CN115304642A - Multidentate phosphine ligand containing cyclosiloxane skeleton and preparation method and application thereof - Google Patents
Multidentate phosphine ligand containing cyclosiloxane skeleton and preparation method and application thereof Download PDFInfo
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- CN115304642A CN115304642A CN202110498348.8A CN202110498348A CN115304642A CN 115304642 A CN115304642 A CN 115304642A CN 202110498348 A CN202110498348 A CN 202110498348A CN 115304642 A CN115304642 A CN 115304642A
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- cyclosiloxane
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 84
- 239000003446 ligand Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- -1 phosphine compound Chemical group 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 150000003254 radicals Chemical group 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- 125000005717 substituted cycloalkylene group Chemical group 0.000 claims abstract description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Chemical group 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 5
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 4
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000005810 carbonylation reaction Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- DJXAJTDFRRFQDI-UHFFFAOYSA-N silyloxy(silyloxysilyloxysilyloxysilyloxy)silane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH3] DJXAJTDFRRFQDI-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZBXBDQPVXIIXJS-UHFFFAOYSA-N 2,4,6,8,10-pentakis(ethenyl)-2,4,6,8,10-pentamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 ZBXBDQPVXIIXJS-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- HDULBKVLSJEMGN-UHFFFAOYSA-N dicyclohexylphosphane Chemical compound C1CCCCC1PC1CCCCC1 HDULBKVLSJEMGN-UHFFFAOYSA-N 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- JDLPYWQTHJDXFQ-UHFFFAOYSA-N 2,4,6,8,10,12-hexakis(ethenyl)-2,4,6,8,10,12-hexamethyl-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 JDLPYWQTHJDXFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YQUNRICKXIRGEE-UHFFFAOYSA-N cyclopentylmethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC1CCCC1 YQUNRICKXIRGEE-UHFFFAOYSA-N 0.000 description 1
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
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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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/248—Bridged ring systems, e.g. 9-phosphabicyclononane
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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Abstract
The invention discloses a multidentate phosphine ligand containing cyclosiloxane skeleton and a preparation method and application thereof. The multidentate phosphine ligand containing cyclosiloxane skeleton has a structure shown in the following formula:
wherein R is 1 、R 2 Each independently selected from C 1 ‑C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 Represents a substituted cycloalkylene group, R 3 ，R 4 Each independently selected from hydrogen, methyl, tert-butyl, methoxy, halogenN is an integer of 3 to 6. The preparation method comprises the following steps: reacting a mixed reaction system containing cyclosiloxane, secondary phosphine compound, free radical initiator and solvent at 60-90 ℃ for 6-32h in protective atmosphere to obtain the multidentate phosphine ligand containing cyclosiloxane skeleton. The multidentate phosphine ligand containing cyclosiloxane skeleton prepared by the invention has good stability, is stable to air and is stable at high temperature; meanwhile, the preparation method provided by the invention is simple and convenient, and the synthesis of the multidentate phosphine ligand is easy to realize diversification.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a multidentate phosphine ligand containing a cyclosiloxane framework, and a preparation method and application thereof.
Background
Multifunctional cyclic oligosiloxanes are important reactants for the synthesis of a variety of polymers and also as precursors for the synthesis of new materials, for example, methyl vinyl cyclosiloxane is an important raw material for the preparation of silicone rubbers, silicone oils and silicone resins. The vinyl in the structure is used as a reactive site, and the requirements of post functionalization, such as crosslinking, hyperbranched and the like, are met. Thioether functional groups can be introduced by using a thiol-ene click reaction between 3-mercaptopropyltrimethoxysilane (MPTMS) and 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane or 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, so that subsequent functional modification (K) is realized.
-Wijas，J.Chojnowski，J InorgOrganometPolym(2012)22：588-594)。
The addition reaction of phosphine alkane, primary phosphine or secondary phosphine and carbon-carbon double bond is called phosphine hydrogenation reaction, and is a method for directly and efficiently preparing organic phosphine compounds. Under the action of free radical initiator, olefin with different structure and secondary phosphine produce phosphine hydrogenating reaction at certain temperature to produce organic tertiary phosphine compounds with different substituent groups. Complexes of tertiary phosphines with many transition metal elements are very important oxo catalysts. For example, in rhodium catalyzed hydroformylation, the electronic effect and steric structure of the phosphine ligand affect the activity of the complex catalyst and the selectivity of the hydroformylation product.
The polydentate phosphine ligand has two or more coordinatable P atoms, is more likely to generate chelating coordination with a central metal to generate an active intermediate containing at least two coordinated P atoms, and can avoid using a large amount of phosphine to improve the regioselectivity and the stability of the active intermediate. In 2001, santelli et al designed to synthesize tetradentate phosphine ligand teicyp (all cis-1,2,3,4-tetrakis [ (diphenylphosphino) methyl ] cyclopentane) based on a cyclopentane framework and used it for palladium catalyzed allylic substitution reactions, but the synthesis of this ligand required 7 steps with great difficulty (j.org.chem., 2001, 66. In 2007, zhang et al designed and synthesized a class of P-C tetradentate phosphine ligands, and this polydentate phosphine ligand and metal Rh were coordinated to form a bidentate coordination system which can efficiently catalyze the hydroformylation reaction of terminal alkene with high regioselectivity, and similarly, the ligand synthesis steps are many and air-sensitive (adv. Synth. Catal.2007, 349, 1582-1586.
Disclosure of Invention
The invention mainly aims to provide a multidentate phosphine ligand containing cyclosiloxane skeleton and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a multidentate phosphine ligand containing cyclosiloxane skeleton, which has a structure shown in a formula (I):
wherein R is 1 、R 2 Each independently selected from C 1 -C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 The combination of (a) represents a substituted cycloalkylene group; r is 3 ，R 4 Each independently selected from any one of hydrogen, methyl, tertiary butyl, methoxy and halogen, and n is an integer from 3 to 6.
The embodiment of the invention also provides a preparation method of the multidentate phosphine ligand containing cyclosiloxane skeleton, which comprises the following steps:
reacting a mixed reaction system containing cyclosiloxane, a secondary phosphine compound, a free radical initiator and a solvent at 60-90 ℃ for 6-32h in a protective atmosphere to prepare a multidentate phosphine ligand containing a cyclosiloxane skeleton;
wherein the cyclosiloxane has a structure as shown in formula (II):
wherein n is an integer from 3 to 6;
the secondary phosphine compound has a structure as shown in formula (III):
HPR 1 R 2
(III)
wherein R is 1 、R 2 Each independently selected from C 1 -C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 Represents a substituted cycloalkylene group, R 3 ，R 4 Each independently selected from any one of hydrogen, methyl, tertiary butyl, methoxy and halogen, and n is an integer from 3 to 6.
The embodiment of the invention also provides a multidentate phosphine ligand containing cyclosiloxane skeleton prepared by the method.
The embodiment of the invention also provides application of the multidentate phosphine ligand containing cyclosiloxane skeleton in metal catalytic reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) The multidentate phosphine ligand containing cyclosiloxane skeleton prepared by the invention has good stability, and is especially stable to air and high temperature;
(2) The multidentate phosphine ligand containing cyclosiloxane skeleton is prepared by a one-step method, the preparation method is simple and convenient, the raw materials are easy to obtain, and the synthesis diversification of the multidentate phosphine ligand containing cyclosiloxane skeleton is easy to realize.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a reaction scheme for preparing multidentate phosphine ligands containing cyclosiloxane backbones in an exemplary embodiment of the present invention;
FIG. 2 is a thermogravimetric analysis (TG) of a multidentate phosphine ligand A containing a cyclosiloxane skeleton prepared in example 1 of the present invention;
FIG. 3 is a thermogravimetric analysis (TG) of a multidentate phosphine ligand D having a cyclosiloxane skeleton prepared in example 4 of the present invention;
FIG. 4 is an infrared spectrum (FTIR) of a multidentate phosphine ligand D containing a cyclosiloxane backbone prepared in example 4 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and carried out a great deal of practice to provide the technical scheme of the present invention, which mainly constructs multidentate phosphine ligands through cyclosiloxane and secondary phosphine compounds in one step, has high yield, and the obtained multidentate phosphine ligands have stable chemical properties and can be used as metal-catalyzed carbonylation reaction ligands.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a multidentate phosphine ligand having a cyclosiloxane backbone, having the structure shown in formula (I):
wherein R is 1 、R 2 Each is independentSelected from C 1 -C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 The combination of (a) represents a substituted cycloalkylene group; r 3 ，R 4 Each independently selected from any one of hydrogen, methyl, tertiary butyl, methoxy and halogen, and n is an integer from 3 to 6.
Further, said C 1 -C 12 The alkyl group of (b) is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl and cycloheptyl.
Further, said R 1 、R 2 Represents a cycloalkylene structure.
In another aspect of the embodiments of the present invention, there is also provided a method for preparing a multidentate phosphine ligand having a cyclosiloxane skeleton, including:
reacting a mixed reaction system containing cyclosiloxane, a secondary phosphine compound, a free radical initiator and a solvent at 60-90 ℃ for 6-32h in a protective atmosphere to prepare a multidentate phosphine ligand containing a cyclosiloxane skeleton;
wherein the cyclosiloxane has a structure as shown in formula (II):
wherein n is selected from an integer of 3 to 6, preferably 4;
the secondary phosphine compound has a structure as shown in formula (III):
HPR 1 R 2
(III)
wherein R is 1 、R 2 Each independently selected from C 1 -C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 The combination of (a) represents a substituted cycloalkylene group; r is 3 ，R 4 Each independently selected from any one of hydrogen, methyl, tertiary butyl, methoxy and halogen, and n is an integer from 3 to 6.
Further, said C 1 -C 12 The alkyl group of (b) is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl and cycloheptyl.
Further, said R 1 、R 2 Represents a cycloalkylene structure.
In some more specific embodiments, the cyclotrisiloxane comprises 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (D) 3 3Vi ) 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D) 4 4Vi ) 1,3,5,7,9 pentamethyl-1,3,5,7,9 Pentacetylcyclopentasiloxane (D) 5 5Vi ) 1,3,5,7,9, 11-hexamethyl-1,3,5,7,9, 11-hexavinylcyclohexasiloxane (D) 6 6Vi ) Any one or a combination of two or more of them, and is not limited thereto.
Further, the cyclosiloxane is 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane.
In some more specific embodiments, the secondary phosphine compounds include compounds having a structure as shown in any one of formulas a-1:
in some more specific embodiments, the free radical initiator comprises any one of, or a combination of, azobisisobutyronitrile, azobisisoheptonitrile, preferably azobisisobutyronitrile.
Further, the solvent comprises any one or a combination of more than two of toluene, trifluorotoluene, p-xylene, m-xylene, o-xylene and tetrahydrofuran, and is preferably toluene.
Further, the protective atmosphere comprises an inert gas atmosphere and/or a nitrogen atmosphere, preferably a nitrogen atmosphere.
In some more specific embodiments, the cyclosiloxane, the secondary phosphine compound, and the free radical initiator are present in a molar ratio of 1: 4 to 10: 0.02 to 0.2.
In some more specific embodiments, the preparation method further comprises: after the reaction is finished, the obtained mixture is washed, separated and dried in vacuum.
In some more specific embodiments, the method for preparing the multidentate phosphine ligand having a cyclosiloxane skeleton specifically comprises (the reaction for preparing the multidentate phosphine ligand is shown in fig. 1):
under the protection of inert gas, in an organic solvent and in the presence of a free radical initiator, controlling the reaction temperature to be 60-90 ℃, and reacting for 6-32 hours under stirring to generate the multidentate phosphine ligand containing the cyclosiloxane skeleton shown in the formula (I).
In another aspect of embodiments of the present invention, there is also provided a multidentate phosphine ligand containing a cyclosiloxane backbone prepared by the foregoing method.
In another aspect of embodiments of the present invention there is also provided the use of a multidentate phosphine ligand comprising a cyclosiloxane backbone as described above in a metal-catalysed reaction.
For example, the use of the multidentate phosphine ligands containing cyclosiloxane frameworks as ligands for metal-catalyzed carbonylation reactions.
The invention selects secondary phosphine compounds with different structures as synthesis building blocks, and the secondary phosphine compounds and the carbon-carbon double bond of the vinyl cyclosiloxane generate addition reaction under the action of a free radical initiator, so that the polydentate phosphine ligand can be conveniently synthesized in one step, the method is simple, and the obtained polydentate phosphine ligand is stable to air. The method not only expands the application field of cyclosiloxane, but also enriches the diversity of phosphine ligand synthesis.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Under the protection of nitrogen, 17.28g (88 mmol) of diphenylphosphine hydrogen (with the structure shown in the formula a) and 6.96g (20 mmol) of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D) are respectively added into a three-neck flask at room temperature 4 4Vi ) 10g of toluene, 0.15g (0.9 mmol) of AIBN; stirring the mixture at 60 ℃ for reaction for 30h, cooling to room temperature after the reaction is finished, washing with 30ml of methanol, removing the solvent by rotary evaporation, and drying in a vacuum drying oven to obtain a colorless sticky substance, namely the multidentate phosphine ligand A containing the cyclosiloxane skeleton, wherein the yield is 93%, and the multidentate phosphine ligand A containing the cyclosiloxane skeleton has the following structure:
and (3) performance characterization: the nuclear magnetic spectrum of the multidentate phosphine ligand A containing cyclosiloxane skeleton prepared in this example is as follows: 31 P NMR(162MHz，C 6 D 6 ) Delta-9.85, -9.91, -9.97, -10.03, -40.00, -40.05, -41.34, thermogravimetric analysis (TG) as shown in figure 2.
Example 2
Under the protection of nitrogen, 17.45g (88 mmol) of dicyclohexylphosphine hydrogen (with the structure shown in the formula b) and 6.96g (20 mmol) of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D4) are respectively added into a three-neck flask at room temperature 4Vi ) 10g of toluene and 0.15g (0.9 mmol) of AIBN, stirring the mixture at 60 ℃ for reaction for 25 hours, cooling to room temperature after the reaction is finished, washing with 30ml of methanol, removing the solvent through rotary evaporation, and drying through a vacuum drying oven to obtain a colorless sticky substance, namely the multidentate phosphine ligand B containing cyclosiloxane skeleton, wherein the yield is 86%, and the multidentate phosphine ligand B containing cyclosiloxane skeleton has the following structure:
example 3
Under the protection of nitrogen, 12.87g (88 mmol) of di-tert-butylphosphine hydride (with the structure shown in the formula c) and 6.96g (20 mmol) of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D) are respectively added into a three-neck flask at room temperature 4 4Vi ) 10g of toluene and 0.15g (0.9 mmol) of AIBN, stirring the mixture at 60 ℃ for reacting for 17 hours, cooling to room temperature after the reaction is finished, washing with 30ml of methanol, removing the solvent by rotary evaporation, and drying through a vacuum drying oven to obtain a colorless sticky substance, namely the multidentate phosphine ligand C containing the cyclosiloxane skeleton, wherein the yield is 80 percent, and the multidentate phosphine ligand C containing the cyclosiloxane skeleton has the following structure:
example 4
7.11g (50 mmol) of 9-phosphabicyclo [3,3,1 ] are added to a three-neck flask respectively at room temperature under the protection of nitrogen]Nonane (having the structure shown in formula D), 3.81g (11 mmol) 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D) 4 4Vi ) 5g of toluene and 0.16g (1 mmol) of AIBN, stirring the mixture at 60 ℃ for reacting for 17 hours, cooling to room temperature after the reaction is finished, washing with 30ml of methanol, removing the solvent by rotary evaporation, and drying through a vacuum drying oven to obtain light yellow sticky matter, namely the multidentate phosphine ligand D containing cyclosiloxane skeleton, wherein the yield is 98%, and the multidentate phosphine ligand D containing cyclosiloxane skeleton has the following structure:
and (3) performance characterization: the thermogravimetric analysis (TG) of the multidentate phosphine ligand D containing cyclosiloxane skeleton prepared in this example is shown in fig. 3; infrared spectroscopy (FTIR) is shown in fig. 4; with multidentate phosphine ligand D exposed to air for 0hThe nuclear magnetic data are as follows: 31 P NMR(162MHz，C 6 D 6 ) δ 8.05, -31.04; nuclear magnetic data for exposure of polydentate phosphine ligand D to air for 2h are as follows: 31 P NMR(162MHz，C 6 D 6 ) δ 8.05, -31.09; nuclear magnetic data for 6h exposure of polydentate phosphine ligand D to air are as follows: 31 P NMR(162MHz，C 6 D 6 ) Delta 8.09, -31.06, it can be seen that the multidentate phosphine ligand D containing cyclosiloxane skeleton prepared in this example has good stability to air.
Example 5
The same as in example 1, except that the diphenylphosphine hydride in example 1 was replaced with a compound having a structure shown by E-1, respectively, and the prepared multidentate phosphine ligand E-L having a cyclosiloxane skeleton had the following structure:
example 6
Under the protection of nitrogen, respectively adding diphenylphosphine hydrogen (with a structure shown in a formula a) 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (D) into a three-neck flask at room temperature 3 3Vi ) Benzotrifluoride, azobisisoheptonitrile (wherein the molar ratio of diphenylphosphine hydride, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane to azobisisoheptonitrile is 10: 1: 0.2); stirring the mixture at 75 ℃ for reaction for 24h, cooling to room temperature after the reaction is finished, washing with 30ml of methanol, removing the solvent by rotary evaporation, and drying through a vacuum drying oven to obtain the multidentate phosphine ligand M containing the cyclosiloxane skeleton, wherein the yield is 85%, and the multidentate phosphine ligand M containing the cyclosiloxane skeleton has the following structure:
example 7
Adding dicyclohexylphosphine hydrogen (with a structure shown as a formula b) into three-neck flasks at room temperature under the protection of nitrogen respectively1,3,5,7,9 pentamethyl-1,3,5,7,9 Pentacetylcyclopentasiloxane (D) 5 5Vi ) P-xylene and AIBN (wherein the molar ratio of dicyclohexylphosphine hydrogen to 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane to AIBN is 4: 1: 0.02), the mixture is stirred and reacted for 32 hours at 60 ℃, after the reaction is finished, the mixture is cooled to room temperature, the mixture is washed by 30ml of methanol, after the solvent is removed by rotary evaporation, and the mixture is dried by a vacuum drying oven, so that the multidentate phosphine ligand N containing the cyclosiloxane skeleton is obtained, the yield is 86%, and the multidentate phosphine ligand N containing the cyclosiloxane skeleton has the following structure:
example 8
Under the protection of argon, adding di-tert-butyl phosphine hydrogen (with a structure shown as a formula c) and 1,3,5,7,9, 11-hexamethyl-1,3,5,7,9, 11-hexavinylcyclohexane hexasiloxane (D) into a three-neck flask at room temperature 6 6Vi ) Tetrahydrofuran and AIBN (wherein the molar ratio of the di-tert-butyl phosphine hydrogen to the 1,3,5,7,9, 11-hexamethyl-1,3,5,7,9, 11-hexavinylcyclohexane hexasiloxane to the AIBN is 8: 1: 0.1), stirring the mixture at 90 ℃ for reaction for 6 hours, cooling to room temperature after the reaction is finished, washing with 30ml of methanol, removing the solvent through rotary evaporation, and drying through a vacuum drying oven to obtain the multidentate phosphine ligand O containing the cyclosiloxane skeleton, wherein the yield is 70%, and the multidentate phosphine ligand O containing the cyclosiloxane skeleton has the following structure:
in addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A multidentate phosphine ligand containing cyclosiloxane skeleton is characterized in that the multidentate phosphine ligand has a structure shown in a formula (I):
wherein R is 1 、R 2 Each independently selected from C 1 -C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 The combination of (a) represents a substituted cycloalkylene group; r 3 ，R 4 Each independently selected from any one of hydrogen, methyl, tertiary butyl, methoxyl and halogen, and n is an integer of 3-6; preferably, said C 1 -C 12 The alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl and cycloheptyl; preferably, said R is 1 、R 2 Represents a cycloalkylene structure.
2. A preparation method of multidentate phosphine ligand containing cyclosiloxane skeleton is characterized by comprising the following steps:
reacting a mixed reaction system containing cyclosiloxane, a secondary phosphine compound, a free radical initiator and a solvent at 60-90 ℃ for 6-32h in a protective atmosphere to prepare a multidentate phosphine ligand containing a cyclosiloxane skeleton;
wherein the cyclosiloxane has a structure as shown in formula (II):
wherein n is an integer from 3 to 6;
the secondary phosphine compound has a structure as shown in formula (III):
HPR 1 R 2
(III)
wherein R is 1 、R 2 Each independently selected from C 1 -C 12 An alkyl group of,
Any one of benzyl, or R 1 、R 2 In combination represents a substituted cycloalkylene group, R 3 ，R 4 Each independently selected from any one of hydrogen, methyl, tert-butyl, methoxy and halogen, and n is an integer from 3 to 6; preferably, said C 1 -C 12 The alkyl group of (b) is any one selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl and cycloheptyl; preferably, said R is 1 、R 2 Represents a cycloalkylene structure.
3. The method of claim 2, wherein: the cyclosiloxane comprises any one or the combination of more than two of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9, 11-hexamethyl-1,3,5,7,9, 11-hexavinylcyclohexane hexasiloxane, preferably 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.
4. The method of claim 2, wherein: the secondary phosphine compound includes a compound having a structure represented by any one of formula a-formula 1:
5. the method of claim 2, wherein: the radical initiator comprises azobisisobutyronitrile and/or azobisisoheptonitrile, preferably azobisisobutyronitrile.
6. The method of claim 2, wherein: the solvent comprises any one or the combination of more than two of toluene, trifluorotoluene, p-xylene, m-xylene, o-xylene and tetrahydrofuran, and is preferably toluene;
and/or the protective atmosphere comprises an inert gas atmosphere and/or a nitrogen atmosphere, preferably a nitrogen atmosphere.
7. The method of claim 2, wherein: the mol ratio of the cyclosiloxane to the secondary phosphine compound to the free radical initiator is 1: 4-10: 0.02-0.2.
8. The method of claim 2, further comprising: after the reaction is finished, the obtained mixture is washed, separated and dried in vacuum.
9. A multidentate phosphine ligand containing a cyclosiloxane backbone prepared by the method of any one of claims 2-8.
10. Use of a multidentate phosphine ligand comprising a cyclosiloxane backbone according to claim 1 or 9 in a metal-catalyzed reaction; preferably as a ligand in a metal catalysed carbonylation reaction.
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