CN107973812A - 一种制备芳基硼酸新戊二醇酯类化合物的方法 - Google Patents
一种制备芳基硼酸新戊二醇酯类化合物的方法 Download PDFInfo
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- CN107973812A CN107973812A CN201711198939.3A CN201711198939A CN107973812A CN 107973812 A CN107973812 A CN 107973812A CN 201711198939 A CN201711198939 A CN 201711198939A CN 107973812 A CN107973812 A CN 107973812A
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- Prior art keywords
- boric acid
- neopentyl glycol
- nickel
- acid neopentyl
- solvent
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- -1 aryl boric acid neopentyl glycol esters compound Chemical class 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 18
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 30
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims abstract description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 75
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000002904 solvent Substances 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 25
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 238000004440 column chromatography Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical class [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical class Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 34
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 31
- 239000003446 ligand Substances 0.000 abstract description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 54
- 239000000047 product Substances 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 36
- 238000012512 characterization method Methods 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- 238000007789 sealing Methods 0.000 description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 18
- 239000012046 mixed solvent Substances 0.000 description 18
- 239000003208 petroleum Substances 0.000 description 18
- 238000000746 purification Methods 0.000 description 18
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 9
- 239000000284 extract Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 6
- 229910000085 borane Inorganic materials 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- 239000002024 ethyl acetate extract Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical class CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 3
- ZCJAYDKWZAWMPR-UHFFFAOYSA-N 1-chloro-2-fluorobenzene Chemical compound FC1=CC=CC=C1Cl ZCJAYDKWZAWMPR-UHFFFAOYSA-N 0.000 description 2
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 description 2
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 description 2
