-1,3-oxazolidin-2-one Chemical compound C1OC(=O)NC1C1=CC=CC=C1 QDMNNMIOWVJVLY-UHFFFAOYSA-N 0.000 description 1
- YHLVEHXOBBYATA-UHFFFAOYSA-N 5,5-dimethyl-1,3-diazinan-2-one Chemical compound CC1(C)CNC(=O)NC1 YHLVEHXOBBYATA-UHFFFAOYSA-N 0.000 description 1
- OGUQHFXVADNTBU-UHFFFAOYSA-N 5,5-dimethyl-1,3-oxazolidin-2-one Chemical compound CC1(C)CNC(=O)O1 OGUQHFXVADNTBU-UHFFFAOYSA-N 0.000 description 1
- BNWQDLHPYANRAV-UHFFFAOYSA-N 5-bromo-3h-1,3-benzothiazol-2-one Chemical compound BrC1=CC=C2SC(=O)NC2=C1 BNWQDLHPYANRAV-UHFFFAOYSA-N 0.000 description 1
- ZXZUZJTXCUZSPM-UHFFFAOYSA-N 5-fluoro-3h-1,3-benzothiazol-2-one Chemical compound FC1=CC=C2SC(=O)NC2=C1 ZXZUZJTXCUZSPM-UHFFFAOYSA-N 0.000 description 1
- STFOYVOEMLDYJL-UHFFFAOYSA-N 5-methoxy-3h-1,3-benzothiazol-2-one Chemical compound COC1=CC=C2SC(=O)NC2=C1 STFOYVOEMLDYJL-UHFFFAOYSA-N 0.000 description 1
- HBRXQSHUXIJOKV-UHFFFAOYSA-N 5-methyl-1,3-oxazolidin-2-one Chemical compound CC1CNC(=O)O1 HBRXQSHUXIJOKV-UHFFFAOYSA-N 0.000 description 1
- SFFGIOWQJIFEJE-UHFFFAOYSA-N 5-methylidene-1,3-thiazolidin-2-one Chemical compound C=C1CNC(=O)S1 SFFGIOWQJIFEJE-UHFFFAOYSA-N 0.000 description 1
- NXQJDVBMMRCKQG-UHFFFAOYSA-N 5-phenylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)NC1C1=CC=CC=C1 NXQJDVBMMRCKQG-UHFFFAOYSA-N 0.000 description 1
- CLYCLRFHPKKUBR-UHFFFAOYSA-N 6-amino-3h-1,3-benzothiazol-2-one Chemical compound NC1=CC=C2N=C(O)SC2=C1 CLYCLRFHPKKUBR-UHFFFAOYSA-N 0.000 description 1
- HCFZOCSVSDAYQF-UHFFFAOYSA-N 6-fluoro-3h-1,3-benzothiazol-2-one Chemical compound C1=C(F)C=C2SC(O)=NC2=C1 HCFZOCSVSDAYQF-UHFFFAOYSA-N 0.000 description 1
- MLYFRFPTIGFBDU-UHFFFAOYSA-N 7-chloro-3h-1,3-benzothiazol-2-one Chemical compound ClC1=CC=CC2=C1SC(=O)N2 MLYFRFPTIGFBDU-UHFFFAOYSA-N 0.000 description 1
- CPCWRGPJUDZREC-UHFFFAOYSA-N 7-methyl-3h-1,3-benzothiazol-2-one Chemical compound CC1=CC=CC2=C1SC(=O)N2 CPCWRGPJUDZREC-UHFFFAOYSA-N 0.000 description 1
- NGVSIJIAVLPKNO-UHFFFAOYSA-N CS(C1=CC=CC(S2)=C1NC2=O)(=O)=O Chemical compound CS(C1=CC=CC(S2)=C1NC2=O)(=O)=O NGVSIJIAVLPKNO-UHFFFAOYSA-N 0.000 description 1
- ISSDPIIIRFZTAU-UHFFFAOYSA-N N-(3-cyano-2-thienyl)acetamide Chemical compound CC(=O)NC=1SC=CC=1C#N ISSDPIIIRFZTAU-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- 150000008641 benzimidazolones Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VKGDINDYGIBXNA-UHFFFAOYSA-N methyl 2-oxo-3h-1,3-benzothiazole-5-carboxylate Chemical compound COC(=O)C1=CC=C2SC(=O)NC2=C1 VKGDINDYGIBXNA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles 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 in position 2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
- C07D233/34—Ethylene-urea
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
- C07D235/26—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D239/08—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms directly attached in position 2
- C07D239/10—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D277/14—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D277/34—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
Definitions
- the invention relates to the field of organic synthesis, in particular, the invention provides a method for catalyzing and activating carbon dioxide as a carbonylation reagent with inorganic sulfur.
- CO 2 is an ideal carbon source component because of its non-toxic, rich content and recyclable characteristics. CO 2 is not only the waste gas emitted by fossil fuels, but also a cheap, non-toxic, non-flammable, and renewable energy source. C1 resources. From the perspective of green chemistry, due to its unique carbonyl structure, chemically converting it as a carbonylation reagent into high-added fine chemicals is not only an effective way to reduce atmospheric CO2 concentration, but also an important strategy for sustainable energy development . Therefore, it is of great significance to utilize CO2 in a sustainable manner to synthesize high value-added chemical products.
- CO2 is used to replace carbon source gases such as CO and phosgene, which are highly toxic and have hidden dangers to user safety.
- CO2 is used to replace carbon source gases such as CO and phosgene, which are highly toxic and have hidden dangers to user safety.
- the carbonylation reaction of CH bond with CO has made remarkable progress due to its high atomicity and high economy.
- the object of the present invention is to develop a method for preparing carbonyl compounds using CO2 as carbonyl source.
- the invention provides a method for preparing carbonyl compounds by using CO 2 as a carbonylation reagent, and in the method, H 2 S is used as a catalyst.
- the present invention also provides a method for preparing carbonyl compounds by using H 2 S to participate in CO 2 as a carbonylation reagent.
- H 2 S not only serves as a catalyst to catalyze the carbonylation reaction, but also participates in the reaction as a reactant. reaction.
- the present invention also provides a method for preparing carbonyl compounds by using H 2 S to participate in CO 2 as a carbonylation reagent.
- H 2 S not only acts as a catalyst to catalyze the carbonylation reaction, but also acts as a reducing agent to participate in the carbonylation reaction. reaction.
- the first aspect of the present invention provides a method for preparing carbonyl compounds with carbon dioxide as a carbonylation reagent, characterized in that the method is carried out in the presence of H 2 S and an optional base.
- the method comprises step (i) or step (ii):
- R 1 and R 2 are each independently selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl (such as substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 6 alkyl C 8 alkyl), substituted or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C 2 -C 6 alkynyl; or said R 1 and R 2 together constitute a group selected from the group consisting of substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted 5-12 Yuan Heteroaryl;
- Ring A is a substituted or unsubstituted C 6 -C 10 aryl group, or a substituted or unsubstituted 5-12-membered heteroaryl group;
- X and Y are each independently selected from the group consisting of halogen, CN, SH, OH, NH2 , NHR, NO2 ;
- R is selected from the group consisting of H, substituted or unsubstituted C 1 -C 12 alkyl (eg substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 8 alkyl), substituted or unsubstituted C 1 -C 8 alkyl or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted C 1 -C 6 alkoxy, SO 2 CH 3 , or unsubstituted or substituted with 1-4 substituents selected from the group consisting of Phenyl: halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 ;
- R 3 is one or more groups on ring A selected from the group consisting of H, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, NH 2 , NO 2 , SO 2 CH 3 , or phenyl unsubstituted or substituted with 1-4 substituents selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 ; or R 5 and R 6 together form -(CH 2 ) n -, wherein n is selected from 2, 3, 4, 5 or 6;
- two substituents adjacent to or attached to the same carbon atom together form -(CH 2 ) n -, wherein n is selected from 2, 3, 4, 5 or 6.
- the base is an organic base; preferably, the base is selected from the following group: C 1 -C 12 tertiary amines, C 1 -C 12 secondary amines, C 1 -C 12 amines 12 primary amines, C 2 -C 12 amidines, C 2 -C 12 guanidines, C 3 -C 12 pyridines, C 3 -C 12 imidazoles; preferably, the base is selected from the following group: DBU , TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or a combination thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0-5 (eg 1:0.1-5).
- the method comprises steps (a), (b), (c), (d), (e), (f) or (g);
- R 4 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted phenyl;
- R 5 , R 6 and R 7 are each independently selected from the group consisting of H, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, phenyl, 5- 12-membered heteroaryl, 5-12-membered saturated or partially unsaturated heterocycle, and said phenyl, heteroaryl or heterocycle is unsubstituted or substituted by 1-4 substituents selected from the group below : halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 ; or R 5 and R 6 together constitute - (CH 2 ) n -, wherein n is selected from 2, 3, 4, 5 or 6;
- R 8 is one or more substituents on the benzene ring selected from the group consisting of H, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl , NO 2 , SO 2 CH 3 , or phenyl unsubstituted or substituted with 1-4 substituents selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 ;
- M is a substituted or unsubstituted C 2 -C 4 alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5-12-membered heteroaryl group, wherein the definition of substitution is as described in claim 2 ;
- R 9 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 12 alkyl (such as substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 8 alkyl), Substituted or unsubstituted C 3 -C 8 cycloalkyl, phenyl, 5-12-membered heteroaryl, 5-12-membered saturated or partially unsaturated heterocycle, and said phenyl, heteroaryl or heterocycle
- the ring is unsubstituted or substituted with 1-4 substituents selected from the group consisting of halogen, C1 - C6 alkyl, C1 - C6 haloalkyl, C1 - C6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 .
- the inert solvent is selected from the following group: NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH 2 Cl 2 , CHCl 3 , CC1 4 , toluene, acetic acid Ethyl ester, supercritical CO2 , or a combination thereof.
- the molar ratio of the reaction substrate to CO 2 is 1:1-100.
- CO 2 is continuously passed into the reactor, and the pressure of the CO 2 in the reactor is 0.1-12 MPa.
- the molar ratio of the reaction substrate to the hydrogen sulfide is 1:0.05-20.
- H 2 S is continuously passed into the reactor, and the pressure of the H 2 S in the reactor is 0.05-1.5 Mpa.
- the reaction temperature is room temperature to 150°C.
- the present invention provides a method for preparing carbonyl compounds with carbon dioxide as a carbonylation reagent, and the method is carried out in the presence of H 2 S.
- the H 2 S can be used as a pure catalyst, or can be used as a reactant at the same time of catalysis, thereby further reacting with the reaction substrate or generating an intermediate.
- the method comprises step (i) or step (ii):
- the compound of formula Ia in an inert solvent, in the presence of a base and an inorganic sulfur reagent, react with a compound of formula Ia with CO to obtain a compound of formula I (wherein, the compound of formula Ia can be a mixture of R 1 -X and R 2 -Y, It can also be a compound with two reactive functional groups of X and Y formed by R 1 -X and R 2 Y together);
- the step is carried out in the presence of a base, which may preferably be an organic base.
- the base is selected from the group consisting of C 1 -C 12 tertiary amines, C 1 -C 12 secondary amines, C 1 -C 12 primary amines, C 2 -C 12 amidines, C 2 -C 12 guanidines, C 3 -C 12 pyridines, C 3 -C 12 imidazoles, DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or their combination; preferably, the molar ratio of the reaction substrate to the base is 1:0.1-5.
- common inert solvents that do not affect the reaction can be used, and preferred solvents include: NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH 2 Cl 2 , CHCl 3 , CC1 4. Toluene, ethyl acetate, or a combination thereof.
- a preferred embodiment is to use supercritical CO 2 as the solvent.
- the molar ratio of reaction substrate to CO 2 is not particularly limited, and can be 1:1-100.
- the pressure of the CO 2 in the reactor is 0.1-12MPa; for example, 0.2-10MPa, 0.5-10MPa, 0.6-10MPa, 0.8-8MPa, or 1MPa, 2MPa, 3MPa, 4MPa, 5MPa or 6MPa.
- the molar ratio of the reaction substrate to the inorganic sulfur is preferably 1:0.05-20.
- H 2 S is continuously passed into the reactor, and the preferred pressure of the H 2 S in the reactor is 0.08-1.5Mpa, such as 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa.
- 0.08-1.5Mpa such as 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa.
- the temperature of the reaction is not particularly limited, preferably at room temperature (usually 0-40°C) to 150°C, such as 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C.
- the base is preferably DABCO, DBU, TBD, or Et3N ; more preferably DBU or Et3N .
- the solvent is preferably NMP or DMF, and the amount of the base is preferably 1-3 equivalents.
- the reactant used is an organic base, or can act as a solvent, the reaction can also be carried out without a solvent, or in the absence of an organic base.
- the pressure ratio of CO 2 and H 2 S is (1-8):(0.1-0.8).
- the method in the step (a), is reacted at 70-100°C, preferably at 80-90°C.
- the pressure of the CO 2 in the reactor is 2-5MPa, and the pressure of the H 2 S in the reactor 0.3-0.5Mpa.
- the base is preferably DBU or Et 3 N; the solvent is preferably NMP, Or NMP/H 2 O; the amount of base is preferably 2-5 equivalents, preferably 2-4 equivalents.
- the pressure ratio of CO 2 and H 2 S is (1-8):(0.5-1.5), preferably 2-4:1.
- the above reaction can be carried out under CuI catalysis.
- the method in another preferred embodiment, is reacted at 70-100°C, preferably at 80-90°C.
- the pressure of the CO 2 in the reactor in another preferred example, is 2-5MPa, and the pressure of the H 2 S in the reactor 0.5-1Mpa.
- R is selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl ;
- R 5 , R 6 and R 7 are each independently selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, or benzene unsubstituted or substituted with 1-3 substituents selected from the group Base: halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 ; or R 5 and R 6 form together -(CH 2 ) n -, wherein n is selected from 2, 3, 4, 5 or 6;
- the base is preferably DBU, Et 3 N, TBD or K 2 CO 3 , more preferably DBU, Et 3 N or TBD;
- the solvent is preferably CH 3 OH, DMF, NMP or DMSO, preferably DMSO; the amount of base is preferably 0.5-1.5 equivalents, preferably 0.6-1.2 equivalents.
- the pressure ratio of CO 2 and H 2 S is 1:(0.2-1.5), preferably 1:0.8-1.2.
- the method in the step (c), is reacted at 20-60°C, preferably at 20-40°C.
- the pressure of the CO 2 in the reactor is 0.8-1.2MPa
- the pressure of the H 2 S in the reactor is 0.8-1.2MPa.
- the pressure is 0.5-1 MPa (preferably 0.8-1 MPa).
- the base is preferably DBU; the solvent is preferably DMF, and the amount of the base is preferably 0.2-2 equivalents, preferably 0.8-2 equivalents.
- the pressure ratio of CO 2 and H 2 S is (2-5):(0.2-1.2), preferably 3-10:1.
- the method in another preferred embodiment, is reacted at 40-60°C, preferably at 45-55°C.
- the pressure of the CO 2 in the reactor is 2-5MPa
- the pressure of the H 2 S in the reactor is 0.4-1Mpa.
- the base is preferably DBU, TMG, or Et 3 N;
- the solvent is preferably NMP, CH 3 OH, 1,4-dioxane, DMSO, more preferably NMP;
- the amount of base is preferably 0.2-2 equivalents, more preferably 0.4-1.2 equivalents.
- the pressure ratio of CO 2 and H 2 S is (1-5):(0.1-1.2).
- the method in the step (e), is reacted at 25-100°C, preferably at 80-90°C.
- the pressure of the CO 2 in the reactor is 1-5MPa, and the pressure of the H 2 S in the reactor 0.2-1.0Mpa.
- U is O, S or NR
- M is a substituted or unsubstituted C 2 -C 4 alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5-12-membered heteroaryl group, wherein substitution is as defined above.
- the base is preferably DABCO, DBU, TMG or Et 3 N, preferably DBU or TMG;
- the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP;
- the amount of base is preferably 0.1-2 equivalent.
- the reactant used is an organic base, or can act as a solvent, the reaction can also be carried out without a solvent, or in the absence of an organic base.
- the pressure ratio of CO 2 and H 2 S is (1-65):1.
