CN109096109A - The synthetic method of 2- butenoate - Google Patents
The synthetic method of 2- butenoate Download PDFInfo
- Publication number
- CN109096109A CN109096109A CN201710473476.0A CN201710473476A CN109096109A CN 109096109 A CN109096109 A CN 109096109A CN 201710473476 A CN201710473476 A CN 201710473476A CN 109096109 A CN109096109 A CN 109096109A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- butenoate
- bis
- synthetic method
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 title claims abstract description 55
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- -1 solve the problems Chemical compound 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 26
- 239000010948 rhodium Substances 0.000 claims abstract description 26
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 17
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
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- 150000001298 alcohols Chemical class 0.000 claims description 4
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 4
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- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
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- LYLFXVKSLNCSCK-UHFFFAOYSA-N C12=CC=C(CC1)C2.[Rh] Chemical compound C12=CC=C(CC1)C2.[Rh] LYLFXVKSLNCSCK-UHFFFAOYSA-N 0.000 claims description 2
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- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- GJMJIOGYTAVWAV-UHFFFAOYSA-N [Rh].B(O)(O)O Chemical compound [Rh].B(O)(O)O GJMJIOGYTAVWAV-UHFFFAOYSA-N 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
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- 238000009776 industrial production Methods 0.000 abstract 1
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- 238000001914 filtration Methods 0.000 description 51
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 18
- 238000000605 extraction Methods 0.000 description 17
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- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 17
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- 239000011734 sodium Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 15
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- 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
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- 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
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Abstract
The present invention relates to the synthetic methods of 2- butenoate, mainly solve the problems, such as that propine conversion ratio is low in the prior art and 2- butenoate is selectively low, the present invention by using 2- butenoate synthetic method, material and carbon monoxide-olefin polymeric haptoreaction including propine and carbon monoxide and alcohol obtain 2- butenoate, the carbon monoxide-olefin polymeric includes the technical solution of rhodium complex and two luxuriant high valent cationic diphosphine compounds, it preferably solves the technical problem, can be used in the industrial production of 2- butenoate.
Description
Technical field
The present invention relates to the synthetic methods of 2- butenoate.
Background technique
2- butenoate is used for fragrance and organic synthesis intermediate, also serves as polymer monomer.20% M Cr with
The copolymer of 80% vinylacetate is transparent solid resin, has softening point height and to be dissolved in such as benzene and chloromethanes organic molten
The characteristic of agent.2- butenoate is used as curing agent and sizing agent in hatting industry, paints softening agent.The present invention realizes this
Demand and other demands that hereafter will be apparent to those skilled in the art with appended claims by reading.
CN1109865 provides a kind of high yield with acetone cyanohydrin and sulfuric acid and manufactures α, beta-unsaturated carboxylic acid ester
Method, which is realized by reducing byproduct of reaction and cyclic process intermediate product.It is high yield manufacture high-purity isobutyl
The method of olefin(e) acid ester.The improved method reduces the waste generated in current manufacturing process.
CN103539666A discloses a kind of preparation method of 2- methyl-3-butenoic acid ester, includes the following steps: that (1) exists
Under the action of elemental iodine, the halogenated butylene of 3- is reacted in ether solvents with magnesium, obtain 3- it is halogenated-butylene Grignard Reagent；(2) step
Suddenly the 3- that (1) obtains is halogenated-and butylene Grignard reagent dropwise carries out substitution reaction into carbonic ester, obtain the 2- methyl -3-
Butenoate.The preparation method using the halogenated butylene of 3- as starting material, be first prepared into 3- it is halogenated-butylene Grignard Reagent, then again
Substitution reaction is carried out with carbonic ester, reaction route is shortened, improves the yield of product, simplify post-processing step, simultaneously should
Route avoids the use of the hydrogen cyanide of severe toxicity, to more environment-friendly.
CN101691329 is related to a kind of 3- fluorin-4-oxygen -2 (anti-)-butenoate synthesis of high stereoselectivity
Method.Join olefin(e) acid ester and fluoro- 1,4- diazabicyclo [2.2.2] octane two (tetrafluoro boric acid) salt of 1- chloromethyl -4- by 2,3-
It in anhydrous acetonitrile, is stirred at 80 DEG C, electrophilic fluorination reaction occurs, synthesizes 3- fluorin-4-oxygen -2 (anti-)-butenoate.The present invention
Easy to operate, raw materials and reagents are easy to get, and react the regio- and stereo-selectivity with height, and the easily separated purifying of product is suitable for
Efficient -2 (anti-)-butenoate of rapid synthesis 3- fluorin-4-oxygen.
Summary of the invention
In the technical problems to be solved by the invention prior art propine route 2- butenoate propine conversion ratio it is low and
The selectively low problem of 2- butenoate, provides carbon monoxide-olefin polymeric, and the composition has for propine route 2- butenoate
Have the advantages that propine high conversion rate and 2- butenoate are selectively high.
In order to solve the above technical problems, technical scheme is as follows:
The synthetic method of 2- butenoate contacts instead including propine with the material of carbon monoxide and alcohol with carbon monoxide-olefin polymeric
2- butenoate should be obtained, the carbon monoxide-olefin polymeric includes rhodium complex and two luxuriant high valent cationic diphosphine compounds.
Present invention employs two luxuriant high valent cationic diphosphine compounds to replace in the prior art two luxuriant low-valent metals
Cation diphosphine compound, in reaction of the propine carbonyl compound at 2- butenoate, significantly improve propine conversion ratio and
The selectivity of 2- butenoate achieves unexpected technical effect.
In above-mentioned technical proposal, reaction temperature is preferably 25 DEG C~150 DEG C, more preferable 90 DEG C~130 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0.01MPa~10MPa, more preferable 0.1MPa~2MPa.
In above-mentioned technical proposal, the molar ratio of rhodium complex and two luxuriant high valent cationic diphosphine compounds is preferably
0.01~100；It is further preferred that the molar ratio of rhodium complex and two luxuriant high valent cationic diphosphine compounds be 0.1~
10, more preferably 0.2~2, most preferably 0.5~1.
In above-mentioned technical proposal, the valence state of the metal is preferably greater than divalent.
In above-mentioned technical proposal, the common rhodium complex in this field may be used to the present invention and obtain comparable technology effect
Fruit, as non limiting example, including rhodium salt, hydrogen complex (hydride complex), carbonyls, halide, oxidation
Object, phosphine composition (phosphinecomplex) and their mixture；More specific non limiting example can be selected from trichlorine
Change rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, (acetylacetone,2,4-pentanedione) (norbornadiene) rhodium, bis- (1,5- cyclo-octadiene) tetrafluoro boron
Bis- (triphen phosphino-) radium chlorides of sour rhodium, bis- (dicyclopentadiene) tetrafluoro boric acid rhodiums, carbonyl, three (triphenylphosphine) carbonyl hydrogenation Rhs,
Bis- (1,5- cyclo-octadiene) dichloride rhodiums, four (triphenylphosphine) hydrogenation Rhs, three (triphenylphosphine) radium chlorides, rhodium phosphine complex or its
Mixture.
In above-mentioned technical proposal, rhodium complex preferably includes dicarbonyl rhodium acetylacetonate.
In above-mentioned technical proposal, metal cation be in the periodic table of elements at least one of iron series metal sun from
Son.The high valent cationic is preferably at least one of trivalent Fe, trivalent Co, trivalent Ni.
In above-mentioned technical proposal, the high valent cationic more preferably includes trivalent Fe, trivalent Co simultaneously, and the two is mentioning
High propine conversion ratio and 2- butenoate selectivity aspect have synergistic effect.
In above-mentioned technical proposal, the high valent cationic more preferably includes trivalent Fe, trivalent Ni simultaneously, and the two is mentioning
High propine conversion ratio and 2- butenoate selectivity aspect have synergistic effect.
In above-mentioned technical proposal, the high valent cationic more preferably includes that trivalent Co and trivalent Ni, the two exist simultaneously
Improving propine conversion ratio and 2- butenoate selectivity aspect has synergistic effect.