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical class C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- GSFNQBFZFXUTBN-UHFFFAOYSA-N 2-chlorothiophene Chemical class ClC1=CC=CS1 GSFNQBFZFXUTBN-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- YTYIMDRWPTUAHP-UHFFFAOYSA-N 6-Chloroindole Chemical class ClC1=CC=C2C=CNC2=C1 YTYIMDRWPTUAHP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- QUEKRLGFNBREBX-UHFFFAOYSA-N boric acid 2,2-dimethylpropane-1,3-diol Chemical compound OB(O)O.OCC(C)(C)CO QUEKRLGFNBREBX-UHFFFAOYSA-N 0.000 description 1
- 125000005620 boronic acid group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ONDPGJBEBGWAKI-UHFFFAOYSA-N diphenylphosphane;propane Chemical compound CCC.C=1C=CC=CC=1PC1=CC=CC=C1 ONDPGJBEBGWAKI-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- KGFLFWRAHYKYEA-UHFFFAOYSA-N trimethyl(2,2,2-trifluoroethoxy)silane Chemical compound C[Si](C)(C)OCC(F)(F)F KGFLFWRAHYKYEA-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明公开了一种制备芳基硼酸新戊二醇酯类化合物的方法,催化剂混配型镍(II)配合物化学式为Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2。本发明的含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物可以在甲醇钾的存在下高效地催化氯代烃与联硼酸新戊二醇酯的交叉偶联反应以制备芳基硼酸新戊二醇酯类化合物,这是以亚磷酸酯和氮杂环卡宾作为辅助配体的混配型镍(II)配合物催化这类交叉偶联反应的第一例。
Description
本发明属于发明名称为含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物、其制备方法与应用,申请号为201610215681.2,申请日2016年4月8日为发明专利的分案申请,属于化合物的制备技术部分。
技术领域
本发明涉及一种镍(II)配合物及其在有机合成领域中的应用,具体涉及一种制备芳基硼酸新戊二醇酯类化合物的方法。
背景技术
芳基硼酸酯类化合物是一类在有机合成领域中非常重要的合成中间体,因此如何简单高效地合成各类芳基硼酸酯类化合物受到了持续的关注(参见:Boronic Acids;Hall,D. G.; Wiley-VCH: Weinheim, Germany, 2005)。合成芳基硼酸酯类化合物的传统方法是卤代烃和三烷基硼酸酯在金属有机试剂(如有机锌试剂,格氏试剂)作用下发生反应,但是这一方法由于需用到敏感的金属有机试剂而有诸多限制(参见:Suzuki, A.; Brown, H.C. Organic Syntheses via Boranes; Aldrich Chemical Co.: Milwaukee, 2003;Vol.3)。为了避免上述金属有机试剂的使用,人们开发了过渡金属催化的卤代烃和硼试剂的交叉偶联反应来合成芳基硼酸酯类化合物,其中使用较多的是钯系催化剂,但是使用钯系催化剂也有一些缺点,最明显的就是其昂贵的价格。
与昂贵的钯系催化剂相比,镍系催化剂的价格是非常便宜的,在工业化应用中具有显著的成本优势。因此,开发镍系催化剂实现卤代烃与硼试剂的交叉偶联反应来合成芳基硼酸酯类化合物受到了越来越多的关注。例如,使用1,3-双(二苯基膦)丙基二氯化镍(II)和1,3-双(二苯基膦)丙烷组成的催化体系,可以实现溴代烃与新戊二醇甲硼烷的交叉偶联;采用1,3-双(二苯基膦)丙基二氯化镍(II)和1,1’- 双(二苯基膦)二茂铁组成的催化体系,以锌粉为添加剂,可以高效地催化碘代烃或溴代烃与新戊二醇甲硼烷的交叉偶联反应,该方法具有更好的底物适用性和更高的催化效率。这些结果表明相对廉价的镍系催化剂在合成芳基硼酸酯类化合物的卤代烃与硼试剂的交叉偶联反应中是有很大的应用前景的,但是这些方法也有一定的缺陷,如反应温度需要100℃的高温、催化剂用量需要10 mol%,尤其存在无法广泛应用于活性较低但价格更为便宜且种类繁多的氯代烃的问题。
以氟化铯为碱,以三甲基(2,2,2-三氟乙氧基)硅烷为添加剂,以二(三甲基膦)二氯化镍(II)为催化剂可以实现氯代烃与联硼酸频哪醇酯的交叉偶联反应(参见:Yamamoto,T.; Morita, T.; Yamakawa, T. Org. Lett. 2011, 13, 5766),但是该方法的反应温度仍需要100℃的高温,而且需要使用毒性较大的三甲基膦和较昂贵的添加剂;使用二异丙基乙胺作碱,采用1,3-双(二苯基膦)丙基二氯化镍(II)和三苯基膦组成的催化体系,可以实现溴代烃和氯代烃与四羟基二硼的交叉偶联反应以制备芳基硼酸类化合物(参见:Molander, G. A.; Cavalcanti, L. N.; García-García, C. J. Org. Chem., 2013,78, 6427);但是该方法也存在一些弊端,主要有:(1)仍需要使用毒性较大的膦配体;(2)涉及的底物大部分为溴代烃,对活性较低、但廉价易得的氯代烃涉及相对较少;(3)对于所涉及的氯代烃大部分仍然需要80℃的高温,等等。因此,很有必要研发更多的催化体系,以高效的催化卤代烃,特别是氯代烃与硼试剂之间的交叉偶联反应。
亚磷酸酯与其他的膦配体(如:三苯基膦、三环己基膦)相比拥有更低廉的价格和更低的毒性,但至今为止,还未见含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物的报道,也未见其催化氯代烃和联硼酸新戊二醇酯的交叉偶联反应的报道。
发明内容
本发明的目的是提供一种含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物,可以在甲醇钾的存在下高效地催化氯代烃与联硼酸新戊二醇酯的交叉偶联反应来合成芳基硼酸新戊二醇酯类化合物,其催化活性和底物适用性都显著优于现有技术。
为达到上述目的,本发明采用的技术方案是:一种含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物,其结构通式如下所示:
其中,R1为乙基或者异丙基;R2为2,4,6-三甲基苯基、2,6-二异丙基苯基或者叔丁基;X为溴或者氯。
本发明的含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物化学式为Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2;其制备方法具体如下:
当X为溴的时候,制备上述混配型镍(II)配合物的方法包括以下步骤,惰性气体中,将二(亚磷酸酯)二溴化镍(II)与氮杂环卡宾溶于溶剂中,于室温下反应2~4小时;然后真空除去溶剂,剩余物经正己烷洗涤后以甲苯萃取,转移清液并除去溶剂甲苯得到镍(II)配合物,即为上述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物。
当X为氯的时候,制备上述混配型镍(II)配合物的方法包括以下步骤,惰性气体中,将二(三苯基膦)二氯化镍(II)与氮杂环卡宾溶于溶剂中,于室温下反应2~4小时;然后真空除去溶剂,剩余物经正己烷洗涤后以甲苯萃取,转移清液并除去溶剂甲苯得到含三苯基膦和氮杂环卡宾的混配型镍(II)配合物;然后将此混配型镍(II)配合物与亚磷酸酯溶于溶剂中,于室温下反应1小时;然后真空除去溶剂,剩余物经正己烷洗涤后以甲苯萃取,转移清液并除去溶剂甲苯得到镍(II)配合物,即为上述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物。
上述技术方案中,所述惰性气体为氩气;二(亚磷酸酯)二溴化镍(II)与氮杂环卡宾的摩尔比为1:1;二(三苯基膦)二氯化镍(II)与氮杂环卡宾的摩尔比为1:1;含三苯基膦和氮杂环卡宾的混配型镍(II)配合物与亚磷酸酯的摩尔比是1:1;溶剂为四氢呋喃。
上述技术方案中,所述溶剂的选择依据是可以溶解氮杂环卡宾,也能溶解含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物和含三苯基膦和氮杂环卡宾的混配型镍(II)配合物;以及不含活性氢。例如:四氢呋喃。
本发明还公开了上述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物作为单组份催化剂在催化氯代烃与联硼酸新戊二醇酯的交叉偶联反应中的应用。
本发明进一步的公开了一种制备芳基硼酸新戊二醇酯类化合物的方法,包括以下步骤,在惰性气体气氛中,依次加入催化剂、甲醇钾、联硼酸新戊二醇酯、氯代烃和溶剂1,4-二氧六环,于38~42℃下反应1.5~4小时,即得到芳基硼酸新戊二醇酯类化合物;所述催化剂为含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物。反应结束后,用水终止反应,反应产物用乙酸乙酯萃取,通过柱层析分离提纯,得到产物收率,可进行定量分析。
上述技术方案中,所述惰性气体为氩气。
上述技术方案中,所述氯代烃为氯代芳烃、取代氯代芳烃或者氯代杂芳烃。
上述技术方案中,催化剂、甲醇钾、联硼酸新戊二醇酯、氯代烃的摩尔比为0.015~0.025:1.5:1.5:1;根据本发明实施例,当氯代烃为氯苯时,以物质的量计,联硼酸新戊二醇酯的用量是氯苯的1.5倍,甲醇钾的用量是氯苯的1.5倍,催化剂的用量是2 mol %;溶剂1,4-二氧六环的用量是1.5毫升,反应温度是40℃,反应时间为2小时;在温和的反应温度、较少的催化剂用量和较短的反应时间下能以90%以上的收率得到苯基硼酸新戊二醇酯,大大的优化了反应条件和提高了产物收率。因此本发明还公开了上述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物在制备芳基硼酸新戊二醇酯类化合物中的应用。
由于上述技术方案的运用,本发明与现有技术相比具有下列优点:
(1)本发明公开的含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物中首次引入亚磷酸酯以替代传统的膦配体,亚磷酸酯或者氮杂环卡宾中的取代基均可多样选择,而且它们的毒性均大大低于传统膦配体,从而开发出一类新的更加绿色和高效的镍催化剂;
(2)本发明以价廉易得的二(亚磷酸酯)二溴化镍(II)或者二(三苯基膦)二氯化镍(II)为镍源,通过与氮杂环卡宾和亚磷酸酯在室温常压的反应制备了含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物,反应简单易操作,产物易提纯、得率高。这类配合物具有明确结构,是在空气中也较稳定的固体,有利于大规模合成与应用;
(3)本发明公开的含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物,可以高效地催化在甲醇钾存在下的氯代烃与联硼酸新戊二醇酯的交叉偶联反应合成芳基硼酸新戊二醇酯类化合物,其催化活性和底物适用性均优于现有技术;根据本发明的实施例,当氯代烃为氯苯,以物质的量计,联硼酸新戊二醇酯的用量是氯苯的1.5倍,甲醇钾的用量是氯苯的1.5倍,催化剂的用量是2 mol %,在1.5毫升1,4-二氧六环中40℃下反应2小时,产率为90%。
具体实施方式
下面结合实施例对本发明作进一步描述:
实施例一:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2=2,4,6-三甲基苯基,X =Br)的合成
将氮杂环卡宾(R2NCH2CH2NR2)C(0.2464g,0.8毫摩尔)加入到二(亚磷酸三乙酯)二溴化镍(II)(0.4400克,0.8毫摩尔)的四氢呋喃溶液中,室温下反应2小时,真空除去溶剂,以正己烷洗涤剩余物,所得剩余物以甲苯萃取,转移清液并除去溶剂甲苯,得红色固体,产率为68 %。
对产物进行元素分析,结果如表1所示:
表1 元素分析结果
C:(%) | H:(%) | N:(%) | |
理论值 | 46.86 | 6.12 | 4.05 |
实际值 | 47.04 | 6.21 | 3.99 |
对产物进行核磁表征,结果如下所示:
将产物溶于C6D6中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, C6D6):δ 6.88 (s, 4H), 3.97 (s, 6H), 3.13 (s, 4H), 2.64 (s,12H), 2.15 (s, 6H), 1.02 (s, 9H) ppm。
实施例二:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3,R2 = 2,6-二异丙基苯基,X = Br)的合成
将氮杂环卡宾(R2NCH2CH2NR2)C(0.3627克,0.93毫摩尔)加入到二(亚磷酸三乙酯)二溴化镍(II)(0.5115克,0.93毫摩尔)的四氢呋喃溶液中,室温下反应2小时,真空除去溶剂,以正己烷洗涤剩余物,所得剩余物以甲苯萃取,转移清液并除去溶剂甲苯,得红色固体,产率为77 %。
对产物进行元素分析,结果如表2所示:
表2 元素分析
C:(%) | H:(%) | N:(%) | |
理论值 | 51.06 | 7.01 | 3.61 |
实际值 | 51.33 | 7.19 | 3.49 |
对产物进行核磁表征,结果如下所示:
将产物溶于C6D6中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, C6D6):δ 7.29 (s, 6H), 3.91 (d, 6H), 3.88 – 3.71 (m, 4H), 3.58(s, 4H), 1.75 (d, 12H), 1.18 (d, 12H), 1.02 (s, 9H) ppm。
实施例三:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH(CH3)2,R2 = 2,6-二异丙基苯基,X = Br)的合成
将氮杂环卡宾(R2NCH2CH2NR2)C(0.3627克,0.93毫摩尔)加入到二(亚磷酸三异丙酯)二溴化镍(II)(0.5905克,0.93毫摩尔)的四氢呋喃溶液中,室温下反应3小时,真空除去溶剂,以正己烷洗涤剩余物,所得剩余物以甲苯萃取,转移清液并除去溶剂甲苯,得红黑色固体,产率为70 %。
对产物进行元素分析,结果如表3所示:
表3 元素分析
C:(%) | H:(%) | N:(%) | |
理论值 | 52.84 | 7.39 | 3.42 |
实际值 | 53.11 | 7.51 | 3.28 |
对产物进行核磁表征,结果如下所示:
将产物溶于C6D6中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, C6D6):δ 7.28 (s, 6H), 4.94 (s, 3H), 3.83 (s, 4H), 3.57 (s,4H), 1.73 (s, 12H), 1.16 (s, 30H) ppm。
实施例四:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3,R2 = C(CH3)3,X = Br)的合成
将氮杂环卡宾(R2NCH2CH2NR2)C(0.1438克,0.78毫摩尔)加入到二(亚磷酸三乙酯)二溴化镍(II)(0.4290克,0.78毫摩尔)的四氢呋喃溶液中,室温下反应1小时,真空除去溶剂,以正己烷洗涤剩余物,所得剩余物以热甲苯萃取,转移清液并除去溶剂甲苯,得黄色固体,产率为60 %。对产物进行元素分析,结果如表4所示:
表4 元素分析
C:(%) | H:(%) | N:(%) | |
理论值 | 35.95 | 6.74 | 4.93 |
实际值 | 36.22 | 6.88 | 4.81 |
对产物进行核磁表征,结果如下所示:
将产物溶于C6D6中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, C6D6):δ 4.29 – 4.07 (m, 5H), 2.73 (t, 4H), 2.26 (s, 6H), 2.00(s, 9H), 1.10 (dt, 9H), 0.45 (s, 4H) ppm。
实施例五:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3,R2 = C(CH3)3,X = Cl)的合成
将氮杂环卡宾(R2NCH2CH2NR2)C(0.1438克,0.78毫摩尔)加入到二(三苯基膦)二氯化镍(II)(0.5101克,0.78毫摩尔)的四氢呋喃溶液中,室温下反应1小时,真空除去溶剂,以正己烷洗涤剩余物,所得剩余物以甲苯萃取,转移清液并除去溶剂甲苯,得粉红色固体,产率为65 %。再将粉红色固体(0.2870克,0.5毫摩尔)与亚磷酸三乙酯(86微升,0.5毫摩尔)混合,加入四氢呋喃作为溶剂,室温下反应1小时,真空抽去溶剂,以正己烷洗涤剩余物,所得剩余物以甲苯萃取,转移清液并除去溶剂甲苯,得黄色固体,产率为90 %。
对产物进行元素分析,结果如表5所示:
表5 元素分析
C:(%) | H:(%) | N:(%) | |
理论值 | 42.62 | 8.00 | 5.85 |
实际值 | 42.95 | 8.11 | 5.73 |
对产物进行核磁表征,结果如下所示:
将产物溶于C6D6中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, C6D6):δ 4.21 (dp, 6H), 2.91 – 2.59 (m, 4H), 2.31 (s, 6H),2.04 (s, 12H), 1.20 (t, 3H), 1.00 (t, 6H) ppm。
实施例六:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的氯苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、氯苯(51微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2 小时,用水终止反应,反应产物用乙酸乙酯萃取,经气相色谱分析产物收率为 95%,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为90 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.80 (d, 2H), 7.43 (t, 1H), 7.36 (t, 2H),3.78 (s, 4H), 1.03 (s, 6H) ppm。
实施例七:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 =2,4,6-三甲基苯基,X=Br)催化的对氯甲苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对氯甲苯(59微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2 小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为92 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.70 (d, 2H), 7.17 (d, 2H), 3.76 (s, 4H),2.36 (s, 3H), 1.02 (s, 6H) ppm。
实施例八:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的间氯甲苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、间氯甲苯(59微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2 小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为88 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS) : δ 7.61 (d, 2H), 7.25 (d, 2H), 3.76 (s,4H), 2.35 (s, 3H), 1.02 (s, 6H) ppm。
实施例九:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的邻氯甲苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、邻氯甲苯(58微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应4小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为73 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.76 (d , 1H), 7.30 (t, 1H),7.18 (t, 2H),3.80 (s, 4H), 2.55 (s, 3H), 1.06 (s, 6H) ppm。
实施例十:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的1-氯萘和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、1-氯萘(68微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂),产率为80 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 8.78 (d, 1H), 8.06 (d, 1H), 7.91 (d, 1H),7.85 (d, 1H), 7.49 (ddt, 3H), 3.90 (s, 4H), 1.11 (s, 6H) ppm。
实施例十一:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的对叔丁基氯苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对叔丁基氯苯(84微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为79 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征: 1H NMR (400 MHz, CDCl3,TMS) : δ 7.76 (d, 2H), 7.40 (d, 2H), 3.77 (s,4H), 1.33 (s, 9H), 1.02 (s, 6H) ppm。
实施例十二:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的对氯苯甲醚和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对氯苯甲醚(61微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为86 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.75 (d, 2H), 6.89 (d, 2H), 3.82 (s, 3H),3.75 (s, 4H), 1.02 (s, 6H) ppm。
实施例十三:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的间氯苯甲醚和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、间氯苯甲醚(63微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为90 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3,TMS) : δ 7.39 (d, 1H), 7.33 (s, 1H), 7.29 (d, 1H),6.97 (d, 1H), 3.83 (s, 3H), 3.77 (s, 4H), 1.02 (s, 6H) ppm。
实施例十四:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的对氯氟苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对氯氟苯(54微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为88 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.80-7.77 (m, 2H),7.03 (t, 2H), 3.76 (s,4H), 1.02 (s, 6H) ppm。
实施例十五:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的对三氟甲基氯苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对三氟甲基氯苯(68微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为78 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.90 (d, 2H), 7.59 (d, 2H), 3.79 (s, 4H),1.03 (s, 6H) ppm。
实施例十六:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的对氯苯乙酮和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(8.65毫克,0.013毫摩尔,2.5mol%)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对氯苯乙酮(65微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应4小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶10的混合溶剂为展开剂),产率为68 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.90 (q, 4H), 3.79 (s, 4H), 2.61 (s, 3H),1.03 (s, 6H) ppm。
实施例十七:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的2-(4-氯苯基)-2-甲基-1,3-二氧五环和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、2-(4-氯苯基)-2-甲基-1,3-二氧五环(82微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应4小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为78 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3,TMS):δ 7.84 (d, 2H), 7.53 (d, 2H), 4.07 (dd, 2H),3.85 – 3.78 (m, 6H), 1.71 (s, 3H), 1.07 (s, 6H) ppm。
实施例十八:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的对氯苯甲酸甲酯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对氯苯甲酸甲酯(85毫克,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应4小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为68 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3,TMS):δ 8.00 (d, 2H), 7.86 (d, 2H), 3.92 (s, 3H),3.78 (s, 4H), 1.03 (s, 6H) ppm。
实施例十九:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的对氯苯甲酸乙酯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、对氯苯甲酸乙酯(78微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应4小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为73 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 8.01 (d, 2H), 7.86 (d, 2H), 4.38 (q, 2H),3.78 (s, 4H), 1.40 (t, 3H), 1.03 (s, 6H) ppm。
实施例二十:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的2-氯噻吩和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、2-氯噻吩(46微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应4小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为54 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.58 (t, 2H), 7.21 – 7.14 (m, 1H), 3.76(s, 4H), 1.03 (s, 6H) ppm。
实施例二十一:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6- 三甲基苯基,X=Br)催化的6-氯吲哚和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、6-氯吲哚(75.8毫克,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为81 %。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.90 (s, 1H), 7.65 (d, 1H), 7.57 (d, 1H),7.25 – 7.22 (m, 1H), 6.55 (s, 1H), 3.81 (s, 4H), 1.05 (s, 6H) ppm。
实施例二十二:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的碘苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、碘苯(56微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为98%。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.80 (d, 2H), 7.43 (t, 1H), 7.36 (t, 2H),3.78 (s, 4H), 1.03 (s, 6H) ppm。
实施例二十三:Ni[P(OR1)3][(R2NCH2CH2NR2)C]X2(R1 = CH2CH3, R2 = 2,4,6-三甲基苯基,X=Br)催化的溴苯和联硼酸新戊二醇酯的交叉偶联反应
氩气保护下,在反应瓶中依次加入催化剂(6.9毫克,0.01毫摩尔,2 mol %)、甲醇钾(52.6毫克,0.75毫摩尔)、联硼酸新戊二醇酯(169.5毫克,0.75毫摩尔)、溴苯(53微升,0.50毫摩尔),1.5 毫升1,4-二氧六环,于40℃下反应2小时,用水终止反应,反应产物用乙酸乙酯萃取,柱层析提纯(以乙酸乙酯/石油醚体积比为1∶20的混合溶剂为展开剂),产率为97%。
将产物溶于CDCl3中(约0.4 mL),封管,室温下于Unity Inova-400型NMR仪上测定表征:1H NMR (400 MHz, CDCl3, TMS):δ 7.80 (d, 2H), 7.43 (t, 1H), 7.36 (t, 2H),3.78 (s, 4H), 1.03 (s, 6H) ppm。
Claims (6)
1.一种制备芳基硼酸新戊二醇酯类化合物的方法,包括以下步骤,在惰性气体气氛中,依次加入催化剂、甲醇钾、联硼酸新戊二醇酯、氯代烃和有机溶剂,于38~42℃下反应1.5~4小时,即得到芳基硼酸新戊二醇酯类化合物;所述催化剂为含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物,其结构通式如下所示:
其中,R1为乙基或者异丙基;R2为2,4,6-三甲基苯基、2,6-二异丙基苯基或者叔丁基;X为溴或者氯。
2.根据权利要求1所述制备芳基硼酸新戊二醇酯类化合物的方法,其特征在于:反应结束后,用水终止反应,反应产物用乙酸乙酯萃取,经过柱层析,即得到芳基硼酸新戊二醇酯类化合物。
3.根据权利要求1所述制备芳基硼酸新戊二醇酯类化合物的方法,其特征在于:所述惰性气体为氩气;所述氯代烃为氯代芳烃、取代氯代芳烃、氯代杂芳烃;所述有机溶剂为1,4-二氧六环。
4.根据权利要求1所述制备芳基硼酸新戊二醇酯类化合物的方法,其特征在于:催化剂、甲醇钾、联硼酸新戊二醇酯、氯代烃的摩尔比为0.015~0.025:1.5:1.5:1。
5.权利要求1所述制备芳基硼酸新戊二醇酯类化合物的方法,其特征在于:所述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物的制备方法为:
当X为溴的时候,惰性气体中,将二(亚磷酸酯)二溴化镍(II)与氮杂环卡宾溶于溶剂中,于室温下反应2~4小时;然后真空除去溶剂,剩余物经正己烷洗涤后以甲苯萃取,转移清液并除去甲苯得到镍(II)配合物,即为上述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物;
当X为氯的时候,惰性气体中,将二(三苯基膦)二氯化镍(II)与氮杂环卡宾溶于溶剂中,于室温下反应2~4小时;然后真空除去溶剂,剩余物经正己烷洗涤后以甲苯萃取,转移清液并除去甲苯得到含三苯基膦和氮杂环卡宾的混配型镍(II)配合物;然后将此混配型镍(II)配合物与亚磷酸酯溶于溶剂中,于室温下反应1小时;然后真空除去溶剂,剩余物经正己烷洗涤后以甲苯萃取,转移清液并除去甲苯得到镍(II)配合物,即为上述含亚磷酸酯和氮杂环卡宾的混配型镍(II)配合物。
6.根据权利要求5所述制备芳基硼酸新戊二醇酯类化合物的方法,其特征在于:所述惰性气体为氩气;二(亚磷酸酯)二溴化镍(II)与氮杂环卡宾的摩尔比为1:1;二(三苯基膦)二氯化镍(II)与氮杂环卡宾的摩尔比为1:1;含三苯基膦和氮杂环卡宾的混配型镍(II)配合物与亚磷酸酯的摩尔比是1:1;溶剂为四氢呋喃。
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