CN106397195B - A method of using carboxylic acid and alcohol as Material synthesis ester - Google Patents
A method of using carboxylic acid and alcohol as Material synthesis ester Download PDFInfo
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- CN106397195B CN106397195B CN201610807446.4A CN201610807446A CN106397195B CN 106397195 B CN106397195 B CN 106397195B CN 201610807446 A CN201610807446 A CN 201610807446A CN 106397195 B CN106397195 B CN 106397195B
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- carboxylic acid
- alcohol
- reaction
- acid
- oxalyl chloride
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000002148 esters Chemical class 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title claims abstract description 10
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 230000003213 activating effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 150000007530 organic bases Chemical class 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 26
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000002253 acid Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 230000005311 nuclear magnetism Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 235000019445 benzyl alcohol Nutrition 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- -1 phosphorus compound Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002561 ketenes Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- INOGLHRUEYDAHX-UHFFFAOYSA-N 1-chlorobenzotriazole Chemical compound C1=CC=C2N(Cl)N=NC2=C1 INOGLHRUEYDAHX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AMOYMEBHYUTMKJ-UHFFFAOYSA-N 2-(2-phenylethoxy)ethylbenzene Chemical compound C=1C=CC=CC=1CCOCCC1=CC=CC=C1 AMOYMEBHYUTMKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a kind of using carboxylic acid and alcohol as the method for Material synthesis ester.This method is using triphen phosphine oxide/oxalyl chloride system as carboxylic acid activating agent, and using organic base as catalyst, carboxylic acid and alcohol react under carboxylic acid activating agent and catalyst action and generates ester.The present invention carries out under inert atmosphere protection, and reaction temperature is 10-40 DEG C, and the reaction time is 0.5-5 hours；Triphen oxygen phosphorus in reaction, oxalyl chloride, carboxylic acid and alcohol the mass ratio of the material be (0.5~2): (0.6~2.3): 1:(0.6~2.3).Reaction temperature of the present invention is low, the reaction time is short, carboxylic acid activating agent is cheap and easy to get, and recyclable recycling, reaction cost are low；Byproduct of reaction only has CO and CO2, atom utilization with higher, suitable for industrial application.
Description
Technical field
The invention belongs to technical field of organic synthetic chemistry, and in particular to a kind of using carboxylic acid and alcohol as the side of Material synthesis ester
Method.
Background technique
Carboxylate is a kind of important organic compound, can be used as organic synthesis raw material, and is important fine
Chemical products are widely used in the industries such as fragrance, daily use chemicals, food, medicine, rubber, coating.
Esterification be it is most basic in organic synthesis, one of most common functional group conversions reaction, it is widely used in carboxylic
The protection of acid functional group, further to react synthesis of natural product[1].Due to the extensive use of esterification, to its side of synthesis
The research of method is of great significance.
The method of traditional synthesizing carboxylate is to use the concentrated sulfuric acid to make for catalyst using corresponding carboxylic acid and alcohol as raw material
It takes.This method is by Fischer E and Speier A[2]It was found for the first time in 1895.This side by acid and the direct synthetic ester of alcohol
Method has the advantages that raw material is easy to get, but the method reaction balance is more difficult to control, needs constantly to remove the water in reaction.Except this it
Outside, the method side reaction is more, aftertreatment technology complexity, equipment seriously corroded, spent acid exhaust emission environment[3].Therefore, the ester is improved
Change method is always the emphasis of chemist's research.Based on disadvantage mentioned above, part researcher begins one's study new catalyst, such as:
Molecular sieve catalyst[4], heteropolyacid catalyst[5], solid super acid catalyst[6], resin catalyst[7], acylate and inorganic
Salt catalyst system[8], ionic liquid catalyst systems[9]Deng.But these catalyst all have certain limitation, and such as easy in inactivation is born
It is loaded solid solid (being not easy solution-off), difficult to recycle, severe reaction conditions, at high cost[10]。
Esterification under sulphuric acid catalysis
It can also be that corresponding derivative is condensed with alcohol again by carboxylic acid, instead other than acid and the method for alcohol direct esterification
It should be in the process in addition to generating ester, the small molecule of releasing is not water but other compounds.Here acid derivative be mainly
Refer to the salt of acid anhydrides, acyl chlorides, carboxylic acid.It is this that carboxylic acid derivates, then the method with alcohol generation esterification are obtained by activating carboxy acid
It is compared with the traditional method, raw material can almost convert completely, therefore the yield of obtained ester is also higher.Wherein use variety classes
Carboxylic acid activating agent, such as: acid halide[11-12], mixed acid anhydride[13], ketenes[14], thioester[15], phosphine chemical combination
Object[16-20], carbodiimides[21]Deng.But these methods still have shortcoming, such as: acid halide easily makes itself unstable
Acid degrade, can also with more sensitive carboxylic acid group generation side reaction；Preparing for mixed acid anhydride is more complicated；Ketenes is certainly
Body has limitation, and preparation is difficult, and use scope is not extensive；The coupling process of thioester is more complicated；Carbodiimides is even
The yield of connection is not high, and by-product is not easy to remove.