- the method in another preferred embodiment, is reacted at 20-60°C, preferably at 30-50°C.
- the pressure of the CO 2 in the reactor is 1-5MPa, and the pressure of the H 2 S in the reactor 0.05-1.5Mpa.
- the base is preferably DBU, TBD, DIPEA or Et 3 N, preferably DBU, DIPEA or Et 3 N;
- the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP; the amount of alkali is preferably It is 0.1-1 equivalent, more preferably 0.2-0.6 equivalent.
- the reactant used is an organic base, or can act as a solvent, the reaction can also be carried out without a solvent, or in the absence of an organic base.
- the pressure ratio of CO 2 and H 2 S is (3-35):1, preferably (3-25):1.
- the method in the step (f), is reacted at 80-120°C.
- the pressure of the CO 2 in the reactor is 1-5MPa, and the pressure of the H 2 S in the reactor 0.2-1Mpa.
- the base is preferably DABCO, DBU, TMG, TBD or Et 3 N, preferably DBU, Et 3 N, or TMG;
- the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP or DMF;
- the amount of base is preferably 0.1-2 equivalents.
- the reaction when the reactant used is an organic base, or can act as a solvent, the reaction can also be carried out without a solvent, or in the absence of an organic base. In addition, it can also be carried out in the absence of a solvent, provided that the pressure of CO and the reaction temperature are suitable for the formation of supercritical carbon dioxide.
- the pressure ratio of CO 2 and H 2 S is (3-25):1.
- the method in the step (f), is reacted at 20-60°C, preferably at 30-50°C.
- the pressure of the CO 2 in the reactor is 3-12MPa, and the pressure of the H 2 S in the reactor 0.2-1.0Mpa.
- R 9 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 12 alkyl (such as substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 8 alkyl), Substituted or unsubstituted C 3 -C 8 cycloalkyl, phenyl, 5-12-membered heteroaryl, 5-12-membered saturated or partially unsaturated heterocycle, and said phenyl, heteroaryl or heterocycle
- the ring is unsubstituted or substituted with 1-4 substituents selected from the group consisting of halogen, C1 - C6 alkyl, C1 - C6 haloalkyl, C1 - C6 alkoxy, OH, NO 2 , NH 2 , SO 2 CH 3 ;
- the base is preferably DBU, TMG or Et 3 N, preferably DBU;
- the solvent is preferably NMP, DMF or methanol, preferably NMP;
- the amount of base is preferably 0.1-2 equivalents, but due to the organic substrate used Amines can be used as bases or solvents, so the reactions described can also be carried out in the absence of organic bases, and/or in the absence of solvents.
- the pressure ratio of CO 2 and H 2 S is (5-20):1.
- the method in the step (f), is reacted at 90-130°C, preferably at 30-50°C.
- the pressure of the CO 2 in the reactor is 5-20MPa, and the pressure of the H 2 S in the reactor is 0.5-2Mpa.
- Type 1 Inorganic sulfur acts both as a raw material and as a catalyst
- the reaction method is as follows:
- reaction kettle was cooled to room temperature, the gas in the reaction kettle was slowly exhausted, the reaction kettle was opened, the reaction solution was transferred to a 250ml separatory funnel, the reaction solution was extracted with ethyl acetate, and anhydrous sulfuric acid was used to extract the reaction solution. The organic phase was dried over magnesium. The product was isolated by column chromatography.
- the raw materials are 1mmol of o-iodoaniline; the solvent is 2ml; the CuI is 0.2mmol; the reaction is 24h.
- the reaction method is as follows:
- reaction kettle was cooled to room temperature, the gas in the reaction kettle was slowly exhausted, the reaction kettle was opened, the reaction solution was transferred to a 250ml separatory funnel, the reaction solution was extracted with ethyl acetate, and anhydrous sulfuric acid was used to extract the reaction solution.
- the organic phase was dried over magnesium and the product was isolated by column chromatography.
- the raw materials are 1mmol of o-iodonitrobenzene; the solvent is 2ml; the CuI is 0.2mmol; the reaction is 24h.
- the raw materials are all 2mmol; 2-methyl-3-butyn-2-amine; the solvent is 2ml; the reaction is 24 hours.
- the raw materials are 2mmol of o-phenylenediamine; the solvent is 1ml.
- the solid product 265mg was obtained by filtration and drying, and the isolated yield was 89.5%.
- the raw materials used are 2mmol o-aminothiophenol; the solvent is 2mL; the reaction time is 24h.
- the raw material used is 0.5mmol disulfide (dimer of o-aminothiophenol); the solvent is 2mL; the molar ratio in the table is the molar ratio of disulfide:DBU; the reaction time is 12h.
- the raw materials are all 2mmol ethylenediamine; the solvent is 2ml NMP.
- ethylenediamine was used as the base and NMP was added as the solvent.
- reaction results are as follows:
- a magnetron was put into a 10 mL stainless steel autoclave, and 1 mmol of anthranilate derivatives, an appropriate amount of H 2 S and 2 ml of solvent were added in sequence, and the reaction kettle was tightened.
- the reaction kettle was filled with carbon dioxide at the specified pressure, and the reaction was stirred for 24 h, the reaction was stopped, and the reaction was cooled.
- the gas in the reactor was slowly exhausted, the reactor was unscrewed, extracted with ethyl acetate and saturated brine, the organic phases were combined, and the crude product was obtained by distillation under reduced pressure.
- the pure target product was obtained by column chromatography with petroleum ether and ethyl acetate.
- the raw materials are 1 mmol o-aminobenzonitrile; the solvent is 2 ml; the molar ratio is the molar ratio of the raw materials and DBU; the reaction is 24h.
- the raw materials are 2 mmol benzylamine; the solvent is 1 ml, NR: no reaction.
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Abstract
本发明提供了一种无机硫催化活化二氧化碳作为羰基化试剂的方法，该方法中二氧化碳在H 2S和碱的存在下能够替代有毒有害羰基化试剂合成含羰基精细化学品。所述的方法具有较高的原子经济性，能够减少副产物的产生。
Description
本发明涉及有机合成领域，具体地，本发明提供了一种无机硫催化活化二氧化碳作为羰基化试剂的方法。
绿色和可持续化有机合成新方法的发展受到人们越来越多的关注，绿色无公害和可以循环利用的基本构成要素在这类方法中发挥着关键的作用。其中CO
2因其具备无毒、含量丰富、可循环利用的特点而作为理想的碳源组分，CO
2既是化石燃料排放的废气，又是一种廉价、无毒、不易燃、可再生的C1资源。从绿色化学的角度来看，由于其独特的羰基结构，将其作为羰基化试剂化学转化为高附加的精细化学品，既是大气CO
2浓度降低的有效途径，又是能源可持续发展的重要战略。因此，以可持续的方式利用CO
2合成高附加值的化学产品具有重要的意义。
在CO
2的各种有机转化中，利用CO
2进行羰基化合成含有羰基的杂环结构已引起越来越多的关注。采用CO
2取代毒性大、对使用者安全有隐患的CO和光气等碳源气体。近年来，C-H键与CO
2的羰基化反应因其高原子性和高经济性等特点而取得了显著的进展，更为重要的是，由于CO
2的碳价比CO高，可以理想化认为是CO与氧化剂(CO
2＝CO+[O])的结合，因而可以满足中性条件下在氧化还原反应中实现此类羰基化，从而实现降低生产成本、降低重金属残留、解决安全隐患等目的。
综上所述，本领域迫切需要开发一种采用CO
2作为碳源制备羰基化合物的方法。
发明内容
本发明的目的是开发一种采用CO
2作为羰基源制备羰基化合物的方法。
本发明提供了一种采用CO
2作为羰基化试剂制备羰基化合物的方法，所述的方法中采用H
2S作为催化剂。
本发明还提供了一种采用H
2S参与CO
2作为羰基化试剂制备羰基化合物反应的方法，所述的方法中，H
2S既作为催化剂催化所述的羰基化反应，也作为反应物参与反应。
本发明还提供了一种采用H
2S参与CO
2作为羰基化试剂制备羰基化合物反应的方法，所述的方法中，H
2S即作为催化剂催化所述的羰基化反应，也作为还原剂参与反应。
本发明的第一方面，提供了一种二氧化碳作为羰基化试剂制备羰基化合物的方法，其特征在于，所述的方法在H
2S和任选的碱存在下进行。
在另一优选例中，所述的方法包括步骤(i)或步骤(ii)：
(i)在任选的惰性溶剂中，在任选的碱和无机硫试剂存在下，用式Ia化合物与CO
2反应，得到式I化合物；
(ii)在任选的惰性溶剂中，在碱和无机硫试剂存在下，用式IIa化合物与CO
2反应，得到式II化合物；
其中，R
1和R
2各自独立地选自下组：取代或未取代的C
1-C
12烷基(如取代或未取代的C
1-C
6烷基、取代或未取代的C
1-C
8烷基)、取代或未取代的C
3-C
8环烷基、取代或未取代的C
2-C
6烯基、取代或未取代的C
2-C
6炔基；或所述的R
1和R
2共同构成选自下组的基团：取代或未取代的C
1-C
6亚烷基、取代或未取代的C
6-C
10芳基、取代或未取代的5-12元杂芳基；
A环为取代或未取代的C
6-C
10芳基，或取代或未取代的5-12元杂芳基；
X和Y各自独立地选自下组：卤素、CN、SH、OH、NH
2、NHR、NO
2；
U和V各自独立地选自下组：NR、S、O、-C(＝S)NH；
R选自下组：H、取代或未取代的C
1-C
12烷基(如取代或未取代的C
1-C
6烷基、取代或未取代的C
1-C
8烷基)、取代或未取代的C
3-C
8环烷基、取代或未取代的C
1-C
6烷氧基、SO
2CH
3，或者未取代或被1-4个选自下组的取代基取代的苯基：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；
R
3为一个或多个位于A环上的选自下组的基团：H、卤素、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6卤代烷基、NH
2、NO
2、SO
2CH
3，或未取代或被1-4个选自下组的取代基取代的苯基：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；或R
5和R
6共同构成-(CH
2)
n-，其中，n选自2、3、4、5或6；
且所述的取代指基团上的一个或多个氢原子被选自下组的取代基替换：卤素、氧原子(即＝O)、C
1-C
6烷基、C
2-C
6烯基、C
2-C
6炔基、C
1-C
6烷氧基、C
1-C
6卤代烷基、NO
2、SO
2CH
3，苯基、5-12元杂芳基、3-8元环烷基、5-12元饱和或部分不饱和的杂环；其中，所述的苯基、杂芳基、环烷基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；
或者，相邻或者连接于同一个碳原子上的两个取代基共同构成-(CH
2)
n-，其中，n选自2、3、4、5或6。
在另一优选例中，所述的碱为有机碱；较佳地，所述的碱选自下组：C
1-C
12叔胺类、C
1-C
12仲胺类、C
1-C
12伯胺类、C
2-C
12脒类、C
2-C
12胍类、C
3-C
12吡啶类、C
3-C
12咪唑类；优选地，所述的碱选自下组：DBU，TBD，MTBD，DBN，TMG，DABCO、乙二胺、三乙胺、DIPEA、DMAP、吡啶，或其组合；优选地，所述反应底物与所述碱的摩尔比为1:0-5(如1:0.1-5)。
在另一优选例中，所述的方法包括步骤(a)、(b)、(c)、(d)、(e)、(f)或(g)；
(a)在任选的惰性溶剂中，在碱存在下，用邻碘苯胺与CO
2和硫化氢反应，得到苯并噻唑酮类衍生物；
(b)在任选的惰性溶剂中，在碱存在下，邻硝基碘苯与CO
2和硫化氢反应合成苯并噻唑酮类衍生物；
(c)在任选的惰性溶剂中，在任选的碱存在下，用炔丙胺衍生物与CO
2和硫化氢反应，合成噻唑烷-2-酮类衍生物；
其中，R
4选自下组：H、取代或未取代的C
1-C
12烷基、取代或未取代的C
3-C
8环烷基、取代或未取代的苯基；
R
5、R
6和R
7各自独立地选自下组：H、取代或未取代的C
1-C
12烷基、取代或未取代的C
3-C
8环烷基、苯基、5-12元杂芳基、5-12元饱和或部分不饱和的杂环，且所述的苯基、杂芳基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；或R
5和R
6共同构成-(CH
2)
n-，其中，n选自2、3、4、5或6；
(d)在任选的惰性溶剂中，在碱存在下，用邻胺基苯腈与CO
2和硫化氢反应，合成硫代喹唑啉二酮类衍生物；
其中，R
8为位于苯环上的一个或多个选自下组的取代基：H、卤素、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6卤代烷基、NO
2、SO
2CH
3，或未取代或被1-4个选自下组的取代基取代的苯基：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；
(e)在任选的惰性溶剂中，在碱存在下，用芳香邻胺基二硫化物与CO
2在硫化氢的作用下反应，合成苯并噻唑酮类衍生物；
(f)在任选的惰性溶剂中，在任选的碱存在下，用二胺、醇胺或巯基胺与CO
2在硫化氢的作用下反应合成咪唑烷酮类衍生物、恶唑烷酮类衍生物或噻唑烷酮类衍生 物；其中，U为O、S或NR；
M为取代或未取代的C
2-C
4亚烷基、取代或未取代的苯基、或取代或未取代的5-12元杂芳基，其中，取代的定义如权利要求2中所述；
(g)在任选的惰性溶剂中，在任选的碱存在下，用胺与CO
2在硫化氢的作用下反应，合成脲类衍生物；
R
9选自下组：H、取代或未取代的C
1-C
12烷基(如取代或未取代的C
1-C
6烷基、取代或未取代的C
1-C
8烷基)、取代或未取代的C
3-C
8环烷基、苯基、5-12元杂芳基、5-12元饱和或部分不饱和的杂环，且所述的苯基、杂芳基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3。
在另一优选例中，所述的惰性溶剂选自下组：NMP、DMF、THF、DMSO、1,4-二氧六环、HMPA、CH
2Cl
2、CHCl
3、CC1
4、甲苯，乙酸乙酯，超临界CO
2，或其组合。
在另一优选例中，所述的反应中，反应底物与CO
2的摩尔比为1:1-100。
在另一优选例中，所述的反应过程中，CO
2持续通入反应器，且所述的CO
2在反应器中的压力为0.1-12MPa。
在另一优选例中，所述的反应中，反应底物与所述硫化氢的摩尔比为1:0.05-20。
在另一优选例中，所述的反应过程中，H
2S持续通入反应器，且所述的H
2S在反应器中的压力为0.05-1.5Mpa。
在另一优选例中，所述的反应中，反应温度为室温～150℃。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
本发明人经过长期而深入的研究，意外地发现，采用H
2S作为催化剂，可以高效率地催化CO
2作为羰基源与一系列底物反应制备羰基化化合物。这一羰基化反应可以单独发生，也可以与其他CO
2或H
2S参与的反应共同发生从而制备得到一系列产物，在精细化学合成领域具有潜在的应用价值。基于上述发现，发明人完成了本发明。
CO
2作为羰基化试剂的合成方法
本发明提供了一种二氧化碳作为羰基化试剂制备羰基化合物的方法，所述的方法在H
2S存在下进行。所述的H
2S可以作为单纯的催化剂，也可以在催化同时作为反应物，从而与反应底物发生进一步反应或者生成中间体。
具体地，所述的方法包括步骤(i)或步骤(ii)：
(i)在惰性溶剂中，在碱和无机硫试剂存在下，用式Ia化合物与CO
2反应，得到式I化合物(其中，式Ia化合物可以为R
1-X和R
2-Y的混合物，也可以是R
1-X和R
2Y共同形成的具有X和Y两个反应性官能团的化合物)；
(ii)在惰性溶剂中，在碱和无机硫试剂存在下，用式IIa化合物与CO
2反应，得到式II化合物；
其中，各个基团的定义如上文中所述。
在本发明的优选实施方式中，所述的步骤在碱存在下进行，所述的碱优选可以是有机碱。较佳地，所述的碱选自下组：C
1-C
12叔胺类、C
1-C
12仲胺类、C
1-C
12伯胺类、C
2-C
12脒类、C
2-C
12胍类、C
3-C
12吡啶类、C
3-C
12咪唑类、DBU，TBD，MTBD，DBN，TMG，DABCO、乙二胺、三乙胺、DIPEA、DMAP、吡啶，或其组合；优选地，所述反应底物与所述碱的摩尔比为1:0.1-5。
所述的方法中，可以采用常见的不影响反应的惰性溶剂，优选的溶剂包括：NMP、DMF、THF、DMSO、1,4-二氧六环、HMPA、CH
2Cl
2、CHCl
3、CC1
4、甲苯，乙酸乙酯，或其组合。特别地，由于本发明方法中需要使用二氧化碳气流，因此一种优选的实施方式是使用超临界CO
2作为溶剂。
所述的方法中，反应底物与CO
2的摩尔比没有特别限制，可以为1:1-100。
所述的反应过程中，CO
2持续通入反应器，优选的反应方法中，所述的CO
2在反应器中的压力为0.1-12MPa；如0.2-10MPa，0.5-10MPa，0.6-10MPa，0.8-8MPa，或1MPa、2MPa、3MPa、4MPa、5MPa或6MPa。
所述的反应中，反应底物与所述无机硫的摩尔比优选为1:0.05-20。
所述的反应过程中，H
2S持续通入反应器，且优选的所述的H
2S在反应器中的压力为0.08-1.5Mpa，如0.1MPa、0.2MPa、0.3MPa、0.4MPa、0.5MPa、0.6MPa、0.7MPa、0.8MPa、0.9MPa、1MPa、1.1MPa、1.2MPa、1.3MPa、1.4MPa。
所述的反应的温度没有特别限制，优选地在室温(通常为0-40℃)～150℃下进行，如20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃。
上述反应可以用于制备一系列具有特征结构的化合物，例如，可以通过步骤(a)、(b)、(c)、(d)、(e)、(f)制备具有对应结构单元的化合物；
(a)邻碘苯胺与CO
2和硫化氢反应，合成苯并噻唑酮类衍生物
在惰性溶剂中，在碱存在下，用邻碘苯胺与CO
2和硫化氢反应，得到苯并噻唑酮类衍生物。在上述反应中，碱优选为DABCO、DBU、TBD，或Et
3N；更优选为DBU或Et
3N。溶剂优选为NMP或DMF，碱用量优选为1-3当量。特别地，当所使用的反 应物为有机碱，或者可以作为溶剂的情况下，所述的反应也可以在无溶剂，或者不存在有机碱的情况下进行。
在另一优选例中，在所述步骤(a)中，CO
2和H
2S的压强比为(1-8):(0.1-0.8)。
在另一优选例中，在所述步骤(a)中，所述的方法在70-100℃下反应，优选在80-90℃下反应。
在另一优选例中，在所述步骤(a)中，所述的方法中，所述的CO
2在反应器中的压力为2-5MPa，所述的H
2S在反应器中的压力为0.3-0.5Mpa。
(b)邻硝基碘苯与CO
2和硫化氢反应，合成苯并噻唑酮类衍生物
在惰性溶剂中，在碱存在下，邻硝基碘苯与CO
2和硫化氢反应合成苯并噻唑酮类衍生物；在上述反应中，碱优选为DBU或Et
3N；溶剂优选为NMP、或NMP/H
2O；碱用量优选为2-5当量，优选为2-4当量。
在另一优选例中，在所述步骤(b)中，CO
2和H
2S的压强比为(1-8):(0.5-1.5)，较佳地为2-4:1。
在另一优选例中，上述的反应可以在CuI催化下进行。
在另一优选例中，在所述步骤(b)中，所述的方法在70-100℃下反应，优选在80-90℃下反应。在另一优选例中，在所述步骤(a)中，所述的方法中，所述的CO
2在反应器中的压力为2-5MPa，所述的H
2S在反应器中的压力为0.5-1Mpa。
(c)炔丙胺与CO
2和硫化氢反应合成噻唑烷-2-酮类衍生物
在惰性溶剂中，在碱存在下，用炔丙胺衍生物与CO
2和硫化氢反应，合成噻唑烷-2-酮类衍生物；
其中，R
4选自下组：H、取代或未取代的C
1-C
6烷基；
R
5、R
6和R
7各自独立地选自下组：H、取代或未取代的C
1-C
6烷基、或未取代或被1-3个选自下组的取代基取代的苯基：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；或R
5和R
6共同构成-(CH
2)
n-，其中，n选自2、3、4、5或6；
在上述反应中，碱优选为DBU、Et
3N、TBD或K
2CO
3，更佳地为DBU、Et
3N或TBD；溶剂优选为CH
3OH、DMF、NMP或DMSO，较佳地为DMSO；碱用量优选为0.5-1.5当量，优选为0.6-1.2当量。
在另一优选例中，在所述步骤(c)中，CO
2和H
2S的压强比为1:(0.2-1.5)，较佳地为1：0.8-1.2。
在另一优选例中，在所述步骤(c)中，所述的方法在20-60℃下反应，优选在20- 40℃下反应。
在另一优选例中，在所述步骤(c)中，所述的方法中，所述的CO
2在反应器中的压力为0.8-1.2MPa，所述的H
2S在反应器中的压力为0.5-1Mpa(优选为0.8-1MPa)。
(d)邻胺基苯腈与CO
2和硫化氢反应，合成硫代苯甲酰胺或硫代喹唑啉二酮类衍生物
在惰性溶剂中，在碱存在下，用邻胺基苯腈与CO
2和硫化氢反应，合成硫代苯甲酰胺或硫代喹唑啉二酮类衍生物；该反应中，CO
2和H
2S共同作为反应物，形成六元环结构。在上述反应中，碱优选为DBU；溶剂优选为DMF，碱用量优选为0.2-2当量，较佳地为0.8-2当量。
在另一优选例中，在所述步骤(d)中，CO
2和H
2S的压强比为(2-5):(0.2-1.2)，较佳地为3-10:1。
在另一优选例中，在所述步骤(d)中，所述的方法在40-60℃下反应，优选在45-55℃下反应。在另一优选例中，在所述步骤(d)中，所述的方法中，所述的CO
2在反应器中的压力为2-5MPa，所述的H
2S在反应器中的压力为0.4-1Mpa。
(e)芳香邻胺基二硫化物与CO
2在硫化氢的作用下反应，合成苯并噻唑酮类衍生物
在惰性溶剂中，在碱存在下，用芳香邻胺基二硫化物与CO
2在硫化氢的作用下反应，合成苯并噻唑酮类衍生物；在上述反应中，碱优选为DBU、TMG，或Et
3N；溶剂优选为NMP、CH
3OH、1,4-二氧六环、DMSO，更佳地为NMP；碱用量优选为0.2-2当量，更佳地为0.4-1.2当量。
在另一优选例中，在所述步骤(e)中，CO
2和H
2S的压强比为(1-5):(0.1-1.2)。
在另一优选例中，在所述步骤(e)中，所述的方法在25-100℃下反应，优选在80-90℃下反应。
在另一优选例中，在所述步骤(e)中，所述的方法中，所述的CO
2在反应器中的压力为1-5MPa，所述的H
2S在反应器中的压力为0.2-1.0Mpa。
(f)二胺、醇胺或巯基胺与CO
2在硫化氢的作用下反应合成咪(噁或噻)唑烷酮类衍生物
在任选的惰性溶剂中，在任选的碱存在下，用二胺、醇胺或巯基胺与CO
2在硫化 氢的作用下反应合成咪唑烷酮类衍生物、恶唑烷酮类衍生物或噻唑烷酮类衍生物；
其中，U为O、S或NR；
M为取代或未取代的C
2-C
4亚烷基、取代或未取代的苯基、或取代或未取代的5-12元杂芳基，其中，取代的定义如上文中所述。
当U为NR且M为取代或未取代的苯基、或取代或未取代的5-12元杂芳基时：
在上述反应中，碱优选为DABCO，DBU，TMG或Et
3N，优选为DBU或TMG；溶剂优选为NMP、DMF、乙二醇或二氯甲烷，优选为NMP；碱用量优选为0.1-2当量。特别地，当所使用的反应物为有机碱，或者可以作为溶剂的情况下，所述的反应也可以在无溶剂，或者不存在有机碱的情况下进行。
在另一优选例中，在所述步骤(f)中，CO
2和H
2S的压强比为(1-65)：1。
在另一优选例中，在所述步骤(f)中，所述的方法在20-60℃下反应，优选在30-50℃下反应。在另一优选例中，在所述步骤(f)中，所述的方法中，所述的CO
2在反应器中的压力为1-5MPa，所述的H
2S在反应器中的压力为0.05-1.5Mpa。
当U为NR且M为取代或未取代的C
2-C
4亚烷基时：
在上述反应中，碱优选为DBU，TBD、DIPEA或Et
3N，优选为DBU、DIPEA或Et
3N；溶剂优选为NMP、DMF、乙二醇或二氯甲烷，优选为NMP；碱用量优选为0.1-1当量，更佳地为0.2-0.6当量。特别地，当所使用的反应物为有机碱，或者可以作为溶剂的情况下，所述的反应也可以在无溶剂，或者不存在有机碱的情况下进行。
在另一优选例中，在所述步骤(f)中，CO
2和H
2S的压强比为(3-35)：1，较佳地为(3-25)：1。
在另一优选例中，在所述步骤(f)中，所述的方法在80-120℃下反应。
在另一优选例中，在所述步骤(f)中，所述的方法中，所述的CO
2在反应器中的压力为1-5MPa，所述的H
2S在反应器中的压力为0.2-1Mpa。
当U为S时：
在上述反应中，碱优选为DABCO，DBU，TMG，TBD或Et
3N，优选为DBU，Et
3N，或TMG；溶剂优选为NMP、DMF、乙二醇或二氯甲烷，优选为NMP或DMF；碱用量优选为0.1-2当量。
特别地，当所使用的反应物为有机碱，或者可以作为溶剂的情况下，所述的反应也可以在无溶剂，或者不存在有机碱的情况下进行。此外，在CO
2的压强和反应温度符合形成超临界二氧化碳的条件情况下，也可以在无溶剂存在的情况下进行。
在另一优选例中，在所述步骤(f)中，CO
2和H
2S的压强比为(3-25)：1。
在另一优选例中，在所述步骤(f)中，所述的方法在20-60℃下反应，优选在30-50℃下反应。
在另一优选例中，在所述步骤(f)中，所述的方法中，所述的CO
2在反应器中的压力为3-12MPa，所述的H
2S在反应器中的压力为0.2-1.0Mpa。
(g)胺与CO
2在硫化氢的作用下反应合成脲类衍生物
在任选的惰性溶剂中，在任选的碱存在下，用胺与CO
2在硫化氢的作用下反应，合成脲类衍生物；
R
9选自下组：H、取代或未取代的C
1-C
12烷基(如取代或未取代的C
1-C
6烷基、取代或未取代的C
1-C
8烷基)、取代或未取代的C
3-C
8环烷基、苯基、5-12元杂芳基、5-12元饱和或部分不饱和的杂环，且所述的苯基、杂芳基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6烷氧基、OH、NO
2、NH
2、SO
2CH
3；
在上述反应中，碱优选为DBU，TMG或Et
3N，优选为DBU；溶剂优选为NMP、DMF或甲醇，优选为NMP；碱用量优选为0.1-2当量，但由于所使用的底物有机胺可以作为碱或溶剂使用，因此所述的反应也可以在不存在有机碱，和/或不存在溶剂的情况下进行。
在另一优选例中，在所述步骤(f)中，CO
2和H
2S的压强比为(5-20)：1。
在另一优选例中，在所述步骤(f)中，所述的方法在90-130℃下反应，优选在30-50℃下反应。
在另一优选例中，在所述步骤(f)中，所述的方法中，所述的CO
2在反应器中的压力为5-20MPa，所述的H
2S在反应器中的压力为0.5-2Mpa。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
第一类 无机硫既作为原料也作为催化剂
实施例1 邻碘苯胺与CO
2和硫化氢反应合成苯并噻唑酮类衍生物
反应方法如下：
称取1mol的邻卤苯胺、2mol的碱、0.2mol的碘化亚铜(CuI)以及2ml的溶剂，依次加入反应釜中，并拧紧反应釜。向反应釜中通入对应量的H
2S，在90℃下搅拌反应30min，然后通入对应量的CO
2至反应釜中，继续在相应温度下搅拌反应24h。反应结束后，将反应釜冷却至室温，缓慢地将反应釜中的气体排尽，打开反应釜，将反应液移至250ml的分液漏斗中，采用乙酸乙酯萃取反应液，利用无水硫酸镁干燥有机相。利用柱层析分离得到产物。
按照上述步骤进行条件优化，反应结果见下表：
注：上述各个反应中，原料均为1mmol邻碘苯胺；溶剂为2ml；CuI为0.2mmol；反应24h。
采用如上述entry 2中的方法，换用其他反应底物，得到如下的各个产物：
化合物的表征：
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离得到白色固体苯并噻唑酮144mg，分离产率为95％。
苯并噻唑-2-酮(2a)的表征数据：
1H NMR(CDCl
3,500MHz):δ(ppm)10.01(brs,1H),7.41(d,1H,J＝7.5Hz),7.30-7.26(m,1H),7.17-7.14(m,2H).
13C NMR(CDCl
3,125MHz):δ(ppm)172.8,135.3,126.5,123.9,123.3,122.6,111.7；MS(EI):m/z calcd for C
7H
5NOS[M]
+:151.0,found 151.0.m.p.:139-140℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3:1做展开剂，分离得到白色固体138mg，分离产率为84％。
6-甲基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d6,500MHz):δ(ppm)11.75(brs,1H),7.36(s,1H),7.07-7.09(m,1H),7.00(d,1H,J＝8Hz),2.30(s,3H)；
13C NMR(DMSO-d6,125MHz):δ(ppm)169.8,133.9,131.7,127.0,123.2,122.5,111.1,20.5；MS(ESI):m/z calcd for C8H7NOS[M+1]
+:166.0,found 165.0.m.p.:170-171℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离得到白色固体134mg，分离产率为82％。
5-甲基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.79(s,1H),7.42(d,J＝7.9Hz,1H),6.98–6.91(m,2H),2.32(s,3H).
13C NMR(DMSO-d
6,126MHz)δ(ppm)170.31,136.34,136.04,123.49,122.37,119.95,111.84,20.98；MS(ESI):m/z calcd for C8H7NOS[M+1]+:166.1,found 165.0.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3:1做展开剂，分离得到白色固体158mg，分离产率为88％。
6-甲氧基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.66(brs,1H),7.23(d,1H,J＝2.5Hz),7.02(d,1H,J＝8.5Hz),6.86(dd,1H,J
1＝8.5Hz,J
2＝2.5Hz),3.73(s,3H)；13C NMR(DMSO-d
6,126MHz):δ(ppm)169.8,155.2,129.9,124.3,113.2,112.1,107.8,55.6；MS(ESI):m/z calcd for C8H7NO2S[M+1]
+:182.1,found 181.1.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3:1做展开剂，分离得到白色固体144mg，分离产率为85％。
6-氟苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d
6)δ(ppm)11.91(s,1H),7.57(ddt,J＝9.1,2.2,0.8Hz,1H),7.16–7.08(m,2H).
13C NMR(DMSO-d
6,126MHz)δ(ppm)169.83,157.89(d,J＝119.3Hz),132.85(d,J＝1.9Hz),124.66(d,J＝5.5Hz),113.55(d,J＝12.0Hz),112.38(d,J＝4.3Hz),109.95(d,J＝13.7Hz).MS(ESI):m/z calcd for C7HFNOS[M+1]+:170.1,found 169.1.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3:1做展开剂，分离得到白色固体175mg，分离产率为81％。
6-三氟甲基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d6,500MHz):δ(ppm)12.22(brs,1H),7.85(d,1H,J＝8.5Hz),7.48(dd,1H,J1＝8.0Hz,J2＝1.0Hz),7.33(d,1H,J＝1.5Hz)；13C NMR(DMSO-d6,125MHz):δ(ppm)169.7,136.7,128.4(d,J＝1.25Hz),126.9(q,J＝31.9.5Hz),124.0(q,J＝270.5Hz),123.8,119.0(q,J＝3.9Hz),107.6(q,J＝4.1Hz)；MS(EI):m/z calcd for C8H4F3NOS[M+1]+:220.0,found 219.0.m.p.:216-218℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体144mg，分离产率为63％。
6-溴苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.02(brs,1H),7.86(d,1H,J＝2.0Hz),7.44(dd,1H,J1＝8.5,J2＝2.5Hz),7.05(d,1H,J＝8.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,135.6,129.2,125.6,125.0,114.0,113.1；MS(EI):m/z calcd for C7H4BrNOS[M+1]+:229.9,found 228.9.m.p.:231-232℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯 (V/V)＝100:3做展开剂，分离得到白色固体121mg，分离产率为66％。
6-氯苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.02(brs,1H),7.74(d,1H,J＝2.0Hz),7.32(dd,1H,J1＝8.5,J2＝2.5Hz),7.11(d,1H,J＝8.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,135.3,126.4,125.2,122.4,122.7；MS(ESI):m/z calcd for C7H4ClNOS[M+1]+:186.0,found 185.0.m.p.:212-214℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝100:3做展开剂，分离得到白色固体124mg，分离产率为76％。
2-甲基苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d
6)δ(ppm)7.64(d,J＝7.8Hz,1H),7.39(t,J＝7.7Hz,1H),7.30(d,J＝8.1Hz,1H),7.21(t,J＝7.6Hz,1H),3.41(s,3H).
13C NMR(126MHz,DMSO-d
6)δ(ppm)137.61,126.60,123.17,122.70,121.28,111.32.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体110mg，分离产率为67％。
6-氨基苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d6)δ(ppm)11.34(s,1H),6.80(d,J＝8.4Hz,1H),6.69(d,J＝2.2Hz,1H),6.51(dd,J＝8.4,2.3Hz,1H),4.94(s,2H).13C NMR(126MHz,DMSO-d6)δ(ppm)169.31,144.70,126.35,124.07,112.92,111.98,107.03.MS(ESI):m/z calcd for C7H6N2OS[M+1]+:167.1,found 166.1.
实施例2 邻硝基碘苯与CO
2和硫化氢反应合成苯并噻唑酮类衍生物
反应方法如下：
称取1mmol的邻卤硝基苯、2mmol的碱、0.2mmol的碘化亚铜(CuI)以及2ml的溶剂，依次加入反应釜中，并拧紧反应釜。向反应釜中通入对应量的H
2S，在于相应温度下搅拌反应30min，然后通入对应量的CO
2至反应釜中，继续在相应温度下搅拌反应24h。反应结束后，将反应釜冷却至室温，缓慢地将反应釜中的气体排尽，打开反应釜，将反应液移至250ml的分液漏斗中，采用乙酸乙酯萃取反应液，利用无水硫酸镁干燥有机相，利用柱层析分离得到产物。
按照上述步骤进行条件优化，反应结果见下表：
注：上述各个反应中，原料均为1mmol邻碘硝基苯；溶剂为2ml；CuI为0.2mmol；反应24h。
采用如上述entry 9中的方法，换用其他反应底物，得到如下的各个产物：
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体117mg，分离产率为71％。
5-甲基苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d
6)δ(ppm)11.80(s,1H),7.42(d,J＝7.9Hz,1H),6.97–6.92(m,2H),2.32(s,3H).
13C NMR(126MHz,DMSO-d
6)δ(ppm)170.35,136.35,136.06,123.52,122.39,119.97,111.87,21.00；MS(ESI):m/z calcd for C8H7NOS[M+1]+:166.0,found 165.0.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体117mg，分离产率为71％。
7-甲基苯并噻唑-2-酮的表征数据：1H NMR(500MHz,DMSO-d6)δ11.87(s,1H),7.20(t,J＝7.8Hz,1H),6.97(dd,J＝7.7,5.0Hz,2H),2.28(s,3H).13C NMR(126MHz,DMSO-d6)δ169.57,136.09,131.62,126.25,123.07,122.98,109.03,19.70；MS(ESI):m/z calcd for C8H7NOS[M+1]+:166.0,found 165.0.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体127mg，分离产率为70％。
5-甲氧基苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d6)δ(ppm)11.80(s,1H),7.44(d,J＝8.7Hz,204H),6.74(dd,J＝8.7,2.5Hz,249H),6.66(d,J＝2.5Hz,245H),3.75(s,704H).
13C NMR(126MHz,DMSO-d6)δ(ppm)170.91,158.48,137.27,123.40,114.19,109.48,97.39,55.39；MS(ESI):m/z calcd for C8H7NO2S[M+1]+:182.1,found 181.1.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体140mg，分离产率为67％。
5-甲酯基苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d6)δ(ppm)12.14(s,1H),7.75–7.68(m,3H),7.63(s,1H),3.87(s,4H).
13C NMR(126MHz,DMSO-d6)δ(ppm)169.69,165.75,136.52,129.31,127.63,123.14,122.96,111.50,111.46,52.29.MS(ESI):m/z calcd for C9H7NO3S[M+1]+:220.0,found 219.0.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝5：1做展开剂，分离得到白色固体116mg，分离产率为63％。
7-氯苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d6)δ(ppm)12.22(s,1H),7.33(t,J＝8.0Hz,1H),7.26(d,J＝7.1Hz,1H),7.11(d,J＝7.9Hz,1H).
13C NMR(126MHz,DMSO-d6)δ(ppm)168.56,137.50,127.83,126.19,122.61,122.19,110.34,110.30,109.54；MS(ESI):m/z calcd for C7H4ClNOS[M+1]+:186.0,found 185.0.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体126mg，分离产率为75％。
5-氟苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d
6)δ(ppm)12.02(s,1H),7.60(dd,J＝8.7,5.4Hz,1H),7.00(td,J＝9.1,2.6Hz,1H),6.93(dd,J＝9.3,2.6Hz,1H).
13C NMR(DMSO-d
6,126MHz)δ(ppm)170.68,161.02(d,J＝57.9Hz),137.31(d,J＝6.1Hz),124.17(d,J＝4.8Hz),118.72(d,J＝1.2Hz),109.74(d,J＝11.7Hz),99.22(d,J＝13.7Hz).MS(EI):m/z calcd for C7H5NOS[M]+:169.0,found 169.0.m.p.:172-174℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体118mg，分离产率为64％。
5-氯苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d6)δ(ppm)12.05(s,1H),7.61(d,J＝8.4Hz,1H),7.19(dd,J＝8.4,2.1Hz,1H),7.12(s,1H).
13C NMR(126MHz,DMSO-d6)δ(ppm)170.12,137.47,130.83,124.26,122.45,122.22,122.19,111.24；MS(ESI):m/z calcd for C7H4ClNOS[M+1]+:186.0,found 185.0.m.p.:224-226℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3：1做展开剂，分离得到白色固体154mg，分离产率为67％。
5-溴苯并噻唑-2-酮的表征数据：
1H NMR(500MHz,DMSO-d6)δ(ppm)12.04(s,1H),7.56(d,J＝8.4Hz,1H),7.31(dd,J＝8.4,2.0Hz,1H),7.24(d,J＝1.9Hz,1H).
13C NMR(126MHz,DMSO-d6)δ(ppm)169.91,137.70,125.20,124.59,122.71,118.74,113.96；MS(ESI):m/z calcd for C7H4BrNOS[M+1]+:229.9,found 228.9.
实施例3 炔丙胺与CO
2和硫化氢反应合成噻唑烷-2-酮类衍生物
将2mmol炔丙胺、1.2mmol碱和2mL溶剂加入10mL反应釜，放入磁子并拧紧反应釜，用N
2气体配合真空泵冲换气三次后充入对应量的H
2S，搅拌至压力不再变化后充入1MPaCO
2，在相应温度下搅拌反应24h。反应结束后，开釜用乙酸乙酯萃取反应液，收集并合并有机相，用无水硫酸镁干燥30min，过滤除去干燥剂，减压除去溶剂，得到粗产物。粗产品经柱层析(洗脱剂：石油醚/乙酸乙酯或二氯甲烷/甲醇)分离提纯得目标产物。
按照上述步骤进行条件优化，反应结果见下表：
注：所投原料均为2mmol；2-甲基-3丁炔-2-胺；溶剂为2ml；反应24小时。
采用如上述entry 3中的的方法，换用其他反应底物，得到如下的各个产物：
化合物的表征
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝1:2做展开剂，分离产率为24％。
5-methylenethiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ6.53(s,1H),5.23(q,J＝2.2Hz,1H),5.18–5.11(m,1H),4.31(s,2H)ppm；
13C NMR(125MHz,CDCl
3)δ173.1,138.8,106.9,49.4ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
4H
5NOS 116.0165；Found 116.0167.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为81％。
4,4-dimethyl-5-methylenethiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ6.32(s,1H),5.19(d,J＝2.2Hz,1H),5.11–5.06(m,1H),1.50(s,6H)ppm；
13C NMR(125MHz,CDCl
3)δ169.7,149.3,104.9,62.7,29.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
6H
9NOS 144.0478；Found 144.0474
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：甲醇(V/V)＝200:1做展开剂，分离产率为80％。
(Z)-5-benzylidene-3-butyl-4,4-diethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.40–7.31(m,4H),7.25–7.21(m,1H),6.39(s,1H),3.21–3.14(m,2H),1.95–1.83(m,2H),1.78–1.69(m,2H),1.69–1.63(m,2H),1.41–1.32(m,2H),0.96(t,J＝7.4Hz,3H),0.86(t,J＝7.2Hz,6H)ppm；
13C NMR(125MHz,CDCl
3)δ168.8,136.4,136.3,128.8,128.1,127.1,118.2,75.9,42.6,34.1,31.0,20.8,13.9,7.8ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
18H
25NOS 304.1730；Found 304.1725.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为92％。
(Z)-4-benzylidene-1-butyl-3-thia-1-azaspiro[4.5]decan-2-one: 1H NMR(500MHz,CDCl
3)δ7.40–7.30(m,4H),7.28–7.22(m,1H),6.96(s,1H),3.29–3.21(m,2H),2.07(d,J＝10.4Hz,2H),1.87–1.72(m,7H),1.63–1.50(m,2H),1.40–1.25(m,3H),0.94(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ168.1,139.6,136.3,128.6,128.5,127.5,122.7,69.7,42.4,33.7,32.2,24.7,22.8,20.5,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
19H
25NOS 316.1730；Found 316.1722.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝3:1做展开剂，分离产率为92％。
(Z)-5-benzylidene-3-butyl-4-phenylthiazolidin-2-one:According to general procedure,the crude residue was purified by flash chromatography(PE/EA＝3/1)to give the product as a yellow solid(589mg,91％).m.p.＝83–86℃；
1H NMR(500MHz,CDCl
3)δ7.45–7.37(m,5H),7.35–7.30(m,2H),7.25–7.19(m,3H),6.31(s,1H),5.48(s,1H),3.76–3.65(m,1H),2.77–2.65(m,1H),1.53–1.42(m,2H),1.33–1.23(m,2H),0.88(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ168.0,139.4,135.7,132.4,129.4,129.1,128.7,128.1,127.4,123.3,69.9,42.9,29.2,20.0,13.8ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
20H
21NOS 324.1417；Found 324.1409.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为99％。
(Z)-4-benzyl-5-benzylidene-3-butylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.33(t,J＝7.6Hz,2H),7.29–7.20(m,4H),7.19–7.11(m,4H),6.07(s,1H),4.69–4.49(m,1H),3.92(dt,J＝14.5,8.0Hz,1H),3.13(dd,J＝13.6,4.1Hz,1H),3.10–2.98(m,2H),1.69–1.55(m,2H),1.41–1.29(m,2H),0.95(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ168.1,135.4,135.2,131.0,129.9,128.6,128.5,127.9,127.3,127.1,122.4,66.6,42.5,40.5,29.6,20.0,13.7ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
21H
23NOS 338.1573；Found 338.1542.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为90％。
(Z)-5-benzylidene-3-butyl-4-propylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.37(t,J＝7.7Hz,2H),7.31(d,J＝7.3Hz,2H),7.23(d,J＝7.3Hz,1H),6.49(s,1H),4.56(s,1H),3.85–3.74(m,1H),3.05–2.93(m,1H),1.97–1.87(m,1H),1.79–1.68(m,1H),1.66–1.49(m,2H),1.47–1.30(m,4H),0.95(t,J＝7.4Hz,6H)ppm；
13C NMR(125MHz,CDCl
3)δ168.1,135.8,132.5,128.8,128.1,127.3,121.1,65.2,42.3,36.4,29.6,20.1,16.1,14.1,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
17H
23NOS 290.1573；Found 290.1558.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为92％。
(Z)-3-butyl-4,4-dimethyl-5-(4-methylbenzylidene)thiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.23(d,J＝8.2Hz,2H),7.17(d,J＝8.0Hz,2H),6.50(s,1H),3.29–3.23(m,2H),2.34(s,3H),1.68–1.59(m,2H),1.55(s,6H),1.41–1.31(m,2H),0.95(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ167.1,138.3,137.1,133.3,129.4,128.1,119.0,68.0,42.5,31.7,28.3,21.3,20.5,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
17H
23NOS290.1573；Found 290.1568.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯 (V/V)＝2:1做展开剂，分离产率为81％。
(Z)-3-butyl-5-(4-methoxybenzylidene)-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.27(d,J＝10.5Hz,2H),6.90(d,J＝8.8Hz,2H),6.47(s,1H),3.82(s,3H),3.29–3.22(m,2H),1.68–1.60(m,2H),1.54(s,6H),1.40–1.31(m,2H),0.95(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ167.2,158.7,136.9,129.5,128.9,118.6,114.2,68.0,55.4,42.5,31.7,28.3,20.5,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
17H
23NO
2S 306.1522；Found 306.1516.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为83％。
(Z)-3-butyl-5-(4-chlorobenzylidene)-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.33(d,J＝8.5Hz,2H),7.26(d,J＝8.7Hz,2H),6.47(s,1H),3.30–3.23(m,2H),1.68–1.60(m,2H),1.55(s,6H),1.42–1.31(m,2H),0.95(t,J＝7.3Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.5,140.5,134.7,132.8,129.4,128.9,117.8,68.1,42.6,31.7,28.3,20.5,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
16H
20ClNOS 310.1027；Found 310.1021.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝1:2做展开剂，分离产率为87％。
(Z)-5-benzylidene-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,DMSO-d
6)δ8.79(s,1H),7.43–7.33(m,4H),7.25(t,J＝7.3Hz,1H),6.74(s,1H),1.50(s,6H)ppm；
13C NMR(125MHz,DMSO-d
6)δ166.1,140.8,136.0,128.6,127.7,126.9,118.7,63.5,29.7ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
12H
13NOS 220.0791；Found 220.0788.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为94％。
(Z)-5-benzylidene-4,4-dimethyl-3-propylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)1δ7.41–7.29(m,4H),7.25–7.21(m,1H),6.53(s,1H),3.27–3.16(m,2H),1.74–1.63(m,2H),1.56(s,6H),0.94(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.9,139.3,136.0,128.6,128.0,127.1,118.9,67.9,44.2,28.2,22.7,11.5ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
15H
19NOS 262.1260；Found 262.1257.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为87％。
(Z)-5-benzylidene-3-butyl-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.39–7.31(m,4H),7.25–7.21(m,1H),6.53(s,1H),3.30–3.24(m,2H),1.69–1.60(m,2H),1.56(s,6H),1.41–1.32(m,2H),0.95(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.9,139.6,136.2,128.7,128.2,127.3,119.0,68.1,42.5,31.7,28.4,20.6,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
16H
21NOS 276.1417；Found 276.1416.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为89％。
(Z)-3-benzyl-5-benzylidene-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.40-7.33(m,4H),7.32-7.29(m,4H),7.27–7.23(m,2H),6.53(s,1H),4.62(s,2H),1.49(s,6H)ppm；
13C NMR(125MHz,CDCl
3)δ168.1,139.1,138.1,136.0,128.8,128.7,128.2,127.5,127.4,127.3,119.3,68.4,45.3,28.5ppm；HRMS(ESI)m/z:[M+H]
+Calcd forC
19H
19NOS 310.1260；Found 310.1250.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为46％。
(Z)-5-benzylidene-3-isopropyl-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.40–7.31(m,4H),7.25–7.20(m,1H),6.46(s,1H),3.58–3.47(m,1H),1.56(s,6H),1.49(d,J＝6.8Hz,6H)ppm；
13C NMR(125MHz,CDCl
3)δ165.6,139.8,136.3,128.7,128.2,127.1,118.8,69.1,47.7,28.3,20.5ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
15H
19NOS 262.1260；Found 262.1256
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为75％。
(Z)-5-(4-bromobenzylidene)-3-butyl-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.49(d,J＝8.5Hz,2H),7.20(d,J＝8.6Hz,2H),6.45(s,1H),3.29–3.24(m,2H),1.68–1.60(m,2H),1.55(s,6H),1.40–1.32(m,2H),0.95(td,J＝7.4,1.1Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.5,140.7,135.1,131.9,129.7,121.0,117.9,68.1,42.6,31.7,28.3,20.6,13.9ppm；MS(ESI)m/z:[M+H]
+Calcd for C
16H
20BrNOS 354.1；Found 354.1.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝1:3做展开剂，分离产率为79％。
(Z)-3-butyl-4,4-dimethyl-5-(pyridin-3-ylmethylene)thiazolidin-2-one: 1H NMR(500 MHz,CDCl
3)δ8.52(d,J＝55.4Hz,2H),7.70(d,J＝7.5Hz,1H),7.32(s,1H),6.49(s,1H),3.31–3.24(m,2H),1.66–1.63(m,2H),1.58(s,6H),1.41–1.32(m,2H),0.95(t,J＝7.3Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.1,150.1,147.9,142.9,134.2,115.4,68.3,42.7,31.7,28.4,20.5,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
15H
22N
2OS277.1369；Found 277.1376.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为82％。
(Z)-3-butyl-4,4-dimethyl-5-(thiophen-2-ylmethylene)thiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.33(d,J＝5.0Hz,1H),7.07–7.04(m,1H),7.02(d,J＝3.1Hz,1H),6.74(s,1H),3.29–3.23(m,2H),1.66–1.61(m,2H),1.54(s,6H),1.40–1.31(m,2H),0.95(t,J＝7.4Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.4,140.2,137.9,127.5,126.6,126.0,112.0,67.7,42.7,31.7,28.3,20.5,13.9ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
14H
19NOS
2 282.0981；Found 282.0981.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为40％。
(Z)-3-butyl-5-(cyclopropylmethylene)-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ4.99(d,J＝8.8Hz,1H),3.22–3.14(m,2H),1.63–1.55(m,2H),1.39(s,6H),1.37–1.28(m,3H),1.23–1.16(m,1H),0.92(t,J＝7.4Hz,3H),0.85–0.78(m,2H),0.44–0.39(m,2H)ppm；
13C NMR(125MHz,CDCl
3)δ167.5,136.9,122.9,66.4,42.3,31.8,28.0,20.5,13.9,13.1,7.3ppm；MS(ESI)m/z:[M+H]
+Calcd for C
13H
21NOS 240.1；Found 240.2.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为72％。
(Z)-5-benzylidene-3-cyclopropyl-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.39–7.31(m,4H),7.25–7.21(m,1H),6.54(s,1H),2.39–2.33(m,1H),1.67(s,6H),0.99–0.94(m,2H),0.93–0.88(m,2H)ppm.
13C NMR(125MHz,CDCl
3)δ168.8,138.9,136.1,128.7,128.2,127.3,119.0,69.6,28.3,24.3,6.4ppm；MS(ESI)m/z:[M+H]
+Calcd for C
15H
17NOS 260.1；Found 260.2.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为85％。
(Z)-5-benzylidene-3-hexyl-4,4-dimethylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.39–7.32(m,4H),7.26–7.21(m,1H),6.53(s,1H),3.29–3.22(m,2H),1.69–1.62(m,2H),1.56(s,6H),1.38–1.28(m,6H),0.89(t,J＝6.3Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.9,139.5,136.2,128.7,128.2,127.2,119.0,68.1,42.7,31.6,29.6,28.4,27.0,22.72,14.1ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
18H
25NOS 304.1730；Found 304.1734.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝2:1做展开剂，分离产率为86％。
(Z)-5-benzylidene-4,4-dimethyl-3-octylthiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.40–7.31(m,4H),7.26–7.21(m,1H),6.53(s,1H),3.28–3.23(m,2H),1.70–1.62(m,2H),1.56(s,6H),1.34–1.23(m,10H),0.88(t,J＝6.7Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ166.9,139.5,136.2,128.7,128.2,127.3,119.0,68.1,42.8,31.9,29.7,29.3(9),29.3(7),28.4,27.3,22.8,14.2ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
20H
29NOS 332.2043；Found 332.2049.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝5:1做展开剂，分离产率为35％。
3-benzyl-5-methylenethiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.39–7.34(m,2H),7.33–7.29(m,1H),7.27(d,J＝7.9Hz,2H),5.17–5.14(m,1H),5.14–5.11(m,1H),4.53(s,2H),4.17–4.13(m,2H)ppm.
13C NMR(125MHz,CDCl
3)δ169.1,135.5,135.4,129.0,128.3,128.2,106.6,53.9,48.3ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
4H
5NOS:206.1；Found 206.0.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为94％。
(Z)-5-benzylidene-3-hexyl-4-(p-tolyl)thiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.31(t,J＝7.7Hz,2H),7.25(d,J＝3.1Hz,2H),7.24–7.17(m,5H),6.28(s,1H),5.43(s,1H),3.73–3.65(m,1H),2.74–2.66(m,1H),2.37(s,3H),1.51–1.43(m,2H),1.33–1.21(m,2H),0.88(t,J＝7.3Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ168.0,139.0,136.4,135.8,132.7,130.0,128.7,128.1,127.3(3),127.3(1),123.1,69.7,42.8,29.2,21.4,20.1,13.8ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
21H
23NOS 338.1573；Found 338.1578.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为66％。
(Z)-5-benzylidene-3-butyl-4-(4-chlorophenyl)thiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.40(d,J＝8.3Hz,2H),7.33(d,J＝8.2Hz,4H),7.23(d,J＝7.6Hz,3H),6.28(s,1H),5.45(s,1H),3.71(dt,J＝15.4,7.9Hz,1H),2.73–2.66(m,1H),1.51–1.42(m,2H),1.34–1.21(m,2H),0.89(t,J＝7.3Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ168.0,138.0,135.5,135.1,131.9,129.7,128.7,128.7,128.1,127.6,123.6,69.1,42.9,29.2,20.0,13.8ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
20H
20ClNOS 358.1027；Found 358.1031.
湿法装柱干法上样柱层析(200-300目硅胶)分离：采用石油醚：乙酸乙酯(V/V)＝4:1做展开剂，分离产率为83％。
(Z)-5-benzylidene-3-butyl-4-(thiophen-3-yl)thiazolidin-2-one: 1H NMR(500MHz,CDCl
3)δ7.39–7.31(m,4H),7.22(dd,J＝13.3,5.9Hz,2H),7.08(d,J＝6.1Hz,1H),6.34(s,1H),5.61(s,1H),3.71–3.63(m,1H),2.84–2.76(m,1H),1.53–1.40(m,2H),1.34–1.22(m,3H),0.89(t,J＝7.3Hz,3H)ppm；
13C NMR(125MHz,CDCl
3)δ167.6,140.2,135.7,131.5,128.7,128.1(3),128.1(2),127.9,127.4,125.8,124.0,123.2,65.4,42.9,29.3,20.1,13.8ppm；HRMS(ESI)m/z:[M+H]
+Calcd for C
18H
19NOS
2 330.0981；Found 330.0981.
第二类 硫化氢作为催化剂
实施例4 邻苯二胺与CO
2在硫化氢的作用下反应合成苯并咪唑酮类衍生物
在15mL的高压反应釜内依次加入2mmol邻苯二胺、有机碱和1mL合适的溶剂，拧紧反应釜；依次向反应釜内通入所需量的H
2S和CO
2气体；最后将反应釜在合适温度下连续反应12小时；反应完毕后，在反应液中加入一定量的蒸馏水，使产物完全沉淀，然后依次通过抽滤、烘干得到目标产物。
按照上述步骤进行条件优化，反应结果见下表：
| Entry | 溶剂 | 碱(mmol) | H 2S(P MPa) | CO 2(P MPa) | t(℃) | 产率(％) |
| 1 | NMP | DBU(3) | 0.08 | 1.5 | 40 | 86 |
| 2 | NMP | DBU(2) | 0.08 | 1.5 | 40 | 86 |
| 3 | NMP | DBU(1) | 0.08 | 1.5 | 40 | 79 |
| 4 | NMP | DBU(2) | 0.3 | 1.5 | 40 | 87 |
| 5 | NMP | DBU(2) | 0.15 | 1.5 | 40 | 87 |
| 6 | NMP | DBU(2) | 0.08 | 1.5 | 40 | 87 |
| 7 | NMP | DBU(2) | 0.03 | 1.5 | 40 | 69 |
| 8 | NMP | DBU(2) | 0 | 1.5 | 40 | NR |
| 9 | NMP | DBU(2) | 0.08 | 5 | 40 | 86 |
| 10 | NMP | DBU(2) | 0.08 | 4 | 40 | 86 |
| 11 | NMP | DBU(2) | 0.08 | 3 | 40 | 87 |
| 12 | NMP | DBU(2) | 0.08 | 1 | 40 | 82 |
| 13 | NMP | DBU(2) | 0.08 | 0 | 40 | NR |
| 14 | NMP | DBU(2) | 0.08 | 1.5 | 60 | 84 |
| 15 | NMP | DBU(2) | 0.08 | 1.5 | 50 | 86 |
| 16 | NMP | DBU(2) | 0.08 | 1.5 | 30 | 85 |
| 17 | NMP | DBU(2) | 0.08 | 1.5 | 20 | 83 |
| 18 | DMSO | DBU(2) | 0.08 | 1.5 | 40 | NR |
| 19 | NMP | DBU(2) | 0.08 | 1.5 | 40 | 87 |
| 20 | NMP | TMG(2) | 0.08 | 1.5 | 40 | 86 |
| 21 | NMP | DBU(2) | 0.08 | 1.5 | 40 | 87 |
注：上述各个反应中，原料均为2mmol邻苯二胺；溶剂为1ml。
采用entry6中的相同的方法，换用其他反应底物，得到以下化合物：
通过过滤、烘干得到白色固体产物233mg，分离产率：87％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.57(s,2H),6.91(s,4H).
13C NMR(126MHz,DMSO-d
6,TMS):δ(ppm)155.28(C),129.67(C),120.43(CH),108.46(CH).
MS(ESI):m/z calcd for C
7H
6NO[M+H]
+:135.06,found 135.1.
通过过滤、烘干得到固体产物265mg，分离产率：89.5％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.47(d,2H,J＝20.0Hz),6.80(d,1H,J＝10.0Hz),6.73(d,2H,J＝10.0Hz),2.27(s,3H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.29,129.72,129.21,127.31,120.75,108.87,108.03,20.91.
通过过滤、烘干得到固体产物266mg，分离产率：90％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.65(s,1H),10.53(s,1H),6.82(t,1H, J1＝J2＝10.0Hz),6.74(t,1H,J1＝J2＝10.0Hz),2.25(s,3H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.47,129.23,128.55,121.56,120.34,117.13,106.05,16.17.
通过过滤、烘干得到固体产物289mg，分离产率：89.2％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.34(s,2H),6.70(s,2H),2.17(s,6H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.41,127.75,109.54.
通过过滤、烘干得到固体产物176mg，分离产率：58％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.74(s,1H),10.63(s,1H),6.87(dd,J＝8.5,4.7Hz,1H),6.80-6.69(m,2H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)158.42,156.13(d,J＝110.2Hz),130.36(d,J＝13.0Hz),126.06,108.77(d,J＝9.6Hz),106.52(d,J＝23.8Hz),96.51(d,J＝28.2Hz).
通过过滤、烘干得到固体产物264mg，分离产率：78％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.76(s,2H),6.97-6.90(m,3H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.19,130.82,128.60,124.47,120.09,109.50,108.36.
通过过滤、烘干得到固体产物421mg，分离产率：98.7％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.76(s,2H),7.05(t,2H,J1＝J2＝10.0Hz),6.88(d,1H,J＝10.0Hz).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.03,131.20,128.98,122.89,111.98,111.02,110.06.
通过过滤、烘干得到固体产物255mg，分离产率：63％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.99(s,2H),7.28(dd,J＝8.2,1.7Hz,1H),7.16(d,J＝1.7Hz,1H),7.09(d,J＝8.1Hz,1H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.36,132.88,129.85,124.89(q,J＝271.8Hz),120.95(q,J＝3.2Hz),117.91(q,J＝4.2Hz),108.58,104.98(q,J＝4.0Hz).
通过过滤、烘干得到固体产物371mg，分离产率：78％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)11.11(s,1H),10.88(s,1H),7.70-7.63(m,3H),7.55(t,2H,J1＝J2＝5.0Hz),7.44(d,1H,J＝10.0Hz),7.33(s,1H),7.08(d,1H,J＝10.0Hz).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)194.98,155.38,138.19,134.02,131.81,129.66,129.38,129.17,128.34,124.44,109.71,107.98.
通过过滤、烘干得到固体产物206mg，分离产率：63％
1H NMR(500MHz,DMSO-d
6,TMS):δ(ppm)10.50(s,1H),10.37(s,1H),6.81(d,1H,J＝5.0Hz),6.52(d,2H,J＝10.0Hz),3.70(s,3H).
13C NMR(125MHz,DMSO-d
6,TMS):δ(ppm)155.64,154.33,130.49,123.56,108.71,106.07,95.27,55.42.
通过过滤、烘干得到固体产物358mg，分离产率：97％
1H NMR(500MHz,DMSO-d6,TMS):δ(ppm)10.07(s,2H),7.21(t,2H,J1＝J2＝5.0Hz),7.11(d,2H,J＝5.0Hz),6.52(d,2H,J＝5.0Hz).
13C NMR(125MHz,DMSO-d6,TMS):δ(ppm)150.09,137.67,134.15,128.03,117.65,113.66,104.01.
实施例5 邻胺基苯硫酚与CO
2在硫化氢的作用下反应合成苯并噻唑酮类衍生物
取2mmol的原料邻氨基苯硫酚类化合物，置于装有磁子的15mL不锈钢高压反应釜，然后向釜中依序加入2mmol碱和2mL溶剂，拧紧反应釜。先充入对应量的硫化氢气体，再通入对应量的CO
2，然后在相应温度下搅拌反应24h。反应结束后冷却至室温，排尽釜中气体，使用乙酸乙酯进行萃取，合并有机相，并用无水硫酸镁干燥。过滤除去干燥剂，减压除去溶剂，得到粗产物，经柱层析分离提纯得目标产物。
按照上述步骤进行条件优化，反应结果见下表：
注：所投原料均为2mmol邻氨基苯硫酚；溶剂为2mL；反应时间为24h。
采用entry 7中的相同的方法，换用其他反应底物，得到以下化合物：
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体143mg，分离产率为94.4％。
苯并噻唑-2-酮(1a)的表征数据：
1H NMR(CDCl
3,500MHz):δ(ppm)10.01(brs,1H),7.41(d,1H,J＝7.5Hz),7.30-7.26(m,1H),7.17-7.14(m,2H).
13C NMR(CDCl
3,125MHz):δ(ppm)172.8,135.3,126.5,123.9,123.3,122.6,111.7；MS(EI):m/z calcd for C
7H
5NOS[M]
+:151.0,found 151.0.m.p.:139-140℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝5:1做展开剂，分离得到白色固体141mg，分离产率为76.2％。
6-氯苯并噻唑-2-酮(1b)的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.02(brs,1H),7.74(d,1H,J＝2.0Hz),7.32(dd,1H,J
1＝8.5,J
2＝2.5Hz),7.11(d,1H,J＝8.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,135.3,126.4,125.2,122.4,122.7；MS(EI):m/z calcd for C
7H
4ClNOS[M]
+:185.1,found 185.0.m.p.:212-214℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体195mg，分离产率为85％。
6-溴苯并噻唑-2-酮(1c)的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.02(brs,1H),7.86(d,1H,J＝2.0Hz),7.44(dd,1H,J
1＝8.5,J
2＝2.5Hz),7.05(d,1H,J＝8.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,135.6,129.2,125.6,125.0,114.0,113.1；MS(EI):m/z calcd for C
7H
4BrNOS[M]
+:228.9,found 228.9.m.p.:231-232℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体149mg，分离产率为67.9％。
6-三氟甲基苯并噻唑-2-酮(1d)的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.22(brs,1H),7.85(d,1H,J＝8.5Hz),7.48(dd,1H,J
1＝8.0Hz,J
2＝1.0Hz),7.33(d,1H,J＝1.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,136.7,128.4(d,J＝1.25Hz),126.9(q,J＝31.9.5Hz),124.0(q,J＝270.5Hz),123.8,119.0(q,J＝3.9Hz),107.6(q,J＝4.1Hz)；MS(EI):m/z calcd for C
8H
4F
3NOS[M]
+:219.2,found 219.0.m.p.:216-218℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝10:1做展开剂，分离得到白色固体170mg，分离产率为94％。
6-甲氧基苯并噻唑-2-酮(1e)的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.658(brs,1H),7.23(d,1H,J＝2.5Hz),7.02(d,1H,J＝8.5Hz),6.86(dd,1H,J
1＝8.5Hz,J
2＝2.5Hz),3.73(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.8,155.2,129.9,124.3,113.2,112.1,107.8,55.6；MS(EI):m/z calcd for C
8H
7NO
2S[M]
+:180.9,found181.0.m.p.:161-163℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝50:1做展开剂，分离得到白色固体160mg，分离产率为96.8％。
6-甲基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.75(brs,1H),7.36(s,1H),7.07-7.09(m,1H),7.00(d,1H,J＝8Hz),2.30(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.8,133.9,131.7,127.0,123.2,122.5,111.1,20.5；MS(EI):m/z calcd for C
8H
7NOS[M]
+:165.0,found 165.0.m.p.:170-171℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝50:1做展开剂，分离得到白色固体94mg，分离产率为51.0％。
5-氯苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.04(brs,1H),7.61(d,1H,J＝8.5Hz),7.19(dd,1H,J
1＝8.5,J
2＝2.5Hz),7.12(d,1H,J＝2.0Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)170.0,137.4,130.8,124.3,122.4,122.2,111.2；MS(EI):m/z calcd for C
7H
4ClNOS[M]
+:184.9,found 185.0.m.p.:224-226℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝5:1做展开剂，分离得到白色固体164mg，分离产率为99.3％。
4-甲基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.73(brs,1H),7.37(dd,1H,J
1＝7.5,J
2＝0.5Hz),7.08-7.09(m,1H),7.03(t,1H,J＝7.5Hz), 2.32(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)170.4,135.0,127.6,122.8,122.5,121.3,120.0,17.4；MS(EI):m/z calcd for C
8H
7NOS[M]
+:165.1,found 165.0.m.p.:211-212℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用乙酸乙酯：石油醚(V/V)＝3:1做展开剂，分离得到白色固体155mg，分离产率为67.9％。
甲砜基基苯并噻唑-2-酮的表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.41(brs,1H),8.22(d,1H,J＝7.0Hz),7.812(dd,1H,J＝7.5Hz,J＝2.0Hz),7.31(d,1H,J＝8.0Hz),3.20(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)170.2,140.4,134.6,125.6,124.2,122.2,111.5,43.9；MS(EI):m/z calcd for C
8H
7NO
3S
2[M]
+:229.0,found 228.8.m.p.:241-244℃。
实施例6 芳香邻胺基二硫化物与CO
2在硫化氢的作用下反应合成苯并噻唑酮类衍生物
取0.5mmol的二硫化物、0.5mmol的碱、以及2ml的溶剂依次加入反应釜中，并拧紧反应釜，冲入适量的H
2S，预热，冲入对应量的CO
2，在相应温度下反应12小时。反应结束后，将反应釜冷却至室温，缓慢地将反应釜中的气体排尽，用乙酸乙酯和饱和食盐水萃取，合并有机相，进行柱层析分离得到目标产物。
按照上述步骤进行条件优化，反应结果见下表：
注：所投原料为0.5mmol二硫化物(邻氨基苯硫酚的二聚体)；溶剂为2mL；表中摩尔配比为二硫化物：DBU的mol比；反应时间为12h。
采用entry 3中的相同的方法，换用其他反应底物，得到以下化合物：
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体148mg，分离产率为98％。
表征数据：
1H NMR(CDCl
3,500MHz):δ(ppm)10.01(brs,1H),7.41(d,1H,J＝7.5Hz),7.30-7.26(m,1H),7.17-7.14(m,2H).
13C NMR(CDCl
3,125MHz):δ(ppm)172.8,135.3,126.5,123.9,123.3,122.6,111.7；MS(EI):m/z calcd for C
7H
5NOS[M]
+:151.0,found 151.0.m.p.:139-140℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体180mg，分离产率为97.2％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.02(brs,1H),7.74(d,1H,J＝2.0Hz),7.32(dd,1H,J
1＝8.5,J
2＝2.5Hz),7.11(d,1H,J＝8.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,135.3,126.4,125.2,122.4,122.7；MS(EI):m/z calcd forC
7H
4ClNOS[M]
+:185.1,found 185.0.m.p.:212-214℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体179mg，分离产率为78.3％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.02(brs,1H),7.86(d,1H,J＝2.0Hz),7.44(dd,1H,J
1＝8.5,J
2＝2.5Hz),7.05(d,1H,J＝8.5Hz)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,135.6,129.2,125.6,125.0,114.0,113.1；MS(EI):m/z calcd for C
7H
4BrNOS[M]
+:228.9,found 228.9.m.p.:231-232℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体169mg，分离产率为93.5％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.658(brs,1H),7.23(d,1H,J＝2.5Hz),7.02(d,1H,J＝8.5Hz),6.86(dd,1H,J
1＝8.5Hz,J
2＝2.5Hz),3.73(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.8,155.2,129.9,124.3,113.2,112.1,107.8,55.6；MS(EI):m/z calcd for C
8H
7NO
2S[M]
+:180.9,found 181.0.m.p.:161-163℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体149mg，分离产率为90％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.73(brs,1H),7.37(dd,1H,J
1＝7.5Hz,J
2＝0.5Hz),7.08-7.09(m,1H),7.03(t,1H,J＝7.5Hz),2.32(s,3H).
13C NMR(DMSO-d
6,125MHz):δ(ppm)170.4,135.0,127.6,122.8,122.5,121.3,120.0,17.4；MS(EI):m/z calcd for C
7H
5NOS[M]
+:165.1,found 165.0.m.p.:211-212℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体157mg，分离产率为95.4％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.75(brs,1H),7.36(s,1H),7.07-7.09(m,1H),7.00(d,1H,J＝8Hz),2.30(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.8,133.9,131.7,127.0,123.2,122.5,111.1,20.5；MS(EI):m/z calcd for C
8H
7NOS[M]
+:165.0,found 165.0.m.p.:170-171℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体154mg，分离产率为93.5％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)11.73(brs,1H),7.37(dd,1H,J
1＝7.5,J
2＝0.5Hz),7.08-7.09(m,1H),7.03(t,1H,J＝7.5Hz),2.32(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)170.4,135.0,127.6,122.8,122.5,121.3,120.0,17.4；MS(EI):m/z calcd for C
8H
7NOS[M]
+:165.1,found 165.0.m.p.:211-212℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝1:2做展开剂，分离得到白色固体140mg，分离产率为61％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.41(brs,1H),8.22(d,1H,J＝ 7.0Hz),7.812(dd,1H,J＝7.5Hz,J＝2.0Hz),7.31(d,1H,J＝8.0Hz),3.20(s,3H)；
13C NMR(DMSO-d
6,125MHz):δ(ppm)170.2,140.4,134.6,125.6,124.2,122.2,111.5,43.9；MS(EI):m/z calcd for C
8H
7NO
3S
2[M]
+:229.0,found 228.8.m.p.:241-244℃。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用二氯甲烷：乙酸乙酯(V/V)＝20:1做展开剂，分离得到白色固体128mg，分离产率为76％。
表征数据：
1H NMR(DMSO-d
6,500MHz):δ(ppm)12.39(brs,1H),7.43(d,1H,J＝7.5Hz),7.12-7.22(m,2H).
13C NMR(DMSO-d
6,125MHz):δ(ppm)169.7,147.1(d,J＝243.8Hz),125.5(d,J＝3.8Hz),124.3(d,J＝14.6Hz),123.0(d,J＝6.5Hz),118.6(d,J＝6.0Hz),112.7(d,J＝16.9Hz)；MS(EI):m/z calcd for C
7H
5NOS[M]
+:169.0,found 169.0.m.p.:172-174℃。
实施例7 二胺、醇胺或巯基胺与CO
2在硫化氢的作用下反应合成咪(噁或噻)唑烷酮类衍生物
称取2mmol的二胺、0.8mmol的碱、以及2ml的溶剂，依次加入反应釜中，并拧紧反应釜。向反应釜中通入对应量的H
2S，在合适的温度下通入对应量的CO
2，然后搅拌反应4h。反应结束后，将反应釜冷却至室温，缓慢地将反应釜中的气体排尽，打开反应釜，通过萃取、柱层析或重结晶得到目标产物。
按照上述步骤进行条件优化，反应结果见下表：
注：所投原料均为2mmol乙二胺；溶剂为2ml NMP。entry 17中，乙二胺作为碱，加入NMP作为溶剂。
采用entry 10中的相同的方法，换用其他反应底物，反应结果如下：
化合物的表征：
乙酸乙酯萃取、柱层析、重结晶得到目标产物纯品170.2mg,产率99％。
imidazolidin-2-one：white solid,
1H NMR(500MHz,CDCl
3)δ3.52(s,1H)。
13C NMR(126MHz,CDCl
3)δ165.64,41.04.
乙酸乙酯萃取、柱层析、重结晶得到目标产物纯品，153.7mg,产率68％。1,3-Dimethylimidazolidin-2-one:Colorless oil,
1HNMR(500MHz,CDCl
3):d＝2.79(s,6H,2CH
3),3.27(s,4H,2CH
2)；
13C NMR(126MHz,CDCl
3):d＝31.3,44.9,161.9.
乙酸乙酯萃取、柱层析得到目标产物纯品216.5mg，产率91％。
4,5-Diphenylimidazolidin-2-one:white solid,
1H NMR(500MHz,CDCl
3):δ7.38-7.34(m,6H),7.27-7.30(m,4H),5.83(s,2H),4.57(s,2H).
13C NMR(126MHz,CDCl
3)δ163.1,140.2,128.7,128.2,126.4,65.9；
乙酸乙酯萃取、多次柱层析得到目标产物纯品241.74mg，产率85％。
1,3-Diethylimidazolidin-2-one:Colorless oil,95％.
1H NMR(500MHz,CDCl
3):δ3.23(s,4H),3.19(q,J＝7.2Hz,4H),1.05(t,J＝7.2Hz,6H).
13C NMR(500MHz,CDCl
3):δ161.3,42.3,38.9,12.9.
乙酸乙酯萃取、柱层析得到目标产物纯品278.49mg，产率为99％。
octahydro-2H-benzo[d]imidazol-2-one：colourless solid,
1H NMR(500MHz,CDCl
3)δ4.75(s,2H),3.67(s,2H),1.66(s,4H),1.61–1.49(m,2H),1.31(dt,J＝9.6,5.5Hz,2H)；
13C NMR(126MHz,CDCl
3)δ77.67,52.45,28.85,20.88.
萃取，柱层析得到产物纯品192mg，产率75％。
1,3-Dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one:
1H NMR(500MHz,CDCl
3):d＝1.97(quintet,J＝6.0Hz,2H,CH
2),2.92(s,6H,2CH
3),3.24(t,J＝6.0Hz,4H,2CH
2)；
13C NMR(126MHz,CDCl
3):d＝22.1,35.5,47.8,156.7.
过滤得到目标产物纯品188mg，产率73％。
5,5-dimethyltetrahydropyrimidin-2(1H)-one:white solid,1H NMR(500MHz,DMSO-d6)δ6.06(s,2H),2.76(s,4H),0.94(s,6H).
13C NMR(126MHz,DMSO-d6)δ155.26,51.06,27.20,23.89.
乙酸乙酯萃取、柱层析得到目标产物纯品174.4mg，产率99％。
5-phenylimidazolidine-2,4-dione:white solid,1H NMR(500MHz,DMSO-d6)δ10.77(s,1H),8.39(s,1H),7.37(d,J＝34.7Hz,6H),5.16(s,1H).13C NMR(126MHz,DMSO-d6)δ174.34,157.65,136.21,128.80,128.39,126.86,61.35.
柱层析、二氯甲烷和乙酸乙酯重结晶得到目标产物182mg，产率91％。
4-methylimidazolidin-2-one:white solid,1H NMR(500MHz,CDCl
3)δ5.00(s,2H),3.92(h,J＝8.3Hz,1H),3.61(t,J＝8.4Hz,1H),3.17–2.99(m,1H),1.25(d,J＝6.4Hz,3H).
13C NMR(126MHz,CDCl
3)δ163.90,48.41,48.01,21.15.
过滤得到目标产物纯品164.1mg，产率72％。
1-methyltetrahydropyrimidin-2(1H)-one:white solid,
1H NMR(500MHz,DMSO-d
6)δ6.11(s,1H),3.15(t,J＝5.5Hz,2H),3.09(t,J＝5.5Hz,2H),2.74(s,3H),1.79(p,J＝6.6,5.9Hz,2H).
13C NMR(126MHz,DMSO-d
6)δ46.95,22.02
乙酸乙酯萃取、柱层析得到目标产物纯品221.1mg，产率97％。
ethylimidazolidin-2-one:Colorless oil，
1H NMR(500MHz,CDCl
3)δ3.50–3.35(m,6H),3.25(q,J＝7.2Hz,2H),1.12(t,J＝7.2Hz,3H).
13C NMR(126MHz,CDCl
3)δ162.59,44.39,38.25,38.09,12.69.
乙酸乙酯萃取，柱层析分离得到目标产物纯品172.4mg，产率为99％。
2-Oxazolidinone:1H NMR(500MHz,CDCl
3)δ3.64(t,2H),4.46(t,2H),6.68(s,1H).
13CNMR(126MHz,CDCl
3),δ41.0,65.5,161.5.
湿法装柱干法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝3:1)做展开剂，分离得到淡黄色固体280.6mg，分离产率为86％。
4-phenyloxazolidin-2-one：
1H NMR(500MHz,CDCl
3)δ(ppm)7.42-7.33(m,5H),5.88(s,1H),4.99-4.92(m,1H),4.74(t,J＝8.7Hz,1H),4.19(dd,J＝8.6,7.0Hz,1H).
13C NMR(126MHz,DMSO-d6)δ(ppm)159.37,141.48,129.19,128.44,126.51,71.84,55.57.ESI-MS calcd for C
9H
10NO
2[M+H]
+164.06,found 164.10.
湿法装柱干法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝3:1)做展开剂，分离得到白色固体229.5mg，分离产率为70％。
5-phenyloxazolidin-2-one:white solid,
1H NMR(500MHz,CDCl
3)δ(ppm)7.43-7.36(m,5H),5.77(brs,1H),5.63(t,J＝8.1Hz,1H),3.99(t,J＝9.0Hz,1H),3.55(t,J＝8.4Hz,1H).
13C NMR(126MHz,CDCl
3)δ(ppm)159.66,138.38,128.92,125.66,77.90,48.29.ESI-MS calcd for C
9H
10NO
2[M+H]
+164.06,found 164.10.
湿法装柱湿法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝1:1)做展开剂，分离得到产物201.6mg，分离产率为99％。
4-methyloxazolidin-2-one：
1H NMR(500MHz,CDCl
3)δ(ppm)6.45(brs,1H),4.50(t,J＝8.1Hz,1H),4.05-3.99(m,1H),3.96-3.93(m,1H),1.30(d,J＝6.1Hz,3H).
13C NMR(126MHz,CDCl
3)δ(ppm)160.11,71.65,48.25,20.78.ESI-MS calcd for C
4H
8NO
2[M+H]
+102.05,found 102.10.
湿法装柱湿法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝1:1)做展开剂，分离得到产物182.2mg，分离产率为90％。
5-methyloxazolidin-2-one:
1H NMR(500MHz,CDCl
3)δ(ppm)5.82(brs,1H),4.81-4.75(m,1H),3.71(t,J＝8.3Hz,1H),3.21(t,J＝7.0Hz,1H),1.46(d,J＝6.3Hz,3H).
13C NMR(126MHz,CDCl
3)δ(ppm)160.04,77.21,73.50,47.40,20.52.ESI-MS calcd for C
4H
8NO
2[M+H]
+102.05,found 102.10.
