CN108863777A - A method of preparing oxalate - Google Patents
A method of preparing oxalate Download PDFInfo
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- CN108863777A CN108863777A CN201810859207.2A CN201810859207A CN108863777A CN 108863777 A CN108863777 A CN 108863777A CN 201810859207 A CN201810859207 A CN 201810859207A CN 108863777 A CN108863777 A CN 108863777A
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- Prior art keywords
- oxalate
- reaction
- compound
- photochemical catalyst
- preparing
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- -1 -Br ketone compounds Chemical class 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 49
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical class ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000005360 2-phenylpyridines Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 94
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 69
- 238000004458 analytical method Methods 0.000 description 29
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 238000010521 absorption reaction Methods 0.000 description 23
- 238000004440 column chromatography Methods 0.000 description 23
- 239000000741 silica gel Substances 0.000 description 23
- 229910002027 silica gel Inorganic materials 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 15
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- CBGDIJWINPWWJW-UHFFFAOYSA-N 6-hydroxy-3,4,5-trimethyl-8-oxo-3,4-dihydroisochromene-7-carboxylic acid Chemical compound O=C1C(C(O)=O)=C(O)C(C)=C2C(C)C(C)OC=C21 CBGDIJWINPWWJW-UHFFFAOYSA-N 0.000 description 3
- 125000003431 oxalo group Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- NWCXDAYQOSEQQS-UHFFFAOYSA-N methyl 4-(3,4-dimethoxyphenyl)-2,4-dioxobutanoate Chemical compound COC(=O)C(=O)CC(=O)C1=CC=C(OC)C(OC)=C1 NWCXDAYQOSEQQS-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- VPMIAOSOTOODMY-KJAPKAAFSA-N (4r)-6-[(e)-2-[6-tert-butyl-4-(4-fluorophenyl)-2-propan-2-ylpyridin-3-yl]ethenyl]-4-hydroxyoxan-2-one Chemical compound C([C@H](O)C1)C(=O)OC1/C=C/C=1C(C(C)C)=NC(C(C)(C)C)=CC=1C1=CC=C(F)C=C1 VPMIAOSOTOODMY-KJAPKAAFSA-N 0.000 description 1
- QRDAPCMJAOQZSU-KQQUZDAGSA-N (e)-3-[4-[(e)-3-(3-fluorophenyl)-3-oxoprop-1-enyl]-1-methylpyrrol-2-yl]-n-hydroxyprop-2-enamide Chemical compound C1=C(\C=C\C(=O)NO)N(C)C=C1\C=C\C(=O)C1=CC=CC(F)=C1 QRDAPCMJAOQZSU-KQQUZDAGSA-N 0.000 description 1
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 description 1
- VAVHMEQFYYBAPR-ITWZMISCSA-N (e,3r,5s)-7-[4-(4-fluorophenyl)-1-phenyl-2-propan-2-ylpyrrol-3-yl]-3,5-dihydroxyhept-6-enoic acid Chemical compound CC(C)C1=C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)C(C=2C=CC(F)=CC=2)=CN1C1=CC=CC=C1 VAVHMEQFYYBAPR-ITWZMISCSA-N 0.000 description 1
- MOXLHAPKZWTHEX-UHFFFAOYSA-N 1,2-dichloronaphthalene Chemical class C1=CC=CC2=C(Cl)C(Cl)=CC=C21 MOXLHAPKZWTHEX-UHFFFAOYSA-N 0.000 description 1
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 description 1
- MWVKLRSIDOXBSE-UHFFFAOYSA-N 5-(1-piperidin-4-ylpyrazol-4-yl)-3-(6-pyrrolidin-1-yl-1,3-benzoxazol-2-yl)pyridin-2-amine Chemical compound NC1=NC=C(C2=CN(N=C2)C2CCNCC2)C=C1C(OC1=C2)=NC1=CC=C2N1CCCC1 MWVKLRSIDOXBSE-UHFFFAOYSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- VCUKKMIXURRDKL-UHFFFAOYSA-N 9-(dimethylamino)-3-(4-ethylphenyl)pyrido[1,2]thieno[3,4-d]pyrimidin-4-one Chemical compound C1=CC(CC)=CC=C1N1C(=O)C(SC=2C3=C(N(C)C)C=CN=2)=C3N=C1 VCUKKMIXURRDKL-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- REDUQXCPUSNJOL-UHFFFAOYSA-N C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O Chemical compound C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O REDUQXCPUSNJOL-UHFFFAOYSA-N 0.000 description 1
- DGJMHKMYSDYOFP-MRXNPFEDSA-N C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O Chemical compound C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O DGJMHKMYSDYOFP-MRXNPFEDSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CYSWUSAYJNCAKA-FYJFLYSWSA-N ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O Chemical compound ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O CYSWUSAYJNCAKA-FYJFLYSWSA-N 0.000 description 1
- QBXVXKRWOVBUDB-GRKNLSHJSA-N ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C Chemical compound ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C QBXVXKRWOVBUDB-GRKNLSHJSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- RRQIDDGRIQVTGM-UHFFFAOYSA-N Orientalone Chemical compound CC1=C(C(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1 RRQIDDGRIQVTGM-UHFFFAOYSA-N 0.000 description 1
- BEXZJJQVPWJPOA-VOTSOKGWSA-N [(e)-hept-2-enyl] 6-methyl-4-(4-nitrophenyl)-2-oxo-3,4-dihydro-1h-pyrimidine-5-carboxylate Chemical compound CCCC\C=C\COC(=O)C1=C(C)NC(=O)NC1C1=CC=C([N+]([O-])=O)C=C1 BEXZJJQVPWJPOA-VOTSOKGWSA-N 0.000 description 1
- HGDWHTASNMRJMP-UHFFFAOYSA-N [1-(hydroxyamino)-1-oxo-5-(3-phenoxyphenyl)pentan-2-yl]phosphonic acid Chemical compound ONC(=O)C(P(O)(O)=O)CCCC1=CC=CC(OC=2C=CC=CC=2)=C1 HGDWHTASNMRJMP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- AVAACINZEOAHHE-VFZPANTDSA-N doripenem Chemical compound C=1([C@H](C)[C@@H]2[C@H](C(N2C=1C(O)=O)=O)[C@H](O)C)S[C@@H]1CN[C@H](CNS(N)(=O)=O)C1 AVAACINZEOAHHE-VFZPANTDSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- JFOZKMSJYSPYLN-QHCPKHFHSA-N lifitegrast Chemical compound CS(=O)(=O)C1=CC=CC(C[C@H](NC(=O)C=2C(=C3CCN(CC3=CC=2Cl)C(=O)C=2C=C3OC=CC3=CC=2)Cl)C(O)=O)=C1 JFOZKMSJYSPYLN-QHCPKHFHSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for preparing oxalate：Using diazonium compound and α-Br ketone compounds as reaction substrate, with O2For oxygen source and oxidant, using organic dyestuff as photochemical catalyst, in organic solvent, oxalate is obtained through radical mechanism using visible light as energy source.Method used in the present invention has the characteristics that：React that more environmentally protective, economy, substrate universality be wider, later period function dough is easier to, reaction condition is mild, can carry out in air, and photochemical catalyst dosage is few, and post-processing is easy.Simultaneously, the raw materials such as reactant, photochemical catalyst that the present invention uses are cheap and easy to get, reaction composition is reasonable, without ligand, Atom economy is high, and reaction step is few, it is only necessary to which single step reaction can obtain higher yield, requirement and the direction for meeting contemporary Green Chemistry and sustainable development, the oxalate for being difficult to the Asymmetrical substitute synthesized suitable for synthesizing conventional method.
Description
Technical field
The present invention relates to a kind of methods for preparing oxalate, belong to technical field of organic synthesis.
Background technique
Oxalate is widely present in natural products, in drug molecule, while being also structural unit common in organic synthesis.
Currently, the method for preparing oxalate has very much, but every kind of method has some shortcomings.Such as：
（1）Tradition oxalyl chloride or oxalyl monochloro and alcohol or ether react and require base catalysis, and wherein oxalyl chloride is not only to sky
Air-sensitive sense is afraid of tide and has high toxicity and corrosivity, and the oxalate synthesized can only be the oxalate symmetrically replaced, if with
Oxalyl monochloro is raw material, then needs first to prepare oxalyl monochloro, and this step is more difficult to control, is synthesized more troublesome；
（2）Transesterification is carried out with oxalate to synthesize new oxalate；
（3）Transition metal-catalyzed CO and CH3The oxidative coupling reaction of OH is only used for synthesizing dimethyl oxalate, and reacts
Need another oxidizer.
（4）Certainly, the ozonisation of alkene is also a kind of method of synthesis of oxalate, but requires the alkene of some special constructions
Hydrocarbon（Such as ascorbic acid and its derivative）It could synthesis of oxalate.
To sum up, there is presently no a kind of methods of the green of synthesis of oxalate.Therefore, it is necessary to research and develop a kind of raw material
Source is abundant, at low cost, safe and environment-friendly, preparation method easy to operate is effectively synthesized oxalic acid ester compound.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesis of oxalate, the reaction raw materials abundance, reaction substrate are general
Adaptive is wide, easy to operate, and this method is the energy source reacted with visible light, using oxygen as oxygen source and oxidant, side
Method is very safe and environment-friendly, green.
To achieve the above object of the invention, the technical solution adopted by the present invention is that：
A method of oxalate is prepared, using diazonium compound and α-Br ketone compounds as reaction substrate, in organic solvent,
In the presence of photochemical catalyst, oxidant, illumination reaction obtains oxalate；
The general formula of the chemical structure of the α-Br ketone compounds is one of following chemical structural formula：
In formula, R1For fluorine, methoxyl group, methyl, chlorine, trifluoromethyl, bromine, hydroxyl；R2Selected from hydrogen or phenyl；
The structural formula of the diazonium compound is as follows：
Diazonium compound and α-Br ketone compounds are that raw material is preparing the application in oxalate；Preferably, diazonium compound and
α-Br ketone compounds are raw material, in organic solvent, in the presence of photochemical catalyst, oxidant, prepare grass using illumination reaction
Acid esters.
The present invention is using diazonium compound and α-Br ketone compounds as reaction substrate, with O2For oxygen source and oxidant, with can
The light-exposed energy source for reaction, using organic dyestuff or metal complex as photochemical catalyst, in organic solvent, through free radical
Course obtains oxalate.
In the present invention, in the general formula of the chemical structure of α-Br ketone compounds, R1Can be the fluorine of ortho position substitution, methoxyl group,
Methyl can be methoxyl group, the methyl, chlorine, trifluoromethyl of meta position substitution, or fluorine, chlorine, bromine, methoxyl group, first that contraposition replaces
Base, hydroxyl；Or disubstituted 3,4- dichloro, naphthalene；Photochemical catalyst is selected from common organic dyes（Such as：Eosin Y（Eosin Y）,
Rhodamine B（RhB）Deng）, metal complex（Six hydration Tris(2,2'- bipyridyl) ruthenium (II) chlorides（Ru(bpy)3Cl2.6H2O）, three (2- phenyl
Pyridine) close iridium（fac-Ir(ppy)3）One of；Organic solvent is petroleum ether, N-Methyl pyrrolidone, dimethyl sulfoxide, N, N-
Dimethylformamide, acetonitrile, toluene, 1,1,2- trichloroethanes etc..
In the present invention, the chemical structural formula of oxalate is following one kind：
Wherein, R1、R2From α-Br ketone compounds；R3From diazonium compound.
In above-mentioned technical proposal, illumination reaction is carried out with LED green light lamp, and power is 7~15 W, and the time is 12~48 small
When；The power of preferred LED green light lamp is 12 W, and the time is 36 hours.
Preferably, the photochemical catalyst is Eosin Y（Eosin Y）；Organic solvent is N,N-dimethylformamide.
In preferred technical solution, the photochemical catalyst dosage is the 1% of α-Br ketone compounds mole, diazo compounds
The molar ratio of object and α-Br ketone compounds is 4.
Reaction of the invention carries out in oxygen, and reaction temperature is room temperature.After reaction, reaction solution is extracted with ethyl acetate
After taking, anhydrous magnesium sulfate is dry, can obtain product oxalate by column chromatography after removing solvent, silica gel absorption.
The invention also discloses the oxalates being prepared according to the above method.
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art:
1. the present invention is using visible light as energy source, using oxygen as oxygen source and oxidant, to realize α-Br ketone compounds and again
The reaction of nitrogen compound carrys out synthesis of oxalate, pre-prepared or material toxicity is big with raw material in the prior art, reacts to be heated to be
Energy source, severe reaction conditions are compared, and the reaction is more economical, environmentally protective, substrate universality is wider, raw material is easy to get, the later period
Function dough is easier to.
2. method reaction condition disclosed by the invention is mild, room temperature can be carried out, and photochemical catalyst dosage is few, post-processing letter
Just.
3. the raw materials such as the reactant that the present invention uses, photochemical catalyst are cheap and easy to get, reaction composition rationally, is not necessarily to ligand, former
Subeconomy is high, and reaction step is few, it is only necessary to single step reaction can obtain higher yield, meet contemporary Green Chemistry requirement and
Direction.
Specific embodiment
The present invention will be further described below with reference to examples：
α-Br ketone compounds of the invention, photochemical catalyst are all market-oriented commodity, can directly be bought, α-Br ketone compounds
It can synthesize to obtain by the ketone compounds and tetrabutyl tribromide amine of the marketization, diazonium compound used in the present invention is city
Fieldization commodity can directly be bought, and diazonium compound can also pass through alcohols chemical combination bromination corresponding with bromoacetyl bromide reaction generation
Object, bromide react to obtain corresponding diazonium compound again with TsNHNHTs.
Embodiment one
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.00 5mol, 3.6 mg), N,N-dimethylformamide (2 mL）；Then in oxygen, 12
It is reacted 36 hours under the irradiation of W green LED lamp；After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous magnesium sulfate
It is dry, solvent, silica gel absorption are removed with Rotary Evaporators, product 3a, yield 85% can be obtained by simple column chromatography.Institute
The main test data that product is made is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.94 – 7.89 (m, 2H), 7.63 (t, J=7.4 Hz, 1H),
7.50 (t, J=7.7 Hz, 2H), 5.55 (s, 2H), 4.40 (q, J=7.1 Hz, 2H), 1.40 (t, J=7.2
Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 189.79, 156.91, 156.88, 134,10, 133.48,
128.84, 127.65, 67.59, 63.35, 13.75; HRMS (ESI-TOF): Anal. Calcd. For C12H12O5:
259.0577, Found: 259.0649 (M+Na+); IR (neat, cm-1): υ 2987, 2941, 1771, 1744,
1702, 1155, 960, 750, 688。
Embodiment two
Compound 1b is added into the Schlenk pipe of 25mL（0.5 mmol, 114.2 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3b by simple column chromatography, yield is
73%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 8.03-7.97 (m, 1H), 7.66-7.59 (m, 1H), 7.33 –
7.27 (m, 1H), 7.24-7.17 (m, 1H), 5.43 (d, J=3.7 Hz, 2H), 4.42 (q, J=7.1 Hz,
2H), 1.42 (t, J=7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 188.00, 187.97,
163.65, 161.12, 157.04, 156.91, 136.10, 136.0, 130.83, 130.80, 125.02,
124.99, 121.84, 121.70, 116.68, 116.45, 70.60, 70.45, 63.44, 13.87; 19F NMR
(376 MHz, CDCl3) δ -107.89; HRMS (ESI-TOF): Anal. Calcd. For C12H11FO5:
277.0483, Found: 277.0479 (M+Na+); IR (neat, cm-1): υ 3675, 2988, 2972, 2901,
1777, 1697, 1076, 1066, 780。
Embodiment three
Compound 1c is added into the Schlenk pipe of 25mL（0.5 mmol, 119.5 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3c by simple column chromatography, yield is
90%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.50-7.36 (m, 3H), 7.18-7.13 (m, 1H), 5.52
(s, 2H), 4.40 (q, J=7.1 Hz, 2H), 3.84 (s, 3H), 1.40 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ 189.64, 159.82, 156.88, 134.69, 129.82, 120.47, 119.98, 111.95,
67.63, 63.29, 55.27, 13.71; HRMS (ESI-TOF): Anal. Calcd. For C13H14O6:
289.0683, Found: 289.0675 (M+Na+); IR (neat, cm-1): υ 2943, 2840, 1771, 1745,
1701, 1153, 973, 782, 685。
Example IV
Compound 1d is added into the Schlenk pipe of 25mL（0.5 mmol, 122.9 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3d by simple column chromatography, yield is
80%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.93 (t, J=1.7 Hz, 1H), 7.85-7.81 (m, 1H),
7.67-7.62 (m, 1H), 7.50 (t, J=7.9 Hz, 1H), 5.54 (s, 2H), 4.46 (q, J=7.1 Hz,
2H), 1.45 (t, J=7.2 Hz, 3H; 13C NMR (101 MHz, CDCl3) δ 188.81, 156.88, 156.85,
135.36, 135.07, 134.16, 130.33, 127.90, 125.83, 67.51, 63.57, 13.87; HRMS
(ESI-TOF): Anal. Calcd. For C12H11ClO5: 293.0187, Found: 293.0175 (M+Na+); IR
(neat, cm-1): υ 2986, 2941, 1772, 17745, 1177, 1156, 725, 680。
Embodiment five
Compound 1e is added into the Schlenk pipe of 25mL（0.5 mmol, 112.1 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3e by simple column chromatography, yield is
81%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.74 – 7.68 (m, 2H), 7.46-7.35 (m, 2H), 5.53
(s, 2H), 4.41 (q, J=7.1 Hz, 2H), 2.41 (s, 3H), 1.41 (t, J=7.2 Hz, 3H); 13C NMR
(101 MHz, CDCl3) δ 189.88, 156.93, 156.91, 138.80, 134.89, 133.55, 128.72,
128.16, 124.85, 67.66, 63.37, 21.18, 13.80; HRMS (ESI-TOF): Anal. Calcd. For
C13H14O5: 273.0733, Found: 273.0722 (M+Na+); IR (neat, cm-1): υ 2988, 2902,
1771, 1745, 1670, 1152, 972, 782, 689。
Embodiment six
Compound 1f is added into the Schlenk pipe of 25mL（0.5 mmol, 140.6 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3f by simple column chromatography, yield is
69%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 8.17 (s, 1H), 8.12 (d, J=7.6 Hz, 1H), 7.90
(d, J=7.5 Hz, 1H), 7.68 (t, J=7.7 Hz, 1H), 5.56 (s, 2H), 4.42 (dd, J = 14.1,
7.0 Hz, 2H), 1.42 (t, J=7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 188.91,
156.89, 156.81, 134.13, 131.78, 131.45, 130.95, 130.58, 130.55, 129.73,
124.68, 124.64, 121.99, 67.54, 63.57, 13.82; 19F NMR (376 MHz, CDCl3) δ -
62.96; HRMS (ESI-TOF): Anal. Calcd. For C13H11F3O5: 327.0451, Found: 327.0456
(M+Na+); IR (neat, cm-1): υ 2997, 2949, 1739, 1711, 1327, 1154, 1128, 1072,
812, 688。
Embodiment seven
Compound 1g is added into the Schlenk pipe of 25mL（0.5 mmol, 114.3 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3g by simple column chromatography, yield is
88%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 8.03-8.97 (m, 1H), 7.66-7.58 (m, 1H), 7.34 –
7.26 (m, 1H), 7.24-7.16 (m, 1H), 5.43 (d, J=3.7 Hz, 2H), 4.42 (q, J=7.1 Hz,
2H), 1.42 (t, J=7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 188.00, 187.95,
163.65, 161.12, 157.04, 156.91, 136.10, 136.01, 130.83, 130.80, 125.02,
124.99, 121.84, 121.70, 116.68, 116.45, 70.60, 70.45, 63.44, 13.87; 19F NMR
(376 MHz, CDCl3) δ -107.89; HRMS (ESI-TOF): Anal. Calcd. For C12H11FO5:
277.0483, Found: 277.0480 (M+Na+); IR (neat, cm-1): υ 2994, 1747, 1695, 1594,
1160, 1104, 966, 836。
Embodiment eight
Compound 1h is added into the Schlenk pipe of 25mL（0.5 mmol, 122.9 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3h by simple column chromatography, yield is
81%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.87 (d, J=8.6 Hz, 2H), 7.49 (d, J=8.6 Hz,
2H), 5.50 (s, 2H), 4.42 (q, J=7.1 Hz, 2H), 1.41 (t, J=7.1 Hz, 3H); 13C NMR
(101 MHz, CDCl3) δ 188.80, 156.91, 156.87, 140.74, 131.89, 129.31, 129.17,
67.45, 63.52, 13.85; HRMS (ESI-TOF): Anal. Calcd. For C12H11ClO5: 293.0187,
Found: 293.0181 (M+Na+); IR (neat, cm-1): υ 2988, 2901, 1740, 1692, 1394,
1185, 1066, 1056。
Embodiment nine
Compound 1i is added into the Schlenk pipe of 25mL（0.5 mmol, 146.3 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3i by simple column chromatography, yield is
86%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.78 (d, J=8.6 Hz, 2H), 7.65 (d, J=8.6 Hz,
2H), 5.49 (s, 2H), 4.42 (q, J=7.1 Hz, 2H), 1.41 (t, J=7.2 Hz, 3H); 13C NMR
(101 MHz, CDCl3) δ 188.99, 156.89, 156.85, 132.30, 129.49, 129.21, 67.42,
63.52, 13.86; HRMS (ESI-TOF): Anal. Calcd. For C12H11BrO5: 336.9682, Found:
336.9671, 338.9658 (M+Na+); IR (neat, cm-1): υ 3011, 2993, 1736, 1691, 1585,
1179, 1165, 1070, 962, 761。
Embodiment ten
Compound 1j is added into the Schlenk pipe of 25mL（0.5 mmol, 120.6 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3j by simple column chromatography, yield is
81%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.9 Hz, 2H), 6.96 (d, J = 8.9
Hz, 2H), 5.50 (s, 2H), 4.41 (q, J = 7.1 Hz, 2H), 3.88 (s, 3H), 1.40 (t, J =
7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 188.17, 164.19, 157.01, 156.97,
130.02, 126.51, 114.07, 67.37, 63.34, 55.45, 13.79; HRMS (ESI-TOF): Anal.
Calcd. For C13H14O6: 289.0683, Found: 289.0690 (M+Na+); IR (neat, cm-1): υ
2986, 2944, 1766, 1742, 1687, 1600, 1159, 961, 843。
Embodiment 11
Compound 1k is added into the Schlenk pipe of 25mL（0.5 mmol, 113.2 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3k by simple column chromatography, yield is
79%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.72 (d, J = 8.1 Hz, 2H), 6.83 (d, J = 8.5
Hz, 2H), 5.42 (s, 2H), 4.37 – 4.25 (m, 2H), 1.29 (t, J = 7.1 Hz, 3H); 13C NMR
(101 MHz, CDCl3) δ 189.16, 162.00, 157.14, 157.12, 130.50, 125.88, 115.92,
67.48, 63.75, 13.78; HRMS (ESI-TOF): Anal. Calcd. For C12H12O6: 275.0526,
Found: 275.0538 (M+Na+); IR (neat, cm-1): υ 3038, 2943, 1742, 1668, 1574,
1371, 1152, 965, 840。
Embodiment 12
Compound 1l is added into the Schlenk pipe of 25mL（0.5 mmol, 112.2 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3l by simple column chromatography, yield is
80%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.1 Hz, 2H), 7.29 (d, J = 7.9
Hz, 2H), 5.52 (s, 2H), 4.41 (q, J = 7.1 Hz, 2H), 2.42 (s, 3H), 1.41 (t, J =
7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 189.33, 157.00, 156.96, 145.21,
131.07, 129.55, 127.79, 67.56, 63.38, 21.65, 13.81; HRMS (ESI-TOF): Anal.
Calcd. For C13H14O5: 273.0733, Found: 273.0734 (M+Na+); IR (neat, cm-1): υ
2994, 2939, 1773, 1743, 1698, 1173, 963, 813, 790。
Embodiment 13
Compound 1m is added into the Schlenk pipe of 25mL（0.5 mmol, 141.0 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3m by simple column chromatography, yield is
84%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 1.9 Hz, 1H), 7.75 (dd, J = 8.4,
1.9 Hz, 1H), 7.60 (d, J = 8.4 Hz, 1H), 5.47 (s, 2H), 4.43 (q, J = 7.1 Hz,
2H), 1.42 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 188.04, 156.86,
156.79, 139.01, 133.87, 133.08, 131.16, 129.81, 126.75, 67.36, 63.63, 13.89;
HRMS (ESI-TOF): Anal. Calcd. For C12H10Cl2O5: 326.9797, Found: 326.9796 (M+Na
+); IR (neat, cm-1): υ 3005, 2946, 1744, 1698, 1188, 975, 853, 830, 672。
Embodiment 14
Compound 1n is added into the Schlenk pipe of 25mL（0.5 mmol, 131.1 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3n by simple column chromatography, yield is
88%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 8.37 (s, 1H), 7.91 (d, J = 8.2 Hz, 2H), 7.89
– 7.82 (m, 2H), 7.60 (t, J = 7.2 Hz, 1H), 7.54 (t, J = 7.3 Hz, 1H), 5.65 (s,
2H), 4.40 (q, J = 7.1 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz,
CDCl3) δ 189.67, 156.97, 156.95, 135.79, 132.11, 130.77, 129.49, 129.43,
128.93, 128.78, 127.72, 127.00, 122.93, 67.68, 63.37, 13.7 ; HRMS (ESI-TOF):
Anal. Calcd. For C16H14O5: 309.0733, Found: 309.0733 (M+Na+); IR (neat, cm-
1): υ 3059, 2988, 2958, 1742, 1702, 1174, 819, 744.
Embodiment 15
Compound 1o is added into the Schlenk pipe of 25mL（0.5 mmol, 144.8 mg）, compound 2a（2 mmol, 224
vL）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system is in oxygen
In, react 36 hours under the irradiations of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL × 3）, anhydrous
Magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, can obtain product 3o by simple column chromatography, yield is
71%.The main test data of obtained product is as follows, by analyzing it is found that practical synthetic product is consistent with theory analysis.
1H NMR (400 MHz, CDCl3) δ 7.95 – 7.90 (m, 2H), 7.52 – 7.47 (m, 3H),
7.40 – 7.33 (m, 5H), 6.96 (s, 1H), 4.34 (q, J = 7.1 Hz, 2H), 1.33 (t, J = 7.1
Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 191.63, 157.07, 157.04,133.92, 133.66,
132.20, 129.69, 129.16, 128.69, 128.73, 128.60, 79.67, 63.24, 13.74; HRMS
(ESI-TOF): Anal. Calcd. For C18H16O5: 335.0890, Found: 335.0891 (M+Na+); IR
(neat, cm-1): υ 2991, 1759, 1695, 1200, 1182, 937, 761, 689。
Embodiment 16
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2b（2 mmol,
269.7 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4a can be obtained by simple column chromatography,
Yield is 90%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.94-7.90(m, 2H), 7.66-7.61 (m, 1H), 7.54-
7.48 (m, 2H), 5.53 (s, 2H), 5.23 (dt, J = 12.6, 6.3 Hz, 1H), 1.39 (d, J = 6.3
Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 189.85, 157.22, 156.58, 134.16, 133.64,
128.93, 127.75, 71.93, 67.57, 21.46; HRMS (ESI-TOF): Anal. Calcd. For
C13H14O5: 273.0733, Found: 273.0735 (M+Na+); IR (neat, cm-1): υ 2986, 2940,
1769, 1739, 1702, 1175, 963, 752, 689。
Embodiment 17
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2c（2 mmol,
299.2 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4b can be obtained by simple column chromatography,
Yield is 85%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.94-7.90(m, 2H), 7.64-7.60 (m, 1H), 7.54-
7.48 (m, 2H), 5.50 (s, 2H), 1.59 (s, 9H); 13C NMR (101 MHz, CDCl3) δ 190.04,
157.70, 156.08, 134.13, 133.75, 128.93, 127.77, 85.35, 67.42, 27.71; HRMS
(ESI-TOF): Anal. Calcd. For C14H16O5: 287.0890, Found: 287.0885 (M+Na+); IR
(neat, cm-1): υ 2983, 2938, 1736, 1703, 1141, 962, 840, 755, 688。
Embodiment 18
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2d（2 mmol,
290.7 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4c can be obtained by simple column chromatography,
Yield is 81%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.94 – 7.90 (m, 2H), 7.67-7.61 (m, 1H),
7.54-7.48 (m, 2H), 5.56 (s, 2H), 4.89 (q, J = 2.3 Hz, 2H), 1.87 (t, J = 2.4
Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 189.69, 156.35, 156.30, 134.22, 133.52,
128.93, 127.74, 85.10, 71.41, 67.79, 55.40, 3.61; HRMS (ESI-TOF): Anal.
Calcd. For C14H12O5: 283.0577, Found: 283.0580 (M+Na+); IR (neat, cm-1): υ
2955, 2921, 2244, 1747, 1697, 1166, 931, 761, 689
Embodiment 19
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2e（2 mmol,
295.0 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4d can be obtained by simple column chromatography,
Yield is 80%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.93–7.89 (m, 2H), 7.65–7.59 (m, 1H), 7.53-
7.46 (m, 2H), 5.97–5.85(m, 1H), 5.71-5.61 (m, 1H), 5.54 (s, 2H), 4.78-4.73
(m, 2H), 1.77–1.71 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 189.74, 156.88, 156.76,
134.17, 133.89, 133.58, 128.92, 127.73, 123.29, 67.91, 67.65, 17.74; HRMS
(ESI-TOF): Anal. Calcd. For C14H14O5: 285.0733, Found: 285.0753 (M+Na+); IR
(neat, cm-1): υ 2946, 1772, 1745, 1702, 1158, 964, 750, 688。
Embodiment 20
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2f（2 mmol,
425.7 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4e can be obtained by simple column chromatography,
Yield is 72%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.92 – 7.87 (m, 2H), 7.61 (t, J = 7.4 Hz,
1H), 7.48 (t, J = 7.7 Hz, 2H), 7.42 – 7.37 (m, 2H), 7.36-7.24 (m, 4H), 6.75
(d, J = 15.8 Hz, 1H), 6.38-6.29 (m, 1H), 5.53 (s, 2H), 4.98 (dd, J = 6.7, 0.7
Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 189.76, 156.78, 156.78, 136.27, 135.63,
134.19, 133.52, 128.91, 128.56, 128.37, 127.73, 126.73, 120.96, 67.78, 67.71;
HRMS (ESI-TOF): Anal. Calcd. For C19H16O5: 347.0890, Found: 347.0886 (M+Na+);
IR (neat, cm-1): υ 3064, 2959, 2921, 1764, 1739, 1695, 1159, 912, 747, 687。
Embodiment 21
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2g（2 mmol,
341.3 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4f can be obtained by simple column chromatography,
Yield is 53%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.97-7.91 (m, 2H), 7.65 (t, J = 7.4 Hz, 1H),
7.52 (t, J = 7.7 Hz, 2H), 7.43 (t, J = 7.9 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H),
7.27 – 7.22 (m, 2H), 5.62 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 189.61), 156.55,
155.30, 149.92, 134.31, 133.56, 129.67, 129.01, 127.80, 126.81, 120.91,
68.00; HRMS (ESI-TOF): Anal. Calcd. For C16H12O5: 307.0577, Found: 307.0576
(M+Na+); IR (neat, cm-1): υ 2950, 1758, 1701, 1189, 1161, 964, 752, 743, 686。
Embodiment 22
Compound 1a is added into the Schlenk pipe of 25mL（0.5 mmol, 101.6 mg）, compound 2h（2 mmol,
413.1 mg）, Eosin Y（Eosin Y）(0.005 mol, 3.6 mg), n,N-Dimethylformamide (2 mL）.Then the system
It is reacted 36 hours in oxygen, under the irradiation of 12 W green LED lamps.After reaction, it is extracted with ethyl acetate（10 mL ×
3）, anhydrous magnesium sulfate is dry, removes solvent, silica gel absorption with Rotary Evaporators, product 4g can be obtained by simple column chromatography,
Yield is 87%.The main test data of obtained product is as follows, by analysis it is found that practical synthetic product and theory analysis one
It causes.
1H NMR (400 MHz, CDCl3) δ 7.94 – 7.89 (m, 2H), 7.63 (t, J = 7.4 Hz,
1H), 7.50 (t, J = 7.7 Hz, 2H), 7.18 (dd, J = 5.1, 1.0 Hz, 1H), 6.97-6.91 (m,
2H), 5.54 (s, 2H), 4.54 (t, J = 7.0 Hz, 2H), 3.29 (t, J = 7.0 Hz, 2H); 13C NMR
(101 MHz, CDCl3) δ 189.68, 156.77, 156.68, 138.39, 134.21, 133.60, 128.95,
127.76, 127.04, 125.99, 124.31, 67.72, 67.17, 28.79; HRMS (ESI-TOF): Anal.
Calcd. For C16H14O5S: 341.0454, Found: 341.0457 (M+Na+); IR (neat, cm-1): υ
2960, 2923, 1770, 1744, 1702, 1168, 959, 753, 688。
Claims (10)
1. a kind of method for preparing oxalate, it is characterised in that：Using diazonium compound and α-Br ketone compounds as reaction substrate,
In organic solvent, in the presence of photochemical catalyst, oxidant, illumination reaction obtains oxalate；
The general formula of the chemical structure of the α-Br ketone compounds is one of following chemical structural formula：
In formula, R1For fluorine, methoxyl group, methyl, chlorine, trifluoromethyl, bromine, hydroxyl；R2Selected from hydrogen or phenyl；
The structural formula of the diazonium compound is as follows：
。
2. preparing the method for oxalate according to claim 1, it is characterised in that：The power of illumination reaction is 7~15 W,
Time is 12~48 hours, and temperature is room temperature.
3. preparing the method for oxalate according to claim 2, it is characterised in that：The power of illumination reaction is 12 W, time
It is 36 hours.
4. preparing the method for oxalate according to claim 1, it is characterised in that：The oxidant is oxygen；The light is urged
Agent is organic dyestuff or metal complex；The organic solvent be petroleum ether, N-Methyl pyrrolidone, dimethyl sulfoxide, N,
Dinethylformamide, acetonitrile, toluene or 1,1,2- trichloroethanes.
5. preparing the method for oxalate according to claim 4, it is characterised in that：The organic dyestuff is Eosin Y, Luo Dan
Bright-B；The metal complex is that six hydration Tris(2,2'- bipyridyl) ruthenium (II) chlorides or three (2- phenylpyridines) close iridium；The organic solvent
For N,N-dimethylformamide.
6. preparing the method for oxalate according to claim 1, it is characterised in that：The photochemical catalyst dosage is α-Br ketone
The molar ratio of the 1% of compound mole, diazonium compound and α-Br ketone compounds is 4.
7. diazonium compound and α-Br ketone compounds are that raw material is preparing the application in oxalate.
8. application according to claim 7, it is characterised in that：Diazonium compound and α-Br ketone compounds are raw material,
In organic solvent, in the presence of photochemical catalyst, oxidant, oxalate is prepared using illumination reaction.
9. application according to claim 8, it is characterised in that：The oxidant is oxygen；The photochemical catalyst is organic
Dyestuff or metal complex；The organic solvent is petroleum ether, N-Methyl pyrrolidone, dimethyl sulfoxide, N, N- dimethyl methyl
Amide, acetonitrile, toluene or 1,1,2- trichloroethanes.
10. application according to claim 8, it is characterised in that：The photochemical catalyst dosage is that α-Br ketone compounds rub
The molar ratio of the 1% of that amount, diazonium compound and α-Br ketone compounds is 4.
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| IGOR D. JURBERG ET AL.,: ""Blue light-promoted photolysis of aryldiazoacetates"", 《CHEM. SCI.》 * |
| MEIHUA MA ET AL.,: ""Interception of Radicals by Molecular Oxygen and Diazo Compounds: Direct Synthesis of Oxalate Esters Using Visible-Light Catalysis"", 《ORG. LETT.》 * |
| ZHAOFENG WANG ET AL.,: ""Generating carbyne equivalents with photoredox catalysis"", 《NATURE》 * |
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