CN100588656C - Forcipated diimidazoline palladium compound and its application in Suzuki reaction - Google Patents
Forcipated diimidazoline palladium compound and its application in Suzuki reaction Download PDFInfo
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- CN100588656C CN100588656C CN200710054070A CN200710054070A CN100588656C CN 100588656 C CN100588656 C CN 100588656C CN 200710054070 A CN200710054070 A CN 200710054070A CN 200710054070 A CN200710054070 A CN 200710054070A CN 100588656 C CN100588656 C CN 100588656C
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- imidazoline
- pincerlike
- palladium
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- palladium compound
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- 238000006069 Suzuki reaction reaction Methods 0.000 title abstract description 6
- 150000002941 palladium compounds Chemical class 0.000 title abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 100
- -1 biaryl compound Chemical class 0.000 claims abstract description 100
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 58
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 238000000605 extraction Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 238000004809 thin layer chromatography Methods 0.000 claims description 23
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 18
- DZPXBTZJEFYBBK-UHFFFAOYSA-N 1-(4,5-dihydroimidazol-1-yl)-4,5-dihydroimidazole Chemical compound C1=NCCN1N1C=NCC1 DZPXBTZJEFYBBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 32
- 239000012074 organic phase Substances 0.000 description 19
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000013019 agitation Methods 0.000 description 15
- 229940125782 compound 2 Drugs 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 12
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- HJKGBRPNSJADMB-UHFFFAOYSA-N 3-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CN=C1 HJKGBRPNSJADMB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 2
- KQMIWCAOEFUBQK-UHFFFAOYSA-N 1-methoxy-3-phenylbenzene Chemical group COC1=CC=CC(C=2C=CC=CC=2)=C1 KQMIWCAOEFUBQK-UHFFFAOYSA-N 0.000 description 2
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical group C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 2
- NPDIDUXTRAITDE-UHFFFAOYSA-N 1-methyl-3-phenylbenzene Chemical group CC1=CC=CC(C=2C=CC=CC=2)=C1 NPDIDUXTRAITDE-UHFFFAOYSA-N 0.000 description 2
- FYRPEHRWMVMHQM-UHFFFAOYSA-N 1-nitro-3-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC(C=2C=CC=CC=2)=C1 FYRPEHRWMVMHQM-UHFFFAOYSA-N 0.000 description 2
- OUMKBAHMPRLISR-UHFFFAOYSA-N 1-phenyl-4-(trifluoromethyl)benzene Chemical group C1=CC(C(F)(F)F)=CC=C1C1=CC=CC=C1 OUMKBAHMPRLISR-UHFFFAOYSA-N 0.000 description 2
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 2
- LCRCBXLHWTVPEQ-UHFFFAOYSA-N 2-phenylbenzaldehyde Chemical group O=CC1=CC=CC=C1C1=CC=CC=C1 LCRCBXLHWTVPEQ-UHFFFAOYSA-N 0.000 description 2
- PJRGDKFLFAYRBV-UHFFFAOYSA-N 2-phenylthiophene Chemical compound C1=CSC(C=2C=CC=CC=2)=C1 PJRGDKFLFAYRBV-UHFFFAOYSA-N 0.000 description 2
- KFKSIUOALVIACE-UHFFFAOYSA-N 3-phenylbenzaldehyde Chemical group O=CC1=CC=CC(C=2C=CC=CC=2)=C1 KFKSIUOALVIACE-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- BAJQRLZAPXASRD-UHFFFAOYSA-N 4-Nitrobiphenyl Chemical group C1=CC([N+](=O)[O-])=CC=C1C1=CC=CC=C1 BAJQRLZAPXASRD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- 210000000080 chela (arthropods) Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 1
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 1
- SSBJOOLBHDYCJX-UHFFFAOYSA-N CC(C=C1)=CC=C1Br.F.F.F Chemical compound CC(C=C1)=CC=C1Br.F.F.F SSBJOOLBHDYCJX-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 238000006761 Kharasch addition reaction Methods 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- GBZBWKNUKKBMKR-UHFFFAOYSA-N [P].[C].[P] Chemical compound [P].[C].[P] GBZBWKNUKKBMKR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000003579 shift reagent Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses one kind of forcipated diimidazoline palladium compound in the structure as shown and its application in Suzuki reaction. The forcipated diimidazoline palladium compound is synthesized through heating and refluxing diimidazoline benzene and palladium acetate in glacial acetic acid, the subsequent evaporating to dry, adding acetone/water solution of lithium chloride,stirring at room temperature to extract, drying, concentrating and thin-layer chromatographic separation. The compound is used in catalyzing coupling Suzuki reaction to synthesize biaryl compound.
Description
Technical field
The invention belongs to the synthetic and applied technical field of organic compound, relate to pincerlike bi-imidazoline palladium compound of a class and the catalytic applications in the Suzuki reaction thereof.
Background technology
Pincerlike metal complexes (pincer type metal complex) is made up of the tridentate ligand and the metal center of a pincer, generally contains a metal-carbon σ key between part and the metal.After the pincerlike metal complexes of first PCP type (phosphorus carbon phosphorus type) in 1976 is synthetic, people increase rapidly the interest of synthetic, structure, reaction and the application of the pincerlike metal complexes of novelty, especially recent years, some significant progress have been obtained in application facet.The pincerlike title complex of various informative aryl is successfully used to Kharasch addition, dehydrating alkanes reaction, Suzuki reaction, the hydrogen transfer reactions (Hydrogen transfer reaction) of ketone, Heck reaction, Michael addition reaction, Diels-Alder and reacts etc.In addition, the biaryl compounds has purposes widely in fields such as chemical industry, medicine, agricultural chemicals, high molecule liquid crystal, food, and for example: the chirality biaryl lopps compound that has atropisomerism in asymmetric synthesis is the very important chiral ligand of a class; In chemical analysis, can be used as shift reagent, chiral stationary phase; In foodstuffs industry, make foodstuff additive etc.Under the palladium catalysis, the Suzuki linked reaction of aryl boric acid and various halogenated aryl hydrocarbons is one of effective meanss of synthetic biaryl compounds, and Kai Fa some effective catalysts are mainly the palladium compound that contains the phosphine part in recent years.Although use the catalyst system activity of organophosphorus ligand higher, also exist some significantly not enough, for example the toxicity of phosphine part is bigger; Usually need polystep reaction synthetic, cost is higher; Less stable needs protection of inert gas during use, operation inconvenience etc.Therefore research and development efficiently, no phosphine palladium complex catalyst is one of important developing direction of Suzuki linked reaction.
Summary of the invention
For research and develop efficiently, no phosphine palladium complex catalyst, increase the kind of pincerlike metal complexes, enlarge such application of compound field, the purpose of this invention is to provide the pincerlike bi-imidazoline palladium compound of a class chirality and achirality, and utilize its as catalyzer in organic phase, by bromo aromatic compound and phenyl-boron dihydroxide prepared in reaction biaryl derivative.Such catalyzer prepares easily, and is stable in empty G﹠W, during catalyzed reaction, needn't protect by noble gas, reacts employed solvent and also needn't handle, simple to operate.
The present invention realizes above-mentioned purpose by the following technical solutions:
A kind of pincerlike bi-imidazoline palladium compound is the compound of following structural formula
R wherein
1Be alkyl, aryl or hydrogen; R
2Be alkyl or aryl.
Described alkyl is C
1-C
15Alkyl; Described aryl is p-methylphenyl, p-methoxyphenyl, p-nitrophenyl or to the itrile group phenyl.
A kind of synthetic method of pincerlike bi-imidazoline palladium compound, its synthesis step: bi-imidazoline base benzene and palladium reflux in Glacial acetic acid between inciting somebody to action, evaporate to dryness then, the acetone solution that adds lithium chloride, stirring at room, extraction, drying, concentrate, the thin-layer chromatography separation promptly gets pincerlike bi-imidazoline palladium compound.
Described bi-imidazoline base benzene: palladium=1: 1-1.5 (mol ratio).
Described bi-imidazoline base benzene and palladium reflux time in Glacial acetic acid are 1-4 days.
The mole dosage of described lithium chloride be between bi-imidazoline base benzene 10-15 doubly, the volume ratio of acetone and water is an acetone in the acetone solution: water=3: 2.
After adding the acetone solution of lithium chloride, the stirring at room time is 1-4 days.
When thin-layer chromatography separated, the developping agent that uses was an acetone as acetone/methylene dichloride mixed solvent, its volume ratio: methylene dichloride=1: 1-70.
The above-mentioned application of pincerlike bi-imidazoline palladium compound in biaryl compounds synthetic method.
Preparation biaryl compounds adopts following steps: the pincerlike bi-imidazoline palladium compound of catalyzer, alkali, bromo aromatic compound, phenyl-boron dihydroxide are joined in the solvent, and in 100-140 ℃ of reaction 4-24 hour, reaction finished, reduce to room temperature, extraction, drying, concentrate, purifying promptly gets product.
Described bromo aromatic compound is the compound of following general formula: R
3-Br
R
4Be hydrogen, methyl, methoxyl group, formyl radical, nitro or trifluoromethyl
The consumption of the pincerlike bi-imidazoline palladium compound of catalyzer is the 0.1%-0.5% (molecular fraction) of bromo aromatic compound; The mol ratio of bromo aromatic compound, phenyl-boron dihydroxide, alkali is the bromo aromatic compound: phenyl-boron dihydroxide: alkali=1: 1-2: 1-3; Alkali is yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide, potassium hydroxide, Potassium monofluoride, Potassium ethanoate, triethylamine; Solvent is DMF, toluene, 1,4-dioxane, tetrahydrofuran (THF).
Positively effect of the present invention is:
The present invention relates to the pincerlike bi-imidazoline palladium compound of a class chirality and achirality, and use it for catalysis Suzuki linked reaction.Pincerlike bi-imidazoline palladium compound prepares easily as a class catalyzer.During catalyzed reaction, use cheap alkali, solvent needn't be handled, and in air, being that raw material is can high productivity synthetic with bromo aromatic compound and phenyl-boron dihydroxide obtains corresponding biaryl compounds.This method has the reaction conditions gentleness, and the reaction substrate scope is wide, and the reaction specificity is strong, the productive rate height, and economy, simple to operate, to advantages such as environmental influence are little.
Embodiment
Further describe the present invention below in conjunction with embodiment:
Used bi-imidazoline base of the present invention benzene is according to document (J.Org.Chem.2002,67,3919-3922) described method preparation.Concrete grammar is: two amido alcohol between chirality or achirality are refluxed in thionyl chloride solution and stir, boil off excessive thionyl chloride then, add the exsiccant ether, remove by filter insolubles, add dry good triethylamine and aromatic amine or aliphatic amide again, stirring at room, add aqueous sodium hydroxide solution then, extraction, drying, concentrate bi-imidazoline base benzene between the thin-layer chromatography separation promptly gets.
Embodiment one: 2,6-two (4,5-dihydro-1-p-methoxyphenyl-1H-imidazoles-2-yl) preparation of phenyl Palladous chloride (II): in the 100mL there-necked flask of stirring and refluxing device is housed, add 1,3-two (4,5-dihydro-1-p-methoxyphenyl-1H-imidazoles-2-yl) benzene (0.43g, 1mmol), palladium (0.27g, 1.2mmol) and the 60mL Glacial acetic acid, lucifuge, stirring and refluxing is two days later under nitrogen atmosphere, steam Glacial acetic acid, (volume ratio of acetone and water is an acetone: water=3: 2 (as follows) for 0.42g, acetone solution 50mL 10mmol) to add lithium chloride then, stirred two days under the room temperature, with dichloromethane extraction (3 times, 30mL is each), merge organic phase, with saturated common salt washing, anhydrous MgSO
4Dry, boil off solvent under the vacuum, utilize the volume ratio of acetone and methylene dichloride to be acetone: the acetone/methylene dichloride mixed solvent of methylene dichloride=1: 1 is made developping agent, thin-layer chromatography separate product, promptly 2, two (4,5-dihydro-1-p-methoxyphenyl-1H-imidazoles-2-yl) the phenyl Palladous chlorides (II) of 6-, productive rate 32.5%.M.p.：＞260℃，IR(KBr)：v?3052，2955，2926，2855，1605，1569，1536，1511，1458，1434，1380，1291，1248，1179，1163，1107，1032，961，923，836，809，725，615cm
-1.
1H?NMR(400MHz，CDCl
3)：δ7.21(d，J＝8.7Hz，4H，N-benzene)，6.94(d，J＝8.6Hz，4H，N-benzene)，6.50(t，J＝7.6Hz，1H，H4?central?benzene)，6.23(d，J＝7.8Hz，2H，H3?and?H5?central?benzene)，4.18(m，t，J＝11.2Hz，4H，imidazoline)，4.04(t，J＝9.3Hz，4H，imidazoline)，3.85(s，6H，OCH
3).
13C?NMR(100MHz，CDCl
3)：δ173.5(C1?central?benzene)，170.5(C2?imidazoline)，159.1(C4?N-benzene)，133.2，132.6，128.1(N-benzene)，126.3(C3?and?C5?central?benzene)，121.9(C4?central?benzene)，114.9(N-benzene)，56.0(imidazoline)，55.5(CH
3)，50.8(imidazoline).MS(m/z，ESI
+)：531(M-C1).high-resolution?MS(m/z，ESI
+)，found?for?M-C1＝531.1019，C
26H
25N
4O
2Pdrequires?531.1012.
Embodiment two: 2,6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-imidazoles-2-yl] preparation of phenyl Palladous chloride (II): in being housed, the 100mL there-necked flask of stirring and refluxing device adds 1,3-pair [(S)-and 4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-imidazoles-2-yl] benzene (0.48g, 1mmol), palladium (0.23g, 1mmol) with the 60mL Glacial acetic acid, lucifuge, stirring and refluxing steamed Glacial acetic acid after one day under nitrogen atmosphere, add lithium chloride (0.50g then, acetone solution 50mL 12mmol) stirred one day under the room temperature, used dichloromethane extraction (3 times, 30mL is each), merge organic phase, with saturated common salt washing, anhydrous MgSO
4Dry, boil off solvent under the vacuum, utilize the volume ratio of acetone and methylene dichloride to be acetone: the acetone/methylene dichloride mixed solvent of methylene dichloride=1: 50 is made developping agent, thin-layer chromatography separate product, promptly 2,6-pair [(S)-and 4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II), productive rate 33.8%.M.p.：＞260℃，IR(KBr)：v?3030，2955，2925，2868，1574，1536，1512，1500，1460，1429，1386，1336，1296，1162，1109，1073，1042，1019，998，821，799，727，672，643cm
-1.
1H?NMR(400MHz，CDCl
3)：δ7.21(d，J＝8.4Hz，4H，N-benzene)，7.11(d，J＝8.0Hz，4H，N-benzene，6.53(t，J＝7.6Hz，1H，H4central?benzene)，6.33(d，J＝7.6Hz，2H，H3and?H5central?benzene?)，4.36(ddd，J＝3.6，5.2，10.8Hz，2H，NCH)，4.02(apt，J＝10.4Hz，2H，CHH)，3.83(dd，J＝5.6，10.0Hz，2H，CHH)，2.93-2.89(m，2H，(CH
3)
2CH)，2.40(s，6H，CH
3)，0.93(d，J＝7.2Hz，6H，CH
3CH)，0.90(d，J＝6.8Hz，6H，CHCH
3).
13C?NMR(100MHz)(CDCl
3)：δ173.2(C1?central?benzene)，168.5(C2?imidazoline)，137.6，137.4，133.2，130.2(N-benzene)，126.6(C3?and?C5?central?benzene)，126.1(N-benzene)，121.7(C4?central?benzene)，66.5(NCH)，54.8(CH
2)，29.9(CH
3)
2CH)，21.2(CH
3)，18.7(CH
3CH)，14.4(CHCH
3).MS(m/z，ESI
+)：583(M-C1).high-resolution?MS(m/z，ESI
+)，found?for?M-C1＝583.2089，C
32H
37N
4Pd?requires?583.2053.
Embodiment three: 2,6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazoles-2-yl] preparation of phenyl Palladous chloride (II): in being housed, the 100mL there-necked flask of stirring and refluxing device adds 1,3-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazoles-2-yl] benzene (0.51g, 1mmol), palladium (0.34g, 1.5mmol) and the 60mL Glacial acetic acid, lucifuge, stirring and refluxing steamed Glacial acetic acid after 4 days under nitrogen atmosphere, add lithium chloride (0.63g then, acetone solution 50mL 15mmol) stirred 4 days under the room temperature, used dichloromethane extraction (3 times, 30mL is each), merge organic phase, with saturated common salt washing, anhydrous MgSO
4Dry, boil off solvent under the vacuum, utilize the volume ratio of acetone and methylene dichloride to be acetone: the acetone/methylene dichloride mixed solvent of methylene dichloride=1: 70 is made developping agent, thin-layer chromatography separate product, promptly 2,6-pair [(S)-and 4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II), productive rate 35.1%.M.p.：＞260℃，IR(KBr)：v?3041，2956，2929，2868，2838，1608，1574，1538，1512，1461，1430，1386，1336，1287，1250，1163，1105，1072，1042，1027，835，800，763，727，670，649cm
-1.
1H?NMR(400MHz，CDCl
3)：δ7.16(d，J＝8.8Hz，4H，N-benzene)，6.92(d，J＝9.0Hz，4H，N-benzene)，6.51(t，J＝7.8Hz，1H，H4?central?benzene)，6.23(d，J＝7.8Hz，2H，H3?and?H5?centralbenzene)，4.36(ddd，J＝3.5，5.5，11.1Hz，2H，NCH)，3.98(apt，J＝10.1Hz，2H，CHH)，3.85(s，6H，OCH
3)，3.81(dd，J＝5.6，10.0Hz，2H，CHH)，2.93-2.87(m，2H，((CH
3)
2CH)，0.94-0.90(m，12H，(CH
3)
2CH).
13C?NMR(100MHz，CDCl
3)：δ173.1(C1?central?benzene)，168.8(C2?imidazoline)，159.0，133.2，132.7，127.9(N-benzene)，126.4(C3?and?C5?central?benzene)，121.8(C4?central?benzene)，114.8(N-benzene)，66.6(NCH)，55.5(OCH
3)，55.0(CH
2)，29.9(CH
3)
2CH)，18.7(CH
3CH)，14.4(CHCH
3).MS(m/z，ESI
+)：615(M-C1).high-resolution?MS(m/z，ESI
+)，found?for?M-C1＝615.1951，C
32H
37N
4O
2Pd?requires?615.1951.
Embodiment four: biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.42mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-two (4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl) phenyl Palladous chloride (II) is made catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the bromobenzene of 0.5mmol (53 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is developping agent with the sherwood oil, separates with silica gel thin-layer chromatography, obtains pure biphenyl, separation yield＞99%.White?plates，m.p.70℃，Lit.70-71℃.
1H?NMR(400MHz，CDCl
3)：δ7.59(4H，d，J＝7.2Hz，Ar-H)，7.43(4H，t，J＝7.3Hz，Ar-H)，7.33(2H，t，J＝7.3Hz，Ar-H).
Embodiment five: 2-methyl diphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.55mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 2-methyl bromobenzene of 0.5mmol (61 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 2-methyl diphenyl, separation yield is 88.1%.Colorless?oil.
1H?NMR(400MHz，CDCl
3)：δ7.40-7.36(2H，m，Ar-H)，7.32-7.29(3H，m，Ar-H)，7.24-7.21(4H，m，Ar-H)，2.26(3H，s，CH
3)。
Embodiment six: 3-methyl diphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.63mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 3-methyl bromobenzene of 0.5mmol (62 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 12: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 3-methyl diphenyl, separation yield is 85.7%.
Embodiment seven: 4-methyl diphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.42mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-two (4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl) phenyl Palladous chloride (II) is made catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 4-methyl bromobenzene of 0.5mmol (61 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 15: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 4-methyl diphenyl, separation yield 76.2%.White?solid，m.p.47-49℃，Lit.48-50℃.
1H?NMR(400MHz，CDCl
3)：δ7.57(2H，d，J＝7.6Hz，Ar-H)，7.49(2H，d，J＝7.4Hz，Ar-H)，7.41(2H，t，J＝7.5Hz，Ar-H)，7.31(1H，t，J＝7.2Hz，Ar-H)，7.24(2H，d，J＝7.6Hz，Ar-H)，2.38(3H，s，CH
3)。
Embodiment eight: 2-methoxyl biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.55mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl]] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 2-methoxyl group bromobenzene of 0.5mmol (62 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 2-methoxyl biphenyl, separation yield is 83.7%.
Embodiment nine: 3-methoxyl biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.63mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 3-methoxyl group bromobenzene of 0.5mmol (63 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 12: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 3-methoxyl biphenyl, separation yield is 83.7%.
Embodiment ten: 4-methoxyl biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.42mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-two (4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl) phenyl Palladous chloride (II) is made catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 4-methoxyl group bromobenzene of 0.5mmol (63 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 15: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 4-methoxyl biphenyl, separation yield 91.3%.White?plates，m.p.92℃，Lit.91-92℃.
1H?NMR(400MHz，CDCl
3)：δ7.56-7.51(4H，m，Ar-H)，7.41(2H，t，J＝7.5Hz，Ar-H)，7.29(1H，t，J＝7.3Hz，Ar-H)，6.97(2H，d，J＝8.7Hz，Ar-H)，3.84(3H，s，CH
3)。
Embodiment 11: 3-nitrobiphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.55mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O, the 3-nitro bromobenzene of adding 0.5mmol (101mg), the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 12: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 3-nitrobiphenyl, separation yield is＞99%.
Embodiment 12: 4-nitrobiphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.63mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O, the 4-nitro bromobenzene of adding 0.5mmol (101mg), the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 15: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 4-nitrobiphenyl, separation yield is＞99%.Yellow?needles，m.p.113-114℃，Lit.112-114℃.
1H?NMR(400MHz，CDCl
3)：δ8.28(2H，d，J＝8.7Hz，Ar-H)，7.72(2H，d，J＝8.7Hz，Ar-H)，7.62(2H，d，J＝7.2Hz，Ar-H)，7.51-7.42(3H，m，Ar-H)。
Embodiment 13: 2-formyl biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.55mg) to the Schlenk of 10mL reaction tubes (a kind of glassware); 6-pair [(S)-4-sec.-propyl-4; 5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O, the 2-formyl radical bromobenzene of adding 0.5mmol (93mg), the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 2-formyl biphenyl, separation yield is 95.6%.
Embodiment 14: 3-formyl biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.63mg) to the Schlenk of 10mL reaction tubes (a kind of glassware); 6-pair [(S)-4-sec.-propyl-4; 5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 3-formyl radical bromobenzene of 0.5mmol (59 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 12: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 3-formyl biphenyl, separation yield is＞99%.
Embodiment 15: 3-phenylpyridine synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.55mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 3-bromopyridine of 0.5mmol (49 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 12: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 3-phenylpyridine, separation yield is 81.2%.
1H?NMR(400MHz，CDCl
3)：δ8.84(1H，s，Ar-H)，8.58(1H，d，J＝3.8Hz，Ar-H)，7.86(1H，d，J＝7.8Hz，Ar-H)，7.53(2H，d，J＝7.4Hz，Ar-H)，7.44(2H，d，J＝7.1Hz，Ar-H)，7.39-7.33(2H，m，Ar-H)。
Embodiment 16: 2-phenyl thiophene synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.63mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 2-bromothiophene of 0.5mmol (48 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 2-phenyl thiophene, separation yield is 73.8%.
Embodiment 17: 4-trifluoromethyl-biphenyl synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.55mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methylphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 4-methyl bromobenzene trifluoride of 0.5mmol (69 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 15: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 4-trifluoromethyl-biphenyl, separation yield is 76.6%.
Embodiment 18: 1-phenylnaphthalene synthetic: the pincerlike bi-imidazoline palladium compound 2 that adds 0.0025mmol (1.63mg) to the Schlenk of 10mL reaction tubes (a kind of glassware), 6-pair [(S)-4-sec.-propyl-4,5-dihydro-1-p-methoxyphenyl-1H-tetrahydroglyoxaline-2-yl] phenyl Palladous chloride (II) makes catalyzer, 1mmol (266mg) K
3PO
43H
2O adds the 1-bromonaphthalene of 0.5mmol (70 μ l) with syringe, and the phenyl-boron dihydroxide of 0.75mmol (92mg) and 3mL solvent DMF are heated to 140 ℃ (oil bath temperatures) with oil bath then under magnetic agitation, reacted 8 hours.Remove oil bath, drop to room temperature, the dichloromethane extraction of usefulness 10mL three times merges organic phase and uses anhydrous MgSO
4Drying is filtered; Rotatory evaporator concentrates, and raffinate is a developping agent with 12: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 1-phenylnaphthalene, separation yield is＞99%.Colorless?oil.
1H?NMR(400MHz，CDCl
3)：δ7.88(2H，t，J＝9.6Hz，Ar-H)，7.82(1H，d，J＝8.1Hz，Ar-H)，7.50-7.43(6H，m，Ar-H)，7.40-7.37(3H，m，Ar-H)。
Claims (8)
1, a kind of pincerlike bi-imidazoline palladium compound is characterized in that: be the compound of following structural formula:
Described alkyl is C
1-C
15Alkyl; Described aryl is p-methylphenyl, p-methoxyphenyl, p-nitrophenyl or to the itrile group phenyl.
2, a kind of synthetic method of pincerlike bi-imidazoline palladium compound as claimed in claim 1, it is characterized in that, bi-imidazoline base benzene and palladium reflux in Glacial acetic acid between inciting somebody to action, evaporate to dryness then adds the acetone solution of lithium chloride, stirring at room, extraction, drying concentrates, and the thin-layer chromatography separation promptly gets pincerlike bi-imidazoline palladium compound.
3, the method for synthetic pincerlike bi-imidazoline palladium compound as claimed in claim 2 is characterized in that, the mol ratio of a bi-imidazoline base benzene and palladium is:
Between bi-imidazoline base benzene: palladium=1: 1-1.5.
4, the method for synthetic pincerlike bi-imidazoline palladium compound as claimed in claim 3 is characterized in that, a bi-imidazoline base benzene and the palladium reflux time in Glacial acetic acid is 1-4 days.
5, the method for synthetic pincerlike bi-imidazoline palladium compound as claimed in claim 4 is characterized in that, the mole dosage of lithium chloride be between bi-imidazoline base benzene 10-15 doubly, the volume ratio of acetone and water is an acetone in the acetone solution: water=3: 2.
6, the method for synthetic pincerlike bi-imidazoline palladium compound as claimed in claim 5 is characterized in that, behind the acetone solution of adding lithium chloride, the stirring at room time is 1-4 days.
7, the method for synthetic pincerlike bi-imidazoline palladium compound as claimed in claim 6 is characterized in that, when thin-layer chromatography separated, the developping agent that uses was an acetone as acetone/methylene dichloride mixed solvent, its volume ratio: methylene dichloride=1: 1-70.
8, the application of a kind of pincerlike bi-imidazoline palladium compound as claimed in claim 1 in biaryl compounds synthetic method, described biaryl compounds synthetic method adopts following steps: the described pincerlike bi-imidazoline palladium compound of claim 1, alkali, bromo aromatic compound, phenyl-boron dihydroxide are joined in the solvent, in 100-140 ℃ of reaction 4-24 hour, reaction finishes, reduce to room temperature, extraction, drying, concentrate, purifying promptly gets the biaryl compounds;
Described bromo aromatic compound is the compound of following general formula: R3-Br;
R
4Be hydrogen, methyl, methoxyl group, formyl radical, nitro or trifluoromethyl.
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| Suzuki偶联反应的最新研究进展. 周少林等.有机化学，第24卷第12期. 2004 |
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| Synthesis, characterization and photoluminescent propertiesof....... Hao, Xin-Qi, et al.Tetrahedron Letters,Vol.47 No.29. 2006 * |
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