It was noticed that using phosphorus compound as carboxylic acid activating agent when, reaction condition is relatively mild[22].But utilize three
When phenyl phosphorus is as carboxylic acid activating agent[18-20], it usually needs activator of other auxiliary agents as triphenylphosphine is added, such as azo pyrrole
Pyridine[18], FePC[19], N- chloro benzo triazole[20]It is asked in the presence of preparation difficulty, low yield, at high cost etc. Deng, these reagents
Topic.Moreover, in this kind of reaction finally, generating the triphen phosphine oxide by-product of monovalent, this greatly reduces the atom of reaction
Utilization rate.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide it is a kind of it is novel, green, efficiently with carboxylic acid
It is the method for Material synthesis ester with alcohol.The method of the present invention can solve in the prior art synthetic ester severe reaction conditions, purification difficult,
Problem at high cost.
It is proposed in the present invention a kind of based on the carboxylic acid activated system of triphen oxygen phosphorus/oxalyl chloride, the triphen oxygen phosphorus/oxalyl chloride body
System effectively activating carboxy acid can generate corresponding carboxylate, thus the progress for promoting carboxylic acid alcohol esterification to react.Meanwhile triphen oxygen
Phosphorus is more easy to get relative to triphenylphosphine, and oxalyl chloride is then a kind of common agents, and therefore, the reagent that this method uses is inexpensive easily
, reaction cost is reduced, while the yield of esterification is also higher.
Technical solution of the present invention is specifically described as follows.
The present invention provide it is a kind of using carboxylic acid and alcohol as the method for Material synthesis ester, using carboxylic acid and alcohol as raw material, with triphen
Oxygen phosphorus/oxalyl chloride system is as carboxylic acid activating agent, and using organic base as catalyst, carboxylic acid and alcohol are made in carboxylic acid activating agent and catalyst
Ester is obtained with lower reaction.
In the present invention, the carboxylic acid is aromatic acid or fatty acid, and the alcohol is aromatic alcohol or fatty alcohol.
In the present invention, under an inert atmosphere, synthetic ester is reacted in organic solvent, reaction temperature is 10-40 DEG C, reaction
Time is 0.5-5 hours, triphen oxygen phosphorus, oxalyl chloride, carboxylic acid and alcohol the mass ratio of the material be (0.5~2): (0.6~2.3): 1:
(0.6~2.3).
In the present invention, organic base is any in triethylamine, pyridine or tetramethylethylenediamine.The dosage of organic base is
Catalytic amount.
In the present invention, organic solvent is acetonitrile, methylene chloride, toluene or 1, any one in 2- dichloroethanes.
Compared with the method for conventional synthesis ester, the beneficial effects of the present invention are:
(1) 85% or more, reaction condition is mild, anti-for the method high conversion rate of synthetic ester provided by the present invention, yield
Answer that system is simple, reaction cost is low；
(2) compared with the general method for promoting Lipase absobed by activating carboxy acid, activator triphen used in the present invention
Oxygen phosphorus is cheap and easy to get, and recycling can be recycled after the completion of reaction, and the by-product of reaction system only has CO and CO2, have
Higher atom utilization and lower reaction cost.
Specific embodiment
The technology of the present invention is described further below by specific example and in conjunction with nuclear magnetic data, but protection of the invention
Range is not limited to following examples.
Embodiment 1 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL is added, magnetic force stirs
The oxalyl chloride that 0.55mL is slowly added dropwise is mixed down, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then it is added
The benzoic acid of 0.61g, the benzyl alcohol of 0.67mL and the triethylamine of catalytic amount react 2 hours at room temperature, and reaction is tracked with TLC,
Purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, and column chromatographs institute
The yield for obtaining benzyl benzoate is 85.37%, nuclear magnetic data:1H NMR(500MHz,CDCl3) δ 8.13 (d, J=7.8Hz,
2H), 7.59 (t, J=7.4Hz, 1H), 7.48 (dt, J=11.8,5.8Hz, 4H), 7.43 (dd, J=14.7,7.3Hz, 2H),
7.40–7.36(m,1H),5.41(s,1H).
Embodiment 2 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL is added, magnetic force stirs
The oxalyl chloride that 0.55mL is slowly added dropwise is mixed down, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then it is added
The benzoic acid of 0.61g, the benzyl alcohol of 0.52mL and the tetramethylethylenediamine of catalytic amount react 2 hours at room temperature, and reaction is used
TLC tracking purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1,
The yield of column chromatography gained benzyl benzoate is 69.37%, nuclear magnetic data:1H NMR(500MHz,CDCl3) δ 8.13 (d, J=
7.8Hz, 2H), 7.59 (t, J=7.4Hz, 1H), 7.48 (dt, J=11.8,5.8Hz, 4H), 7.43 (dd, J=14.7,
7.3Hz,2H),7.40–7.36(m,1H),5.41(s,1H).
Embodiment 3 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.5)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.63mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.68g is added
P-methylbenzoic acid, the benzyl alcohol of 0.67mL and the triethylamine of catalytic amount react 2 hours at room temperature, reaction with TLC with
Track purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column layer
The yield of analysis gained p-methylbenzoic acid benzene methyl is 84.25%, nuclear magnetic data:1H NMR(500MHz,CDCl3)δ8.09–
8.02 (m, 2H), 7.53-7.39 (m, 5H), 7.29 (d, J=7.9Hz, 2H), 5.42 (s, 2H), 2.45 (s, 3H)
Embodiment 4 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/2/1.5)
The triphen phosphine oxide of 2.80g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.63mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.68g is added
P-methylbenzoic acid, the benzyl alcohol of 0.67mL and the triethylamine of catalytic amount react 2 hours at room temperature, reaction with TLC with
Track purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column layer
The yield of analysis gained p-methylbenzoic acid benzene methyl is 78.25%, nuclear magnetic data:1H NMR(500MHz,CDCl3)δ8.09–
8.02 (m, 2H), 7.53-7.39 (m, 5H), 7.29 (d, J=7.9Hz, 2H), 5.42 (s, 2H), 2.45 (s, 3H)
Embodiment 5 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/0.5)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.21mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.76g is added
P-methoxybenzoic acid, the benzyl alcohol of 0.67mL and the pyridine of catalytic amount react 2 hours at room temperature, reaction with TLC with
Track purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column layer
The yield of analysis gained P-methoxybenzoic acid benzene methyl is 70.21%, nuclear magnetic data:1H NMR(500MHz,CDCl3)δ8.07
(d, J=8.7Hz, 2H), 7.46 (t, J=11.2Hz, 2H), 7.42-7.30 (m, 3H), 6.94 (d, J=8.8Hz, 2H), 5.37
(s,2H),3.87(s,3H).
Embodiment 6 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.84g is added
Paranitrobenzoic acid, the benzyl alcohol of 0.67mL and the triethylamine of catalytic amount react 2 hours at room temperature, reaction with TLC with
Track purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column layer
The yield of analysis gained paranitrobenzoic acid benzene methyl is 90.31%, nuclear magnetic data:1H NMR(500MHz,CDCl3)δ8.28(dd,
J=22.5,8.9Hz, 4H), 7.57-7.29 (m, 5H), 5.43 (s, 2H)
Embodiment 7 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.61g is added
Benzoic acid, the cyclohexanol of 0.60mL and the triethylamine of catalytic amount react 2 hours at room temperature, and reaction is tracked with TLC, with column layer
Analysis purify quantitatively, is carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column chromatography gained benzene first
The yield of sour cyclohexyl is 85.27%, nuclear magnetic data:1H NMR(500MHz,CDCl3) δ 8.07 (d, J=7.5Hz, 2H), 7.57
(t, J=7.4Hz, 1H), 7.45 (t, J=7.7Hz, 2H), 4.40-4.31 (m, 2H), 1.77 (dd, J=14.6,6.9Hz,
2H), 1.55-1.46 (m, 2H), 1.00 (t, J=7.4Hz, 3H)
Embodiment 8 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then it is added
The acetic acid of 0.29ml, the benzyl alcohol of 0.67mL and the triethylamine of catalytic amount react 2 hours at room temperature, and reaction is tracked with TLC,
Purify quantitatively with column chromatography, be carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, and column chromatographs institute
The yield for obtaining phenylmethyl acetate is 70.09%, nuclear magnetic data:1H NMR(500MHz,CDCl3)δ7.47–7.27(m,5H),5.14
(s,2H),2.13(s,3H).