湿法装柱湿法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝5:1)做展开剂，分离得到产物225.6mg，分离产率为99％。
4-ethyloxazolidin-2-one:
1H NMR(500MHz,CDCl
3)δ(ppm)5.80(brs,1H),4.04(dd,J＝8.6,6.0Hz,1H),3.84-3.79(m,1H),1.57-1.66(m,2H),0.95(t,J＝7.5Hz,3H).
13C NMR(126MHz,CDCl
3)δ(ppm)159.73,69.95,53.75,28.15,9.29.ESI-MS calcd for C
5H
10NO
2[M+H]
+116.06,found 116.10.
湿法装柱湿法上样柱层析(200-300目硅胶)分离，采用甲醇与二氯甲烷(V/V＝1:5)做展开剂，分离得到白色固体225.9mg，分离产率为100％。
5,5-dimethyloxazolidin-2-one:
1H NMR(500MHz,CDCl
3)δ(ppm)5.11(brs,1H),3.35(s,2H),1.48(s,6H).
13C NMR(126MHz,CDCl
3)δ(ppm)159.34,81.02,52.64,27.19.ESI-MS calcd for C
5H
10NO
2[M+H]
+116.06,found 116.15.
湿法装柱湿法上样柱层析(200-300目硅胶)分离，采用甲醇与二氯甲烷(V/V＝1:5)做展开剂，分离得到白色固体93.5mg，分离产率为41％。
4,4-dimethyloxazolidin-2-one:
1H NMR(500MHz,CDCl
3)δ(ppm)6.11(brs,1H),4.09(s,2H),1.37(s,6H).
13C NMR(126MHz,CDCl
3)δ(ppm)158.84,76.90,55.19,27.59.ESI-MS calcd for C
5H
10NO
2[M+H]
+116.06,found 116.10.
湿法装柱干法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝2：1)做展开剂，分离得到白色固体317.3mg，分离产率为90％。
(R)-4-benzyloxazolidin-2-one:
1H NMR(500MHz,DMSO-d6)δ(ppm)7.78(brs,1H),7.33-7.21(m,5H),4.25(t,J＝8.3Hz,1H),4.08-3.96(m,2H),2.84-2.72(m,2H).
13C NMR(126MHz,DMSO-d6)δ(ppm)159.04,136.99,129.82,128.84,126.98,68.46,52.93,40.68.ESI-MS calcd for C
10H
12NO
2[M+H]
+178.08,found 178.05.
湿法装柱湿法上样柱层析(200-300目硅胶)分离，采用二氯甲烷与乙酸乙酯(V/V＝2：1)做展开剂，分离得到白色固体237.2mg，分离产率为94％。
(S)-4-isopropyloxazolidin-2-one:
1H NMR(500MHz,CDCl
3)δ(ppm)6.47(brs),4.44 (t,J＝8.7Hz,1H),4.10(dd,J＝8.7,6.3Hz,1H),3.63-3.59(m,1H),1.77-1.70(m,1H),0.97(d,J＝6.7Hz,3H),0.90(d,J＝6.8Hz,3H).
13C NMR(126MHz,CDCl
3)δ(ppm)160.25,68.59,58.34,32.67,17.99,17.62.ESI-MS calcd for C
6H
12NO
2[M+H]
+130.08,found130.10.
乙酸乙酯萃取，柱层析分离得到目标产物纯品172.0mg，产率为86％。
1,3-Oxazinan-2-one:
1H NMR(500MHz,DMSO d
6)δ1.77-1.85(m,2H,NH-CH2-CH2-CH2-O),3.12-3.19(m,2H),4.15(t,J＝5.4Hz,2H),7.13(s,1H,).
13C NMR(126MHz,DMSO d
6)δ21.79,39.78,67.04,153.74.
乙酸乙酯萃取，柱层析分离得到目标产物纯品171.0mg，产率为84％。
thiazolidin-2-one:
1H NMR(500MHz,CDCl
3)δ3.37(t,J＝3.6Hz,2H),3.59(t,J＝3.6Hz,2H),6.99(s,1H)
实施例8 邻氨基苯腈与CO
2在H
2S作用下反应合成硫代喹唑啉二酮类衍生物
向10mL不锈钢高压反应釜中放入磁子，并依次加入1mmol邻氨基苯腈衍生物、适量H
2S和2ml溶剂，拧紧反应釜。向反应釜中充入指定压力的二氧化碳，搅拌反应24h，停止反应，冷却。缓慢排尽反应釜内的气体，拧开反应釜，用乙酸乙酯和饱和食盐水萃取，合并有机相，减压蒸馏得到粗产物。用石油醚和乙酸乙酯的柱层析得到目标产物纯品。
按照上述步骤进行条件优化，反应结果见下表：
注：上述各个反应中，原料均为1mmol邻胺基苯腈；溶剂为2ml；摩尔配比为原料和DBU的摩尔比；反应24h。
采用entry 9中的方法，换用不同底物，得到以下各个化合物：
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝1：1，分离后得到黄色固体6,7-二甲氧基-2-氧-4-硫喹唑啉二酮235.2mg，柱层析分离产率为99％。分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.50(s,1H),11.46(s,1H),7.69(s,1H),6.64(s,1H),3.84(s,3H),3.79(s,3H).
13C NMR(126MHz,DMSO-d
6)δ＝188.97,156.06,147.50,144.71,134.94,113.90,110.09,97.30,56.05,55.63.MS(ESI):m/z calcd for C
10H
10N
2O
3S[M]
+:239.04,found 239.2
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，后增加极性至1：1，分离后得到黄色固体6-氟-2-氧-4-硫喹唑啉二酮184mg，柱层析分离产率为94％。分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.91(s,1H),11.67(s,1H),7.96(dd,J＝9.7,3.0Hz,1H),7.58(td,J＝8.5,3.0Hz,1H),7.20(dd,J＝9.0,4.6Hz,1H).
13C NMR(126MHz,DMSO-d
6)δ＝190.86(d,J＝3.3Hz),157.63(d,J＝240.0Hz),147.13,134.92,123.63(d,J＝24.9Hz),120.94(d,J＝8.19Hz),118.26(d,J＝8.06Hz),114.76(d,J＝25.3Hz).MS(ESI):m/z calcd for C
8H
5FN
2OS[M]
+:197.01,found196.9
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝3：1，分离后得到白色固体6-溴-2-氧-4-硫喹唑啉二酮217mg，柱层析分离产率为85％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.94(s,1H),11.75(s,1H),8.37(dd,J＝2.4,1.0Hz,1H),7.83(ddd,J＝8.6,2.4,1.0Hz,1H),7.13(dd,J＝8.7,1.1Hz,1H).
13C NMR(126MHz,DMSO-d
6)δ＝189.50,147.08,138.29,137.44,132.05,121.64,118.36,114.79.MS (ESI):m/z calcd for C
8H
5BrN
2OS[M]
+:257.9,found 257.1。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，分离后得到黄色固体7-氟-2-氧-4-硫代喹唑啉二酮162mg，柱层析分离产率为83％。分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.77(s,1H),11.65(s,1H),8.27(t,J＝7.3Hz,1H),7.59(dd,J＝8.8,6.6Hz,1H),7.37–7.29(m,1H).
13C NMR(126MHz,DMSO-d
6)δ＝190.80,162.40,150.31,146.01,141.27,127.28,120.12,111.07(d,J＝11.3Hz).MS(ESI):m/z calcd for C
8H
5FN
2OS[M]
+:,197.01found 197.3.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，分离后得到黄色固体7-三氟甲基-2-氧-4-硫喹唑啉二酮219mg，柱层析分离产率为89％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝13.05(s,1H),11.81(s,1H),8.47(d,J＝8.5Hz,1H),7.53–7.47(m,1H),7.45(d,J＝1.7Hz,1H).
13C NMR(126MHz,DMSO-d
6)δ＝191.30,147.06,138.48,134.17(q,J＝32.8Hz),132.04,123.34(q,J＝273.7Hz),122.36,118.84(q,J＝3.8Hz),113.15(q,J＝3.8Hz).MS(ESI):m/z calcd for C
9H
5F
3N
2OS[M]
+:247.01,found 247.3.
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，分离后得到黄色固体7-氯-2-氧-4-硫喹唑啉二酮138mg，柱层析分离产率为65％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.71(s,1H),11.56(s,1H),8.23(t,J＝8.4Hz,1H),7.48(dd,J＝8.5,1.2Hz,1H),6.54–6.40(m,1H).
13C NMR(126MHz,DMSO-d
6)δ＝191.92,170.17,151.67,136.49,130.76,115.32,113.52,112.55.MS(ESI):m/z calcd for C
8H
5ClN
2OS[M]
+:212.65,found 212.3。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸 乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，分离后得到黄色固体7-甲基-2-氧-4-硫喹唑啉二酮172mg，柱层析分离产率为89％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.66(s,1H),11.56(s,1H),8.19(d,J＝8.3Hz,1H),7.03(d,J＝8.4Hz,1H),6.94(s,1H),2.35(s,3H).
13C NMR(126MHz,DMSO-d
6))δ＝188.97,148.23,146.65,137.75,131.11,125.24,119.85,114.69.MS(ESI):m/z calcd for C
9H
8N
2OS[M]
+:193.04,found193.2。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝1：1，分离后得到棕色固体6-硝基-2-氧-4-硫代喹唑啉二酮80mg，柱层析分离产率为36％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝12.51(s,1H),11.28(s,1H),7.48(d,J＝2.6Hz,1H),7.00(dd,J＝8.7,2.6Hz,1H),6.92–6.89(m,1H).
13C NMR(126MHz,DMSO-d
6)δ＝191.01,158.80,144.50,128.55,123.74,122.13,116.09,111.20.MS(ESI):m/z calcd for C
8H
5N
3O
3S[M]
+:223.01,found 223.4。
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，分离后得到黄色色固体5-氟-2-氧-4-硫代喹唑啉二酮133mg，柱层析分离产率为68％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝11.85(s,1H),11.20(s,1H),7.35(t,J＝8.1Hz,1H),6.68(d,J＝8.3Hz,1H),6.50(d,J＝7.8Hz,1H).
13C NMR(126MHz,DMSO-d
6)δ＝186.47,154.09,147.11,141.12,134.24,111.58,110.66,104.63.MS(ESI):m/z calcd for C
8H
5FN
2OS[M]
+:197.01,found 197.2
干法装柱干法上样柱层析(200-300目硅胶)分离：采用梯度洗脱，石油醚和乙酸乙酯做淋洗剂，石油醚：乙酸乙酯(V/V)＝2：1，分离后得到黄色固体6-三氟甲基-2-氧-4-硫喹唑啉二酮240mg，柱层析分离产率为97％，分析结果表明，获得的目标产物结构正确。
1H NMR(500MHz,DMSO-d
6)δ＝13.06(s,1H),11.97(d,J＝3.8Hz,1H),8.57–8.53(m,1H),8.01–7.94(m,1H),7.34(dd,J＝8.6,3.8Hz,1H).
13C NMR(126MHz,DMSO-d
6)δ＝191.24,147.13,141.10,131.40(q,J＝3.0Hz),127.52(q,J＝4.4Hz),123.84(q,J＝272.2Hz),123.36(q,J＝32.8Hz),119.82,117.43.MS(ESI): m/z calcd for C
9H
5F
3N
2OS[M]
+:247.01,found 247.3.
实施例10 苄胺与CO
2在硫化氢的作用下反应合成取代脲类衍生物
在15mL的高压反应釜内依次加入2mmol苄胺、DBU和1mL合适的溶剂，拧紧反应釜；依次向反应釜内通入所需量的H
2S和CO
2气体；最后将反应釜在合适温度下连续反应24小时；反应完毕后，在反应液中加入一定量的蒸馏水，使产物完全沉淀，然后依次通过抽滤、烘干得到目标产物。
按照上述步骤进行条件优化，反应结果见下表：
注：上述各个反应中，原料均为2mmol苄胺；溶剂为1ml，NR:no reaction。
采用entry4中相同的方法，换用其他反应底物，得到以下化合物：
通过过滤，烘干得到白色粉末状产物205mg，产率为91％
1H NMR(500MHz,DMSO-d
6)δ7.31(t,J＝7.5Hz,4H),7.28–7.18(m,6H),6.43(t,J＝6.1Hz,2H),4.23(d,J＝6.0Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ158.08,140.89,128.19,126.96,126.52,42.98.
MS(ESI):m/z calcd for C
15H
17N
2O[M+H]
+:241.10,found 241.13,m.p.:168-169℃
通过过滤，烘干得到淡黄色粉末状产物244mg，产率为86％
1H NMR(500MHz,Chloroform-d)δ4.58(s,2H),3.18–3.10(m,4H),1.47(q,J＝6.8Hz,4H),1.28(d,J＝10.4Hz,20H),0.88(t,J＝6.4Hz,6H).
13C NMR(126MHz,Chloroform-d)δ158.50,40.63,31.83,30.31,29.36,29.27,26.96,22.66,14.09.
MS(ESI):m/z calcd for C
19H
40N
3O[M+H+CH
3CN]
+:326.30,found 326.32,m.p.:89-91℃
通过过滤，烘干得到白色粉末状产物163mg，产率为71％
1H NMR(500MHz,DMSO-d
6)δ5.72(t,J＝5.7Hz,2H),2.94(q,J＝6.8,6.4Hz,4H),1.32(q,J＝6.8Hz,4H),1.27–1.18(m,12H),0.85(t,J＝6.7Hz,6H).
13C NMR(126MHz,Chloroform-d)δ158.62,40.58,31.59,30.29,26.63,22.60,14.03.
MS(ESI):m/z calcd for C
13H
29N
2O[M+H]
+:229.20,found 229.23,m.p.:73-76℃
通过过滤，烘干得到白色粉末状产物129mg，产率为64％
1H NMR(500MHz,DMSO-d
6)δ5.71(t,J＝5.9Hz,2H),2.95(q,J＝6.7Hz,4H),1.34(p,J＝7.1Hz,4H),1.31–1.18(m,8H),0.86(t,J＝7.1Hz,6H).
13C NMR(126MHz,DMSO-d
6)δ158.52,40.55,30.19,29.06,22.35,14.39.
MS(ESI):m/z calcd for C
11H
25N
2O[M+H]
+:201.15,found 201.20,m.p.:86-88℃
反应36h后，通过过滤，烘干得到白色晶状产物157mg，产率为73％
1H NMR(500MHz,TFA-d)δ5.11(s,2H),3.54(d,J＝9.8Hz,4H),3.35(d,J＝10.0Hz,4H),3.22(d,J＝11.6Hz,2H),2.86(ddt,J＝42.0,22.0,11.2Hz,12H).
13C NMR(126MHz,TFA-d)δ159.93,55.32,35.04,27.30,26.93.
MS(ESI):m/z calcd for C
13H
25N
2O[M+H]
+:225.10,found 225.20,m.p.:229-230℃
通过过滤，烘干得到黄色粉末状产物243mg，产率为91％
1H NMR(500MHz,DMSO-d
6)δ7.35–7.15(m,10H),6.27(d,J＝8.1Hz,2H),4.72(q,J＝7.0Hz,2H),1.30(dd,J＝10.8,7.5Hz,6H).
13C NMR(126MHz,DMSO-d
6)δ156.54,145.67,128.27,126.50,125.72,48.50,23.40.
MS(ESI):m/z calcd for C
17H
21N
2O[M+H]
+:269.10,found 269.17,m.p.:122-123℃
通过过滤，烘干得到银白色粉末状产物244mg，产率为91％
1H NMR(500MHz,DMSO-d
6)δ7.29(t,J＝7.5Hz,4H),7.23–7.16(m,6H),5.89(t,J＝5.1Hz,2H),3.22(q,J＝6.7Hz,4H),2.67(d,J＝7.2Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ157.97,139.81,128.72,128.35,126.02,40.97,36.23.
MS(ESI):m/z calcd for C
17H
21N
2O[M+H]
+:269.10,found 269.17,m.p.:138-140℃
通过过滤，烘干得到白色粉末状产物285mg，产率为96％
1H NMR(500MHz,DMSO-d
6)δ7.26(t,J＝7.5Hz,2H),7.17(dd,J＝15.1,7.4Hz,3H),5.88(d,J＝5.3Hz,1H),2.98(t,J＝6.6Hz,2H),2.58–2.53(m,2H),1.66(q,J＝7.3Hz,2H).
13C NMR(126MHz,DMSO-d
6)δ158.22,141.91,128.33,128.32,125.74,38.84,32.58,31.93.
MS(ESI):m/z calcd for C
19H
25N
2O[M+H]
+:297.20,found 297.20,m.p.:92-93℃
通过过滤，烘干得到白色粉末状产物233mg，产率为86％
1H NMR(500MHz,DMSO-d
6)δ7.20(d,J＝4.7Hz,1H),7.14(s,3H),6.27(t,J＝5.5Hz,1H),4.21(d,J＝4.9Hz,2H),2.26(s,3H).
13C NMR(126MHz,DMSO-d
6)δ157.93,138.37,135.45,129.94,127.22,126.73,125.77,41.02,18.58.
MS(ESI):m/z calcd for C
17H
21N
2O[M+H]
+:269.10,found 269.17,m.p.:237-238℃
通过过滤，烘干得到白色晶状产物260mg，产率为84％
1H NMR(500MHz,DMSO-d
6)δ7.35(d,J＝8.3Hz,4H),7.26(d,J＝8.2Hz,4H),6.66(t,J＝5.8Hz,2H),4.20(d,J＝5.7Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ158.20,140.09,131.09,128.88,128.19,42.34.
MS(ESI):m/z calcd for C
15H
16Cl
2N
2NaO
2[M+Na+H
2O]
+:350.05,found 350.05,m.p.:253-254℃
通过过滤，烘干得到灰白色晶状产物344mg，产率为86％
1H NMR(500MHz,DMSO-d
6)δ7.49(d,J＝7.9Hz,4H),7.19(d,J＝7.9Hz,4H),6.53(t,J＝5.8Hz,2H),4.18(d,J＝6.0Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ158.10,140.50,131.11,129.27,119.56,42.42.
MS(ESI):m/z calcd for C
15H
16Br
2N
2NaO
2[M+Na+H
2O]
+:439.95,found 439.95,m.p.:268-270℃
通过过滤，烘干得到白色粉末状产物257mg，产率为85％
1H NMR(500MHz,DMSO-d
6)δ7.17(d,J＝8.5Hz,4H),6.86(d,J＝8.6Hz,4H),6.30(s,2H),4.14(s,4H),3.72(s,6H).
13C NMR(126MHz,DMSO-d
6)δ158.15,132.79,128.40,113.70,55.13,42.50.
MS(ESI):m/z calcd for C
17H
21N
2O
3[M+H]
+:301.10,found 301.16,m.p.:178-180℃
通过过滤，烘干得到淡黄色固体产物290mg，产率为74％
1H NMR(500MHz,DMSO-d
6)δ7.31(d,J＝6.9Hz,8H),7.28–7.18(m,12H),6.95(d,J＝8.1Hz,2H),5.88(d,J＝8.0Hz,2H).
13C NMR(126MHz,DMSO-d
6)δ156.79,144.01,128.87,127.25,127.22,57.41.
MS(ESI):m/z calcd for C
27H
25N
2O[M+H]
+:393.15,found 393.20,m.p.:283-284℃
通过过滤，烘干得到灰白色粉末状产物106mg，产率为39％
1H NMR(500MHz,DMSO-d
6)δ9.23(s,2H),7.04(d,J＝8.1Hz,4H),6.69(d,J＝7.2Hz,4H),6.18(d,J＝6.0Hz,2H),4.09(d,J＝5.8Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ157.97,156.08,130.92,128.38,114.95,42.57.
MS(ESI):m/z calcd for C
15H
17N
2O
3[M+H]
+:273.05,found 273.12,m.p.:185-187℃
通过过滤，烘干得到白色晶状产物240mg，产率为89％
1H NMR(500MHz,DMSO-d
6)δ7.17–7.08(m,8H),6.33(t,J＝6.1Hz,2H),4.17(d,J＝6.0Hz,4H),2.27(s,6H).
13C NMR(126MHz,DMSO-d
6)δ157.91,137.68,135.41,128.62,126.87,42.59,20.54.
MS(ESI):m/z calcd for C
17H
21N
2O[M+H]
+:269.10,found 269.17,m.p.:216-218℃
通过过滤，烘干得到白色固体产物203mg，产率为63％
1H NMR(500MHz,DMSO-d
6)δ7.16(s,8H),6.33(t,J＝6.0Hz,2H),4.18(d,J＝5.9Hz,4H),2.85(hept,J＝6.7Hz,2H),1.18(d,J＝6.9Hz,12H).
13C NMR(126MHz,DMSO-d
6)δ157.92,146.59,138.11,126.98,125.97,42.67,33.01,23.87.
MS(ESI):m/z calcd for C
21H
29N
2O[M+H]
+:325.15,found 325.23,m.p.:122-123℃
通过过滤，烘干得到白色粉末状产物287mg，产率为78％
1H NMR(500MHz,DMSO-d
6)δ8.15(d,J＝8.4Hz,1H),8.08(d,J＝9.5Hz,1H),7.97–7.89(m,2H),7.85–7.77(m,2H),7.60–7.42(m,8H),6.42(dd,J＝20.3,8.1Hz,2H),5.55(h,J＝6.9Hz,2H),1.46(dd,J＝22.3,6.9Hz,6H).
13C NMR(126MHz,DMSO-d
6)δ156.36,141.29,133.41,130.42,128.57,127.14,126.04,125.54,123.24,121.84,44.65,22.53.
MS(ESI):m/z calcd for C
25H
25N
2O[M+H]
+:369.15,found 369.20,m.p.:223-225℃
通过过滤，烘干得到淡黄色固体产物331mg，产率为87％
1H NMR(500MHz,DMSO-d
6)δ7.56(d,J＝8.2Hz,2H),7.46(d,J＝2.0Hz,2H),7.24(dd,J＝8.3,2.0Hz,2H),6.69(t,J＝6.2Hz,2H),4.21(d,J＝6.1Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ157.97,142.39,130.80,130.36,128.96,128.83,127.29,41.96.
MS(ESI):m/z calcd for C
15H
14Cl
4N
2NaO
2[M+Na+H
2O]
+:419.95,found 419.97,m.p.:174-176℃
通过过滤，烘干得到白色粉末状产物196mg，产率为89％
1H NMR(500MHz,DMSO-d
6)δ7.55(s,2H),6.40–6.30(m,4H),6.18(d,J＝3.2Hz,2H),4.20(d,J＝5.7Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ157.40,153.54,141.89,110.41,106.22,40.02,39.85,39.69,39.52,39.35,39.19,39.02,36.37.
MS(ESI):m/z calcd for C
11H
13N
2O
3[M+H]
+:221.00,found 221.09,m.p.:126-128℃
通过分离柱得到黄色油状物，产率为89％
1H NMR(500MHz,DMSO-d
6)δ6.08–6.02(m,2H),3.75(dq,J＝13.9,6.4Hz,4H),3.59(q,J＝7.5Hz,2H),3.10(dq,J＝14.3,5.2Hz,2H),3.05–2.95(m,2H),1.89–1.72(m,6H),1.52–1.41(m,2H).
13C NMR(126MHz,DMSO-d
6)δ158.68,78.10,67.40,43.56,28.43,25.50.
MS(ESI):m/z calcd for C
11H
21N
2O
3[M+H]
+:229.10,found 229.16,Pyrolysistemperature:140℃
通过过滤，烘干得到黄色固体产物370mg，产率为93％
1H NMR(500MHz,TFA-d)δ4.92(t,J＝7.1Hz,4H),3.23(p,J＝6.9Hz,4H),2.90(d,J＝31.6Hz,36H),2.43(td,J＝6.7,2.9Hz,6H).
13C NMR(126MHz,TFA-d)δ160.26,109.99,43.49,33.13,30.76,30.65,30.55,30.51,30.18,29.82,27.62,23.70,14.05.
MS(ESI):m/z calcd for C
25H
52KN
2O[M+K]
+:435.30,found 435.37,m.p.:105-106℃
通过过滤，烘干得到白色固体产物311mg，产率为83％
1H NMR(500MHz,DMSO-d
6)δ7.67(d,J＝8.0Hz,4H),7.46(d,J＝7.9Hz,4H),6.69(t,J＝6.2Hz,2H),4.32(d,J＝6.0Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ158.14,145.99,127.57,127.30(q,J＝32.1Hz),125.09(q,J＝3.9Hz),124.44(q,J＝272.4Hz),42.67.
MS(ESI):m/z calcd for C
17H
15F
6N
2O[M+H]
+:377.05,found 377.11,m.p.:106-161℃
通过分离柱得到淡黄色油状物，产率为92％
1H NMR(500MHz,DMSO-d
6)δ8.50(d,J＝4.7Hz,2H),7.76(t,J＝7.6Hz,2H),7.30(d,J＝7.8Hz,2H),7.28–7.21(m,2H),6.75(t,J＝5.8Hz,2H),4.34(d,J＝5.8Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ159.69,158.12,148.69,136.62,121.90,120.84,44.96.
通过过滤，烘干得到棕黄色粉末状产物197mg，产率为78％
1H NMR(500MHz,DMSO-d
6)δ7.36(d,J＝4.7Hz,2H),6.93(d,J＝4.3Hz,4H),6.50(t,J＝6.0Hz,2H),4.38(d,J＝5.8Hz,4H).
13C NMR(126MHz,DMSO-d
6)δ157.40,144.22,126.60,124.66,38.12.
MS(ESI):m/z calcd for C
11H
13N
2OS
2[M+H]
+:253.00,found 253.05,m.p.:163-165℃
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (10)
- 一种二氧化碳作为羰基化试剂制备羰基化合物的方法，其特征在于，所述的方法在H 2S和任选的碱存在下进行。
- 如权利要求1所述的方法，其特征在于，所述的方法包括步骤(i)或步骤(ii)：
(i)在任选的惰性溶剂中，在任选的碱和无机硫试剂存在下，用式Ia化合物与CO 2反应，得到式I化合物；
(ii)在任选的惰性溶剂中，在碱和无机硫试剂存在下，用式IIa化合物与CO 2反应，得到式II化合物；其中，R 1和R 2各自独立地选自下组：取代或未取代的C 1-C 12烷基(如取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 8烷基)、取代或未取代的C 3-C 8环烷基、取代或未取代的C 2-C 6烯基、取代或未取代的C 2-C 6炔基；或所述的R 1和R 2共同构成选自下组的基团：取代或未取代的C 1-C 6亚烷基、取代或未取代的C 6-C 10芳基、取代或未取代的5-12元杂芳基；A环为取代或未取代的C 6-C 10芳基，或取代或未取代的5-12元杂芳基；X和Y各自独立地选自下组：卤素、CN、SH、OH、NH 2、NHR、NO 2；U和V各自独立地选自下组：NR、S、O、-C(＝S)NH；R选自下组：H、取代或未取代的C 1-C 12烷基(如取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 8烷基)、取代或未取代的C 3-C 8环烷基、取代或未取代的C 1-C 6烷氧基、SO 2CH 3，或者未取代或被1-4个选自下组的取代基取代的苯基：卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、OH、NO 2、NH 2、SO 2CH 3；R 3为一个或多个位于A环上的选自下组的基团：H、卤素、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6卤代烷基、NH 2、NO 2、SO 2CH 3，或未取代或被1-4个选自下组的取代基取代的苯基：卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、OH、NO 2、NH 2、SO 2CH 3；或R 5和R 6共同构成-(CH 2) n-，其中，n选自2、3、4、5或6；且所述的取代指基团上的一个或多个氢原子被选自下组的取代基替换：卤素、氧原子(即＝O)、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 1-C 6烷氧基、C 1-C 6卤代烷基、NO 2、SO 2CH 3，苯基、5-12元杂芳基、3-8元环烷基、5-12元饱和或部分不饱和的杂环；其中，所述的苯基、杂芳基、环烷基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、OH、NO 2、NH 2、SO 2CH 3；或者，相邻或者连接于同一个碳原子上的两个取代基共同构成-(CH 2) n-，其中，n选自 2、3、4、5或6。 - 如权利要求1所述的方法，其特征在于，所述的碱为有机碱；较佳地，所述的碱选自下组：C 1-C 12叔胺类、C 1-C 12仲胺类、C 1-C 12伯胺类、C 2-C 12脒类、C 2-C 12胍类、C 3-C 12吡啶类、C 3-C 12咪唑类；优选地，所述的碱选自下组：DBU，TBD，MTBD，DBN，TMG，DABCO、乙二胺(EDA)、三乙胺(EtN 3)、二异丙基乙基胺(DIPEA)、DMAP、吡啶，或其组合；优选地，所述反应底物与所述碱的摩尔比为1:0-5(如1:0.1-5)。
- 如权利要求1所述的方法，其特征在于，所述的方法包括步骤(a)、(b)、(c)、(d)、(e)、(f)或(g)；
(a)在任选的惰性溶剂中，在碱存在下，用邻碘苯胺与CO 2和硫化氢反应，得到苯并噻唑酮类衍生物；
(b)在任选的惰性溶剂中，在碱存在下，邻硝基碘苯与CO 2和硫化氢反应合成苯并噻唑酮类衍生物；
(c)在任选的惰性溶剂中，在任选的碱存在下，用炔丙胺衍生物与CO 2和硫化氢反应，合成噻唑烷-2-酮类衍生物；其中，R 4选自下组：H、取代或未取代的C 1-C 12烷基、取代或未取代的C 3-C 8环烷基、取代或未取代的苯基；R 5、R 6和R 7各自独立地选自下组：H、取代或未取代的C 1-C 12烷基、取代或未取代的C 3-C 8环烷基、苯基、5-12元杂芳基、5-12元饱和或部分不饱和的杂环，且所述的苯基、杂芳基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、OH、NO 2、NH 2、SO 2CH 3；或R 5和R 6共同构成-(CH 2) n-，其中，n选自2、3、4、5或6；
(d)在任选的惰性溶剂中，在碱存在下，用邻胺基苯腈与CO 2和硫化氢反应，合成硫代喹唑啉二酮类衍生物；其中，R 8为位于苯环上的一个或多个选自下组的取代基：H、卤素、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6卤代烷基、NO 2、SO 2CH 3，或未取代或被1-4个选自下组的取代基取代的苯基：卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、OH、NO 2、NH 2、 SO 2CH 3；
(e)在任选的惰性溶剂中，在碱存在下，用芳香邻胺基二硫化物与CO 2在硫化氢的作用下反应，合成苯并噻唑酮类衍生物；
(f)在任选的惰性溶剂中，在任选的碱存在下，用二胺、醇胺或巯基胺与CO 2在硫化氢的作用下反应合成咪唑烷酮类衍生物、恶唑烷酮类衍生物或噻唑烷酮类衍生物；其中，U为O、S或NR；M为取代或未取代的C 2-C 4亚烷基、取代或未取代的苯基、或取代或未取代的5-12元杂芳基，其中，取代的定义如权利要求2中所述；(g)在任选的惰性溶剂中，在任选的碱存在下，用胺与CO 2在硫化氢的作用下反应，合成脲类衍生物；
R 9选自下组：H、取代或未取代的C 1-C 12烷基(如取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 8烷基)、取代或未取代的C 3-C 8环烷基、苯基、5-12元杂芳基、5-12元饱和或部分不饱和的杂环，且所述的苯基、杂芳基或杂环是未取代或被1-4个选自下组的取代基所取代：卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、OH、NO 2、NH 2、SO 2CH 3。 - 如权利要求1所述的方法，其特征在于，所述的惰性溶剂选自下组：NMP、DMF、THF、DMSO、1,4-二氧六环、HMPA、CH 2Cl 2、CHCl 3、CC1 4、甲苯，乙酸乙酯，超临界CO 2，或其组合。
- 如权利要求1所述的方法，其特征在于，所述的反应中，反应底物与CO 2的摩尔比为1:1-100。
- 如权利要求1所述的方法，其特征在于，所述的反应过程中，CO 2持续通入反应器，且所述的CO 2在反应器中的压力为0.1-12MPa。
- 如权利要求1所述的方法，其特征在于，所述的反应中，反应底物与所述硫化氢的摩尔比为1:0.05-20。
- 如权利要求1所述的方法，其特征在于，所述的反应过程中，H 2S持续通入反应器，且所述的H 2S在反应器中的压力为0.05-1.5Mpa。
- 如权利要求1所述的方法，其特征在于，所述的反应中，反应温度为室温～150℃。
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