CN104003863B - A kind of benzoic green synthesis method - Google Patents
A kind of benzoic green synthesis method Download PDFInfo
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- CN104003863B CN104003863B CN201410268160.4A CN201410268160A CN104003863B CN 104003863 B CN104003863 B CN 104003863B CN 201410268160 A CN201410268160 A CN 201410268160A CN 104003863 B CN104003863 B CN 104003863B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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Abstract
The invention discloses a kind of benzoic green synthesis method.Comprise the following steps: phenyl aldehyde and imidazole hydrochloride are 1:0.003 ~ 0.015 by (1) in molar ratio, drop into reactor, add 60 ~ 75% anhydrous ethanol solvents accounting for phenyl aldehyde quality again, adjustment reacting system PH value is 7.8 ~ 8.5, at 70 ~ 90 DEG C, react 1.5-2.5h; (2), after reaction terminates, described reactor is put into ice-water bath crystallization and filter; Obtain crystalline mother solution and light yellow solid, described light yellow solid washing with alcohol, obtains white needle-like crystals, constant pressure and dry, is st-yrax finished product.Potassium cyanide or the sodium cyanide catalyzer of alternative traditional severe toxicity is come, to reach the green chemical synthesis novel method reducing by product by the method.Solve the large or catalyst toxicity of catalyst toxicity that the synthesis of st-yrax in current industry exists compared with little but synthesis difficulty, consumption is large, catalytic efficiency is lower, production cost is high problem.
Description
Technical field
The present invention relates to a kind of benzoic green synthesis method.
Background technology
St-yrax has another name called bitter almond oil camphor, and chemistry 1,2-phenylbenzene dehydrated alcohol ketone by name is a kind of white needle-like crystals.Bitter almond oil camphor is as important industrial chemicals, be widely used as the anticrater agent of the photosensitizers of photoresist, dyestuff intermediate and powder coating, also be a kind of important medicinal intermediates, as the preparation etc. of the synthesis of antiepileptic drug diphenyl hydantoin and diphenylthanedione, diphenylthanedione oxime, acetic acid st-yrax compounds.
Traditional st-yrax synthetic method in the ethanol solution of heat, does catalyzer synthesis with phenyl aldehyde with potassium cyanide or sodium cyanide, this method yield is higher, processing ease, and unique defect is catalyzer is severe poisonous chemicals, in the storage of catalyzer, comparatively bother in the operations such as recovery.Not only producing, all there is huge risk in secure context, and wastewater treatment difficulty, does not meet the requirement that green safety is produced.
Nineteen forty-three Ukai etc. find that thiazole salt has the catalytic performance identical with cyanogen negative ion, the catalyzer of benzoic condensation reaction can be used as equally, VITMAIN B1 can generate thiazole salt in the basic conditions, hydrogen atom between S and N on thiazole ring in VB1 molecule has larger acidity, carbanion is formed under the effect of alkali, the aldehyde radical of attack phenyl aldehyde, makes carbonyl carbon reversal of poles, the formation of catalysis bitter almond oil camphor.Therefore the VITMAIN B1 easily obtained can be used as catalyzer and is used for carrying out benzoic condensation reaction.But find in actually operating, VITMAIN B1 catalyzed reaction productive rate is low and unstable, poor repeatability.Jia Xiaohong etc. are by adding micro-quaternary ammonium salt bromination dodecyl dimethyl hexadecyldimethyl benzyl ammonium as phase-transfer catalyst on VITMAIN B1 method basis, and impel reaction to carry out smoothly, productive rate reaches 72.3%, and circulation ratio is fine.Although the benzoic condensation reaction relevant report of VITMAIN B1 catalysis is a lot, due to catalyzer VITMAIN B1 large usage quantity, and price comparison is high, so VITMAIN B1 catalysis method does not realize suitability for industrialized production.
After within 1958, Breslow proposes the mechanism of benzoic condensation, it is found that thiazole salt has the active group similar with VITMAIN B1.Davis uses the benzoic condensation of similar thiazole salt catalysis phenyl aldehyde to react first, solvent is made with toluene, obtain higher bitter almond oil camphor yield, research has afterwards found the thiazole salt catalyzer a series of thiazole ring connecting different substituents, by comparing the thiazole ring substituents of thiazole salt and optimize, find that the substituting group of nitrogen-atoms on thiazole salt catalyzer has significant impact to phenyl aldehyde benzoic condensation Reactive Synthesis bitter almond oil camphor.Under this thiazole salt catalysis, without the need to adding any organic solvent, bitter almond oil camphor separation yield can reach 72.5%.After this, also start continuous appearance, the most commonly 4-methyl-2-hydroxy ethylthiazole hydrochloride with thiazole salt as the catalyzer of benzoic condensation, but this thiazole salt requires to reaction conditions harsh, and be difficult in atmosphere stablize.Although these catalyzer have the low advantage of toxicity, all there is catalyzer synthesis difficulty, expensive; Catalyst levels is large simultaneously, and unit product catalyst consumption amount is high, and catalytic efficiency is less, the shortcoming that production cost is high, does not all realize suitability for industrialized production.
In current industry there is the hypertoxic catalyzer of use in st-yrax synthesis, or use the catalyzer that other toxicity are less, but catalyzer synthesizes difficulty and expensive problem; It is large also to there is catalyst levels in st-yrax synthesis simultaneously, the problem that catalytic efficiency is lower and production cost is high.
Summary of the invention
The object of this invention is to provide a kind of benzoic green synthesis method.Solve the catalyzer synthesis difficulty that st-yrax synthesis in current industry exists, the problem that consumption is large, catalytic efficiency is lower, production cost is high.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme:
A kind of benzoic green synthesis method, comprises the following steps:
(1) be 1:0.003 ~ 0.015 in molar ratio by phenyl aldehyde and imidazole hydrochloride, drop into reactor, add 60 ~ 75% anhydrous ethanol solvents accounting for phenyl aldehyde quality again, with SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic as buffered soln, adjustment pH value 7.8 ~ 8.5, reacts 1.5-2.5h at 70 ~ 90 DEG C;
(2), after reaction terminates, described reactor is put into ice-water bath crystallization and filter; Obtain crystalline mother solution and light yellow solid, described light yellow solid washing with alcohol, obtains white needle-like crystals, constant pressure and dry, is st-yrax finished product.
(3) continue to add phenyl aldehyde and imidazole hydrochloride that mol ratio is 1:0.003 ~ 0.015 in the crystalline mother solution in described step (2), account for 60 ~ 75% anhydrous ethanol solvents of phenyl aldehyde quality, continuation SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic are as buffered soln, adjustment pH value 7.8 ~ 8.5, reacts 1.5-2.5h at 70 ~ 90 DEG C;
(4), after reaction terminates, described reactor is put into ice-water bath crystallization and filter; Obtain secondary crystal mother liquor and light yellow solid, described light yellow solid washing with alcohol, obtains white needle-like crystals, constant pressure and dry, is st-yrax finished product.
Repeating step (3), step (4) 1 ~ 5 times.
Preferably, in described step (1), phenyl aldehyde is 106g (1mol), imidazole hydrochloride 0.8-1.2g, dehydrated alcohol 70-75g, with SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic as buffered soln, adjustment pH value 7.8 ~ 8.5, reacts 2h at 80-85 DEG C.
Benzoic condensation principle is groped in the prolonged and repeated research of contriver, use glyoxaline compound as catalyzer in benzoic condensation reaction, although use in glyoxaline compound document abroad and early have report, the people such as MonicaOrsini are with 1,3-dialkylimidazolium ionic liquid replaces VITMAIN B1 to make benzoic condensation catalyzer by the N-heterocycle carbine that electrochemistry produces, and productive rate is higher.But the imidazoles material that the method is mentioned is expensive, severe reaction conditions, although obtain higher yield, aborning and inapplicable.The raw material sources that the present invention uses, and synthesize the catalyzer of hydrochloride as benzoic condensation of all fairly simple imidazoles, and with the use of the buffered soln of SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic, obtain good reaction effect in an experiment, there is larger commercial exploitation and be worth.
Simple by imidazoles synthesis imidazole hydrochloride technique.The present invention uses imidazole hydrochloride as the catalyzer of benzoic condensation, coordinate the reaction system of alkaline buffer solution again, in reaction system glyoxaline compound molecule in 1, the atom N of 3 is to the electron attraction of 2 carbon atoms, 2 carbon atoms are made to have certain acidity, this material, under the effect of alkali, makes 2 carbon atoms with negative electricity, thus the condensation of catalysis phenyl aldehyde.This reaction is similar to thiazole salt from principle, can obtain good effect.The present invention uses the buffered soln of Sodium phosphate dibasic and SODIUM PHOSPHATE, MONOBASIC, not only can ensure that reaction is carried out in the basic conditions, and guarantee that reaction system still keeps the weakly alkaline of system in continuous reaction process.
The invention has the beneficial effects as follows:
1, the abundant raw material source of imidazole hydrochloride, synthesis mode is simple, and use imidazole hydrochloride as the catalyzer of benzoic condensation and thiazole salt, VB1 compares and greatly reduces the cost of reaction.
2, with VB1 as catalyzer synthesis st-yrax reaction in, need the pH value 9-10 keeping solution by dripping quantitative sodium hydroxide solution.And the present invention uses the buffered soln of Sodium phosphate dibasic and SODIUM PHOSPHATE, MONOBASIC configuration to regulate the pH value of reaction system.Use the damping fluid of SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic can better control the pH value of reaction system, the pH value of reaction system is changed in a less scope.
3, due to imidazole salts, relative to potassium cyanide or sodium cyanide, still cost is relatively high, therefore the present invention is by recycling crystalline mother solution, improve the yield of reaction on the one hand, also the discharge of by product (raffinate) is reduced on the other hand, because the accumulation of by product increases, the number of times recycled is too many, will affect the effect of last crystallization, comparatively sticky by product can affect the precipitation of crystal, and the number of times therefore recycled controls below 5 times.
Embodiment
The synthesis of embodiment 1 imidazole hydrochloride
The imidazoles of 68g is added in four-hole boiling flask, be dissolved in 100ml tetrahydrofuran (THF), in flask, slowly 85ml37% hydrochloric acid soln is dripped by dropping funnel, temperature of reaction remains on 60-70 DEG C, put into ice-water bath crystallization after reaction 1h, filter, drying obtains imidazole hydrochloride, obtain imidazole hydrochloride 98.6g, yield about 95%.
The benzoic synthesis of embodiment 2-1
Add benzene feedstock formaldehyde 106g, imidazole hydrochloride 1.0g, dehydrated alcohol 72g in a kettle., certain proportioning buffered soln Lin acid dihydride Na ﹑ Sodium phosphate dibasic, adjustment pH value 7.8 ~ 8.5, reacts 2h at 80 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 98.8g finished product.
Comparative example 2-2
Add phenyl aldehyde 106g in a kettle., 4-Ethyl-2-Methyl thiazole hydrochloride 1g, dehydrated alcohol 80g, drips a certain amount of sodium hydroxide solution, adjustment PH8-10.4h is reacted at 90 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 88.8g finished product.
Comparative example 2-3
In reaction four-hole boiling flask, add phenyl aldehyde 106g, VB1 catalyzer 2g, dehydrated alcohol 80g, drip a certain amount of sodium hydroxide solution, at 70 DEG C, react 6h.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 82.1g finished product.
Comparative example 2-4
Add benzene feedstock formaldehyde 106g, imidazole hydrochloride 1.0g, dehydrated alcohol 72g in reaction four-hole boiling flask, add a certain amount of sodium hydroxide solution, adjustment pH value 7.8 ~ 8.5, reacts 2h at 80 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 91.3g finished product.
Under above-mentioned different catalysts, alkaline solution embodiment condition, each index is in table 1:
Table 1 different catalysts is on the benzoic impact of synthesis
Significantly can find out from upper table, adopt yield that imidazole hydrochloride reacts as the benzoic condensation of catalyzer apparently higher than another two kinds of catalyzer, and product purity and other two kinds similar.And the price of imidazole hydrochloride is also better than thiazole hydrochloride and VB1, possesses the value of commercial exploitation.Along with the requirement of society to environmental protection is more and more higher, use potassium cyanide will be more and more narrow as the benzoic condensation technique of catalyzer.The condition optimizing experiment of embodiment 3 st-yrax building-up reactions
Embodiment 3-1
Add benzene feedstock formaldehyde 106g, imidazole hydrochloride 0.31g, dehydrated alcohol 79.5g in a kettle., certain proportioning buffered soln Lin acid dihydride Na ﹑ Sodium phosphate dibasic, adjustment pH value 7.8 ~ 8.5, reacts 2.5h at 90 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 97.6g finished product.
Embodiment 3-2
Add benzene feedstock formaldehyde 106g, imidazole hydrochloride 1.57g, dehydrated alcohol 63.6g in a kettle., certain proportioning buffered soln Lin acid dihydride Na ﹑ Sodium phosphate dibasic, adjustment pH value 7.8 ~ 8.5, reacts 1.5h at 70 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 98.6g finished product.
Embodiment 3-3
Add benzene feedstock formaldehyde 106g, imidazole hydrochloride 0.8g, dehydrated alcohol 75g in a kettle., certain proportioning buffered soln Lin acid dihydride Na ﹑ Sodium phosphate dibasic, adjustment pH value 7.8 ~ 8.5, reacts 2.5h at 85 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 98.7g finished product.
Embodiment 3-4
Add benzene feedstock formaldehyde 106g, imidazole hydrochloride 1.2g, dehydrated alcohol 70g in a kettle., certain proportioning buffered soln Lin acid dihydride Na ﹑ Sodium phosphate dibasic, adjustment pH value 7.8 ~ 8.5, reacts 1.5h at 80 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 98.6g finished product.
Find out from above-described embodiment, when each reaction raw materials, when reaction conditions changes in scope described in claims, Shuaiing ﹑ quality to the Shou of reaction does not all have large change.
Embodiment 4 st-yrax synthesis cycle uses the method for crystalline mother solution
St-yrax synthesis cycle uses the method for crystalline mother solution to comprise the steps:
Embodiment 4-1 adds benzene feedstock formaldehyde 104g, imidazole hydrochloride 0.6g in a kettle., the crystalline mother solution filtered in embodiment 2-1, dehydrated alcohol 72g, certain proportioning buffered soln Lin acid dihydride Na ﹑ Sodium phosphate dibasic, adjustment pH value 7.8 ~ 8.5, reacts 2h at 80 DEG C.Put into ice-water bath crystallization to filter, obtain light yellow st-yrax solid, and use a small amount of washing with alcohol, obtain white needle-like crystals, constant pressure and dry, obtain 98.7g finished product.
Embodiment 4-2, in the crystalline mother solution of step (1) described filtration, adds catalyzer imidazole hydrochloride 0.4g, and all the other same steps (1), obtain 98.9g finished product.
Embodiment 4-3, in the crystalline mother solution of step (2) described filtration, adds catalyzer imidazole hydrochloride 0.3g, and all the other same steps (1), obtain 99.1g finished product.
Embodiment 4-4, in the crystalline mother solution of step (3) described filtration, adds catalyzer imidazole hydrochloride 0.3g, and all the other same steps (1), obtain 99.0g finished product.
Embodiment 4-5, in the crystalline mother solution of step (4) described filtration, adds catalyzer imidazole hydrochloride 0.2g, and all the other same steps (1), obtain 99.2g finished product.
Result shows to be recycled by five times, and the usage quantity of catalyzer is reduced, and benzoic yield is further enhanced, and also consequently reduces the discharge of by product simultaneously, and the purity of product does not have large change.But along with recycling increasing of number of times, the filtrate after crystallization is also more and more thicker, and difficulty in filtration is increased, and circulate after four times, productive rate also no longer improves simultaneously.
In sum, use nontoxic imidazole hydrochloride as catalyzer, Sodium phosphate dibasic and SODIUM PHOSPHATE, MONOBASIC mixed solution have current benzoic condensation as the st-yrax reaction system of damping fluid and react the advantage do not had, and possess the advantage of industry aluminium extrusions.Also than use VB1 and thiazole hydrochloride, there is yield high, and catalyzer is cheap, the advantages such as processing ease simultaneously.
Claims (3)
1. a benzoic green synthesis method, comprises the following steps:
(1) be 1:0.003 ~ 0.015 in molar ratio by phenyl aldehyde and imidazole hydrochloride, drop into reactor, add 60 ~ 75% anhydrous ethanol solvents accounting for phenyl aldehyde quality again, with SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic as buffered soln, adjustment reacting system PH value is 7.8 ~ 8.5, at 70 ~ 90 DEG C, react 1.5-2.5h;
(2), after reaction terminates, described reactor is put into ice-water bath crystallization and filter; Obtain crystalline mother solution and light yellow solid, described light yellow solid washing with alcohol, obtains white needle-like crystals, constant pressure and dry, is st-yrax finished product.
2. benzoic green synthesis method as claimed in claim 1, is characterized in that: continue to add phenyl aldehyde and imidazole hydrochloride that mol ratio is 1:0.003 ~ 0.015 in the crystalline mother solution in described step (2), synthesis st-yrax finished product.
3. benzoic green synthesis method as claimed in claim 1, it is characterized in that: in described step (1), phenyl aldehyde is 106g, imidazole hydrochloride 0.8-1.2g, dehydrated alcohol 70-75g, with SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic as buffered soln, adjustment pH value 7.8 ~ 8.5, reacts 2h at 80-85 DEG C.
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| CN105906499B (en) * | 2016-06-20 | 2018-03-13 | 赵三虎 | One kind circulation prepares benzoic green synthesis method |
| CN108558628B (en) * | 2018-04-03 | 2021-06-25 | 宁夏医科大学 | Preparation method of benzoin |
| CN110746279A (en) * | 2019-10-30 | 2020-02-04 | 阜阳市诗雅涤新材料科技有限公司 | Continuous synthesis method of benzoin |
| CN111018681B (en) * | 2019-12-31 | 2022-10-14 | 天津久日新材料股份有限公司 | Method for preparing benzoin in micro-reaction device |
| CN111592449B (en) * | 2020-05-23 | 2023-01-03 | 绍兴佳英感光材料科技有限公司 | Production process of benzoin |
| CN113548950B (en) * | 2021-08-05 | 2023-05-09 | 广州明药科技有限公司 | Ultrasonic-assisted aqueous phase synthesis of benzoin and derivatives |
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