CN109694324A - A kind of preparation method of methyl benzoate - Google Patents
A kind of preparation method of methyl benzoate Download PDFInfo
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- CN109694324A CN109694324A CN201711002640.6A CN201711002640A CN109694324A CN 109694324 A CN109694324 A CN 109694324A CN 201711002640 A CN201711002640 A CN 201711002640A CN 109694324 A CN109694324 A CN 109694324A
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- methyl benzoate
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- catalyst
- ionic liquid
- phosphonium salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (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 preparation method of methyl benzoate, preparation process are as follows: benzoic acid, methanol and catalyst are put into reactor and carry out esterification, separation is then carried out and purification obtains methyl benzoate.Catalyst Wei quaternary phosphonium salt ionic liquid catalyst, the general formula of the quaternary phosphonium salt ionic liquid are [Bu3PR]+X‑, in which: R C6‑C16Straight chained alkyl, naphthenic base or isomery alkyl, the X‑For p-C7H7SO3 ‑、CF3SO3 ‑、HSO4 ‑Or H2PO4 ‑.The present invention carries out esterification with quaternary phosphonium salt ionic liquid catalyst and generates methyl benzoate, optimizes the effect of esterification, and catalyst activity is high, and by-product is few, and performance height is recycled, and is conducive to improve product selectivity and product yield, reduces production cost.
Description
Technical field
The invention belongs to chemicals preparation technical fields, are related to a kind of preparation method of methyl benzoate.
Background technique
Methyl benzoate chemically can be considered the product of benzoic acid or benzoyl oxide or chlorobenzoyl chloride Methanolysis.Nothing
Color transparency liquid.It can be miscible with methanol, ethyl alcohol, ether.It is not soluble in water.Industrially can be used as organic synthesis intermediate, solvent,
Fragrance.Food is also largely used to for preparing perfume fragrance and artificial essential oil with strong wintergreen and You Nan character used in proper names and in rendering some foreign names incense oil gas
In.
The method of industrial synthesizing benzoic acids methyl esters mainly uses the concentrated sulfuric acid to make catalyst, anti-with methanol by benzoic acid
It should be made, the disadvantages of that there are by-products is more for the process route, corrosivity is big, product separating technique is complicated, pollution environment.
104592027 A Chinese invention patent application of Publication No. CN disclose " a kind of preparation method of methyl benzoate,
It is related to methyl benzoate.By benzoic acid and methanol Hybrid Heating in batching kettle, reactive distillation column is input to by feed pump and is urged
Agent filled section top, benzoic acid and methanol react under the action of catalyst ... ..., obtained methyl benzoate product purity
Height is free of methanol, eliminates postprocessing working procedures ".But the catalyst that the patent application uses is solid catalyst, and is loaded
In fractionating column.Solid catalyst preparation process is complicated, expensive, and frequent regeneration is needed in production process.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of methyl benzoate, and using ionic liquid as catalyst, optimization is urged
Change reaction process, improve product selectivity and yield, reduces production cost.
The technical scheme is that the preparation method of methyl benzoate, preparation process are as follows: by benzoic acid, methanol and urge
Agent is put into reactor and carries out esterification, then carries out separation and distilation is prepared into methyl benzoate.Catalyst is season
Phosphonium salt ionic-liquid catalyst, the general formula of the quaternary phosphonium salt ionic liquid are [Bu3PR]+X-, in which: R C6-C16Straight chained alkyl,
Naphthenic base or isomery alkyl, the X-For p-C7H7SO3 -、CF3SO3 -、HSO4 -Or H2PO4 -。
It is preferred that R is C8~C14Straight chained alkyl, naphthenic base or isomery alkyl, X-For p-C7H7SO3 -Or CF3SO3 - -.Benzene first
The molar ratio of acid and methanol is 1: 1~10, preferably 2: 2-5.The dosage of quaternary phosphonium salt ionic liquid is the 3~40 of reactant weight
%(weight), preferably 5~20%(weight), reactant weight is the total weight of benzoic acid and methanol.The condition of esterification are as follows: anti-
Answer 50~200 DEG C of temperature, preferably 65~150 DEG C；Reaction time 1~10 hour, preferably 2~6 hours.
After the esterification of benzoic acid and alcohol, by obtained ester and the carboxylic not reacted completely by way of distillation
Acid and/or the organic matter containing hydroxyl are separated from obtained product, distill remaining bottom liquid urging as esterification
Agent is recycled.
The preparation method of methyl benzoate of the present invention carries out esterification as catalyst using quaternary phosphonium salt ionic liquid and generates benzene
Methyl formate optimizes esterification effect, and catalyst activity is high, and by-product is few, and performance height is recycled, and is conducive to
Product selectivity and product yield are improved, production cost is reduced.The present invention prepares methyl benzoate phase with traditional sulfuric acid catalyst
Than having preparation process without caustic scrubbing step, being environmentally protective chemical process the advantages of no waste water and waste sludge discharge.
Detailed description of the invention
Fig. 1 is the methyl benzoate chromatogram of methyl benzoate preparation method of the present invention preparation；
Fig. 2 is the chromatogram of commercially available methyl benzoate；
Fig. 3 is [Bu3PC14H29]+[CF3SO3]-TG and DSC curve figure；
Fig. 4 is [Bu3PC14H29]+[CF3SO3]-infrared spectrogram.
Specific embodiment
The present invention is described in detail below.The scope of protection of the present invention is not limited to the embodiment, and those skilled in the art exist
Claim makes any change and also belongs to the scope of protection of the invention in the range of limiting.
The preparation of 1 quaternary phosphonium salt ionic liquid catalyst of embodiment
The present invention is prepared in accordance with the following steps using quaternary phosphonium salt ionic liquid: under the conditions of ion-exchange reactions, by
Yi quaternary alkylphosphonium salt is contacted with Bronsted acid, obtains product of contact.Wherein, the general formula of mono- quaternary alkylphosphonium salt is [Bu3PR]+Z-, R C6-C16's
Linear or branched alkyl group, Z are halogen.The general formula of Bronsted acid is H+X-, X-Selected from p-C7H7SO3 -、CF3SO3 -、HSO4 -And H2PO4 -In
At least one.Mono- quaternary alkylphosphonium salt can be commercially available, and can also be prepared using method well known to those skilled in the art
It obtains, mono- quaternary alkylphosphonium salt includes but is not limited to [Bu3PC12H25]+ Cl-、[Bu3PC14H29]+C-、[Bu3PC10H21]+Cl-With
[Bu3PC8H17]+Cl-。
Quaternary phosphonium salt ionic liquid is [Bu3PC14H29]+[CF3SO3]-Preparation: n-tetradecane base tributyl phosphonium chloride (is purchased from
Jiangxi Run Yu Science and Technology Ltd.) it is added in the reaction flask with stirring, thermometer and reflux condensation mode, stirring is opened, is then delayed
It is slow that trifluoromethanesulfonic acid (analytical reagents recovers fine chemistry industry research institute purchased from Tianjin) is added dropwise, it is stirred at room temperature after dripping
1h is mixed, is then to slowly warm up to 95 DEG C, insulation reaction 18 hours；Wherein, relative to 1 mole of the n-tetradecane base tributyl
Phosphonium chloride, the dosage of trifluoromethanesulfonic acid are 1.05 moles.
After reaction, reaction product is washed to pH with trifluoromethanesulfonic acid saturated aqueous solution of sodium is 2~3, then by water
Organic layer after washing carries out vacuum distillation water removal, is filtered again after cooling, removes a small amount of salinity of precipitation, obtain filtrate.It is right
Filtrate carries out TG and DSC and infrared spectrum analysis, Fig. 4 infrared spectrogram, and Fig. 3 is TG and DSC curve, wherein 1259 cm-1For O
=S=O antisymmetric stretching vibration absorption peak, 1151 cm-1For S=O stretching vibration absworption peak, 1032 cm-1It symmetrically stretches for O=S=O
Vibration absorption peak, it was demonstrated that obtained filtrate is quaternary phosphonium salt ionic liquid [Bu3PC14H29]+[CF3SO3]-。
The preparation of 2 methyl benzoate of embodiment
(1) esterification: 61.73 benzoic acid, 80.96g methanol and 7.14g quaternary phosphine salt ion are added in 500ml autoclave
Liquid (molar ratio of benzoic acid and methanol is the 5%(weight that 1:5 , quaternary phosphonium salt ionic liquid catalyst is reactant total weight),
Quaternary phosphonium salt ionic liquid is [Bu3PC14H29]+[ p-C7H7SO3]-.Starting stirring (350 revs/min), then starting heating will
High pressure temperature in the kettle starts timing to 130 DEG C, reacts 3h；
(2) methyl benzoate isolates and purifies: 1. after reaction, closing heating power supply, is cooled to room temperature, stops stirring, will react
Liquid is transferred to distilling apparatus (normal pressure), heat temperature raising, and distillation steams unreacted methanol.After 2. no methanol steams, heating is closed,
Cooling, is changed to vacuum distillation apparatus (circulating water type vacuum pump) for atmospheric distillation plant, heats up again, collects fraction (kettle temperature 150
DEG C).Fraction 42.92g is collected altogether；
(3) analysis detection: the sampling of the fraction that vacuum distillation is obtained, i.e. methyl benzoate carries out gas chromatographic analysis, purity
99.3%；
The yield that can be calculated methyl benzoate is 62.4%(based on benzoic acid).
The preparation of 3 methyl benzoate of embodiment
(1) esterification: be added in 500ml autoclave 54.05 benzoic acid, 70.88g methanol and 24.99g quaternary alkylphosphonium salt from
(molar ratio of benzoic acid and methanol is the 20%(weight that 1:5 , quaternary phosphonium salt ionic liquid catalyst is reactant total weight to sub- liquid
Amount) , quaternary phosphonium salt ionic liquid is [Bu3PC14H29]+[ p-C7H7SO3]-.Starting stirring (350 revs/min), then starting adds
Heat by high pressure temperature in the kettle to 130 DEG C, and starts timing, reacts 3h；
(2) methyl benzoate isolates and purifies: operating method and step collect fraction 44.37g with embodiment 2 altogether；
(3) analysis detection: the sampling of the fraction that vacuum distillation is obtained, i.e. methyl benzoate carries out gas chromatographic analysis, purity
99.6%；
The yield that can be calculated methyl benzoate is 73.1%(based on benzoic acid).
The preparation of 4 methyl benzoate of embodiment
(1) esterification: be added in 500ml autoclave 40.38 benzoic acid, 84.84g methanol and 25.00g quaternary alkylphosphonium salt from
(molar ratio of benzoic acid and methanol is the 20%(weight that 1:8 , quaternary phosphonium salt ionic liquid catalyst is reactant total weight to sub- liquid
Amount) , quaternary phosphonium salt ionic liquid is [Bu3PC14H29]+[ p-C7H7SO3]-.Starting stirring (350 revs/min), then starting adds
Heat by high pressure temperature in the kettle to 130 DEG C, and starts timing, reacts 3h；
(2) methyl benzoate isolates and purifies: operating method and step collect fraction 35.63g with embodiment 2 altogether；
(3) analysis detection: the sampling of the fraction that vacuum distillation is obtained, i.e. methyl benzoate carries out gas chromatographic analysis, purity
99.7%。
The yield that can be calculated methyl benzoate is 79.16%(based on benzoic acid).
Qualified products
The gas of the gas chromatogram (shown in Fig. 1) of the methyl benzoate made from embodiment 2 and commercially available analysis purified petroleum benzin Ethyl formate
Phase chromatogram (shown in Fig. 2) is compared, and shows that preparing product is methyl benzoate.
Claims (6)
1. a kind of preparation method of methyl benzoate, preparation process are as follows: by benzoic acid, methanol and catalyst be put into reactor into
Row esterification, then carries out separation and purification obtains methyl benzoate, it is characterized in that: the catalyst Wei quaternary alkylphosphonium salt ionic liquid
Body catalyst, the general formula of the quaternary phosphonium salt ionic liquid are [Bu3PR]+X-, in which: R C6-C16Straight chained alkyl, naphthenic base or different
Structure alkyl, the X-For p-C7H7SO3 -、CF3SO3 -、HSO4 -Or H2PO4 -。
2. the preparation method of methyl benzoate according to claim 1, it is characterized in that: the R is C8~C14Straight chained alkyl,
Naphthenic base or isomery alkyl, the X-For p-C7H7SO3 -Or CF3SO3 -。
3. the preparation method of methyl benzoate according to claim 1, it is characterized in that: the molar ratio of the benzoic acid and methanol
It is 1: 1~10.
4. the preparation method of methyl benzoate according to claim 1, it is characterized in that: the dosage of the quaternary phosphonium salt ionic liquid
For 3~40 %(weight of reactant weight), the reactant weight is the total weight of benzoic acid and methanol.
5. the preparation method of methyl benzoate according to claim 6, it is characterized in that: the dosage of the quaternary phosphonium salt ionic liquid
For 5~20%(weight of reactant weight).
6. the preparation method of methyl benzoate according to claim 1, it is characterized in that: the condition of the esterification are as follows: anti-
Answer 50~200 DEG C of temperature, the reaction time 1~10 hour.
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| CN201711002640.6A CN109694324A (en) | 2017-10-24 | 2017-10-24 | A kind of preparation method of methyl benzoate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950552A (en) * | 2022-06-23 | 2022-08-30 | 江西大地制药有限责任公司 | Novel sulphonamido silicone oil ionic liquid acid catalyst |
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| CN106939014A (en) * | 2016-01-04 | 2017-07-11 | 中化化工科学技术研究总院 | A kind of quaternary phosphonium salt ionic liquid and its production and use |
| CN106938969A (en) * | 2016-01-04 | 2017-07-11 | 中化化工科学技术研究总院 | A kind of method of quaternary phosphonium salt ionic liquid catalytic esterification synthetic ester |
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2017
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| CN101058560A (en) * | 2007-05-16 | 2007-10-24 | 中国科学院新疆理化技术研究所 | Acidic ionic liquid based on 1-methyl-3-benzyl imidazole cation, synthetic method and use |
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| CN101948387A (en) * | 2010-08-30 | 2011-01-19 | 安徽佳先功能助剂股份有限公司 | Preparation technology of methyl benzoate |
| CN106939014A (en) * | 2016-01-04 | 2017-07-11 | 中化化工科学技术研究总院 | A kind of quaternary phosphonium salt ionic liquid and its production and use |
| CN106938969A (en) * | 2016-01-04 | 2017-07-11 | 中化化工科学技术研究总院 | A kind of method of quaternary phosphonium salt ionic liquid catalytic esterification synthetic ester |
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Application publication date: 20190430 |