In above-mentioned technical proposal, described two luxuriant high valent cationic diphosphine compounds are preferably with such as flowering structure:
Wherein M is at least one of Fe, Co, Ni, and R is that some representative examples are phenyl, halogenophenyl, such as 4- fluorobenzene
Base, 2,6- difluorophenyl, 2,5- dichlorophenyl, 3,4- dichlorophenyl, 3- chlorphenyl, 3- bromophenyl, 4- bromophenyl, 3,4- dibromo
Phenyl, 2- fluorophenyl etc.；Single or two (methyl) aryl, such as 4- aminomethyl phenyl, 3- aminomethyl phenyl, 2,4- 3,5-dimethylphenyl, 3,
5- 3,5-dimethylphenyl etc., X-For BF4 -And/or PF6 -。
Above-mentioned reaction preferably carries out in a solvent, the solvent preferably those carbon monoxide-olefin polymeric can be dissolved that
A bit, the saturated alcohols of C1~C10 are (as reactant and solvent；Such as, but not limited to methanol, ethyl alcohol, propyl alcohol, ethylene glycol, glycerine
Etc.), ether (such as, but not limited to ethyl methyl ether, ether, tetrahydrofuran, the 3- methyltetrahydrofuran, dioxane of C3~C10
Deng), contain alkyl-substituted phenyl (such as, but not limited to toluene, ethylbenzene, isopropylbenzene, the diformazan of 7~10 carbon atoms in molecule
Benzene, diethylbenzene, diisopropylbenzene (DIPB), trimethylbenzene, durene etc.), halogenated hydrocarbons (the such as, but not limited to methylene chloride, three of C1~C10
Chloromethanes, 1,2- dichloroethanes) and their mixture.
The preparation method of inventive catalyst composition is not particularly limited, such as after the component being simply mixed
Preparation for 2- butenoate is reacted, and the component can also be simultaneously or successively added in reaction system and be used, for adding
The sequencing for entering reaction system is not particularly limited, available comparable technical effect.
Alcohol as described in the above technical scheme is preferably the saturated alcohols of C1~C10.Corresponding 2- butenoate is at this time
CH3CH=CH-COOR, wherein R is the alkyl of C1~C10.
The luxuriant high valent cationic diphosphine compounds of two be related in the present invention the preparation method is as follows:
In above-mentioned reaction equation, LiCp, TiCp respectively indicate luxuriant lithium and luxuriant titanium；
TiOEt indicates titanium ethanolate；
[O] indicates oxidant, can be 1,4-benzoquinone and/or perchloroethane.
The luxuriant lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, diaryl phosphonium chloride is added,
It is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, the anhydrous ether solution of titanium ethanolate, spontaneous recovery room are added dropwise
Temperature stirs 2 hours.At least one of Fe, Co, Ni is added, flows back 12 hours.Solution is cooled to room temperature, be added 1,4-benzoquinone or
Perchloroethane reacts 10 minutes, and evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, and diatomite filtering removes under reduced pressure molten
Agent, residue are dissolved in acetone, and fluoboric acid or sodium fluoborate is added, and add water, and solution is instilled ether by methylene chloride extraction
In, solid is obtained by filtration, then obtain two luxuriant high valent cationic diphosphine compounds with methylene chloride/Diethyl ether recrystallization.
The dosage of carbon monoxide-olefin polymeric in the reaction is not particularly limited, those skilled in the art can according to need into
Row rationally determines that such as, but not limited to the molar ratio of propine and carbon monoxide-olefin polymeric is 1~10000.
Above-mentioned reaction preferably carries out in a solvent, the solvent preferably those carbon monoxide-olefin polymeric can be dissolved that
A bit, the saturated alcohols of C1~C10 (can also do reaction raw materials, such as, but not limited to methanol, ethyl alcohol, propyl alcohol, ethylene glycol, the third three simultaneously
Alcohol etc.), ether (such as, but not limited to ethyl methyl ether, ether, tetrahydrofuran, the 3- methyltetrahydrofuran, dioxane of C3~C10
Deng), contain alkyl-substituted phenyl (such as, but not limited to toluene, ethylbenzene, isopropylbenzene, the diformazan of 7~10 carbon atoms in molecule
Benzene, diethylbenzene, diisopropylbenzene (DIPB), trimethylbenzene, durene etc.), halogenated hydrocarbons (the such as, but not limited to methylene chloride, three of C1~C10
Chloromethanes, 1,2- dichloroethanes) and their mixture.
It obtains carbon monoxide-olefin polymeric of the invention and does not need special technology, but the catalyst group of high activity in order to obtain
Object is closed, preferably carries out the operation of rhodium and phosphine cooperation base, inert atmosphere, that is, nitrogen, argon gas etc. in an inert atmosphere.Present invention catalysis
Agent composition uses after can mixing before reaction system applied by it is added, can also be according to the group of carbon monoxide-olefin polymeric
At its application response system is simultaneously or separately added, when being separately added into reaction system applied by it to the successive suitable of addition
Sequence does not also specially require, and can reach the purpose of the present invention and obtain comparable technical effect.
The amount of propine can change in a wide range in reaction mixture.In practice, in reactor higher concentration raw material
Be conducive to reaction rate.
If not specializing, the 2- butenoate being related in the present invention is the mixture of cis and trans.
The present invention is described in more detail below by the embodiment of embodiment of the present invention, although it is understood that these are implemented
Example is only to illustrate purpose and be added and be not intended to limit the scope of the invention.Unless otherwise indicated, all percentages are all the amount of substance
Percentage.
Using technical solution of the present invention, the conversion ratio of propine is reachable up to the selectivity of 86.4%, 2- butenoate
91.2%, achieve preferable technical effect.
Specific embodiment
[embodiment 1]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphonate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state
It amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, showing propine conversion ratio as 82.3%, 2- butenoate is selectively 89.5%.For convenient for comparing, by the group of catalyst
Table 1 is listed at reaction result.
[comparative example 1]
By propine carbonylation at 2- butenoate in tetrahydrofuran
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of divalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2Displacement reaction
Device.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state total 3 small
When.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content, show
Propine conversion ratio is that 36.1%, 2- butenoate is selectively 66.9%.For convenient for comparing, the composition of catalyst and reaction are tied
Fruit is listed in table 1.
[embodiment 2]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol cobalt chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent cobaltocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent cobaltocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state
It amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, showing propine conversion ratio as 74.6%, 2- butenoate is selectively 88.1%.For convenient for comparing, by the group of catalyst
Table 1 is listed at reaction result.
[embodiment 3]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol nickel chloride is added, flows back 12 hours.Solution is cooled to room temperature, is added
60mmol 1,4-benzoquinone or perchloroethane react 10 minutes, and evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatomite
Filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent dicyclopentadienyl nickel cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent dicyclopentadienyl nickel cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state
It amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, shows propine conversion ratio 79.6%, and 2- butenoate is selectively 85.2%.For convenient for comparing, by the composition of catalyst
Table 1 is listed in reaction result.
[embodiment 4]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol cobalt chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent cobaltocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.06mmol), bis- (diphenyl) the phosphine hexafluorophosphates (0.04mmol) of trivalent cobaltocene cation.Add
Enter tetrahydrofuran (25mL), methanol (10g) and propine (50mmol), then in N2Metathesis reactor.Reactor is pressurizeed with CO
To 2.0MPa and it is heated to 120 DEG C.Agitated autoclave, and 120 DEG C of state is maintained to amount to 3 hours.Then autoclave, row are cooled down
Extra gas is put, content is recycled.With internal standard gas chromatography analysis content, propine conversion ratio/86.4%, 2- is shown
Butenoate is selectively 91.2%.For convenient for comparing, the composition of catalyst and reaction result are listed in table 1.
[embodiment 5]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol nickel chloride is added, flows back 12 hours.Solution is cooled to room temperature, is added
60mmol 1,4-benzoquinone or perchloroethane react 10 minutes, and evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatomite
Filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent dicyclopentadienyl nickel cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.05mmol), bis- (diphenyl) the phosphine hexafluorophosphates (0.05mmol) of trivalent dicyclopentadienyl nickel cation.Add
Enter tetrahydrofuran (25mL), methanol (10g) and propine (50mmol), then in N2Metathesis reactor.Reactor is pressurizeed with CO
To 2.0MPa and it is heated to 120 DEG C.Agitated autoclave, and 120 DEG C of state is maintained to amount to 3 hours.Then autoclave, row are cooled down
Extra gas is put, content is recycled.With internal standard gas chromatography analysis content, showing propine conversion ratio is 84.1%,
2- butenoate is selectively 90.0%.For convenient for comparing, the composition of catalyst and reaction result are listed in table 1.
[embodiment 6]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol cobalt chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent cobaltocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol nickel chloride is added, flows back 12 hours.Solution is cooled to room temperature, is added
60mmol 1,4-benzoquinone or perchloroethane react 10 minutes, and evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatomite
Filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent dicyclopentadienyl nickel cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent dicyclopentadienyl nickel cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.03mmol), bis- (diphenyl) the phosphine hexafluorophosphates (0.07mmol) of trivalent cobaltocene cation.Add
Enter tetrahydrofuran (25mL), methanol (10g) and propine (50mmol), then in N2Metathesis reactor.Reactor is pressurizeed with CO
To 2.0MPa and it is heated to 120 DEG C.Agitated autoclave, and 120 DEG C of state is maintained to amount to 3 hours.Then autoclave, row are cooled down
Extra gas is put, content is recycled.With internal standard gas chromatography analysis content, showing propine conversion ratio is 86.1%,
2- butenoate is selectively 89.9%.For convenient for comparing, the composition of catalyst and reaction result are listed in table 1.
[embodiment 7]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Naphthalene phosphonium chloride is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (dinaphthyls of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphonate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state
It amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, showing propine conversion ratio as 64.0%, 2- butenoate is selectively 92.5%.For convenient for comparing, by the group of catalyst
Table 1 is listed at reaction result.
[embodiment 8]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium tetrafluoroborate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine tetrafluoroborates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine tetrafluoroborate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state
It amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, shows propine conversion ratio 78.1%, and 2- butenoate is selectively 88.7%.For convenient for comparing, by the composition of catalyst
Table 1 is listed in reaction result.
[embodiment 9]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
It is double that four (triphenylphosphine) hydrogenation Rhs (0.05mmol), trivalent ferrocene cation are packed into 150 milliliters of autoclaves
(diphenyl) phosphine hexafluorophosphonate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, so
Afterwards in N2Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C
State amount to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis
Content, showing propine conversion ratio as 75.6%, 2- butenoate is selectively 95.4%.For convenient for comparing, by catalyst
Composition and reaction result be listed in table 1.
[embodiment 10]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in toluene by propine carbonylation at 2- butenoate
Dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation bis- (two are packed into 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphate (0.10mmol).Toluene (25mL), methanol (10g) and propine (50mmol) is added, then in N2It sets
Change reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state total
Meter 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content,
It is selectively 87.6% that propine conversion ratio, which is shown, as 83.5%, 2- butenoate.
[embodiment 11]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.005mmol), trivalent ferrocene cation bis- (two are packed into 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphonate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then exists
N2Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 120 DEG C.Agitated autoclave, and maintain 120 DEG C of shape
State amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, shows propine conversion ratio 50.0%, and 2- butenoate is selectively 81.1%.
[embodiment 12]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphonate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 150 DEG C.Agitated autoclave, and maintain 150 DEG C of state
It amounts to 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content
Object, shows propine conversion ratio 82.1%, and 2- butenoate is selectively 86.4%.
[embodiment 13]
1, the synthesis of ligand
The 50mmol cyclopentadienyl lithium of brand-new or luxuriant titanium are dissolved in anhydrous ether, system is cooled to -30 DEG C, and 50mmol bis- is added
Tetraphenylphosphonium chloride phosphine is stirred at room temperature 2 hours.Diatomite filtering, filtrate are cooled to -78 DEG C, and the anhydrous second of 50mmol titanium ethanolate is added dropwise
Ethereal solution, spontaneous recovery room temperature stir 2 hours.25mmol frerrous chloride is added, flows back 12 hours.Solution is cooled to room temperature, adds
Enter 60mmol 1,4-benzoquinone or perchloroethane, reacts 10 minutes, evaporating solvent under reduced pressure, residue is dissolved with methylene chloride, diatom
Soil filtering, evaporating solvent under reduced pressure, residue are dissolved in acetone, and 75mmol sodium hexafluoro phosphate is added, and add water, methylene chloride extraction
It takes, solution is instilled in ether, solid is obtained by filtration, then obtain trivalent ferrocene cation with methylene chloride/Diethyl ether recrystallization
Bis- (diphenyl) phosphine hexafluorophosphonates.
2, in tetrahydrofuran by propine carbonylation at 2- butenoate
Carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), the bis- (hexichol of trivalent ferrocene cation are packed into 150 milliliters of autoclaves
Base) phosphine hexafluorophosphonate (0.10mmol).Tetrahydrofuran (25mL), methanol (10g) and propine (50mmol) is added, then in N2
Metathesis reactor.Reactor is pressurized to 2.0MPa with CO and is heated to 60 DEG C.Agitated autoclave, and maintain 60 DEG C of state total
Meter 3 hours.Then autoclave is cooled down, extra gas is discharged, recycles content.With internal standard gas chromatography analysis content,
Propine conversion ratio 35.2% is shown, 2- butenoate is selectively 93.8%.
Table 1
Claims (9)
- The synthetic method of 1.2- butenoate, material and carbon monoxide-olefin polymeric haptoreaction including propine and carbon monoxide and alcohol 2- butenoate is obtained, the carbon monoxide-olefin polymeric includes rhodium complex and two luxuriant high valent cationic diphosphine compounds.
- 2. synthetic method according to claim 1, it is characterised in that reaction temperature is 25 DEG C~150 DEG C.
- 3. synthetic method according to claim 1, it is characterised in that reaction pressure is 0.01MPa~10MPa.
- 4. synthetic method according to claim 1, it is characterised in that rhodium complex and the two luxuriant double phosphines of high valent cationic The molar ratio of compound is 0.01~100.
- 5. synthetic method according to claim 1, it is characterised in that the valence state of the metal is greater than divalent.
- 6. synthetic method according to claim 1, it is characterised in that rhodium complex is selected from rhodium chloride, rhodium acetate, two carbonyls Ethylacetoacetone rhodium, (acetylacetone,2,4-pentanedione) (norbornadiene) rhodium, bis- (1,5- cyclo-octadiene) tetrafluoro boric acid rhodiums, bis- (bicyclic penta 2 Alkene) tetrafluoro boric acid rhodium, bis- (triphen phosphino-) radium chlorides of carbonyl, three (triphenylphosphine) carbonyl hydrogenation Rhs, bis- (1,5- cyclo-octadiene) Or mixtures thereof dichloride rhodium, four (triphenylphosphine) hydrogenation Rhs, three (triphenylphosphine) radium chlorides, rhodium phosphine complex.
- 7. synthetic method according to claim 6, it is characterised in that rhodium complex includes dicarbonyl rhodium acetylacetonate.
- 8. synthetic method according to claim 1, it is characterised in that metal cation is the iron series in the periodic table of elements At least one of metal cation.
- 9. synthetic method according to claim 1, it is characterised in that the alcohol is the saturated alcohols of C1~C10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1217417A (en) * | 1967-07-14 | 1970-12-31 | Nat Distillers Chem Corp | Organometallic complexes and chemical process using same |
| CN1068105A (en) * | 1991-07-03 | 1993-01-20 | 国际壳牌研究有限公司 | Continuous process for carbonylation of acetylenes |
| CN1127245A (en) * | 1994-07-22 | 1996-07-24 | 大世吕化学工业株式会社 | Catalytic systems and methods for carbonylation |
| CN1203581A (en) * | 1995-12-07 | 1998-12-30 | 国际壳牌研究有限公司 | Process for carbonylation of acetylenically unsaturated compounds |
| CN1241558A (en) * | 1998-03-31 | 2000-01-19 | 盖尔德马研究及发展公司 | Bicyclic aromatic compound and its application in human medicines or animal medicines and cosmetics teconology |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1217417A (en) * | 1967-07-14 | 1970-12-31 | Nat Distillers Chem Corp | Organometallic complexes and chemical process using same |
| CN1068105A (en) * | 1991-07-03 | 1993-01-20 | 国际壳牌研究有限公司 | Continuous process for carbonylation of acetylenes |
| CN1127245A (en) * | 1994-07-22 | 1996-07-24 | 大世吕化学工业株式会社 | Catalytic systems and methods for carbonylation |
| CN1203581A (en) * | 1995-12-07 | 1998-12-30 | 国际壳牌研究有限公司 | Process for carbonylation of acetylenically unsaturated compounds |
| CN1241558A (en) * | 1998-03-31 | 2000-01-19 | 盖尔德马研究及发展公司 | Bicyclic aromatic compound and its application in human medicines or animal medicines and cosmetics teconology |
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