CN113457746A - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113457746A CN113457746A CN202110739238.6A CN202110739238A CN113457746A CN 113457746 A CN113457746 A CN 113457746A CN 202110739238 A CN202110739238 A CN 202110739238A CN 113457746 A CN113457746 A CN 113457746A
- Authority
- CN
- China
- Prior art keywords
- silver
- bis
- catalyst
- dichloromethane
- ligand
- 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.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 6
- -1 5-methylfuran-2-yl Chemical group 0.000 claims description 53
- 239000003446 ligand Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 17
- VVAOPCKKNIUEEU-UHFFFAOYSA-L cycloocta-1,5-diene;platinum(2+);dichloride Chemical compound Cl[Pt]Cl.C1CC=CCCC=C1 VVAOPCKKNIUEEU-UHFFFAOYSA-L 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 125000005499 phosphonyl group Chemical group 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 7
- JXOOJRJCLCEMNC-UHFFFAOYSA-N peri-naphtho-1,3-dioxin Chemical compound C1=CC(OCO2)=C3C2=CC=CC3=C1 JXOOJRJCLCEMNC-UHFFFAOYSA-N 0.000 claims description 6
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 5
- HFLCCHAOKSABAA-UHFFFAOYSA-L cycloocta-1,5-diene;dibromoplatinum Chemical compound Br[Pt]Br.C1CC=CCCC=C1 HFLCCHAOKSABAA-UHFFFAOYSA-L 0.000 claims description 4
- SGSFNZOKVYTGRR-UHFFFAOYSA-L cycloocta-1,5-diene;diiodoplatinum Chemical compound [I-].[I-].[Pt+2].C1CC=CCCC=C1 SGSFNZOKVYTGRR-UHFFFAOYSA-L 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 3
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- YVXVNGVYXSQARS-UHFFFAOYSA-N diethyl(oxo)phosphanium Chemical compound CC[P+](=O)CC YVXVNGVYXSQARS-UHFFFAOYSA-N 0.000 claims description 3
- WQAWEUZTDVWTDB-UHFFFAOYSA-N dimethyl(oxo)phosphanium Chemical compound C[P+](C)=O WQAWEUZTDVWTDB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RDTBXOYKOSIVTQ-UHFFFAOYSA-N oxo-di(propan-2-yl)phosphanium Chemical compound CC(C)[P+](=O)C(C)C RDTBXOYKOSIVTQ-UHFFFAOYSA-N 0.000 claims description 3
- QBRQTQSIWMMJGR-UHFFFAOYSA-N 1-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]phosphonoylbenzene Chemical compound C1=CC(C(F)(F)F)=CC=C1P(=O)C1=CC=C(C(F)(F)F)C=C1 QBRQTQSIWMMJGR-UHFFFAOYSA-N 0.000 claims description 2
- BHXDMDIDPRWOLN-UHFFFAOYSA-N CCCC[P](=O)CCCC Chemical compound CCCC[P](=O)CCCC BHXDMDIDPRWOLN-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- RREGWFNURZJKNB-UHFFFAOYSA-N bis(4-methoxyphenyl)-oxophosphanium Chemical compound C1=CC(OC)=CC=C1[P+](=O)C1=CC=C(OC)C=C1 RREGWFNURZJKNB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 243
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 97
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 84
- 239000007787 solid Substances 0.000 description 66
- 239000000706 filtrate Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 46
- 238000001914 filtration Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 238000012512 characterization method Methods 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000004679 31P NMR spectroscopy Methods 0.000 description 12
- MSACNODAXJVUDF-UHFFFAOYSA-N CP(C)[O] Chemical compound CP(C)[O] MSACNODAXJVUDF-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- TUSAQDPIJTZJSK-UHFFFAOYSA-N dimethylphosphinous acid Chemical compound CP(C)O TUSAQDPIJTZJSK-UHFFFAOYSA-N 0.000 description 11
- 238000004293 19F NMR spectroscopy Methods 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- XNKIEKXYLNHGBX-UHFFFAOYSA-N 1,8-bis(diphenylphosphoryl)naphthalene Chemical compound C=1C=CC=CC=1P(C=1C2=C(C=CC=C2C=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 XNKIEKXYLNHGBX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BZMDVLQBAQJGLI-UHFFFAOYSA-N 1,2-bis(diphenylphosphoryl)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 BZMDVLQBAQJGLI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 150000004799 α-ketoamides Chemical class 0.000 description 2
- RUNJHCZDNSMWGF-UHFFFAOYSA-N 1-propylphosphonoylpropane Chemical compound CCCP(=O)CCC RUNJHCZDNSMWGF-UHFFFAOYSA-N 0.000 description 1
- SDAVAYGIXVCNCF-UHFFFAOYSA-N 2,3-bis(diphenylphosphoryl)naphthalene Chemical compound C=1C=CC=CC=1P(C=1C(=CC2=CC=CC=C2C=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 SDAVAYGIXVCNCF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JMCNGFNJWDJIIV-UHFFFAOYSA-N dibutyl(oxo)phosphanium Chemical compound CCCC[P+](=O)CCCC JMCNGFNJWDJIIV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical class [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with an alkyl or cycloalkyl radical attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/80—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0003—Androstane derivatives
- C07J1/0018—Androstane derivatives substituted in position 17 beta, not substituted in position 17 alfa
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl 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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalyst and a preparation method and application thereof, wherein the structure of the catalyst is shown as a formula I: wherein R is1Selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C12 aryl or substituted or unsubstituted C4-C12 heteroaryl, R2、R3Independently selected from substituted or unsubstituted C1-C12 alkyl or substituted or unsubstituted C4-C12 aryl, X is selected from any one of Cl, Br or I, L‑Selected from the group consisting of counterions. The catalyst provided by the invention has good universality, mild reaction conditions and small usage amount.
Description
Technical Field
The invention belongs to the technical field of preparation of a cyanohydrin hydration catalyst. In particular to a catalyst and a preparation method and application thereof, and especially relates to a catalyst with good universality and a preparation method and application thereof.
Background
The alpha-hydroxyamide compound is widely applied to the preparation of functional polymers, natural products and drug molecules, can be used as a structural unit of a natural product with physiological activity, and is an important organic synthetic intermediate. At present, alpha-hydroxyamide is mainly obtained by strong acid and strong base catalysis, boric acid catalysis and other modes, and has the defects that the application range of a substrate is greatly limited by the tolerance of a functional group, and a large amount of waste materials are generated in the reaction process due to the addition of a large amount of acid and alkali, so that the atom utilization rate is low. The method for directly preparing the alpha-hydroxyamide by hydrating the cyanohydrin has the natural advantages of simple post-reaction treatment, less experimental waste and high atom economy. However, the direct preparation of α -hydroxyamides by hydration of cyanohydrins presents a significant challenge, mainly because cyanohydrins themselves have poor stability and can easily explain the release of HCN poisoning catalysts, especially under alkaline and high temperature conditions. At present, only a few catalysts realize the hydration of the cyanohydrin compounds, but the loading capacity of the catalysts is high, the application range of the substrates is narrow, the application of the catalysts is greatly limited, and the existing alpha-hydroxyamide has low productivity, complex technical route and poor environmental protection, and needs to obtain technical breakthrough.
CN107417562A discloses a novel method for preparing chiral α -hydroxyamides, which is a series of chiral α -hydroxyamide compounds prepared by asymmetric hydrogenation of α -ketoamides with prochiral chirality using a novel tridentate phosphorane ligand, the method comprising: adding prochiral alpha-ketoamide and alkali to perform asymmetric hydrogenation reaction in the presence of a catalyst in a hydrogen atmosphere to obtain chiral alpha-hydroxyamide; the catalyst is obtained by complexing metal iridium salt and a chiral ligand. The ligand used by the method is easy to synthesize, the reaction has the characteristics of high enantioselectivity, high yield and high conversion number, most substrates obtain more than 99% of conversion rate and more than 97% -99% of ee value under the condition that the dosage of the catalyst is one ten thousandth, the highest conversion number reaches 100000, and the method has extremely high industrial value.
The production capacity of alpha-hydroxyamides is low due to the current limitations of catalysts, the technical route is complex and the environmental protection is poor. Therefore, how to provide a catalyst for catalytic synthesis of alpha-hydroxyamide with good universality becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst, a preparation method and application thereof, in particular to a catalyst with good universality, and a preparation method and application thereof. The catalyst provided by the invention has good universality, mild reaction conditions and small usage amount.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst, the structure of which is shown in formula I:
wherein R is1Is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C12 aryl and substituted or unsubstituted C4-C12 heteroaryl, R2、R3Independently selected from substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C4-C12 aryl, X is selected from any one of Cl, Br or I, L-Selected from the group consisting of counterions.
Wherein, C1-C12 respectively represent that the structure contains one carbon atom, two carbon atoms, three carbon atoms, four carbon atoms and the like, and the description is omitted.
The catalyst with the specific structure can catalyze the reaction of the cyanohydrin compound to generate the alpha-hydroxyamide under mild conditions, and has the advantages of high conversion rate, wide substrate application range, good universality and capability of obviously reducing the equivalent weight of the catalyst.
Preferably, said R is1Is selected from
Preferably, said R is2Is selected from
Any one of them.
Preferably, said R is3Is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、
Any one of them.
Preferably, the counter ion is selected from OTf-、BF4 -、PF6 -、SbF6 -Or CF3COO-Any one of them.
In a second aspect, the present invention provides a process for the preparation of a catalyst as described above, comprising the steps of:
(1) mixing the precursor and the first ligand for reaction to obtain an intermediate;
(2) and (2) mixing the intermediate obtained in the step (1), a second ligand and a first silver salt for reaction to obtain the catalyst.
Wherein the structure of the precursor, the first ligand, the intermediate and the second ligand is shown as formula II:
wherein, X, R1、R2、R3And L-Having the same limitations as described above.
Preferably, the precursor is selected from any one of (1, 5-cyclooctadiene) platinum chloride, (1, 5-cyclooctadiene) platinum bromide or (1, 5-cyclooctadiene) platinum iodide or a combination of at least two of the above.
Preferably, the first ligand is selected from the group consisting of 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 8-bis (diphenylphosphonyl) naphthalene, 6, 7-bis (diphenylphosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 2-bis (diphenylphosphonyl) benzene, 2, 3-bis (diphenylphosphonyl) naphthalene, 1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (5-methylfuran-2-yl) phosphonyl) benzene, (4, 5-dimethoxy-1, 2-phenylene) bis (5-methylfuran-2-yl) phosphine), 1, 2-bis (5-methylfuran-2-yl) phosphonyl) ethane and 2, any one or a combination of at least two of 3-bis (5-methylfuran-2-yl) phosphonyl) naphthalene.
The second ligand is selected from any one of dimethyl phosphine oxide, diethyl phosphine oxide, diisopropyl phosphine oxide, dipropylene phosphorus oxide, dibutyl phosphorus oxide, diphenyl phosphorus oxide, bis (4-methoxyphenyl) phosphine oxide or bis (4- (trifluoromethyl) phenyl) phosphine oxide or a combination of at least two of the two.
Preferably, the first silver salt is selected from any one of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate or silver trifluoroacetate or a combination of at least two thereof.
Wherein the precursor may be a combination of (1, 5-cyclooctadiene) platinum chloride and (1, 5-cyclooctadiene) platinum bromide, a combination of (1, 5-cyclooctadiene) platinum bromide and (1, 5-cyclooctadiene) platinum iodide, a combination of (1, 5-cyclooctadiene) platinum chloride and (1, 5-cyclooctadiene) platinum iodide, or the like, and the first ligand may be a combination of 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin and 1, 8-bis (diphenylphosphinyl) naphthalene, a combination of 1, 8-bis (diphenylphosphinyl) naphthalene and 6, 7-bis (diphenylphosphinyl) naphtho [1,8-de ] [1,3] dioxin, or a combination of 1, 2-bis (diphenylphosphinyl) benzene and 2, 3-bis (diphenylphosphinyl) naphthalene, etc., the second ligand may be a combination of dimethylphosphine oxide and diethylphosphine oxide, a combination of diisopropylphosphine oxide and dipropylphosphine oxide, or a combination of dibutylphosphine oxide and diphenylphosphinyloxy, etc., and the first silver salt may be a combination of silver trifluoromethanesulfonate and silver tetrafluoroborate, a combination of silver hexafluoroantimonate and silver hexafluorophosphate, or a combination of silver tetrafluoroborate and silver hexafluoroantimonate, etc., but is not limited to the above-listed combinations, and other combinations not listed within the above-mentioned combination range are also applicable.
Preferably, the molar ratio of the precursor to the first ligand is from 1:1 to 1: 1.1.
Preferably, the molar ratio of the intermediate to the second ligand is from 1:1 to 1: 1.1.
Preferably, the molar ratio of the intermediate to the first silver salt is from 1:0.9 to 1: 1.1.
Preferably, the temperature of the reaction of step (1) is 20-40 ℃.
Preferably, the temperature of the reaction of step (2) is 20-40 ℃.
Wherein the molar ratio of the precursor to the first ligand may be 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.1, the molar ratio of the intermediate to the second ligand may be 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.1, the molar ratio of the intermediate to the first silver salt may be 1:0.9, 1:0.95, 1:1, 1:1.05 or 1:1.1, etc., the reaction temperature in step (1) may be 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 38 ℃, 34 ℃, 38 ℃, or 38 ℃ or the reaction temperature in step (1) may be 20 ℃, 22 ℃, or the reaction temperature may be 20 ℃, 30 ℃ or the reaction temperature in step (1), but not limited to, the above-listed numerical values, and other numerical values not listed in the above numerical range are also applicable.
In a third aspect, the present invention provides the use of a catalyst as described above for the preparation of an α -hydroxy amide compound.
In a fourth aspect, the present invention also provides a method for preparing an α -hydroxyamide compound, said method comprising the steps of: and mixing the catalyst, the second silver salt and the cyanhydrin compound for reaction to obtain the alpha-hydroxy amide compound.
Preferably, the second silver salt is selected from any one or a combination of at least two of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate or silver trifluoroacetate, such as a combination of silver triflate and silver tetrafluoroborate, a combination of silver hexafluoroantimonate and silver hexafluorophosphate or a combination of silver hexafluorophosphate and silver trifluoroacetate, and the like, but is not limited to the combinations enumerated above, and other combinations not enumerated within the scope of the combinations listed above are equally applicable.
Preferably, the cyanohydrin compound is selected from
Preferably, the molar percentage of the catalyst relative to the cyanohydrin compound is from 0.03 to 2 mol%.
Preferably, the molar percentage of the second silver salt relative to the cyanohydrin compound is 0.03 to 2 mol%.
The mole percentage of the catalyst to the cyanohydrin compound may be 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.1 mol%, 0.3 mol%, 0.67 mol%, 0.8 mol%, 1 mol%, 1.2 mol%, 1.4 mol%, 1.6 mol%, 1.8 mol%, or 2 mol%, and the mole percentage of the second silver salt to the cyanohydrin compound may be 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.1 mol%, 0.3 mol%, 0.67 mol%, 0.8 mol%, 1 mol%, 1.2 mol%, 1.4 mol%, 1.6 mol%, 1.8 mol%, or 2 mol%, but is not limited thereto, and other values not listed in the above range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst with a specific structure provided by the invention can catalyze the reaction of the cyanohydrin compound to generate the alpha-hydroxyamide under a mild condition, has high conversion rate and wide substrate application range, can catalyze various cyanohydrin compounds to hydrolyze into the alpha-hydroxyamide compounds, has good universality, and can obviously reduce the equivalent weight of the catalyst.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
In the following preparation examples and examples, mass spectrometry was performed by using an Agilent 6200Series TOF mass spectrometer, single crystal structure testing was performed by using a Bruker D8venture X-ray diffraction tester, and nuclear magnetic testing was performed by using a Bruker AV III HD 600 spectrometer nuclear magnetic resonance tester.
