CN1517354A - 铜络合物及其用途 - Google Patents
铜络合物及其用途 Download PDFInfo
- Publication number
- CN1517354A CN1517354A CNA2004100038471A CN200410003847A CN1517354A CN 1517354 A CN1517354 A CN 1517354A CN A2004100038471 A CNA2004100038471 A CN A2004100038471A CN 200410003847 A CN200410003847 A CN 200410003847A CN 1517354 A CN1517354 A CN 1517354A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- compound
- aryl
- group
- biphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000004699 copper complex Chemical class 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- -1 phosphate radical Chemical class 0.000 claims description 78
- 150000001875 compounds Chemical class 0.000 claims description 59
- 239000002585 base Substances 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- CNXMDTWQWLGCPE-UHFFFAOYSA-N ditert-butyl-(2-phenylphenyl)phosphane Chemical group CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1C1=CC=CC=C1 CNXMDTWQWLGCPE-UHFFFAOYSA-N 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LCSNDSFWVKMJCT-UHFFFAOYSA-N dicyclohexyl-(2-phenylphenyl)phosphane Chemical group C1CCCCC1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1CCCCC1 LCSNDSFWVKMJCT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910006384 μ-Br Inorganic materials 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- BPWYLEBPBUZPMU-UHFFFAOYSA-N [PH2](O)=O.C1(=CC=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound [PH2](O)=O.C1(=CC=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 BPWYLEBPBUZPMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 2
- YFUNEQCKCIBDMY-UHFFFAOYSA-N 4h-1,3,2-dioxaphosphocine Chemical compound C1OPOC=CC=C1 YFUNEQCKCIBDMY-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 2
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 13
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 13
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 12
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 11
- 235000015320 potassium carbonate Nutrition 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 230000006837 decompression Effects 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229960003280 cupric chloride Drugs 0.000 description 5
- 238000003810 ethyl acetate extraction Methods 0.000 description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 5
- 125000005259 triarylamine group Chemical group 0.000 description 5
- SKGRFPGOGCHDPC-UHFFFAOYSA-N 1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C=C1 SKGRFPGOGCHDPC-UHFFFAOYSA-N 0.000 description 4
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 4
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 4
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- ICKJJQMINSDAOV-UHFFFAOYSA-L copper dioxidophosphanium Chemical compound [Cu++].[O-][PH2]=O.[O-][PH2]=O ICKJJQMINSDAOV-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 3
- OOIXIALNQUCJJK-UHFFFAOYSA-N 4-isopropoxydinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine Chemical compound C1=CC2=CC=CC=C2C2=C1OP(OC(C)C)OC1=C2C2=CC=CC=C2C=C1 OOIXIALNQUCJJK-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- RRMIKQFUEXQAQP-UHFFFAOYSA-N copper;phosphane Chemical compound P.[Cu] RRMIKQFUEXQAQP-UHFFFAOYSA-N 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- OCYFYTLTLGVUMO-UHFFFAOYSA-N 1-(4-acetylphenyl)pyridin-2-one Chemical compound C1=CC(C(=O)C)=CC=C1N1C(=O)C=CC=C1 OCYFYTLTLGVUMO-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HXULLAVCVPDLTG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene;propan-2-yl dihydrogen phosphite Chemical compound CC(C)OP(O)O.C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 HXULLAVCVPDLTG-UHFFFAOYSA-N 0.000 description 1
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NDUJQDZEJYRLRB-UHFFFAOYSA-N C(CCCC)OCC(C(OOCCC(C)C)(OCC(CC)C)OC(CCC)C)(C)C Chemical compound C(CCCC)OCC(C(OOCCC(C)C)(OCC(CC)C)OC(CCC)C)(C)C NDUJQDZEJYRLRB-UHFFFAOYSA-N 0.000 description 1
- QNIUYZOPQBHPGV-UHFFFAOYSA-N CCCCCCCCCCCC[O] Chemical compound CCCCCCCCCCCC[O] QNIUYZOPQBHPGV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical group CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000434 field desorption mass spectrometry Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- KCJVTGHUUAEZOS-UHFFFAOYSA-N n,n-dimethyl-2-phenylaniline Chemical group CN(C)C1=CC=CC=C1C1=CC=CC=C1 KCJVTGHUUAEZOS-UHFFFAOYSA-N 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical group [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及磷化合物的铜络合物,其制备方法及其在催化偶合反应中的应用。
Description
本发明涉及磷化合物的铜络合物,其制备方法及其在催化偶合反应中的应用。
文献中对由芳基卤铜络合物或带杂原子官能团,如硫醇、胺和酰胺的芳基磺酸酯铜络合物催化的偶合反应进行了很多描述。
所用配体通常为氧或磷化合物。例如,Venkataraman等(Tetrahedron Letters,2001,42,4791-4793)公开了使用预制的二溴化铜和三苯基膦的络合物,将芳基卤加到芳族仲胺上。但迄今所知的磷化合物的铜络合物的缺点在于化学选择性通常较低,并且只有少数反应能获得工业上可接受的转化和转化率。
因此,需要提供磷化合物的铜络合物,其易于制备且在偶合反应中以优良收率生产所希望的产物。
为此,本发明提供式(I)的化合物
其中
Het1,Het2,Het3各自独立地为缺省(即不存在),或为氧或NR1,其中R1为C1-C8-烷基、C5-C18-芳基或C6-C19-芳烷基,和
B1和B2各自独立为C1-C8-烷基、C5-C18-芳基或C6-C19-芳烷基,或B1和B2基团一起可以构成碳原子总数为2-40的二价基团,和
B3为C1-C8-烷基、C5-C18-芳基、C6-C19-芳烷基或碳原子总数为2-40且化合价为n的基团,X为卤素、(C1-C8-卤代烷基)羧酸根、(C1-C8-烷基)羧酸根、(C1-C8-卤代烷基)磺酸根、(C5-C18-芳基)磺酸根、氰根(cyanide)、任选被氟代的乙酰丙酮根、硝酸根、8-羟基喹啉根、磷酸根、碳酸根、六氟磷酸根、四苯基硼酸根、四(五氟苯基)硼酸根或四氟硼酸根,和
p为0,1或2,和
n为1,2或3,和
m为1,2,3,4,5或6。
在本发明的范围内,上述及以下列出的所有基团定义、参数和说明,在通常或优选范围内,即,在特别范围和优选范围内,可以随意进行组合。
烷基、烷氧基、亚烷基和亚链烯基各自独立为直链、环状、支链或非支链烷基、烷氧基、亚烷基和亚链烯基,每个所提到的基团还可任选被C1-C4-烷氧基取代。上述同样应用于芳烷基基团的非芳族部分。
C1-C4-烷基为,如甲基、乙基、正丙基、异丙基、正丁基、仲丁基和叔丁基,C1-C8-烷基还可以为,如正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、新戊基、1-乙基丙基、环己基、环戊基、正己基、1,1-二甲基丙基、1,2-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、1-乙基-2-甲基丙基、正庚基和正辛基,C1-C12-烷基又可以为,如金刚烷基、异构的薄荷基、正壬基、正癸基和正十二烷基,C1-C18-烷基还可以为,如正十八烷基。
C1-C4-烷氧基为,如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基和叔丁氧基,C1-C8-烷氧基又可以为正戊氧基、1-甲基丁氧基、2-甲基丁氧基、3-甲基丁氧基、新戊基氧基、1-乙基丙氧基、环己氧基、环戊氧基、正己氧基和正辛氧基,C1-C12-烷氧基还可以为,如金刚烷基氧基、异构的薄荷基氧基、正癸氧基和正十二烷基氧基。
C1-C8-亚烷基为,如亚甲基、1,1-亚乙基、1,2-亚乙基、1,1-亚丙基、1,3-亚丙基、1,4-亚丁基、1,2-cyclohexoxylene和1,2-亚环戊基。
卤代烷基在各种情况下独立为被氯或氟原子单、多或全取代的直链、环状、支链或非支链烷基基团。
C1-C8-卤代烷基为,如三氟甲基、氯二氟甲基、2,2,2-三氟乙基、五氟乙基、九氟丁基、七氟异丙基和全氟辛基。
芳基在各种情况下独立为具有5-18个骨架碳原子的杂芳基团,其每个环有零、一、二或三个骨架碳原子可以被杂原子代替,但在整个分子中至少一个骨架碳原子被杂原子代替,所述杂原子选自氮、硫或氧,但优选为具有6-18个骨架碳原子的碳环芳基。
具有6-18个骨架碳原子的碳环芳基的例子为,苯基、萘基、菲基、蒽基或芴基,具有5-14个骨架碳原子、每个环有零、一、二或三个骨架碳可被选自氮、硫或氧的杂原子代替、但整个分子中至少一个骨架碳原子被所述杂原子代替的杂芳基为,如吡啶基、噁唑基、苯并呋喃基、氧芴基(dibenzofuranyl)或喹啉基。
碳环芳基或杂芳基的每个环还可被多至五个的相同或不同的选自下列的取代基取代:游离的或被保护的羟基、氰基、氯、氟、C1-C12-烷基、CO(C1-C12-烷基)、COO(C1-C12-烷基)、CO(C5-C18-芳基)、COO(C5-C18-芳基)、CON(C1-C12-烷基)2、C5-C18-芳基、C1-C12-卤代烷基、C1-C12烷氧基、C1-C12-卤代烷氧基、二(C1-C8-烷基)氨基或三(C1-C6-烷基)硅烷氧基。
在各种情况下芳基烷基独立为如上定义的直链、环状或支链或非支链烷基,并且,可被按上述定义的芳基单、多或全取代。
优选的取代方式定义如下:
Het1,Het2,Het3优选各自独立为氧或缺省,
B1和B2优选各自独立为C3-C8-仲烷基或C4-C8-叔烷基、C5-C18-芳基或双(C5-C18-芳基),或B1和B2一起构成二价基团,该二价基团选自:1,2-亚苯基、1,3-亚苯基、1,2-环己基、1,1’-二茂铁基、1,2-二茂铁基、2,2’-(1,1’-联萘基)和1,1’-联苯基,且上述基团可任选被氰基、氯、氟、C1-C12-烷基、C1-C12-卤代烷基、C1-C12-烷氧基、C1-C12-卤代烷氧基、二(C1-C8-烷基)氨基或三(C1-C8-烷基)硅烷氧基单或多取代,
B3优选为C3-C8-仲烷基或C4-C8-叔烷基、C5-C18-芳基、C6-C19-芳烷基或碳原子总数为2-40且化合价为n的基团,
X优选为氯、溴或碘、三氟甲烷磺酸根、三氟乙酸根、甲磺酸根、苯磺酸根、氰根、任选被氟代的乙酰丙酮根、六氟磷酸根或四氟硼酸根,更优选为氯、溴或碘。
n优选为1或2,
m优选为1或2。
已发现,尤其当配体含有至少一个多(C5-C18)芳基或(C9-C18)芳基结构元素时,或配体含有至少一个邻位被仲或叔烷基取代的(C5-C18)芳基结构元素时,或在配体含多于一个磷原子情况下,B3不是1,1’-二亚芳基、2,2’-二亚芳基、1,2-亚芳基或1,2-、1,3-或1,4-(C1-C8)亚烷基时,可以很容易或自动得到式(I)所示络合物的铜与磷原子比。
式(I)特别包括铜-膦络合物、铜-亚膦酸酯络合物和铜-亚磷酸酯络合物。
优选的铜-膦络合物为,例如,含有下面膦配体的络合物:
双(2-二环己基膦基)2’-(N,N-二甲基氨基)联苯、2-(二环己基膦基)联苯、2-(二环己基膦基)-2’-甲基联苯、2-(二叔丁基膦基)联苯或2-(双二苯基膦基)联萘。
优选为2-(二叔丁基膦基)联苯或2-(二环己基膦基)联苯。
更优选的铜-膦络合物为[(μ-Br)2{2-(二叔丁基膦基)联苯}2Cu2]、[(μ-三氟甲磺酸根)2{2-(二叔丁基膦基)联苯}2Cu2]、[(μ-Br)2{2-(二环己基膦基)联苯}2Cu2]和[(μ-三氟甲磺酸根)2{2-(二环己基膦基)联苯}2Cu2]。
优选的铜-亚膦酸酯络合物为,例如,含有下面亚膦酸酯配体的络合物:1,1’-联苯-2-基二烷基亚膦酸酯,例如,优选1,1’-联苯-2-基二环己基亚膦酸酯和1,1’-联苯-2-基二叔丁基亚膦酸酯,3-[(二异丙基膦基)氧基]苯基二异丙基亚膦酸酯,3-[(二叔丁基膦基)氧基]苯基二叔丁基亚膦酸酯,3-[(二苯基膦基)氧基]苯基二苯基亚膦酸酯或3-[(二环己基膦基)氧基]苯基二环己基亚膦酸酯,更优选为3-[(二异丙基膦基)氧基]苯基二异丙基亚膦酸酯。
更优选的铜-亚膦酸酯络合物为[(μ-Br)2{2-(二叔丁基膦基)联苯}2Cu2]。
优选的铜-亚磷酸酯络合物为,例如,含有下面亚磷酸酯配体的络合物:1,1’-联萘基-2,2’-二基异丙基亚磷酸酯、2,4,8,10-四叔丁基-6-苯氧基-12H-二苯并[d,g][1,3,2]dioxaphosphocine,更优选为1,1’-联萘-2,2’-二基异丙基亚磷酸酯和三(2,4-二叔丁基苯基)亚磷酸酯。
更优选的铜-亚磷酸酯络合物为[(μ-Br)2{1,1’-联萘-2,2’-二基异丙基亚磷酸酯}2Cu2]。
根据本发明式(I)的铜-磷络合物可以按照已知的方式制备,如将式(II)的磷化合物
其中n,B1,B2,B3,Het1,Het2和Het3各自具有式(I)中所指定的定义和优选范围,与式(III)的化合物反应
Cu-Xp(III)
其中X和p各自具有式(I)中所指定的定义和优选范围。
在其中p=0的情况下,也可使用例如铜粉。优选的式(III)化合物为:氧化铜(I)、氧化铜(II)、氯化铜(I)、三氟甲磺酸铜(I)、溴化铜(I)、碘化铜(I)、溴化铜(II)、氯化铜(II)、乙酸铜(II)、乙酰丙酮化铜或其混合物。
制备式(I)络合物时,式(II)化合物中的磷原子与式(III)化合物中的铜原子的摩尔比通常可为10∶1-0.5∶1,优选2∶1-1∶1,更优选1.2∶1-1∶1。
可在适于该目的的惰性有机溶剂,如四氢呋喃、二***、甲苯、二甲苯、氯仿、二氯甲烷、甲醇和/或乙醇中独立制备式(I)化合物。
可通过适合的预试验确定最适合的溶剂用量。
由所述的式(II)和式(III)起始化合物制备式(I)化合物,如通过室温下在溶液中简单混合两种起始化合物。
也可在催化混合物中就地制备式(I)化合物。为此,还可使用鏻盐形式的式(II)化合物,如四氟硼酸盐(又见Netherton,M.R.;Fu,G..C.;OrganicLetters(2001),3(26),4295-429)。
本发明式(I)化合物尤其适于形成碳-氮、碳-氧和碳-硫键,也适于制备芳炔烃。
本发明还包括含式(I)化合物的催化剂。
此外,本发明还包括制备式(IV)化合物的方法
Ar-(F-R2)n (IV)
其中
n为1,2或3,和
Ar为取代或未取代的芳基,和
F为氧、硫、NR3、NR3CO或乙炔二基,其中R3为氢、C1-C12-烷基、C5-C18-芳基或C6-C19-芳烷基,和
R2为Ar、C1-C12-烷基、C1-C12-卤代烷基、C2-C12-链烯基或C6-C19-芳烷基,其特征在于:式(V)的化合物,
Ar-Z (V)
其中
Ar如上所定义,和
Z为氯、溴、碘、重氮盐或磺酸盐,
与式(VI)的化合物反应,
H-F-R2(VI)
其中
F和R2各自如上所定义,并且
该转化在碱和式(I)化合物存在下进行。
式(IV)至(VI)化合物的优选范围定义如下:
Ar优选为具有6-24个骨架碳原子的碳环芳基或具有5-24个骨架碳原子的杂芳基,所述杂芳基的每个环中有零、一、二或三个骨架碳原子为杂原子,但整个分子中至少一个骨架原子为杂原子,所述杂原子选自氮、硫和氧。碳环芳基或杂芳基每个环还可被多至五个相同或不同的取代基取代,所述取代基选自羟基、氯、氟、硝基、氰基、游离的或被保护的甲酰基、C1-C12-烷基、C5-C14-芳基、C6-C15-芳烷基、-PO-[(C1-C8)烷基]2、-PO-[(C5-C14)-芳基]2、-PO-[(C1-C8)烷基)(C5-C14)芳基)]、三(C1-C8-烷基)甲硅烷氧基或式(VIIa-f)的基团
A-B-D-E (VIIa) A-E (VIIb)
A-SO2-E (VIIc) A-B-SO2R4 (VIId)
A-SO3-W (VIIe) A-COW (VIIf)
其中,各自独立地,
A缺省或为C1-C8-亚烷基,和
B缺省或为氧、硫或NR4,
其中R4为氢、C1-C8烷基、C6-C15-芳烷基或C5-C14-芳基,和D为羰基,和
E为R5、OR5、NHR6或N(R6)2,
其中R5为C1-C8-烷基、C6-C15-芳烷基、C1-C8-卤代烷基或C5-C14-芳基,和R6在各种情况下独立为C1-C8-烷基、C6-C15-芳烷基或C5-C14-芳基,或N(R6)2一起构成环状氨基,和
W为OH、NH2或OM,其中M可为碱金属离子、半当量的碱土金属离子、铵离子或有机铵离子,
Ar更优选为苯基、萘基、菲基、蒽基、联苯基、联萘基、芴基、吡啶基、噁唑基、噻吩基、苯并呋喃基、苯并噻吩基、氧芴基、硫芴基(dibenzothiophenyl)、呋喃基、吲哚基、哒嗪基、吡嗪基、嘧啶基、***基和喹啉基,且所述基团每个环还可被零、一、二或三个基团取代,每个基团独立选自氟、硝基、氰基、二(C1-C4-烷基)氨基、C1-C4-烷基、C5-C10-芳基、C1-C8-氟代烷基、C1-C8氟代烷氧基、C1-C8-烷氧基、CO(C1-C4-烷基)、COO-(C1-C4-烷基)、-CON(C1-C4-烷基)2,
Ar进一步优选为苯基,其可进一步被零、一、二或三个基团取代,每个基团独立选自硝基、氟、氰基、C1-C4-烷基、C1-C4-烷氧基、三氟甲基、三氟甲氧基、CO-(C1-C4-烷基)、COO-(C1-C4-烷基)和-CON(C1-C4-烷基)2,
n优选为1,
Z优选为氯、溴或碘,
F优选为氧、硫、NR3或乙炔二基,其中R3为氢、C1-C4-烷基或C5-C18-芳基,R2优选为Ar或C1-C12-烷基。
根据本发明的方法,基于所用的式(IV)化合物,式(I)化合物的用量通常为0.02mol%-10mol%,优选0.1mol%-3mol%。
在本发明方法中,所用碱,例如为且优选为碱金属和/或碱土金属碳酸盐、碳酸氢盐、醇盐、磷酸盐、氟化物和/或氢氧化物,且应特别提出碳酸钾和/或碳酸钠、碳酸铯、碳酸氢铯、甲醇钠、叔丁醇钾、potassium amylate、氟化铯、磷酸钾和氢氧化钡。优选使用碳酸钾、碳酸钠、碳酸铯和/或碳酸氢铯。
更优选使用碳酸钾。
在式(IV)的化合物中,例如,每交换1摩尔卤素,可使用0.05-10mol碱,优选0.3-2mol。
根据本发明的方法,对所用碱进行研磨和/或干燥预处理是有利的。
研磨后,碱的比表面积优选约0.1-10m2/g,更优选0.2-1m2/g(BET)。
在本发明方法中,作为使用具有显著吸湿性的碱的结果,尤其是磷酸盐和碳酸盐易于或多或少地吸收大气组分,如水和二氧化碳。吸收约30%重量的大气组分,则可检测到对转化带来的明显影响。因此,通常适宜除了对碱进行研磨外还要进行干燥。
根据所用碱的性质,例如,在大约0.01-100bar的减压下,通过将其加热至约50~200℃,优选100~160℃,加热数小时来干燥碱。
式(VI)化合物与式(IV)化合物的摩尔比可为,如0.8-10,优选1-6,更优选1-4。
根据本发明的方法可以在如20-250℃温度下,优选100-150℃下实施。优化的反应温度尤其取决于起始物、催化剂和所用碱类型,并可通过简单的预备试验确定。
根据本发明的方法可在存在或不存在适合溶剂的条件下进行。适用的溶剂为,例如,脂肪族、脂环族或芳族烃,如汽油、苯、甲苯、二甲苯、石油醚、己烷、环己烷;醚,如二***、二异丙醚、二噁烷、四氢呋喃或乙二醇二甲醚或乙二醇二***;酰胺,如N,N-二甲基甲酰胺,N,N-二甲基乙酰胺,N-甲基N-甲酰苯胺,N-甲基吡咯烷酮或六甲基磷酰胺;酯,如乙酸甲酯或乙酸乙酯,或所述溶剂的混合物。
在一些情况下,过量的式(VI)化合物也可作为反应介质。
根据本发明的方法可任选加入共沸剂,其在共沸蒸馏过程中连续除去反应过程中形成的水。
根据本发明的方法可按传统方法以连续或间歇方式进行。
本发明的优点特别在于式(I)化合物易于制备,及本发明的铜络合物可用于以高效率制备式(VI)的化合物。
实施例
式(I)化合物的制备
实施例1
双(溴化2-(二叔丁基膦基)联苯合铜(I))的制备
加热50ml脱气、无水甲醇至回流温度,将2.36g(7.9mmol)2-(二叔丁基膦基)联苯慢慢加入甲醇中,直至膦化合物完全溶解。随后,将0.59g(2.6mmol)溴化铜(II)逐份加入溶液中。加入溴化铜后,在回流温度下将溶液再加热15min,然后冷却溶液。待溶液冷却后,沉淀固体并过滤,以少量乙醇和二***洗涤并随后干燥。得到0.93g(1.1mmol)上述化合物。收率为理论值的80%。
实施例2
双(溴化N-[2’-(二环己基膦基)-1,1’-联苯-2-基]-N,N-二甲基胺合铜(I))二聚体的制备
加热50ml脱气、无水甲醇至回流温度,将2.00g(5.1mmol)N-([2’-(二环己基膦基)-1,1’-联苯-2-基]-N,N-二甲基胺慢慢加入甲醇中,直至膦化合物完全溶解。随后,将0.8g(3.7mmol)溴化铜(II)逐份加入溶液中。加入溴化铜后,在回流温度下将溶液再加热15min,然后冷却溶液。待溶液冷却后,沉淀固体并过滤,以少量乙醇和二***洗涤并随后干燥。得到1.5g(1.4mmol,M=1073.8g/mol)上述化合物。以FD-MS分析检测其结构(m/e=1074)。收率为理论值的73%。
实施例3
氯化(3-[(二苯基膦基)氧基]苯基二苯基亚膦酸酯合铜(I))的制备
在圆底烧瓶中,将5g(10.4mmol)3-[(二苯基膦基)氧基]苯基二苯基亚膦酸酯溶解于脱气、无水二氯甲烷,并加热至40℃。加入0.35g(0.35mmol)氯化铜(I)。搅拌30分钟后,减压除去溶剂。获得上述化合物。
实施例4
双[氯化(1,1’-联苯-2-基二环己基亚膦酸酯)合铜(I)]的制备
在圆底烧瓶中,将5g(13.6mmol)1,1’-联苯-2-基二环己基亚膦酸酯溶解于无水、脱气氯仿。在逆流氩气氛下,加入0.45g(4.5mmol)氯化铜(I),室温下将混合物搅拌6小时。减压除去溶剂,并将残余物吸收至无水***中。将混合物冷却至-78℃,沉淀出产物。
实施例5
氯化双[4-异丙氧基二萘并[2,1-d:1’,2’-f][1,3,2]dioxaphosphepine]合铜(I)的制备
在圆底烧瓶中,将5g(13.4mmol)4-异丙氧基二萘并[2,1-d:1’,2’-f][1,3,2]dioxaphosphepine(rac-联萘基异丙基亚磷酸酯(rac-binaphthyl isopropylphosphite))溶解于二氯甲烷。在逆流氩气氛下加入0.44g(0.45mmol)氯化铜(I),搅拌30分钟后,减压除去溶剂。
实施例6-24
实施例1和2的催化剂在偶合反应中的应用。
实施例6
p-溴代苯乙酮与n-辛硫醇的偶合反应(实施例1的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,1.0g(6.7mmol)n-辛硫醇,1.8g(13.5mmol)碳酸钾和300mg(0.7mmol)实施例1的催化剂在50ml二噁烷中搅拌12h。随后将反应液与40ml氨水混合,并用乙酸乙酯萃取,减压下干燥合并的有机萃取液。以柱色谱法(己烷)处理后得产物1.24g(70%)。
GC-MS/EI: 264(M)
实施例7
p-溴代苯乙酮与n-辛硫醇的偶合反应(实施例2的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,1.0g(6.7mmol)n-辛硫醇,1.8g(13.5mmol)碳酸钾和360mg(0.7mmol)实施例2的催化剂在50ml二噁烷中搅拌12h。随后将反应液与40ml氨水混合,并用乙酸乙酯萃取,减压下干燥合并的有机萃取液。以柱色谱法(己烷)处理后得产物733mg(40%)。
实施例8
p-溴代苯乙酮与苯硫酚的偶合反应(实施例1的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,0.75g(6.7mmol)苯硫酚,1.8g(13.5mmol)碳酸钾和300mg(0.7mmol)实施例1的催化剂在50ml二噁烷中搅拌12h。随后将反应液与20ml氨水混合,并用乙酸乙酯萃取,减压下干燥合并的有机萃取液。以柱色谱法(己烷)处理后得产物970mg(65%)。GC-MS/EI:228(M)
实施例9
p-溴代苯乙酮与苯硫酚的偶合反应(实施例2的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,0.75g(6.7mmol)苯硫酚,1.8g(13.5mmol)碳酸钾和360mg(0.7mmol)实施例2的催化剂在50ml二噁烷中搅拌12h。粗产物的GC分析表明产物以75%的转化率形成。
实施例10
p-溴代苯乙酮与苯酚的偶合反应(实施例1的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,630mg(6.7mmol)苯酚,1.8g(13.5mmol)碳酸钾和300mg(0.7mmol)实施例1的催化剂在50ml二噁烷中搅拌12h。随后将反应液与40ml氨水混合,并用乙酸乙酯萃取,减压下干燥合并的有机萃取液。以柱色谱法(己烷)处理后得产物280mg(20%)。
GC-MS/EI:212
实施例11
p-溴代苯乙酮与苯酚的偶合反应(实施例2的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,630mg(6.7mmol)苯酚,1.8g(13.5mmol)碳酸钾和360mg(0.7mmol)实施例2的催化剂在50ml二噁烷中搅拌12h。粗产物的GC分析表明产物以18%的转化率形成。
实施例12
p-溴代苯乙酮与2-羟基吡啶的偶合反应(实施例1的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,650mg(6.7mmol)2-羟基吡啶,1.8g(13.5mmol)碳酸钾和300mg(0.7mmol)实施例1的催化剂在50ml二噁烷中搅拌12h。随后将反应液与40ml氨水混合,并用乙酸乙酯萃取,减压下干燥合并的有机萃取液。以柱色谱法(己烷)处理后得产物混合物N-4-乙酰苯基pyridinone和4-乙酰苯氧基2-吡啶(比6∶1)740mg(52%)。
GC-MS/EI:213(M)
实施例13
p-溴代苯乙酮与2-羟基吡啶的偶合反应(实施例2的催化剂)
在110℃氩气氛下,将1.35g(6.7mmol)p-溴代苯乙酮,650mg(6.7mmol)o-羟基吡啶,1.8g(13.5mmol)碳酸钾和360mg(0.7mmol)实施例2的催化剂在50ml二噁烷中搅拌12h。粗产物的GC分析表明产物以42%的转化率形成。
实施例14
p-溴代苯乙酮与甲醇的偶合反应(实施例1的催化剂)
在氩气氛下,将1.34g(13.5mmol)p-溴代苯乙酮,2ml(20mmol)乙酸乙酯,17.5ml 30%的甲醇钠溶液和300mg(0.7mmol)实施例1的催化剂回流12h。随后将反应液小心水解,并用二氯甲烷萃取,减压下干燥合并的有机萃取液。除大部分产物(35%)外,GC显示有羟醛副产物碎片。以柱色谱法(己烷)处理后得产物820mg(41%)。
GC-MS/EI:150(M)
实施例15
p-溴代苯乙酮与甲醇的偶合反应(实施例2的催化剂)
在氩气氛下,将1.34(13.5mmol)p-溴代苯乙酮,2ml(20mmol)乙酸乙酯,17.5ml30%的甲醇钠溶液和360mg(0.7mmol)实施例2的催化剂回流12h。随后将反应液小心水解,并用二氯甲烷萃取,减压下干燥合并有机萃取液。除大部分产物(28%)外,GC显示有羟醛副产物碎片。
实施例16
4-碘代三氟甲基苯与苯乙炔的偶合反应(实施例1的催化剂)
在110℃氩气氛下,将2.7g(10mmol)4-碘代三氟甲基苯,1.3g(12.5mmol)苯乙炔,2.2g(20mmol)叔丁醇钾和300mg(0.7mmol)实施例1的催化剂在100ml二噁烷中搅拌21h。减压下过滤并干燥反应液。以柱色谱法(己烷)处理后得产物1.88g(75%)。
GC-MS/EI:246(M)
实施例17
4-碘代三氟甲基苯与苯乙炔的偶合反应(实施例2的催化剂)
在110℃氩气氛下,将2.7g(10mmol)4-碘代三氟甲基苯,1.3g(12.5mmol)苯乙炔,2.2g(20mmol)叔丁醇钾和360mg(0.7mmol)实施例2的催化剂在100ml二噁烷中搅拌21h。粗产物的GC分析表明产物以62%的转化率形成(与GC-MS/EI GZN 283-4比较)。
实施例18
p-甲苯基碘与苯乙炔的偶合反应(实施例1的催化剂)
在110℃氩气氛下,将2.2g(10mmol)p-甲苯基碘,1.3g(12.5mmol)苯乙炔,2.2g(20mmol)叔丁醇钾和300mg(0.7mmol)实施例1的催化剂在100ml二噁烷中搅拌21h。减压下过滤并干燥反应液。以柱色谱法(己烷)处理后得产物1.75g(91%)。
GC-MS/EI:192(M)
实施例19
p-甲苯基碘与苯乙炔的偶合反应(实施例2的催化剂)
在110℃氩气氛下,将2.2g(10mmol)p-甲苯基碘,1.3g(12.5mmol)苯乙炔,2.2g(20mmol)叔丁醇钾和360mg(0.7mmol)实施例2的催化剂在100ml二噁烷中搅拌21h。粗产物的GC分析表明产物以50%的转化率形成(与GC-MS/EIGZN 277-8比较)。
实施例20
溴苯与苯胺的偶合反应(实施例1的催化剂)
在170℃氩气氛下,将1.05g(6.7mmol)溴苯,14g(10.1mmol)碳酸铯和300mg(0.7mmol)实施例1的催化剂在2ml苯胺中搅拌12h。粗产物的GC分析表明选择性形成单芳基化合物,GC-MS/EI:169(M));转化率5%;未检测到三芳基胺。
实施例21
碘苯与苯胺的偶合反应(实施例1的催化剂)
在170℃氩气氛下,将1.37g(6.7mmol)碘苯,1.4g(10.1mmol)碳酸铯和300mg(0.7mmol)实施例1的催化剂在2ml苯胺中搅拌12h。粗产物的GC分析表明选择性形成单芳基化合物(与GC-MS/EI 1126-7比较;未检测到三芳基胺。以柱色谱法处理后得产物810mg(72%)。
实施例22
p-氯硝基苯与苯胺的偶合反应(实施例1的催化剂)
在170℃氩气氛下,将1.06g(6.7mmol)p-氯硝基苯,1.4g(10.1mmol)碳酸铯和300mg(0.7mmol)实施例1的催化剂在2ml苯胺中搅拌12h。粗产物的GC分析表明选择性形成单芳基化合物,转化率83%;未检测到三芳基胺。以柱色谱法处理后得产物1.14g(80%)。
GC-MS/EI:214(M)
实施例23
碘苯与苯胺的偶合反应(实施例2的催化剂)
在170℃氩气氛下,将1.37g(6.7mmol)碘苯,1.4g(10.1mmol)碳酸铯和360mg(0.7mmol)实施例2的催化剂在2ml苯胺中搅拌12h。粗产物的GC分析表明选择性形成单芳基化合物并完全转化;未检测到三芳基胺。
实施例24
p-氯硝基苯与苯胺的偶合反应(实施例2的催化剂)
在170℃氩气氛下,将1.06g(6.7mmol)p-氯硝基苯,1.4g(10.1mmol)碳酸铯和360mg(0.7mmol)实施例2的催化剂在2ml苯胺中搅拌12h。粗产物的GC分析表明选择形成单芳基化合物(与GC-MS/EI 1101-7比较),转化率91%;未检测到三芳基胺。
Claims (17)
1.式(I)的化合物
其中
Het1,Het2和Het3各自独立地为缺省,或为氧或NR1,其中R1为C1-C8-烷基、C5-C18-芳基或C6-C19-芳烷基,和
B1和B2各自独立为C1-C8-烷基、C5-C18-芳基或C6-C19-芳烷基,或B1和B2基团一起可构成碳原子总数为2-40的二价基团,和
B3为C1-C8-烷基、C5-C18-芳基、C6-C19-芳烷基或碳原子总数为2-40且化合价为n的基团,
X为卤素、(C1-C8-卤代烷基)羧酸根、(C1-C8-烷基)羧酸根,(C1-C8-卤代烷基)磺酸根、(C5-C18-芳基)磺酸根、氰根、任选被氟代的乙酰丙酮根、硝酸根、8-羟基喹啉根、磷酸根、碳酸根、六氟磷酸根、四苯基硼酸根、四(五氟苯基)硼酸根或四氟硼酸根,和
p为0,1或2,和
n为1,2或3,和
m为1,2,3,4,5或6。
2.根据权利要求1的化合物,其特征在于,Het1,Het2,Het3各自独立为氧或不存在。
3.根据权利要求1和2中至少一项的化合物,其特征在于,B1和B2各自独立为C3-C8-仲烷基或C4-C8-叔烷基、C5-C18-芳基或双(C5-C18-芳基),或B1和B2一起构成二价基团,该二价基团选自1,2-亚苯基、1,3-亚苯基、1,2-环己基、1,1’-二茂铁基、1,2-二茂铁基、2,2’-(1,1’-联萘基)和1,1’-联苯基,且上述基团可任选被氰基、氯、氟、C1-C12-烷基、C1-C12-卤代烷基、C1-C12-烷氧基、C1-C12-卤代烷氧基、二(C1-C8-烷基)氨基或三(C1-C8-烷基)硅烷氧基单或多取代。
4.根据权利要求1-3中至少一项的化合物,其特征在于,B3为C3-C8-仲烷基或C4-C8-叔烷基、C5-C18-芳基、C6-C19-芳烷基或碳原子总数为2-40且化合价为n的基团。
5.根据权利要求1-4中至少一项的化合物,其特征在于,X为氯、溴或碘、三氟甲烷磺酸根、三氟乙酸根、甲磺酸根、苯磺酸根、氰根、任选被氟代的乙酰丙酮根、六氟磷酸根或四氟硼酸根。
6.根据权利要求1-5中至少一项的化合物,其特征在于,n为1或2和m为1或2。
7.根据权利要求1-6中至少一项的化合物,其特征在于,它们含有下列磷化合物作为配体:双(2-二环己基膦基)-2’(N,N-二甲基氨基)联苯、2-(二环己基膦基)联苯、2-(二环己基膦基)-2’-甲基联苯、2-(二叔丁基膦基)联苯、2-(双二苯基膦基)联萘、2-(二叔丁基膦基)联苯、2-(二环己基膦基)联苯、1,1’-联苯-2-基二环己基亚膦酸酯、1,1’-联苯-2-基二叔丁基亚膦酸酯、3-[(二异丙基膦基)氧基]苯基二异丙基亚膦酸酯、3-[(二叔丁基膦基)氧基]苯基二叔丁基亚膦酸酯、3-[(二苯基膦基)氧基]苯基二苯基亚膦酸酯、3-[(二环己基膦基)氧基]苯基二环己基亚膦酸酯、1,1’-联萘-2,2’-二基异丙基亚磷酸酯和2,4,8,10-四叔丁基-6-苯氧基-12H-二苯并[d,g][1,3,2]dioxaphosphocine。
8.[(μ-Br)2{2-(二叔丁基膦基)联苯}2Cu2]、[(μ-三氟甲磺酸根)2{2-(二叔丁基膦基)联苯}2Cu2]、[(μ-Br)2{2-(二环己基膦基)联苯}2Cu2]、[(μ-三氟甲磺酸根)2{2-(二环己基膦基)联苯}2Cu2和[(μ-Br)2{1,1’-联萘-2,2’-二基异丙基亚磷酸酯}2Cu2]。
9.根据权利要求1-8中至少一项的化合物用于形成碳-氮、碳-氧和碳-硫键和用于制备芳炔的用途。
10.包含根据权利要求1-9中至少一项的化合物的催化剂。
11.制备式(IV)化合物的方法,
Ar-(F-R2)n (IV)
其中
n为1,2或3,和
Ar为取代或未取代的芳基,和
F为氧、硫、NR3、NR3CO或乙炔二基,其中R3为氢、C1-C12-烷基、C5-C18-芳基或C6-C19-芳烷基,和
R2为Ar、C1-C12-烷基、C1-C12-卤代烷基、C2-C12-链烯基或C6-C19-芳烷基,其特征在于:式(V)的化合物,
Ar-Z (V)
其中
Ar如上所定义,和
Z为氯、溴、碘、重氮盐或磺酸盐,
与式(VI)的化合物反应,
H-F-R2 (VI)
其中
F和R2各自如上所定义,和
该转化在碱和根据权利要求1-8中至少一项的化合物存在下进行。
12.根据权利要求11的方法,其特征在于,使用分离出来的式(I)化合物或者使用就地生成的式(I)化合物。
13.根据权利要求10-12中至少一项的方法,其特征在于,Ar为具有6-24个骨架碳原子的碳环芳基或具有5-24个骨架原子的杂芳基,所述杂芳基的每个环中有零、一、二或三个骨架原子,但整个分子中至少一个骨架原子为杂原子,所述杂原子选自氮、硫或氧,碳环芳基或杂芳基的每个环还可被多至五个相同或不同的取代基取代,所述取代基选自羟基、氯、氟、硝基、氰基、游离的或被保护的甲酰基、C1-C12-烷基、C5-C14-芳基、C6-C15-芳烷基、-PO-[(C1-C8)烷基]2、-PO-[(C5-C14)-芳基]2、-PO-[(C1-C8)烷基)(C5-C14)芳基)]、三(C1-C8-烷基)甲硅烷氧基或式(VIIa-f)的基团
A-B-D-E (VIIa) A-E (VIIb)
A-SO2-E (VIIc) A-B-SO2R4 (VIId)
A-SO3-W (VIIe) A-COW (VIIf)
其中,各自独立地,
A不存在或为C1-C8-亚烷基,和
B不存在或为氧、硫或NR4,
其中R4为氢、C1-C8烷基、C6-C15-芳烷基或C5-C14-芳基,和D为羰基,和
E为R5、OR5、NHR6或N(R6)2,
其中R5为C1-C8-烷基、C6-C15-芳烷基、C1-C8-卤代烷基或C5-C14-芳基,和R6在各种情况下独立为C1-C8-烷基、C6-C15-芳烷基或C5-C14-芳基,或N(R6)2一起为环状氨基,和
W为OH、NH2或OM,其中M可为碱金属离子、半当量的碱土金属离子、铵离子或有机铵离子。
14.根据权利要求10-13中至少一项的方法,其特征在于,R2为Ar或C1-C12-烷基。
15.根据权利要求10-14中至少一项的方法,其特征在于,基于所用的式(IV)化合物,式(I)化合物的用量为0.02mol%-10mol%。
16.根据权利要求10-15中至少一项的方法,其特征在于,所用碱为碱金属和/或碱土金属碳酸盐、碳酸氢盐、醇盐、磷酸盐、氟化物和/或氢氧化物。
17.根据权利要求10-16中至少一项的方法,其特征在于,对所用碱进行研磨和/或干燥预处理。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10300097.6 | 2003-01-07 | ||
DE10300097A DE10300097A1 (de) | 2003-01-07 | 2003-01-07 | Kupfer-Komplexe und ihre Verwendung |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1517354A true CN1517354A (zh) | 2004-08-04 |
Family
ID=32478148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2004100038471A Pending CN1517354A (zh) | 2003-01-07 | 2004-01-07 | 铜络合物及其用途 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7179946B2 (zh) |
EP (1) | EP1437356B1 (zh) |
CN (1) | CN1517354A (zh) |
AT (1) | ATE321765T1 (zh) |
DE (2) | DE10300097A1 (zh) |
ES (1) | ES2259128T3 (zh) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200813014A (en) * | 2002-03-28 | 2008-03-16 | Astrazeneca Ab | Quinazoline derivatives |
DE10300126A1 (de) * | 2003-01-07 | 2004-07-15 | Bayer Aktiengesellschaft | Verfahren zur Herstellung von Aminodiphenylaminen |
EP1667992B1 (en) * | 2003-09-19 | 2007-01-24 | Astrazeneca AB | Quinazoline derivatives |
JP5261870B2 (ja) * | 2004-10-20 | 2013-08-14 | 三菱化学株式会社 | アミン化合物の製造方法 |
AU2009247782C1 (en) | 2008-05-13 | 2013-09-19 | Astrazeneca Ab | Fumarate salt of 4- (3-chloro-2-fluoroanilino) -7-methoxy-6- { [1- (N-methylcarbamoylmethyl) piperidin- 4-yl] oxy } quinazoline |
JP5753844B2 (ja) | 2009-07-08 | 2015-07-22 | ダーミラ(カナダ),インコーポレーテッド | 皮膚疾患または病変の治療に有用なtofa類似体 |
CN102351622B (zh) * | 2011-08-19 | 2013-12-25 | 浙江大学 | 一种由金属铜盐催化制备(z)-1,2-二硫醚-1-烯烃的方法 |
US9581751B2 (en) | 2013-01-30 | 2017-02-28 | Cree, Inc. | Optical waveguide and lamp including same |
US10209429B2 (en) | 2013-03-15 | 2019-02-19 | Cree, Inc. | Luminaire with selectable luminous intensity pattern |
US9645303B2 (en) | 2013-03-15 | 2017-05-09 | Cree, Inc. | Luminaires utilizing edge coupling |
EP3054936B1 (en) | 2013-10-10 | 2023-10-18 | Eastern Virginia Medical School | 4-((2-hydroxy-3-methoxybenzyl)amino) benzenesulfonamide derivatives as 12-lipoxygenase inhibitors |
US11719882B2 (en) | 2016-05-06 | 2023-08-08 | Ideal Industries Lighting Llc | Waveguide-based light sources with dynamic beam shaping |
US10416377B2 (en) | 2016-05-06 | 2019-09-17 | Cree, Inc. | Luminaire with controllable light emission |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3703561A (en) * | 1968-03-28 | 1972-11-21 | Phillips Petroleum Co | Olefin conversion using complexes of cu,ag and au with organoaluminums |
US3839459A (en) * | 1970-12-28 | 1974-10-01 | Texaco Inc | Hydroformylation process utilizing homogeneous cuprous chloride complexes as catalysts |
US3933878A (en) * | 1972-06-02 | 1976-01-20 | Exxon Research And Engineering Company | Ligand complexes of cu(1)salts |
DE2431330A1 (de) * | 1974-06-29 | 1976-01-15 | Roehm Gmbh | Verfahren zur herstellung von kohlensaeureestern |
GB2025403A (en) * | 1978-03-09 | 1980-01-23 | Albright & Wilson | Improvements in and Relating to the Ullmann Reaction |
US4319050A (en) * | 1981-02-13 | 1982-03-09 | Exxon Research & Engineering Co. | Copper complex as catalyst for formate ester decarbonylation |