Embodiment 9 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.61g is added
Benzoic acid, the benzyl carbinol of 0.78mL and the triethylamine of catalytic amount react 2 hours at room temperature, and reaction is tracked with TLC, with column layer
Analysis purify quantitatively, is carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column chromatography gained benzene first
The yield of sour phenethyl ester is 72.57%, nuclear magnetic data:1H NMR(500MHz,CDCl3) δ 8.08 (d, J=7.4Hz, 2H), 7.59
(t, J=7.4Hz, 1H), 7.47 (t, J=7.7Hz, 2H), 7.40-7.30 (m, 5H), 4.59 (t, J=7.0Hz, 2H), 3.13
(t, J=7.0Hz, 2H)
Embodiment 10 (acid: alcohol: triphen oxygen phosphorus: oxalyl chloride=1/1.3/1/1.3)
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flask, vacuumizes logical N2, the acetonitrile of 5mL, magnetic agitation is added
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction at this time acutely, releases a large amount of gas, reacts 10 minutes.Then 0.61g is added
Cinnamic acid, the benzyl alcohol of 0.67mL and the triethylamine of catalytic amount react 2 hours at room temperature, and reaction is tracked with TLC, with column layer
Analysis purify quantitatively, is carried out with nuclear-magnetism qualitative.Solvent (petrol ether/ethyl acetate) proportion is 4:1, column chromatography gained cortex cinnamomi
The yield of acid benzyl ester is 95.04%, nuclear magnetic data:1H NMR(501MHz,CDCl3) δ 7.80 (d, J=16.0Hz, 1H), 7.56
(s, 2H), 7.50-7.38 (m, 8H), 6.55 (d, J=16.0Hz, 1H), 5.32 (s, 2H)
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Claims (5)
1. a kind of using carboxylic acid and alcohol as the method for Material synthesis ester, which is characterized in that it is using carboxylic acid and alcohol as raw material, with triphen oxygen
Phosphorus/oxalyl chloride system is as carboxylic acid activating agent, and using organic base as catalyst, carboxylic acid and alcohol are in carboxylic acid activating agent and catalyst action
Lower reaction obtains ester, and the organic base is any in triethylamine, pyridine or tetramethylethylenediamine.
2. the method according to claim 1, wherein the carboxylic acid is aromatic acid or fatty acid.
3. the method according to claim 1, wherein the alcohol is aromatic alcohol or fatty alcohol.
4. the method according to claim 1, wherein under an inert atmosphere, react synthetic ester in organic solvent,
Its reaction temperature is 10-40 DEG C, and the reaction time is 0.5-5 hours, the mass ratio of the material of triphen oxygen phosphorus, oxalyl chloride, carboxylic acid and alcohol
It is (0.5~2): (0.6~2.3): 1:(0.6~2.3).
5. the method according to claim 1, wherein organic solvent is acetonitrile, methylene chloride, toluene or 1,2- bis-
Any one in chloroethanes.
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| A novel and highly efficient esterification process using triphenylphosphine oxide with oxalyl chloride;Mingzhu Jia et al.;《Roral society open science》;20180116;1-12 |
| A procedure for Appel halogenations and dehydrations using a polystyrene supported phosphine oxide;Xiaoping Tang et al.;《Tetrahedron Letters》;20141231;799-802 |
| Phosphine oxide-catalysed chlorination reactions of alcohols under Appel conditions;Ross M. Denton et al.;《ChemComm》;20101231;3025-3027 |
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