Preparation example 1
This preparation provides a catalyst a, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin in a molar ratio of 1:1 in dichloromethane, stirring at 25 ℃ for 12 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 25 ℃ for 12h to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl phosphorus oxide is 1:1.05, and the molar ratio of the intermediate to the silver trifluoromethanesulfonate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain the catalyst A, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 5. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.96(dd,J＝13.4,8.3Hz,1H),7.77(dq,J＝8.4,2.0Hz,1H),7.12(dd,J＝23.2,8.3Hz,2H),6.70(t,J＝2.3Hz,2H),6.55(t,J＝2.3Hz,2H),6.18–6.02(m,4H),5.65(s,2H),2.33(d,J＝27.0Hz,12H),1.98–1.78(m,6.0Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ162.0(dd,J＝7.1,3.6Hz),161.8(d,J＝6.3Hz),155.7,141.3(t,J＝4.3Hz),140.7(d,J＝8.3Hz),139.5(d,J＝27.5Hz),138.7(d,J＝2.9Hz),128.5(d,J＝18.1Hz),127.6(dd,J＝18.2,3.6Hz),117.3,(t,J＝11.0Hz),111.47(d,J＝9.7Hz),111.05(d,J＝12.1Hz),109.72(d,J＝8.1Hz),108.91(d,J＝7.8Hz),91.8,20.4(d,J＝39.4Hz),15.1ppm；
31P NMR(243MHz,CD2Cl2):δ96.0(dd,2Jp-p＝456.8,9.72Hz,1JPt-P＝2891.7Hz),-23.4(dd,2Jp-p＝454.4,38.9Hz,1JPt-P＝1946.4Hz),-33.1(dt,2Jp-p＝38.9,9.72Hz,1JPt-P＝3146.9Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C33H33ClO7P3Pt[M-OTf]+:864.0772,found 864.0770；
P’-Pt-P(Me2OH)＝167.52°，P-Pt-P’＝91.69°，Cl-Pt-P(Me2OH)＝89.35°。
preparation example 2
This preparation example provides a catalyst B, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 2-bis (diphenylphosphinyl) benzene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst B, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.75–7.56(m,16H),7.53–7.50(m,8H),1.72(dd,J＝12.0,6.0Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ143.5(dq,J＝36.3,3.1Hz),138.0(q,J＝26.1Hz),133.8(d,J＝12.0Hz),134.2(d,J＝11.3Hz),134.1,133.0(d,J＝2.2Hz),132.6(d,J＝2.8Hz),129.7(t,J＝10.9Hz),128.1(dd,J＝57.4Hz),127.6(d,J＝67.7Hz),120.8(d,J＝319.5Hz,CF3SO3 -),18.9(dd,J＝36.6,4.9Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ100.6(dd,2Jp-p＝445.9,17.0Hz,1JPt-P＝2868.6Hz),50.2(dd,2Jp-p＝443.5,4.9Hz,1JPt-P＝2084.9Hz),42.2(dd,2Jp-p＝17.0,4.9Hz,1JPt-P＝3542.9Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C32H31ClOP3Pt[M-OTf]+:754.0919,found 754.0919；
P’-Pt-P(Me2OH)＝176.0°，P-Pt-P’＝87.0°，Cl-Pt-P(Me2OH)＝90.4°。
preparation example 3
This preparation provides a catalyst C, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 2-bis (diphenylphosphino) ethane in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst C, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.85(dd,J＝13.0,7.4Hz,4H),7.71(dd,J＝12.2,7.6Hz,4H),7.66(t,J＝6.8Hz,2H),7.56(dt,J＝7.9,5.1Hz,6H),7.45(td,J＝7.7,2.5Hz,2H),4.47(d,J＝32.7Hz,4H),4.24(d,J＝2.3Hz,2H),4.11(d,J＝2.7Hz,2H),1.45(dd,J＝10.6,2.5Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.2(d,J＝11.2Hz),134.5(d,J＝11.8Hz),133.7(d,J＝2.2Hz),132.3(d,J＝2.7Hz),129.9(d,J＝11.6Hz),128.9(d,J＝10.9Hz),76.5(d,J＝10.3Hz),76.3(d,J＝11.5Hz),75.5(d,J＝7.7Hz),75.0(d,J＝8.6Hz),19.0(dd,J＝41.4,5.0Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ90.4(dd,2Jp-p＝448.3,19.4Hz,1JPt-P＝2614.7Hz),20.2(dd,2Jp-p＝445.9,9.7Hz,1JPt-P＝2291.5Hz),10.2(dd,2Jp-p＝20.4,14.8Hz,1JPt-P＝3837.0Hz)ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt+[M-SbF6 -]+:862.0581,found 862.0576。
preparation example 4
This preparation example provides a catalyst D, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, diphenyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst D, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2)δ7.86(dd,J＝11.8,7.6Hz,4H),7.71(dd,J＝13.0,7.6Hz,4H),7.58(dd,J＝7.5,2.0Hz,2H),7.51(td,J＝7.7,2.5Hz,4H),7.47–7.38(m,8H),7.28(dt,J＝36.0,5.0Hz,8H),4.60(s,2H),4.51(d,J＝2.3Hz,2H),4.34(t,J＝1.9Hz,2H),3.85(q,J＝1.9Hz,2H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.3(d,J＝10.8Hz),134.9(d,J＝11.5Hz),132.4(d,J＝12.1Hz),131.9(d,J＝2.6Hz),128.9(d,J＝10.9Hz),128.7(d,J＝11.9Hz),128.4(d,J＝12.0Hz),120.8(q,J＝320.3Hz,CF3SO3 -),76.6(d,J＝11.3Hz),75.8(d,J＝9.8Hz),74.9(d,J＝8.5Hz),74.5(d,J＝7.0Hz),69.9(d,J＝58.4Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ81.6(dd,2Jp-p＝481.14Hz,1JPt-P＝2971.89Hz),21.3(dd,2Jp-p＝481.14Hz,1JPt-P＝2208.87Hz),15.0(dd,2Jp-p＝21.87Hz,1JPt-P＝3807.81Hz)ppm；
19F NMR(565MHz,CD2Cl2)δ-78.9ppm；
HRMS(ESI+):calc’d for C46H39ClFeOP3Pt+[M-OTf]+:986.0894,found 986.0890。
preparation example 5
This preparation provides a catalyst E, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 8-bis (5-methylfuran-2-yl) phosphino) naphthalene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst E, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ8.22(dd,J＝11.9,8.3Hz,2H),7.98(dd,J＝13.8,7.4,Hz,1H),7.78(dd,J＝16.8,7.4Hz,1H),7.64(dt,J＝18.6,7.6Hz,2H),6.71(s,2H),6.51(s,2H),6.10(d,J＝8.4Hz,2H),2.31(d,J＝30.0Hz,12H),1.86(d,J＝10.7Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ162.1(d,J＝7.8Hz),161.9(d,J＝6.2Hz),139.4,139.2(d,J＝4.3Hz),138.7(d,J＝7.6Hz),138.5,136.5,136.2,136.1,128.7(d,J＝17.8Hz),127.8(dd,J＝17.8,9.2Hz),127.4(dd,J＝23.7,10.9Hz).109.8(d,J＝7.6Hz),109.0(d,J＝7.8Hz),20.4(dd,J＝39.1,5.4Hz),15.1ppm；
31P NMR(243MHz,CD2Cl2):δ96.2(dd,2Jp-p＝449.5,7.3Hz,1JPt-P＝2886.8Hz),-23.4(dd,2Jp-p＝432.5,38.9Hz,1JPt-P＝1934.3Hz),-33.7(dd,2Jp-p＝38.9,7.3Hz,1JPt-P＝3397.1Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C32H33ClO5P3Pt[M-OTf]+:820.0872,found 820.0870。
preparation example 6
This preparation provides a catalyst F, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,2- (bis (5-methylfuran-2-yl) phosphonyl) benzene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst F, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CDCl3):δ8.20(t,J＝8.0Hz,1H),7.81(t,J＝8.0Hz,1H),7.68–7.63(m,2H),7.18(t,J＝2.9Hz,2H),7.13(t,J＝2.9Hz,2H),6.19(d,J＝23.0Hz,4H),2.36(d,J＝10.6Hz,12H),1.92(dd,J＝11.1,2.7Hz,6H)ppm；
13C NMR(151MHz,CDCl3):δ161.1(d,J＝5.3Hz),160.7(d,J＝6.3Hz),138.1(d,J＝4.8Hz),137.5(d,J＝5.2Hz),134.3(d,J＝15.1Hz),133.4(dt,J＝11.7,7.0Hz),128.0(d,J＝22.6Hz),126.9(d,J＝19.7Hz),δ120.5(d,J＝319.7Hz,CF3SO3 -),108.95(d,J＝8.4Hz),108.61(d,J＝8.7Hz),19.0(dd,J＝38.0,5.4Hz),14.2(d,J＝16.8Hz)ppm；
31P NMR(243MHz,CDCl3):δ97.8(q,2Jp-p＝466.6,14.6Hz,1JPt-P＝2908.7Hz),14.4(dd,2Jp-p＝469.0,4.9Hz,1JPt-P＝2092.2Hz),2.9(dd,2Jp-p＝14.6,4.9Hz,1JPt-P＝3319.4Hz)ppm；
19F NMR(565MHz,CDCl3):δ-78.3ppm；
HRMS(ESI+):calc’d for C28H31ClO5P3Pt[M-OTf]+:770.0715,found 770.0712。
preparation example 7
This preparation example provides a catalyst G, the structure of which is shown below:
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 6, 7-bis (diphenylphosphinyl) naphtho [1,8-de ] [1,3] dioxin in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst G, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.54–7.37(m,6H),7.35–7.21(m,16H),6.98(dd,J＝10.1,8.1Hz,2H),5.63(s,2H),1.71(d,J＝10.6Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ155.5(d,J＝23.3Hz),142.0(t,J＝4.6Hz),141.5(d,J＝7.3Hz),140.53(dd,J＝15.1,12.2Hz),135.2(d,J＝10.9Hz),134.8(d,J＝11.8Hz),133.5(t,J＝3.6Hz),132.8(d,J＝2.0Hz),130.3(dd,J＝12.1,3.3Hz),130.0(d,J＝11.6Hz),129.3,128.9,117.4(t,J＝9.7Hz),111.4(d,J＝8.8Hz),110.8(d,J＝11.1Hz),20.3(dt,J＝38.1,5.7Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ96.1(d,2Jp-p＝437.4Hz,1JPt-P＝2920.9Hz),7.3(dd,2Jp-p＝437.4,38.9Hz,1JPt-P＝1941.6Hz),5.1(d,2Jp-p＝38.9Hz,1JPt-P＝3450.6Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C37H33ClO3P3Pt[M-OTf]+:848.0972,found 848.0973。
preparation example 8
This preparation example provides a catalyst H, the structure of which is shown below:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 8-bis (diphenylphosphinyl) naphthalene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst H, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ8.13(m,2H),7.55–7.40(m,8H),7.37–7.24(m,16H),1.68(dd,J＝10.7,2.4Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ139.6(t,J＝4.3Hz),139.2(d,J＝6.7Hz),138.1(dd,J＝12.9,10.3Hz),136.2(t,J＝7.6Hz),136.0(d,J＝10.2Hz),135.4(d,J＝11.5Hz),135.0(d,J＝11.8Hz),133.6(d,J＝3.1Hz),132.9(d,J＝2.9Hz),130.3(d,J＝12.2Hz),130.0(d,J＝11.5Hz),129.1,128.7,127.2(dd,J＝31.9,10.1Hz),20.1(dd,J＝37.7,4.6Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ96.5(dd,2Jp-p＝433.8,7.3Hz,1JPt-P＝2891.7Hz),6.98(dd,2Jp-p＝432.5,38.9Hz,1JPt-P＝1934.3Hz),5.3(dd,2Jp-p＝38.9,7.3Hz,1JPt-P＝3423.9Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C36H33ClOP3Pt[M-OTf]+:804.1081,found 804.1083。
preparation example 9
This preparation provides a catalyst I, the structure of which is shown below:
example (b)
Dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and bis (trifluoromethanesulfonyl) imide silver salt in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain the catalyst I, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.87(dd,J＝12.9,7.8Hz,4H),7.74(dd,J＝12.9,7.8Hz,4H),7.68–7.62(m,2H),7.60–7.54(m,6H),7.47(td,J＝7.8,2.3Hz,4H),4.49(d,J＝1.9Hz,2H),4.40(d,J＝1.9Hz,2H),4.30(d,J＝2.0Hz,2H),4.06(d,J＝2.0Hz,2H),1.54(dd,J＝10.8,2.5Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.29(d,J＝11.2Hz),134.52(d,J＝11.8Hz),133.20(d,J＝2.7Hz),132.17(d,J＝2.7Hz),129.55(d,J＝11.8Hz),128.84(d,J＝10.4Hz),120.2(d,J＝321.5Hz,CF3),76.38(d,J＝10.2Hz),76.11(d,J＝11.4Hz),75.29(d,J＝7.5Hz),74.74(d,J＝8.2Hz),19.10(dd,J＝41.0,5.0Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ93.0(dd,2Jp-p＝458.0,4.9Hz,1JPt-P 2700.9Hz),23.8(dd,2Jp-p＝459.3,14.6Hz,1JPt-P＝1807.9Hz),14.3(dd,2Jp-p＝14.6,4.9Hz,1JPt-P＝3841.8Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.3ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-N(Tf)2 -]+:862.0581,found 862.0575。
preparation example 10
This preparation provides a catalyst J, the structure of which is shown below:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoroacetate in dichloromethane, and stirring for 4 hours at 40 ℃ to obtain a second reaction liquid, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst J, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.93(dd,J＝12.9,7.6Hz,4H),7.77(dd,J＝11.7,7.7Hz,4H),7.59(t,J＝7.1Hz,2H),7.55–7.51(m,6H),7.47–7.44(m,4H),4.45(s,2H),4.40(s,2H),4.30(s,2H),3.96(s,2H),1.76(d,J＝11.7Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ160.6(q,J＝35.2Hz),135.4(d,J＝11.2Hz),134.7(d,J＝11.7Hz),132.2(d,J＝2.7Hz),131.7(d,J＝2.4Hz),128.76(d,J＝11.7Hz),128.6(d,J＝10.7Hz),116.8(q,J＝295.1Hz,CF3),76.0(d,J＝10.6Hz),75.7(d,J＝10.4Hz),74.8(d,J＝7.0Hz),74.0(d,J＝7.7Hz),20.0(dd,J＝41.5,5.6Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ56.4(t,2Jp-p＝17.6Hz,1JPt-P＝3589.1Hz),24.1(dd,2Jp-p＝459.3,17.0Hz,1JPt-P＝2058.2Hz),15.7(t,2Jp-p＝17.0Hz,1JPt-P＝4009.5Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-76.0ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-CF3COO-]+:862.0581,found 862.0573。
preparation example 11
This preparation provides a catalyst K, the structure of which is shown below:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoroacetate in dichloromethane, and stirring for 4 hours at 40 ℃ to obtain a second reaction liquid, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain the catalyst K, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.88(dd,J＝12.9,7.6Hz,4H),7.76(dd,J＝11.9,7.6Hz,4H),7.59(td,J＝7.3,1.8Hz,2H),7.56–7.50(m,6H),7.46(td,J＝7.8,2.4Hz,4H),4.48(s,2H),4.38(s,2H),4.35(s,2H),4.02(s,2H),1.58(d,J＝11.3Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.4(d,J＝11.1Hz),134.6(d,J＝11.7Hz),132.5(d,J＝2.8Hz),131.9(d,J＝2.6Hz),129.0(d,J＝11.8Hz),128.7(d,J＝10.1Hz),76.1(d,J＝10.6Hz),75.8(d,J＝10.7Hz),75.1(d,J＝7.3Hz),74.3(d,J＝7.9Hz),19.3(dd,J＝41.0,4.9Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ87.4(dd,2Jp-p＝469.0,19.4Hz,1JPt-P＝2790.8Hz),24.0(dd,2Jp-p＝467.8,17.0Hz,1JPt-P＝2182.1Hz),15.3(t,2Jp-p＝17.0Hz,1JPt-P＝3873.4Hz),-19.4,-144.5ppm；
19F NMR(565MHz,CD2Cl2):δ-72.8,-74.1,-81.6,-83.3ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-PF6 -]+:862.0581,found 862.0577。
preparation example 12
This preparation example provides a catalyst L, the structure of which is shown below:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver hexafluoroantimonate in dichloromethane, and stirring for 4 hours at 40 ℃ to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst L, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.85(dd,J＝13.0,7.4Hz,4H),7.71(dd,J＝12.2,7.6Hz,4H),7.66(t,J＝6.8Hz,2H),7.56(dt,J＝7.9,5.1Hz,6H),7.45(td,J＝7.7,2.5Hz,2H),4.47(d,J＝32.7Hz,4H),4.24(d,J＝2.3Hz,2H),4.11(d,J＝2.7Hz,2H),1.45(dd,J＝10.6,2.5Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.2(d,J＝11.2Hz),134.5(d,J＝11.8Hz),133.7(d,J＝2.2Hz),132.3(d,J＝2.7Hz),129.9(d,J＝11.6Hz),128.9(d,J＝10.9Hz),76.5(d,J＝10.3Hz),76.3(d,J＝11.5Hz),75.5(d,J＝7.7Hz),75.0(d,J＝8.6Hz),19.0(dd,J＝41.4,5.0Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ90.4(dd,2Jp-p＝448.3,19.4Hz,1JPt-P＝2614.7Hz),20.2(dd,2Jp-p＝445.9,9.7Hz,1JPt-P＝2291.5Hz),10.2(dd,2Jp-p＝20.4,14.8Hz,1JPt-P＝3837.0Hz)ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-SbF6 -]+:862.0581,found 862.0576。
examples 1 to 45
Examples 1-45 provide methods for preparing 45 α -hydroxy amide compounds, respectively, comprising the steps of:
dissolving the catalysts A-L obtained in the preparation examples 1-11 and silver salt corresponding to counter ions in a mixed solution of tetrahydrofuran and water, uniformly mixing, adding a cyanohydrin compound A1, and stirring at the temperature represented by C1 for 4 hours to obtain an alpha-hydroxyamide compound, wherein the molar percentage of the catalysts A-L relative to a nitrile-based compound is B1, the molar percentage of the silver salt corresponding to the counter ions relative to the cyanohydrin compound is B2, and the volume ratio of the tetrahydrofuran to the water is D1; adding water into the alpha-hydroxyamide compound to obtain a dispersion, extracting the dispersion for 2 times by using ethyl acetate, and separating to obtain an organic solution; adding saturated salt solution into the organic solution to wash the organic solution, and then adding anhydrous sodium sulfate into the organic solution to dry the organic solution; filtering the washed and dried organic solution to obtain a filtrate; and carrying out reduced pressure distillation on the filtrate to obtain an alpha-hydroxy amide compound solid, and recrystallizing the alpha-hydroxy amide compound solid by adopting dichloromethane and normal hexane to obtain a purified alpha-hydroxy amide compound.
The raw materials and the mixture ratio and the preparation parameters used in the examples are as follows:
the yields of the hydration of the cyanohydrin compound to the α -hydroxy amide compound and the number of substrate molecules per active site (TON) converted in examples 1 to 45 using the catalysts a to L were measured, and the results are as follows. Wherein, the yield is obtained by a recrystallization method, and the number of the substrate molecules converted per unit active site is obtained by a method of dividing the mole number of the product by the mole number of the catalyst:
the characterization data of the α -hydroxyamide compounds obtained in the above examples 1-45 are shown below:
the results show that the catalyst provided by the invention has high conversion rate and wide substrate application range, can catalyze various cyanohydrin compounds to hydrolyze into alpha-hydroxy amide compounds, and has low reaction temperature and mild reaction conditions.
The applicant states that the catalyst, the preparation method and the application thereof are illustrated by the above examples, but the invention is not limited to the above examples, i.e. the invention does not mean that the invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A catalyst, wherein the structure of the catalyst is shown in formula I:
wherein R is1Is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C12 aryl and substituted or unsubstituted C4-C12 heteroaryl, R2、R3Independently selected from substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C4-C12 aryl, X is selected from any one of Cl, Br or I, L-Selected from the group consisting of counterions.
2. The catalyst of claim 1, wherein R is1Is selected from
Preferably, said R is2Is selected from
Any one of them;
preferably, said R is3Is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、
Any one of them;
preferably, the counter ion is selected from OTf-、BF4 -、PF6 -、SbF6 -Or CF3COO-Any one of them.
3. A method for preparing a catalyst according to claim 1 or 2, characterized in that it comprises the following steps:
(1) mixing the precursor and the first ligand for reaction to obtain an intermediate;
(2) mixing the intermediate obtained in the step (1), a second ligand and a first silver salt for reaction to obtain the catalyst;
wherein the structure of the precursor, the first ligand, the intermediate and the second ligand is shown as formula II:
wherein, X, R1、R2、R3And L-Having the same limits as in claim 1 or 2.
4. The method for preparing a catalyst according to claim 3, wherein the precursor is selected from any one of (1, 5-cyclooctadiene) platinum chloride, (1, 5-cyclooctadiene) platinum bromide, or (1, 5-cyclooctadiene) platinum iodide or a combination of at least two thereof;
preferably, the first ligand is selected from the group consisting of 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 8-bis (diphenylphosphonyl) naphthalene, 6, 7-bis (diphenylphosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 2-bis (diphenylphosphonyl) benzene, 2, 3-bis (diphenylphosphonyl) naphthalene, 1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (5-methylfuran-2-yl) phosphonyl) benzene, (4, 5-dimethoxy-1, 2-phenylene) bis (5-methylfuran-2-yl) phosphine), 1, 2-bis (5-methylfuran-2-yl) phosphonyl) ethane and 2, any one or a combination of at least two of 3-bis (5-methylfuran-2-yl) phosphonyl) naphthalene;
the second ligand is selected from any one of dimethyl phosphine oxide, diethyl phosphine oxide, diisopropyl phosphine oxide, dipropylene phosphorus oxide, dibutyl phosphorus oxide, diphenyl phosphorus oxide, bis (4-methoxyphenyl) phosphine oxide or bis (4- (trifluoromethyl) phenyl) phosphine oxide or a combination of at least two of the two.
5. The method for preparing a catalyst according to claim 3 or 4, wherein the first silver salt is selected from any one of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate or silver trifluoroacetate or a combination of at least two thereof.
6. The method for preparing a catalyst according to any one of claims 3 to 5, wherein the molar ratio of the precursor to the first ligand is from 1:1 to 1: 1.1;
preferably, the molar ratio of the intermediate to the second ligand is 1:1 to 1: 1.1;
preferably, the molar ratio of the intermediate to the first silver salt is from 1:0.9 to 1: 1.1.
7. The method for preparing a catalyst according to any one of claims 3 to 6, wherein the temperature of the reaction of step (1) is 20 to 40 ℃;
preferably, the temperature of the reaction of step (2) is 20-40 ℃.
8. Use of a catalyst according to claim 1 or 2 for the preparation of an α -hydroxy amide compound.
9. A method for producing an α -hydroxyamide compound, said method comprising the steps of: mixing the catalyst of claim 1 or 2, a second silver salt, and a cyanohydrin compound to obtain the α -hydroxyamide compound.
10. The method for producing an α -hydroxyamide compound according to claim 9, wherein said second silver salt is selected from any one of or a combination of at least two of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate and silver trifluoroacetate;
preferably, the cyanohydrin compound is selected from
preferably, the molar percentage of the catalyst relative to the cyanohydrin compound is from 0.03 to 2 mol%;
preferably, the molar percentage of the second silver salt relative to the cyanohydrin compound is 0.03 to 2 mol%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9506389D0 (en) * | 1995-03-29 | 1995-05-17 | King S College London | Catalyst and process for preparing amides |
| AU1281197A (en) * | 1995-12-06 | 1997-06-27 | Union Carbide Chemicals & Plastics Technology Corporation | Improved metal-ligand complex catalyzed processes |
| CN110642895A (en) * | 2018-06-27 | 2020-01-03 | 南方科技大学 | Catalyst, process for producing the same, and process for producing amide compound |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9506389D0 (en) * | 1995-03-29 | 1995-05-17 | King S College London | Catalyst and process for preparing amides |
| AU1281197A (en) * | 1995-12-06 | 1997-06-27 | Union Carbide Chemicals & Plastics Technology Corporation | Improved metal-ligand complex catalyzed processes |
| CN110642895A (en) * | 2018-06-27 | 2020-01-03 | 南方科技大学 | Catalyst, process for producing the same, and process for producing amide compound |
Non-Patent Citations (1)
| Title |
|---|
| SPRING MELODY M. KNAPP，ET AL.: "Platinum Phosphinito Catalysts for Nitrile Hydration", vol. 24, pages 145 - 156 * |
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