CA1238854A (en) * | 1984-02-01 | 1988-07-05 | David T. Hill | ANTITUMOR PHARMACEUTICAL COMPOSITIONS AND METHODS FOR TREATING TUMORS EMPLOYING ¬.alpha.,W- BIS(DISUBSTITUTEDPHOSPHINO)HYDROCARBON| DIGOLD (I) DIGOLD (III), DISILVER (I) AND DICOPPER (I) DERIVATIVES |
IT1215961B (it) * | 1988-03-02 | 1990-02-22 | Euron Spa | Composizione lubrificanti contenenti complessi con attivita'antiossidante. |
DE4414964A1 (de) * | 1994-04-28 | 1995-11-02 | Wacker Chemie Gmbh | Katalysator zur Herstellung von 1-Chlor-3-methyl-but-2-en |
AU2003221028A1 (en) | 2002-03-19 | 2003-09-29 | Mitsubishi Chemical Corporation | 3-hydroxy-3-(2-thienyl)propionamide compound, process for producing the same, and process for producing 3-amino-1-(2-thienyl)-1-propanol compound therefrom |
-
2003
- 2003-01-07 DE DE10300097A patent/DE10300097A1/de not_active Withdrawn
- 2003-12-30 EP EP03029975A patent/EP1437356B1/de not_active Expired - Lifetime
- 2003-12-30 ES ES03029975T patent/ES2259128T3/es not_active Expired - Lifetime
- 2003-12-30 AT AT03029975T patent/ATE321765T1/de not_active IP Right Cessation
- 2003-12-30 DE DE50302801T patent/DE50302801D1/de not_active Expired - Fee Related
-
2004
- 2004-01-06 US US10/752,413 patent/US7179946B2/en not_active Expired - Fee Related
- 2004-01-07 CN CNA2004100038471A patent/CN1517354A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
US20040198997A1 (en) | 2004-10-07 |
EP1437356A1 (de) | 2004-07-14 |
DE50302801D1 (de) | 2006-05-18 |
DE10300097A1 (de) | 2004-07-22 |
ES2259128T3 (es) | 2006-09-16 |
ATE321765T1 (de) | 2006-04-15 |
EP1437356B1 (de) | 2006-03-29 |
US7179946B2 (en) | 2007-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1517354A (zh) | 铜络合物及其用途 | |
CN1293942C (zh) | 用于氢氰化的含Ni(0)的催化剂体系 | |
CN1145633C (zh) | 使用多齿亚磷酸酯配体进行的加氢甲酰化 | |
CN1914162A (zh) | 二腈的制备方法 | |
CN1054129C (zh) | 3-芳基苯并呋喃酮的制备方法 | |
CN1356335A (zh) | 亚磷酸酯衍生物,其制备方法以及含亚磷酸酯的催化剂前体 | |
CN1610688A (zh) | 邻位取代的手性膦和三价膦酸酯及其在不对称催化反应中的用途 | |
CN1914157A (zh) | 连续制备线性戊烯腈的方法 | |
CN1517351A (zh) | 铜-碳烯络合物及其应用 | |
CN1485323A (zh) | 5-硝基苯并呋喃 | |
CN1946670A (zh) | 使用铜(i)催化剂制备1,3-烯炔的方法 | |
CN1914197A (zh) | 可用于制备(1h-四唑-5-基)-联苯衍生物的偶联反应 | |
CN1627990A (zh) | 使用含呫吨桥接配体的催化剂的加氢甲酰化方法 | |
CN1498881A (zh) | 多卤烷芳基化物 | |
CN1927830A (zh) | 光学纯亚磺酰胺化合物及其应用 | |
CN1874844A (zh) | 镍(0)-磷配体配合物的制备方法 | |
CN1898255A (zh) | 制备吡啶衍生物的方法 | |
CN1218803A (zh) | 卤化剂 | |
CN1874845A (zh) | 镍(0)-磷配体配合物的制备方法 | |
CN1646476A (zh) | 制备考布他汀的方法 | |
CN101054355A (zh) | 光学纯双亚磺酰胺化合物及其应用 | |
CN1993179A (zh) | 单供体亚膦酸酯配体 | |
CN1871199A (zh) | 连续制备醛的方法 | |
CN1761641A (zh) | 含氧化合物的制造方法 | |
CN1960959A (zh) | 经济、实用的泛醌合成法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
ASS | Succession or assignment of patent right |
Owner name: LANXESS DEUTSCHLAND GMBH Free format text: FORMER OWNER: BAYER CHEMICALS AG Effective date: 20070608 |
|
C41 | Transfer of patent application or patent right or utility model | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20070608 Address after: The Federal Republic of Germany Leverkusen Applicant after: Blue Aike Sheth limited liability company Address before: The Federal Republic of Germany Leverkusen Applicant before: Bayer AG |
|
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |