CN114163474B - Polyketone catalyst ligand and synthesis method thereof - Google Patents
Polyketone catalyst ligand and synthesis method thereof Download PDFInfo
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- CN114163474B CN114163474B CN202111525265.XA CN202111525265A CN114163474B CN 114163474 B CN114163474 B CN 114163474B CN 202111525265 A CN202111525265 A CN 202111525265A CN 114163474 B CN114163474 B CN 114163474B
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- 239000003446 ligand Substances 0.000 title claims abstract description 61
- 229920001470 polyketone Polymers 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000001308 synthesis method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 32
- MWYXORYWUKRJEX-UHFFFAOYSA-N bis(2-methoxyphenyl)-oxophosphanium Chemical compound COC1=CC=CC=C1[P+](=O)C1=CC=CC=C1OC MWYXORYWUKRJEX-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000010189 synthetic method Methods 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkyl lithium Chemical compound 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical group Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005052 trichlorosilane Substances 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical group [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000012074 organic phase Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- SXXPTCXIFIOPQF-UHFFFAOYSA-N 3-bis(2-methoxyphenyl)phosphanylpropyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CCCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC SXXPTCXIFIOPQF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- HFEAMIKDDWKNAG-UHFFFAOYSA-N bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1PC1=CC=CC=C1OC HFEAMIKDDWKNAG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZGEZPSPEVXDOMG-UHFFFAOYSA-N lithium;phosphane Chemical compound [Li].P ZGEZPSPEVXDOMG-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IIKVDSGDRQSJPE-UHFFFAOYSA-N [3-[bis(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxaspiro[5.5]undecan-3-yl]methyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CC1(CP(C=2C(=CC=CC=2)OC)C=2C(=CC=CC=2)OC)COC2(CCCCC2)OC1 IIKVDSGDRQSJPE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2531/824—Palladium
-
- 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)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a polyketone catalyst ligand and a synthesis method thereof; the synthesis method comprises the following steps: a) Carrying out a first reaction on dihydric alcohol and p-toluenesulfonyl chloride in a solvent to obtain an intermediate A; b) Carrying out a second reaction on the bis (2-methoxyphenyl) phosphine oxide and the intermediate A obtained in the step a) in a solvent to obtain an intermediate B; c) And B) carrying out reduction reaction on the intermediate B obtained in the step B) to obtain the polyketone catalyst ligand. Compared with the prior art, the method selects specific raw materials to synthesize the polyketone catalyst ligand according to specific process steps, realizes better overall interaction, ensures that the activity of the synthesized novel polyketone catalyst ligand is higher than 26 kg/(g-Pd.h), and meets the technical requirements of polyketone production in the market; meanwhile, the synthetic method has the advantages of simple reaction route, simple required equipment, low energy consumption, high product yield, good quality, safety and easy industrialization.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a polyketone catalyst ligand and a synthesis method thereof.
Background
Polyketone (POK) is a novel green polymer material synthesized from carbon monoxide, olefins (ethylene, propylene, styrene), has photodegradation and biodegradation properties, and can be further chemically modified, and has excellent and wide performance, so that the polyketone is a 'natural' thermoplastic engineering plastic. In the polyketone preparation, the polymerization catalyst is usually composed of Pd (II)/bisphosphine ligand/acid system, and the bisphosphine ligand used has high catalytic activity, such as 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane, ((2, 2-dimethyl-1, 3-dioxane-5, 5-diyl) bis (methylene)) bis (2-methoxyphenyl) phosphine), 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl ] -1, 5-dioxa-spiro [5,5] undecane, etc.
At present, the catalytic activity of 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane is relatively low, while ((2, 2-dimethyl-1, 3-dioxane-5, 5-diyl) bis (methylene)) bis (2-methoxyphenyl) phosphine, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl ] -1, 5-dioxa-spiro [5,5] undecane can be prepared only by reacting phosphine hydrogen with an intermediate carbon chain, and the influence of air on the intermediate and ligand needs to be considered in two steps of the synthesis.
Disclosure of Invention
In view of the above, the invention aims to provide a novel polyketone catalyst ligand and a synthesis method thereof, wherein the synthesis method has the advantages of simple reaction route, high product yield, good quality, safety and easy industrialization; the activity of the synthesized novel polyketone catalyst ligand is higher than 26 kg/(g-Pd.h), and the technical requirement of polyketone production in the market is met.
The invention provides a polyketone catalyst ligand, which has a structure shown in a formula (I):
in the formula (I), n is 0, 1 or 2.
The invention also provides a synthesis method of the polyketone catalyst ligand, which comprises the following steps:
a) Carrying out a first reaction on dihydric alcohol and p-toluenesulfonyl chloride in a solvent to obtain an intermediate A;
b) Carrying out a second reaction on the bis (2-methoxyphenyl) phosphine oxide and the intermediate A obtained in the step a) in a solvent to obtain an intermediate B;
c) And B) carrying out reduction reaction on the intermediate B obtained in the step B) to obtain the polyketone catalyst ligand.
Preferably, the diol in step a) has a structure represented by formula (II):
in formula (II), n=0, 1 or 2.
Preferably, the first reaction in step a) is carried out in the presence of an inorganic strong base; the temperature of the first reaction is-10 ℃ to 5 ℃ and the time is 1h to 2h.
Preferably, the molar ratio of diol, p-toluenesulfonyl chloride and inorganic strong base in step a) is 1: (2.05-2.5): (6-10).
Preferably, the second reaction in step b) is carried out in the presence of an alkyl lithium; the temperature of the second reaction is-10 ℃ to 5 ℃ and the time is 1h to 2h.
Preferably, the alkyl lithium in step b) is ethyl lithium and/or n-BuLi; the molar ratio of the bis (2-methoxyphenyl) phosphine oxide, the intermediate A and the alkyl lithium is 1: (0.45-0.5): (1.05-1.5).
Preferably, the reduction reaction in step c) is specifically performed by:
c1 Mixing the intermediate B, tertiary amine and solvent to obtain a mixed solution of the intermediate B;
c2 And c) controlling the temperature to be between minus 5 and 15 ℃, dropwise adding a reducing agent into the mixed solution of the intermediate B obtained in the step c 1) for 0.4 to 0.6h, heating to between 65 and 75 ℃, and tracking the liquid quality until the reaction is complete to obtain the polyketone catalyst ligand.
Preferably, the tertiary amine is triethylamine and/or tributylamine; the solvent is one or more of acetonitrile, toluene and xylene; the reducing agent is trichlorosilane.
Preferably, the molar ratio of the intermediate B, the reducing agent and the tertiary amine is 1: (3-8): (3-8).
The invention provides a polyketone catalyst ligand and a synthesis method thereof; the synthesis method comprises the following steps: a) Carrying out a first reaction on dihydric alcohol and p-toluenesulfonyl chloride in a solvent to obtain an intermediate A; b) Carrying out a second reaction on the bis (2-methoxyphenyl) phosphine oxide and the intermediate A obtained in the step a) in a solvent to obtain an intermediate B; c) And B) carrying out reduction reaction on the intermediate B obtained in the step B) to obtain the polyketone catalyst ligand. Compared with the prior art, the method selects specific raw materials to synthesize the polyketone catalyst ligand according to specific process steps, realizes better overall interaction, ensures that the activity of the synthesized novel polyketone catalyst ligand is higher than 26 kg/(g-Pd.h), and meets the technical requirements of polyketone production in the market; meanwhile, the synthetic method has the advantages of simple reaction route, simple required equipment, low energy consumption, high product yield, good quality, safety and easy industrialization.
Drawings
FIG. 1 shows a polyketone catalyst ligand obtained by the synthesis method of example 1 of the present invention 1 H NMR。
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyketone catalyst ligand, which has a structure shown in a formula (I):
in the formula (I), n is 0, 1 or 2.
In the present invention, when n is 0, the polyketone catalyst ligand has a structure represented by formula (I-1):
when n is 1, the polyketone catalyst ligand has a structure shown in formula (I-2):
when n is 2, the polyketone catalyst ligand has a structure shown in formula (I-3):
the activity of the polyketone catalyst ligand with the novel structure provided by the invention is higher than 26 kg/(g-Pd.h), and the technical requirement of polyketone production in the market is met.
The invention also provides a synthesis method of the polyketone catalyst ligand, which comprises the following steps:
a) Carrying out a first reaction on dihydric alcohol and p-toluenesulfonyl chloride in a solvent to obtain an intermediate A;
b) Carrying out a second reaction on the bis (2-methoxyphenyl) phosphine oxide and the intermediate A obtained in the step a) in a solvent to obtain an intermediate B;
c) And B) carrying out reduction reaction on the intermediate B obtained in the step B) to obtain the polyketone catalyst ligand.
Firstly, dihydric alcohol and p-toluenesulfonyl chloride are subjected to a first reaction in a solvent to obtain an intermediate A.
In the present invention, the diol preferably has a structure represented by formula (II):
in formula (II), n=0, 1 or 2.
In the present invention, when n is 0, the diol has a structure represented by formula (II-1):
when n is 1, the diol has a structure represented by formula (II-2):
when n is 2, the polyketone catalyst ligand has a structure shown in formula (II-3):
the source of the glycol is not particularly limited in the present invention, and commercially available products or self-made products well known to those skilled in the art may be used.
In the present invention, the structural formula of p-toluenesulfonyl chloride (TsCl) is as follows:
the source of the p-toluenesulfonyl chloride is not particularly limited in the present invention, and commercially available products or self-made products known to those skilled in the art may be used.
In the present invention, the solvent is preferably tetrahydrofuran or diethyl ether; the source of the present invention is not particularly limited.
In the present invention, the first reaction is preferably carried out in the presence of an inorganic strong base; the inorganic strong base preferably comprises sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide or potassium hydroxide. The source of the inorganic strong base is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the molar ratio of the glycol, the p-toluenesulfonyl chloride and the inorganic strong base is preferably 1: (2.05-2.5): (6 to 10), more preferably 1: (2.05-2.2): (6-8).
In the invention, the temperature of the first reaction is preferably-10-5 ℃ and the time is preferably 1-2 h; the specific reaction formula is as follows (n=0 for example):
on this basis, the process of the first reaction is preferably specifically:
a1 Mixing dihydric alcohol, inorganic strong base and solvent to obtain dihydric alcohol mixed solution;
a2 The temperature is controlled to be minus 10 ℃ to 5 ℃, the solution of the p-toluenesulfonyl chloride is dripped into the dihydric alcohol mixed solution obtained in the step a 1), the dripping time is 0.4h to 0.6h, the reaction is carried out for 1h to 2h after the dripping is finished, and the intermediate A is obtained after the reaction is finished. In the present invention, in order to avoid the reaction being too severe, the temperature of the glycol mixture is preferably controlled to-10 to 5 ℃ when the solution of p-toluenesulfonyl chloride is added dropwise, and specifically may be-10 ℃, -5 ℃, 0 ℃ or 5 ℃; after the dripping is finished, stirring is preferably carried out for 1-2 hours at the temperature, and the stirring time can be 1 hour, 1.5 hours or 2 hours; the stirring speed is preferably 50r/min to 80r/min.
In the present invention, the completion of the reaction is preferably detected by tracking the completion of the reaction; then, the invention filters out excessive inorganic strong alkali solid, adds water and methylene dichloride into the filtrate with 10 ml-30 ml, divides liquid, washes with water, dries, decompresses and reclaims solvent to obtain intermediate A.
After the intermediate A is obtained, the bis (2-methoxyphenyl) phosphine oxide and the obtained intermediate A are subjected to a second reaction in a solvent to obtain an intermediate B.
In the present invention, the bis (2-methoxyphenyl) phosphine oxide has the following structural formula:
the source of the p-toluenesulfonyl chloride is not particularly limited in the present invention, and commercially available products or self-made products known to those skilled in the art may be used.
In the present invention, the solvent is preferably tetrahydrofuran or diethyl ether; the source of the present invention is not particularly limited.
In the present invention, the second reaction is preferably carried out in the presence of an alkyl lithium; the alkyl lithium is preferably ethyl lithium and/or n-BuLi, more preferably ethyl lithium or n-BuLi. The source of the alkyl lithium is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the molar ratio of the bis (2-methoxyphenyl) phosphine oxide, intermediate a and alkyl lithium is preferably 1: (0.45-0.5): (1.05-1.5).
In the invention, the temperature of the second reaction is preferably-10-5 ℃ and the time is preferably 1-2 h; the specific reaction formula is as follows:
on this basis, the process of the second reaction is preferably specifically:
b1 Controlling the temperature to minus 10 ℃ to 5 ℃, dripping the alkyl lithium into the solvent of the bis (2-methoxyphenyl) phosphine oxide for 0.8h to 1.2h, heating to a normal temperature state after the dripping is finished, and tracking and detecting the reaction completely to obtain a lithium phosphine salt solution;
b2 The temperature is controlled to be minus 10 ℃ to 5 ℃, the solution of the intermediate A is dripped into the lithium phosphine salt solution obtained in the step b 1), the dripping time is 1.3h to 1.76h, the reaction is carried out for 1h to 2h after the dripping is finished, and the intermediate b is obtained after the reaction is finished. In the present invention, in the above step b 1), the temperature of the solution of bis (2-methoxyphenyl) phosphine oxide at the time of adding lithium alkyl dropwise is preferably controlled to be-10 to 5 ℃, specifically, -10 ℃, -5 ℃, 0 ℃ or 5 ℃; after the dripping is finished, stirring is preferably carried out for 1-2 hours at the temperature, and the stirring time can be 1 hour, 1.5 hours or 2 hours; the stirring speed is preferably 50 r/min-80 r/min; and then heating to normal temperature until the reaction is complete.
In the present invention, the completion of the reaction is preferably detected by tracking the completion of the reaction; then, water and 20 ml-40 ml of dichloromethane are added, standing and liquid separation are carried out, an organic phase is separated, dichloromethane is extracted twice, the organic phases are combined, anhydrous sodium sulfate is dried, and reduced pressure distillation recrystallization is carried out, so as to obtain an intermediate B.
After the intermediate B is obtained, the intermediate B is subjected to reduction reaction to obtain the polyketone catalyst ligand. In the present invention, the reduction reaction is preferably performed by:
c1 Mixing the intermediate B, tertiary amine and solvent to obtain a mixed solution of the intermediate B;
c2 And c) controlling the temperature to be between minus 5 and 15 ℃, dropwise adding a reducing agent into the mixed solution of the intermediate B obtained in the step c 1) for 0.4 to 0.6h, heating to between 65 and 75 ℃, and tracking the liquid quality until the reaction is complete to obtain the polyketone catalyst ligand.
In the present invention, the tertiary amine is preferably triethylamine and/or tributylamine, more preferably triethylamine or tributylamine; the solvent is preferably one or more of acetonitrile, toluene and xylene, more preferably acetonitrile, toluene or xylene; the reducing agent is preferably trichlorosilane (HSiCl) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The source of the above tertiary amine, solvent and reducing agent is not particularly limited, and commercially available products known to those skilled in the art can be used.
In the present invention, the molar ratio of the intermediate B, the reducing agent and the tertiary amine is preferably 1: (3-8): (3-8).
In the invention, the reflux reaction is carried out after the temperature is raised to 65-75 ℃, and the reaction time is preferably 2-5 h until the reaction is complete.
In the present invention, after the completion of the reaction, the liquid is preferably further comprising:
cooling, adding 8-12 times of HSiCl 3 Quenching reaction with 20-40 wt% molar equivalent sodium hydroxide water solution, standing for separating liquid, separating out organic phase, acetonitrile extraction twice, merging organic phase, water washing with saturated saline water once, drying with anhydrous sodium sulfate, decompressing, distilling and recrystallizing to obtain polyketone catalyst ligand.
The synthesis method provided by the invention has the advantages of simple reaction, high conversion rate, excellent product quality and capability of safely producing polyketone catalyst ligand with the content of more than 99%; and the operation steps are simple, the required equipment is simple, and the energy consumption is low.
The invention provides a polyketone catalyst ligand and a synthesis method thereof; the synthesis method comprises the following steps: a) Carrying out a first reaction on dihydric alcohol and p-toluenesulfonyl chloride in a solvent to obtain an intermediate A; b) Carrying out a second reaction on the bis (2-methoxyphenyl) phosphine oxide and the intermediate A obtained in the step a) in a solvent to obtain an intermediate B; c) And B) carrying out reduction reaction on the intermediate B obtained in the step B) to obtain the polyketone catalyst ligand. Compared with the prior art, the method selects specific raw materials to synthesize the polyketone catalyst ligand according to specific process steps, realizes better overall interaction, ensures that the activity of the synthesized novel polyketone catalyst ligand is higher than 26 kg/(g-Pd.h), and meets the technical requirements of polyketone production in the market; meanwhile, the synthetic method has the advantages of simple reaction route, simple required equipment, low energy consumption, high product yield, good quality, safety and easy industrialization.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
(1) Preparation of intermediate a:
adding 2.60g of dihydric alcohol (n=0) and 4.80g of sodium hydroxide into 20ml of tetrahydrofuran under anhydrous and anaerobic conditions, cooling to-10 ℃, starting to control 20ml of tetrahydrofuran solution of Wen Dijia 7.82.82 g of p-toluenesulfonyl chloride, controlling the temperature and stirring for 2 hours after the dripping is finished, filtering to remove excessive sodium hydroxide solid after the completion of tracking detection reaction, adding 20ml of water and dichloromethane into filtrate, separating liquid, washing with water, drying, and recovering solvent under reduced pressure to obtain 5.32g of white crystalline solid intermediate A with the purity of 98.74 percent and the yield of 92.48 percent;
the intermediate A is specifically
(2) Preparation of intermediate B:
adding 10.76g of bis (2-methoxyphenyl) phosphine oxide into 40mL of tetrahydrofuran under anhydrous and anaerobic conditions, cooling to 0 ℃, controlling Wen Dijia n-BuLi 26.61mL, heating to normal temperature after dripping, tracking and detecting that the reaction is complete, cooling to-10 ℃, starting controlling Wen Di to add 10mL of intermediate A5.32g of tetrahydrofuran solution, controlling the temperature after dripping, stirring for 2 hours, and then heating to room temperature until the reaction is completed; adding 30ml of water and 30ml of dichloromethane respectively, standing for separating liquid, separating out an organic phase, extracting the dichloromethane twice, combining the organic phases, drying the organic phases by anhydrous sodium sulfate, distilling under reduced pressure for recrystallization to obtain an intermediate B10.88g, wherein the purity is 98.13%, and the yield is 93.74%;
the intermediate B is specifically
(3) Preparation of the ligand:
under the condition of no water and no oxygen, adding 10.88g of intermediate B and 7.00g of triethylamine into 40ml of acetonitrile, dropwise adding 9.43g of trichlorosilane at the temperature of 0 ℃, heating to a reflux state after the dropwise adding is finished, cooling after tracking and detecting the reaction to be complete, adding 10 times of HSiCl 3 Quenching reaction by 30wt% molar equivalent sodium hydroxide aqueous solution, standing and separating liquid, separating out an organic phase, extracting twice by acetonitrile, combining the organic phases, washing the organic phase once by saturated saline water, drying by anhydrous sodium sulfate, distilling under reduced pressure and recrystallizing to obtain 9.78g of polyketone catalyst ligand, wherein the purity is 99.15%, and the yield is 95.82%;
the polyketone catalyst ligand is specifically 1 H NMR is shown in figure 1.
Example 2
(1) Preparation of intermediate a:
under the anhydrous and anaerobic condition, adding 2.60g of dihydric alcohol (n=0) and 5.60g of sodium hydroxide into 20ml of tetrahydrofuran, cooling to-10 ℃, starting to control 20ml of tetrahydrofuran solution of Wen Dijia 8.01.01 g of p-toluenesulfonyl chloride, controlling the temperature and stirring for 1h after the dripping is finished, filtering to remove excessive sodium hydroxide solid after the completion of tracking and detecting reaction, adding 20ml of water and dichloromethane into filtrate, separating liquid, washing with water, drying, and recovering solvent under reduced pressure to obtain 5.45g of white crystalline solid intermediate A with the purity of 98.88 percent and the yield of 94.80 percent;
the intermediate A is specifically
(2) Preparation of intermediate B:
under the anhydrous and anaerobic condition, adding 11.04g of bis (2-methoxyphenyl) phosphine oxide into 40mL of tetrahydrofuran, cooling to 0 ℃, controlling Wen Dijia n-BuLi to 27.66mL, heating to a normal temperature state after the dripping is finished, tracking and detecting the reaction completely, cooling to-5 ℃, starting to control Wen Di, adding 5.45g of intermediate A to 10mL of tetrahydrofuran solution, controlling the temperature after the dripping is finished, stirring for 1h, and then heating to room temperature until the reaction is finished; adding 30ml of water and 30ml of dichloromethane respectively, standing for separating liquid, separating out an organic phase, extracting the dichloromethane twice, combining the organic phases, drying the organic phases by anhydrous sodium sulfate, distilling under reduced pressure for recrystallization to obtain an intermediate B11.05g, wherein the purity is 98.32%, and the yield is 93.12%;
the intermediate B is specifically
(3) Preparation of the ligand:
under the condition of no water and no oxygen, adding 11.05g of intermediate B and 7.00g of triethylamine into 40ml of acetonitrile, controlling the temperature to be 0 ℃, dropwise adding 9.59g of trichlorosilane, heating to a reflux state after the dropwise adding is finished, tracking, detecting the reaction completely, cooling, adding 10 times of HSiCl 3 Quenching reaction by 30wt% molar equivalent sodium hydroxide aqueous solution, standing and separating liquid, separating out an organic phase, extracting twice by acetonitrile, combining the organic phases, washing the organic phase once by saturated saline water, drying by anhydrous sodium sulfate, distilling under reduced pressure and recrystallizing to obtain 9.89g of polyketone catalyst ligand, wherein the purity is 99.32%, and the yield is 95.46%;
the polyketone catalyst ligand is specifically
Example 3
(1) Preparation of intermediate a:
adding 2.88g of dihydric alcohol (n=1) and 6.40g of sodium hydroxide into 20ml of tetrahydrofuran under anhydrous and anaerobic conditions, cooling to 0 ℃, starting to control 20ml of tetrahydrofuran solution of Wen Dijia 8.01.01 g of p-toluenesulfonyl chloride, controlling the temperature and stirring for 2 hours after the dripping is finished, filtering to remove excessive sodium hydroxide solid after the completion of tracking detection reaction, adding 20ml of water and dichloromethane into filtrate, separating liquid, washing, drying, and recovering solvent under reduced pressure to obtain 5.60g of white crystalline solid intermediate A with the purity of 99.12 percent and the yield of 93.13 percent;
the intermediate A is specifically
(2) Preparation of intermediate B:
adding 9.75g of bis (2-methoxyphenyl) phosphine oxide into 40mL of diethyl ether under anhydrous and anaerobic conditions, cooling to-10 ℃, controlling Wen Dijia n-BuLi34.91mL, heating to normal temperature after dripping, tracking and detecting completely, cooling to-10 ℃, starting to control Wen Di, adding 10mL of intermediate A5.60g diethyl ether solution, controlling the temperature after dripping, stirring for 2 hours, and then heating to room temperature until the reaction is completed; adding 30ml of water and 30ml of dichloromethane respectively, standing for separating liquid, separating out an organic phase, extracting the dichloromethane twice, combining the organic phases, drying the organic phases by anhydrous sodium sulfate, distilling under reduced pressure for recrystallization to obtain 11.20g of intermediate B, wherein the purity is 99.10%, and the yield is 94.62%;
the intermediate B is specifically
(3) Preparation of the ligand:
under the condition of no water and no oxygen, 11.20g of intermediate B and 19.56g of tributylamine are added into 40ml of toluene, 14.38g of trichlorosilane is dripped at the temperature of 10 ℃, the temperature is raised to a reflux state after the dripping is finished, the mixture is cooled after the tracking detection reaction is complete, and 10 times of HSiCl is added 3 Quenching reaction by 30wt% molar equivalent sodium hydroxide aqueous solution, standing and separating liquid, separating out an organic phase, extracting by toluene for two times, combining the organic phases, washing by saturated saline water once, drying by anhydrous sodium sulfate, distilling under reduced pressure and recrystallizing to obtain 9.75g of polyketone catalyst ligand, wherein the purity is 99.45%, and the yield is 92.00%;
the polyketone catalyst ligand is specifically
Example 4
(1) Preparation of intermediate a:
under the anhydrous and anaerobic condition, 3.20g of dihydric alcohol (n=2) and 8.96g of potassium hydroxide are added into 20ml of tetrahydrofuran, the temperature is reduced to-10 ℃, the temperature is controlled to be Wen Dijia 8.39.39 g of tetrahydrofuran solution of p-toluenesulfonyl chloride, the mixture is stirred for 1h under the control of temperature after the dripping is finished, the excessive potassium hydroxide solid is filtered and removed after the tracking detection reaction is completed, 20ml of water and dichloromethane are respectively added into the filtrate, the filtrate is separated, washed, dried and the solvent is recovered under reduced pressure, so that 5.80g of white crystal solid intermediate A with the purity of 98.50 percent and the yield of 91.55 percent is obtained;
the intermediate A is specifically
(2) Preparation of intermediate B:
adding 9.60g of bis (2-methoxyphenyl) phosphine oxide into 40mL of tetrahydrofuran under anhydrous and anaerobic conditions, cooling to 0 ℃, controlling Wen Dijia n-BuLi34.32ml, heating to a normal temperature state after dripping, tracking and detecting completely, cooling to-10 ℃, starting to control Wen Di, adding 10mL of tetrahydrofuran solution of 5.80g of intermediate A, controlling the temperature after dripping, stirring for 2 hours, and then heating to room temperature until the reaction is completed; adding 30ml of water and 30ml of dichloromethane respectively, standing for separating liquid, separating out an organic phase, extracting the dichloromethane twice, combining the organic phases, drying the organic phases by anhydrous sodium sulfate, distilling under reduced pressure for recrystallization to obtain 11.25g of intermediate B, wherein the purity is 97.92%, and the yield is 93.43%;
the intermediate B is specifically
(3) Preparation of the ligand:
under the condition of no water and oxygen, 11.25g of intermediate B and 10.36g of triethylamine are added into 40ml of dimethylbenzene, 13.96g of trichlorosilane is dripped at the temperature of 0 ℃, the temperature is raised to a reflux state after the dripping is finished, the mixture is cooled after tracking and detecting the reaction to be complete, and 10 times of HSiCl is added 3 Quenching reaction with 30wt% molar equivalent sodium hydroxide water solution, standing for separating liquid, separating out organic phase, extracting with xylene twice, mixing the organic phase, washing with saturated saline water once, drying with anhydrous sodium sulfate, vacuum distilling, recrystallizing to obtain polyketone catalyst ligand 9.56g with purity of 99.32%, yield90.69％；
The polyketone catalyst ligand is specifically
Comparative example 1
The ligand 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane (BDOMPP).
Comparative example 2
The ligand 3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl ] -1, 5-dioxa-spiro [5,5] undecane.
Application examples
The polyketone catalyst ligand obtained by the synthesis method provided in examples 1 to 4 and the catalyst ligand provided in comparative examples 1 to 2 were used for carrying out polymerization experiments, and the specific steps are as follows:
250mL of methanol, 9.7mg of p-benzoquinone, 1% by mass of trifluoromethanesulfonic acid based on the mass of methanol, and 0.0075mmol of catalyst were charged into a 500mL autoclave.
After the substances are added, nitrogen is filled into the autoclave for pressure maintaining and replacement, and CO and C are filled 2 H 4 The mass ratio is 1:1 to 3.5MPa, starting heating, setting the temperature to 50 ℃, stirring at 400r/min, and continuously supplementing CO and C when the temperature rises to 50 DEG C 2 H 4 The mass ratio is 1:1, maintaining the reaction pressure at 5.0MPa, and reacting for 6 hours; and (5) processing and drying to obtain a polyketone product.
The experimental results are shown in table 1.
Table 1 Experimental data for carrying out polymerization reactions on polyketone catalyst ligands obtained by the synthetic methods provided in examples 1 to 4 and catalyst ligands provided in comparative examples 1 to 2
Experimental results show that under the same polymerization conditions, the catalytic activity of the polyketone catalyst ligand obtained by the synthesis method provided in examples 1-4 is higher than that of the catalyst ligand for preparing polyketone known in the prior art, and specifically > 26 kg/(g-Pd.h).
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A method for synthesizing polyketone catalyst ligand, comprising the following steps:
a) Carrying out a first reaction on dihydric alcohol and p-toluenesulfonyl chloride in a solvent to obtain an intermediate A; the first reaction is carried out in the presence of an inorganic strong base; the temperature of the first reaction is-10 ℃ to 5 ℃ and the time is 1h to 2h; the solvent in step a) is tetrahydrofuran;
the dihydric alcohol has a structure shown in a formula (II-3):
formula (II-3);
the intermediate A specifically comprises the following components:
；
b) Carrying out a second reaction on the bis (2-methoxyphenyl) phosphine oxide and the intermediate A obtained in the step a) in a solvent to obtain an intermediate B; the second reaction is carried out in the presence of an alkyl lithium; the temperature of the second reaction is-10 ℃ to 5 ℃ and the time is 1h to 2h; the solvent in the step b) is tetrahydrofuran or diethyl ether; the alkyl lithium is n-BuLi;
the intermediate B specifically comprises the following components:
；
c) Carrying out reduction reaction on the intermediate B obtained in the step B) to obtain a polyketone catalyst ligand; the reduction reaction process specifically comprises the following steps:
c1 Mixing the intermediate B, tertiary amine and solvent to obtain a mixed solution of the intermediate B;
c2 Dropwise adding a reducing agent into the intermediate B mixed solution obtained in the step c 1) at the temperature of-5-15 ℃ for 0.4-0.6 h, heating to 65-75 ℃, and tracking the liquid quality until the reaction is complete to obtain a polyketone catalyst ligand;
the tertiary amine is triethylamine or tributylamine; the solvent is acetonitrile, toluene or xylene; the reducing agent is trichlorosilane;
the polyketone catalyst ligand is specifically as follows:
。
2. the synthetic method according to claim 1, wherein the molar ratio of diol, p-toluenesulfonyl chloride and inorganic strong base in step a) is 1: (2.05-2.5): (6-10).
3. The synthetic method according to claim 1, characterized in that the molar ratio of bis (2-methoxyphenyl) phosphine oxide, intermediate a and alkyl lithium in step b) is 1: (0.45-0.5): (1.05-1.5).
4. The synthetic method according to claim 1, wherein the molar ratio of the intermediate B, the reducing agent and the tertiary amine is 1: (3-8): (3-8).
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