CN106431921B - The synthetic method of 3- hydroxy propionates - Google Patents

The synthetic method of 3- hydroxy propionates Download PDF

Info

Publication number
CN106431921B
CN106431921B CN201510493269.2A CN201510493269A CN106431921B CN 106431921 B CN106431921 B CN 106431921B CN 201510493269 A CN201510493269 A CN 201510493269A CN 106431921 B CN106431921 B CN 106431921B
Authority
CN
China
Prior art keywords
reaction
synthetic method
propionates
hydroxy
alcohol
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.)
Active
Application number
CN201510493269.2A
Other languages
Chinese (zh)
Other versions
CN106431921A (en
Inventor
刘波
吕建刚
金照生
李晓明
周海春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201510493269.2A priority Critical patent/CN106431921B/en
Publication of CN106431921A publication Critical patent/CN106431921A/en
Application granted granted Critical
Publication of CN106431921B publication Critical patent/CN106431921B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a kind of synthetic methods of 3- hydroxy propionates, mainly solve the problems, such as that the selectivity of 3- hydroxy propionates in the prior art is low, by using the synthetic method of 3- hydroxy propionates, include the following steps：I, so that ligand shown in formula (I) is carried out complexation reaction in a solvent with carbonyl cobalt and obtain catalyst solution, the solvent is alcohol or the solvent of containing alcohol；Wherein R1~R3The one kind being independently selected from alkyl or alkenyl, aryl or substituted aryl, Azacyclyl, and R1~R3It is middle independently to contain 1~6 carbon atom；Ii, into above-mentioned catalyst solution, ethylene oxide and carbon monoxide is added, the technical solution of the 3- hydroxy propionates is obtained by the reaction, preferably solves the technical problem, can be used in the industrial production of 3- hydroxy propionates.

Description

The synthetic method of 3- hydroxy propionates
Technical field
The present invention relates to a kind of synthetic methods of 3- hydroxy propionates.
Background technology
1,3-PD is a kind of important organic fine chemicals, can be used as produce antifreezing agent, plasticizer, preservative and The raw material of emulsifier, is also widely used in the industries such as food, cosmetics and pharmacy, and most important application is synthesized as monomer Polypropylene terephthalate (PTT) polyester fiber, compared with common polyethylene terephthalate (PET) fiber, Ptt fiber not only had light resistance, water suction less, the excellent performances such as stability is good, but also it is good with resilience, easily biological-degradable with The advantages that environmental pollution is small is with a wide range of applications, and is the focus researched and developed at present.
3- hydroxy propionates are the important intermediates for synthesizing 1,3-PD, and hydrogenation under appropriate conditions can be obtained 1,3- propylene glycol.3- hydroxy propionates can be prepared by ethylene oxide hydroesterification reaction, by taking 3- hydroxy methyl propionates as an example, be closed Indicate as follows at reaction：
The major progress obtained at present is as follows：
Nineteen ninety, US4973741 are disclosed using Noble Metal Rhodium catalyst and triphenylphosphine ligand, ethylene oxide hydrogen methyl esters Base is combined to 3- hydroxy methyl propionates, but reaction needs the high pressure of 14MPa, and ethylene oxide conversion ratio and target product Selectivity is relatively low.
2001, US6191321 was disclosed using Co2(CO)8The catalyst system of/1,10- phenanthroline, methyl- tert fourth Base ether is that solvent reacts 18 hours, ethylene oxide conversion ratio is only 11%, target product 3- at 90 DEG C under conditions of 7.8MPa The selectivity of hydroxy methyl propionate is 74%.
2002, EP1179524A1 was disclosed using cobalt salt as catalyst, and N- alkyl azole compounds are ligand, and methanol is The method that solvent synthesizes 3- hydroxy methyl propionates, wherein target product selectivity is up to 90%.
2003, US6521801 was disclosed using cobalt salt as catalyst, and nitrogen-containing heterocycle compound is ligand, in carbon monoxide Pressure is 6MPa, and reaction temperature is under 75 DEG C of reaction condition, ethylene oxide conversion ratio is 94%, target product 3- hydracrylic acids The selectivity of methyl esters is 78%.
2007, CN101020635A (preparation method of 3- hydroxy propionates and 1,3-PD) is disclosed was with cobalt salt Catalyst, pyridine, quinoline and its respective derivative are ligand, and alkaline or alkaline-earth salts are accelerating agent, pressure be 3.0MPa~ 7.0MPa, reaction temperature are 50 DEG C~100 DEG C, are reacted 3 hours~5 hours, the selectivity of target product 3- hydroxy methyl propionates Up to 90%.
2011, CN101973881A was disclosed using carbonyl cobalt functionalized ion liquid as catalyst, is cyclized with nitrogen-containing hetero It is ligand to close object or organic phosphine, and the pressure of carbon monoxide is 3.0MPa~7.0MPa, and reaction temperature is 50 DEG C~100 DEG C, reaction Time is 6 hours~18 hours, and for the conversion ratio of ethylene oxide up to 98.1%, the yield of target product 3- hydroxy methyl propionates can Up to 90.8%.
But prior art reaction temperature is relatively high, and energy consumption is big, and the selectivity of 3- hydroxy propionates is still relatively low.
Invention content
The technical problem to be solved by the present invention is to the low problems of the selectivity of 3- hydroxy propionates in the prior art, provide A kind of synthetic method of new 3- hydroxy propionates, this method have the advantages that 3- hydroxy propionate high selectivities.
In order to solve the above technical problems, technical scheme is as follows：The synthetic method of 3- hydroxy propionates, including such as Lower step：
I, so that ligand shown in formula (I) is carried out complexation reaction in a solvent with carbonyl cobalt and obtain catalyst solution, it is described molten Agent is alcohol or the solvent of containing alcohol；
Wherein R1~R3The one kind being independently selected from alkyl or alkenyl, aryl or substituted aryl, Azacyclyl, and R1~ R3It is middle independently to contain 1~6 carbon atom；
Ii, into above-mentioned catalyst solution, ethylene oxide and carbon monoxide is added, the 3- hydracrylic acids are obtained by the reaction Ester.
In above-mentioned technical proposal, the alcohol is preferably the linear chain or branched chain alcohol of C1~C5, such as, but not limited to methanol, second Alcohol.
In above-mentioned technical proposal, R1~R3Independently it preferably is selected from methyl, isopropyl, tertiary butyl, allyl, phenyl, 2,4,6- tri- Aminomethyl phenyl, 2,6- diisopropyl phenyls, benzyl, 2- pyrimidine radicals, 2- pyridyl groups or 2- picolyls.
In above-mentioned technical proposal, the ligand is preferably (1~5) with carbonyl cobalt molar ratio:1.
In above-mentioned technical proposal, it includes alcohol and selected from methyl tertiary butyl ether(MTBE), tetrahydrofuran, 1 that the solvent of the containing alcohol is optional, At least one of 4- dioxane, 1,3- dioxolanes, toluene and chlorobenzene.
In above-mentioned technical proposal, the molar ratio of the methanol and ethylene oxide is preferably (2~25):1.
In above-mentioned technical proposal, reaction pressure is preferably 3MPa~8MPa.
In above-mentioned technical proposal, reaction temperature is preferably 45 DEG C~100 DEG C；More preferably 50 DEG C~80 DEG C.
In above-mentioned technical proposal, the reaction time is preferably 3 hours~8 hours.
The present invention is by designing multiple tooth cheland, polygamy site and Co2(CO)8Collaboration coordination, further increases catalyst Stability, while by change ligand auxiliary group, regulate and control space and the electronic property of ligand, increase the work of catalyst Property, improve the conversion ratio of ethylene oxide and the selectivity of target product.
The present invention can be carried out specifically as follows：
The multiple tooth chelands of i and Co2(CO)8The complexation reaction in the solvent of containing alcohol obtains the solution of catalyst, this is molten Liquid is transferred in reaction kettle；
Ii purges reaction kettle three times with nitrogen, and ethylene oxide is added and CO is reacted；
Iii reactions terminate, and autoclave body is cooled sufficiently to 0 DEG C, and slow pressure release to normal pressure purges reaction kettle three times with nitrogen；
Iv sampling analyses, the conversion ratio of ethylene oxide, the yield of 3- hydroxy propionates are quantitative using gas-chromatography.
Co2(CO)8With toxicity and be easy decompose, therefore catalyst preparation preferably the argon gas of glove box protection under into Row.
The selectivity of 3- hydroxy propionates is improved using the method for the present invention.Experiment shows in carbonyl cobalt, ligand F (see reality Apply example 6), ethylene oxide, Methanol Molar ratio be 1:3:50:Under 740 ratio, reaction pressure 4MPa, reaction 4 is small at 50 DEG C When, the high selectivity of 3- hydroxy propionates achieves preferable technique effect, can be used for the industry of 3- hydroxy propionates up to 95% In production.
Further instruction is given to the present invention below by example, but does not limit present disclosure.
Specific implementation mode
Embodiment 1
1, synthetic ligands A
Addition 1312mg (10mmol) three propargyl amine in 100mL reaction tubes, 2988mg (36mmol) allyl nitrine, 250mg (1mmol) hydrated copper sulfates (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate, the 40mL tert-butyl alcohols and 10mL water, System is replaced three times with nitrogen, and under nitrogen atmosphere, 60 DEG C are reacted 24 hours.Reaction finishes, and 100mL water, dichloromethane is added Extraction solution is multiple, merges organic phase, is concentrated after dry, finally obtaining 1900mg light yellow solids using pillar layer separation is Ligand A.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand A of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 75%, The selectivity of 3- hydroxy methyl propionates is 81%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
Embodiment 2
1, synthetic ligands B
According to the experimentation of embodiment 1, with three propargyl amine of 1312mg (10mmol), 3564mg (36mmol) allyl Nitrine, 375mg (1.5mmol) hydrated copper sulfates (CuSO4·5H2O), 300mg (1.5mmol) sodium ascorbate is raw material, synthesis It is ligand B to obtain 1712mg brown solids.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand B of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 83%, The selectivity of 3- hydroxy methyl propionates is 90%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
Embodiment 3
1, synthetic ligands C
According to the experimentation of embodiment 1, with three propargyl amine of 1312mg (10mmol), 4284mg (36mmol) phenyl Nitrine, 250mg (1mmol) hydrated copper sulfates (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2196mg white solids are ligand C.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand C of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 88%, The selectivity of 3- hydroxy methyl propionates is 74%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
Embodiment 4
1, synthetic ligands D
According to the experimentation of embodiment 1, with three propargyl amine of 1312mg (10mmol), 5796mg (36mmol) equal front three Aziminobenzene, 500mg (2mmol) hydrated copper sulfates (CuSO4·5H2O), 400mg (2mmol) sodium ascorbate is raw material, is obtained 1842mg yellow solids are ligand D.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand D of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is The selectivity of 77%, 3- hydroxy methyl propionate is 91%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
Embodiment 5
1, synthetic ligands E
According to the experimentation of embodiment 1, with three propargyl amine of 1312mg (10mmol), 4788mg (36mmol) benzyl is folded Nitrogen, 250mg (1mmol) hydrated copper sulfates (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2915mg light yellow solids are ligand E.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand E of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 84%, The selectivity of 3- hydroxy methyl propionates is 82%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
Embodiment 6
1, synthetic ligands F
According to the experimentation of embodiment 1, with three propargyl amine of 1312mg (10mmol), 4356mg (36mmol) pyrimidine radicals Nitrine, 250mg (1mmol) hydrated copper sulfates (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2616mg brown solids are ligand F.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand F of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 92%, The selectivity of 3- hydroxy methyl propionates is 95%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
Embodiment 7
1, synthetic ligands G
According to the experimentation of embodiment 1, with three propargyl amine of 1312mg (10mmol), 4824mg (36mmol) pyridine Methyl azide, 250mg (1mmol) hydrated copper sulfates (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, synthesis It is ligand G to obtain 2140mg yellow solids.
2,3- hydroxy methyl propionates synthesize
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the ligand G of 3.0mmol, room temperature is added Lower stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, 50mmol is added Ethylene oxide, carbon monoxide, make system pressure be 4.0MPa, reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 89%, The selectivity of 3- hydroxy methyl propionates is 92%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
【Comparative example 1】
Other than replacing ligand A using pyridine, 3- hydroxy methyl propionate synthesis conditions are same as Example 1, specially：
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the pyridine of 3.0mmol is added, at room temperature Stirring 2 hours.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, is added 50mmol's Ethylene oxide, carbon monoxide, it is 4.0MPa to make system pressure, is reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently to 0 DEG C, is delayed Slow pressure release purges reaction kettle three times to normal pressure, with nitrogen, sampling analysis, the results showed that：The conversion ratio of ethylene oxide is 81%, 3- The selectivity of hydroxy methyl propionate is 76%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
【Comparative example 2】
In addition to using 2,2 '-bipyridyls to replace other than ligand A, 3- hydroxy methyl propionate synthesis conditions are same as Example 1, Specially：
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the 2 of 3.0mmol, 2 '-connection pyrroles is added Pyridine is stirred 2 hours at room temperature.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, is added Ethylene oxide, the carbon monoxide for entering 50mmol, it is 4.0MPa to make system pressure, is reacted 4 hours at 50 DEG C.Autoclave body is through fully cold But to 0 DEG C, slow pressure release to normal pressure purges reaction kettle three times, sampling analysis with nitrogen, the results showed that：The conversion of ethylene oxide Rate is that the selectivity of 53%, 3- hydroxy methyl propionates is 68%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
【Comparative example 3】
In addition to using 1,10- phenanthrolines to replace other than ligand A, 3- hydroxy methyl propionates synthesis condition and 1 phase of embodiment Together, specially：
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the adjacent luxuriant and rich with fragrance hello of 1,10- of 3.0mmol is added Quinoline stirs 2 hours at room temperature.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, is added Ethylene oxide, the carbon monoxide for entering 50mmol, it is 4.0MPa to make system pressure, is reacted 4 hours at 50 DEG C.Autoclave body is through fully cold But to 0 DEG C, slow pressure release to normal pressure purges reaction kettle three times, sampling analysis with nitrogen, the results showed that：The conversion of ethylene oxide Rate is that the selectivity of 62%, 3- hydroxy methyl propionates is 75%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
【Comparative example 4】
Other than replacing ligand A using N- methylimidazoles, 3- hydroxy methyl propionate synthesis conditions are same as Example 1, Specially：
By the Co of 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the N- methylimidazoles of 3.0mmol is added, It stirs 2 hours at room temperature.Catalyst solution is transferred in the reaction kettle of 100mL, three times with nitrogen purging reaction kettle, is added Ethylene oxide, the carbon monoxide of 50mmol, it is 4.0MPa to make system pressure, is reacted 4 hours at 50 DEG C.Autoclave body is cooled sufficiently To 0 DEG C, slow pressure release to normal pressure purges reaction kettle three times, sampling analysis with nitrogen, the results showed that：The conversion ratio of ethylene oxide Selectivity for 74%, 3- hydroxy methyl propionates is 80%.
For ease of comparing, by 3- hydroxy methyl propionates synthetic reaction, the results are shown in Table 1.
From the data in table it is found that common ligand compared with the existing technology, the multiple tooth cheland that we design can be with Significantly increase the activity of catalyst, and the selectivity of reaction, it is expected in the industrial production of 3- hydroxy propionates.Table 1

Claims (8)

1. a kind of synthetic method of 3- hydroxy propionates, includes the following steps：
I, so that ligand shown in formula (I) is carried out complexation reaction in a solvent with carbonyl cobalt and obtain catalyst solution, the solvent is The solvent of alcohol or containing alcohol；
Wherein, R1~R3It is independently selected from methyl, isopropyl, tertiary butyl, allyl, phenyl, 2,4,6- trimethylphenyls, 2,6- bis- Isopropyl phenyl, benzyl, 2- pyrimidine radicals, 2- pyridyl groups or 2- picolyls；
Ii, into above-mentioned catalyst solution, ethylene oxide and carbon monoxide is added, the 3- hydroxy propionates are obtained by the reaction.
2. synthetic method according to claim 1, it is characterised in that alcohol is the linear chain or branched chain alcohol of C1~C5.
3. synthetic method according to claim 1, it is characterised in that the ligand is (1~5) with carbonyl cobalt molar ratio:1.
4. synthetic method according to claim 1, it is characterised in that the solvent of the containing alcohol include alcohol and be selected from methyl- tert At least one of butyl ether, tetrahydrofuran, 1,4- dioxane, 1,3- dioxolanes, toluene and chlorobenzene.
5. synthetic method according to claim 1, which is characterized in that the molar ratio of the alcohol and ethylene oxide be (2~ 25):1。
6. synthetic method according to claim 1, it is characterised in that reaction pressure is 3MPa~8MPa.
7. synthetic method according to claim 1, it is characterised in that reaction temperature is 45 DEG C~100 DEG C.
8. synthetic method according to claim 1, which is characterized in that the reaction time is 3 hours~8 hours.
CN201510493269.2A 2015-08-12 2015-08-12 The synthetic method of 3- hydroxy propionates Active CN106431921B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510493269.2A CN106431921B (en) 2015-08-12 2015-08-12 The synthetic method of 3- hydroxy propionates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510493269.2A CN106431921B (en) 2015-08-12 2015-08-12 The synthetic method of 3- hydroxy propionates

Publications (2)

Publication Number Publication Date
CN106431921A CN106431921A (en) 2017-02-22
CN106431921B true CN106431921B (en) 2018-10-23

Family

ID=58092877

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510493269.2A Active CN106431921B (en) 2015-08-12 2015-08-12 The synthetic method of 3- hydroxy propionates

Country Status (1)

Country Link
CN (1) CN106431921B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678710B (en) * 2017-10-19 2022-02-01 中国石油化工股份有限公司 Synthesis method of methyl 3-hydroxypropionate
CN114425451B (en) * 2020-10-14 2024-01-30 中国石油化工股份有限公司 Catalyst for synthesizing 3-hydroxy propionate and preparation and use methods thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260738A (en) * 1965-08-09 1966-07-12 Shell Oil Co Hydracrylate ester production
CN1267569A (en) * 1999-03-09 2000-09-27 三星电子株式会社 Carbonylation method for epoxide derivate
CN101143823A (en) * 2006-09-11 2008-03-19 中国科学院兰州化学物理研究所 Method for preparing optical activity 3-hydroxycarboxylate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260738A (en) * 1965-08-09 1966-07-12 Shell Oil Co Hydracrylate ester production
CN1267569A (en) * 1999-03-09 2000-09-27 三星电子株式会社 Carbonylation method for epoxide derivate
CN101143823A (en) * 2006-09-11 2008-03-19 中国科学院兰州化学物理研究所 Method for preparing optical activity 3-hydroxycarboxylate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
环氧乙烷氢甲酯化的催化体系研究;张业 等;《精细化工》;20130831;第29卷(第8期);全文 *

Also Published As

Publication number Publication date
CN106431921A (en) 2017-02-22

Similar Documents

Publication Publication Date Title
Song et al. Efficient chemical fixation of CO 2 promoted by a bifunctional Ag 2 WO 4/Ph 3 P system
EP2744815B1 (en) Hydrogenation and dehydrogenation catalyst, and methods of making and using the same
CN111205198B (en) Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation through porous material
Clarke et al. Highly Regioselective Rhodium‐Catalysed Hydroformylation of Unsaturated Esters: The First Practical Method for Quaternary Selective Carbonylation
WO2015083007A1 (en) Metal-ligand cooperative catalysis through n-h arm deprotonation/pyridine dearomatiztion for efficient hydrogen generation from formic acid
Shi et al. Ruthenium complexes bearing an unsymmetrical pincer ligand with a 2-hydroxypyridylmethylene fragment: active catalysts for transfer hydrogenation of ketones
CN106431921B (en) The synthetic method of 3- hydroxy propionates
WO2022050236A1 (en) Production method for alkaline earth metal formate
Liu et al. Synthesis, characterization and catalytic performances of benzimidazolin-2-iminato actinide (IV) complexes in the Tishchenko reactions for symmetrical and unsymmetrical esters
Yu et al. Imidazolium chiral ionic liquid derived carbene-catalyzed conjugate umpolung for synthesis of γ-butyrolactones
CN105688987A (en) Novel chiral phosphoric acid catalyst as well as synthetic method and application thereof
KR20140041711A (en) Palladium complex and method for producing same, method for producing vinyl ether compound, and method for collecting palladium complex
CN107459451A (en) The preparation method of 3 hydroxy methyl propionates
CN109942433A (en) A kind of chemical synthesis process of 3 ', 4 ', 5 '-three fluoro- 2- aminobphenyls
AU2018260727B2 (en) Process for the preparation of deuterated ethanol from D2O
CN105884692A (en) Method for preparing 5-substituted chiral hydantoin
EP2242579B1 (en) Method for preparing ester compounds
Guyon et al. Transition-Metal-Free Enantioselective Reactions of Organomagnesium Reagents Mediated by Chiral Ligands
TWI233922B (en) One step hydroformylation and hydrogenation process for preparing a 1,3-diol
JP6345531B2 (en) Carbon monoxide production method
CN109020922B (en) Preparation method of cyclic sulfonamide compound
CN114425451B (en) Catalyst for synthesizing 3-hydroxy propionate and preparation and use methods thereof
CN109954516B (en) Salen/Ru catalyst for preparing chiral trans-first chrysanthemic acid
JP5854345B2 (en) Method for producing dimer
CN109678710B (en) Synthesis method of methyl 3-hydroxypropionate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant