CN109665953A - A method of preparing styrax class compound - Google Patents
A method of preparing styrax class compound Download PDFInfo
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- CN109665953A CN109665953A CN201811571446.4A CN201811571446A CN109665953A CN 109665953 A CN109665953 A CN 109665953A CN 201811571446 A CN201811571446 A CN 201811571446A CN 109665953 A CN109665953 A CN 109665953A
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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
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- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
- B01J31/127—Silicones or siloxanes or comprising such units the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention provides a kind of methods for preparing styrax class compound.Specifically, method provided by the invention uses the immobilized imidazole salt ionic liquid of mesoporous material as catalyst, it is catalyzed aromatic aldehyde and obtains a variety of styrax class compounds.This method reaction condition is mild, and catalyst can reuse, and feed stock conversion is high, and process flow is easy, and technical scale metaplasia is suitble to produce.
Description
Technical field
The present invention relates to a kind of methods for preparing styrax class compound, belong to chemical field.
Background technique
Styrax is also known as benzoin, entitled 2- hydroxyl -1, the 2- diphenylethan of chemical system.Styrax is important
Industrial chemicals, it is also possible to make medicine intermediate, such as can be used for the synthesis of antiepileptic diphenyl hydantoin；It can also be used for pacifying
The synthesis of breath fragrant double methyl ether, photosensitizer benzoin ethyl ether, benzils etc..
Currently, preparing benzoic catalyst method can be roughly divided into two types: one kind is using potassium cyanide, Cymag as generation
The advantages of organic catalyst of table, this kind of catalyst is efficient, the disadvantage is that the toxicity of Cymag or potassium cyanide is big, welding,
It is again unhealthful；Another kind of catalyst is aza carbone catalyst, and common aza carbone catalyst has vitamin B1, three
Azoles salt, thiazoles ionic liquid and some thiazole salts being modified, for example, Zhao Sanhu etc. has synthesized five kinds of imidazolium ion liquid
Body, result of study showFor benzoic conden-sation almost without catalytic action, only suitable imidazoles particle salt pair
In the catalytic action that benzoic conden-sation has had.Li Linyan etc. reports the styrax of Neo Heliopan AP ion liquid catalyzing benzene formaldehyde
It is condensed (referring to " organic chemistry " .2012,33 (1): 1022-1025), separately having others, prior art discloses imidazole-like ionics
Liquid can be used for being catalyzed benzoic conden-sation and specifically include: CN102153525A, CN103242153A etc., although utilizing above-mentioned imidazoles
Ionic liquid can be catalyzed the benzoic conden-sation reaction of aldehyde, but above-mentioned report technique all more or less has technical lack
It falls into, the recycling such as the catalyst in these reactions is relatively difficult.
In consideration of it, the present invention provides a kind of new methods for preparing styrax class compound.This method has good ring
Border friendly, catalyst recycling repeatedly has no that catalytic activity obviously decays, and process operability is strong, high income, is convenient for
Industrial production.
Summary of the invention
The present invention provides a kind of methods for preparing styrax class compound.
Specifically, the present invention provides a kind of preparation method of styrax class compound shown in formula (III), including shown in formula (I)
Compound reacts to obtain step under the catalyst shown in formula (II),
Wherein Ar is aryl perhaps heteroaryl preferably phenyl, halogen or C in compound shown in formula (I)1To C6Alkyl
Substituted phenyl or C1To C6Alkoxy replace phenyl.
In catalyst shown in formula (II) B be mesopore molecular sieve carrier, selected from molecular sieve SBA-15, molecular sieve MCM-41 or
Silica solution Ludox HS, preferred molecular sieve SBA-15；
R1Selected from C1To C6Alkyl or alkenyl, preferably methyl；
N is selected from 0,1,2,3,4,5,6, preferably 4；
The X is selected from Cl-、Br-、Al Cl4 -、Al2Cl4 -、BF4 -、PF6 -、CF3COO-、MeSO4 -、CF3SO3 -、AsF6 -、Sb
F6 -, preferably BF4 -。
Part and compound shown in formula (I) shown in formula (IV) in catalyst shown in Chinese style (II) of the present invention
The amount of substance is 0.01:1-1:1, preferably 0.05:1-0.1:1, most preferably 0.05:1；Wherein R1, X it is as described above；n
Selected from 3 or 4.
It reacts described in preparation method prepared by the present invention and carries out under alkaline condition, the alkaline condition is by being selected from three second
Amine, N, N- diisopropylethylamine, n-BuLi, lithium diisopropylamine, lithium hexamethyldisilazide, potassium acetate, the tert-butyl alcohol
Sodium, potassium tert-butoxide, sodium hydride, potassium phosphate, sodium carbonate, potassium carbonate, potassium acetate, cesium carbonate, sodium hydroxide and lithium hydroxide one
Kind or a variety of alkaline matters provide, preferably sodium hydroxide.
In the preferred embodiment of the invention, in catalyst shown in formula (II)
B is SBA-15；
R1For methyl；
N is 4；
The X is BF4 -；
I.e.
Ar is phenyl, halogen or C in compound shown in formula (I)1To C6Alkyl-substituted phenyl, C1To C6Alcoxyl
The phenyl that base replaces.
In the preferred embodiment of the invention, Ar is selected from phenyl, p-methylphenyl, o-methyl-phenyl, p-bromophenyl, m-chloro
Phenyl and Chloro-O-Phenyl.
Reaction dissolvent is selected from methanol, ethyl alcohol, isopropanol, n-butanol, tetrahydrofuran, two in preparation method provided by the invention
Six ring of oxygen, acetone, n,N-Dimethylformamide, DMSO, preferably tetrahydrofuran.
Controlling suitable reaction temperature is also to guarantee to react the condition gone on smoothly in preparation method provided by the invention, is closed
Suitable reaction temperature can avoid the disproportionation of aldehyde compound, while guarantee the conversion ratio of aldehyde compound, and the present invention is in optional reality
Apply in scheme, the reaction temperature be selected from 40-80 DEG C, concretely 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, preferably
60-80 DEG C, most preferably 70 DEG C.
Reaction temperature is selected from 40-80 DEG C in preparation method provided by the invention, preferably 60-80 DEG C, most preferably 70 DEG C；Reaction
Time is selected from 4-16h, preferably 5-7h, most preferably 6h.
Preparation method neutral and alkali substance dosage provided by the invention is the 1%- of the amount of combinations of materials shown in formula (I)
30%, concretely 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%,
15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%,
30%, preferably 5%-20%, most preferably 10%-20%.
The preparation method of compound shown in formula (III) provided by the invention, reaction optionally occur under inert gas protection,
The inert gas is selected from helium, argon gas, nitrogen, preferably nitrogen.
In the preferred embodiment of the invention,
In compound shown in formula (I) Ar be selected from phenyl, p-methylphenyl, o-methyl-phenyl, p-bromophenyl, chlorphenyl and
Chloro-O-Phenyl；
In catalyst shown in formula (II)
B is SBA-15；
R1For methyl；
N is 4；
The X is BF4 -；
The amount of imidazole salts part and the substance of compound shown in formula (I) is 0.05:1 in catalyst shown in formula (II)；
The alkaline condition is provided by sodium hydroxide, and dosage is compound by weight 10%-20% shown in formula (I)；
Reaction dissolvent is tetrahydrofuran；
Reaction temperature is 70 DEG C；Reaction time is selected from 5-7h, preferably 6h；
The reaction carries out under nitrogen protection.
The method of compound shown in preparation formula (III) provided by the invention further comprises suction filtration (filtering), washing, dense
The step of contracting, vacuum distillation and post separation.
Catalyst shown in Chinese style (II) of the present invention can refer to the preparation of similar approach disclosed in prior art CN107876105
Or it is bought by commercial channel.
The present invention has following technical advantage:
1) all raw material of the present invention belong to the malicious reagent of non-easy system, and from a wealth of sources, preparation is convenient；
2) catalytic activity of the present invention is high, dosage is few and excellent catalytic effect；
3) catalyst in the present invention reuses multiple catalytic activity and has no obvious decaying.
Detailed description of the invention
Unless stated to the contrary, otherwise following that there are following meanings with term in the specification and in the claims.
Term " aryl " refers to that 6 to 14 yuan of full carbon monocycles of the pi-electron system with conjugation or fused polycycle are (namely shared
The ring of adjacent carbon atoms pair) group, preferably 6 to 10 yuan, such as phenyl and naphthalene.More preferable phenyl.The aryl rings can be with
It condenses on heteroaryl, heterocycle or cycloalkyl ring, wherein be aryl rings with the ring that precursor structure links together, it is unrestricted
Property example includes:
Aryl can be substituted or non-substituted, and when substituted, substituent group is preferably one or more following groups,
It is independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio group, alkyl amino, halogen, sulfydryl, hydroxyl, nitro, cyano, ring
Alkyl, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyloxy, heterocyclylalkoxy groups, cycloalkylthio, heterocycle alkylthio group, carboxyl or carboxylic acid
Ester group.
Term " heteroaryl " refers to the heteroaromatic system comprising 1 to 4 hetero atom, 5 to 14 annular atoms, and wherein hetero atom selects
From oxygen, sulphur and nitrogen.Heteroaryl is preferably 5 to 10 yuan, contains 1 to 3 hetero atom；It is more preferably 5- or 6-membered, contain 1 to 2 miscellaneous original
Son；It is preferred that such as imidazole radicals, furyl, thienyl, thiazolyl, pyrazolyl, oxazolyl, pyrrole radicals, tetrazole radical, pyridyl group, phonetic
Piperidinyl, thiadiazoles, pyrazinyl etc., preferably imidazole radicals, tetrazole radical, pyridyl group, thienyl, pyrazolyl or pyrimidine radicals, thiazolyl；
More select pyridyl group.The heteroaryl ring can be condensed on aryl, heterocycle or cycloalkyl ring, wherein connecting with precursor structure
Ring together is heteroaryl ring, and non-limiting example includes:
Heteroaryl can be it is optionally replacing or non-substituted, when substituted, substituent group be preferably it is one or more with
Lower group, independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio group, alkyl amino, halogen, sulfydryl, hydroxyl, nitro,
Cyano, naphthenic base, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyloxy, heterocyclylalkoxy groups, cycloalkylthio, heterocycle alkylthio group, carboxyl
And carboxylate.
" halogen " is selected from fluorine, chlorine, bromine or iodine element, preferably is selected from chlorine, bromine or iodine.
" substituted " refers to one or more hydrogen atoms in group, preferably at most 5, more preferably 1~3 hydrogen atom
Replaced independently of one another by the substituent group of respective number.Self-evident, substituent group is only in their possible chemical position, this
Field technical staff, which can determine in the case where not paying excessive make great efforts and (pass through experiment or theoretical), may or impossible take
Generation.
Term " methyl " refers to-CH3。
Specific embodiment
The present invention will be further described for the following examples, and the purpose is to can be best understood from the contents of the present invention.But
It is that embodiment does not limit the scope of the invention in any way.The technical staff of this professional domain is in scope of the invention as claimed
The modifications and adaptations inside made also should belong to right and protection scope of the invention.
Embodiment 1
In 50ml reaction flask, compound shown in addition-formula (II-A) (0.5g contains imidazole salts 0.02mmol), benzaldehyde
(0.41ml, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml), in nitrogen atmosphere, being heated to 70 DEG C, to be stirred to react 6 small
When, it filters, concentration removal solvent, methylene chloride is added, washing, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography obtains mesh
Mark product 1,2- diphenyl -2- hydroxyethanone, yield 78%.
Embodiment 2
In 50ml reaction flask, compound shown in formula (II-A) (0.5g contains imidazole salts 0.02mmol) is added, to methylbenzene
It is anti-to be heated to 70 DEG C of stirrings in nitrogen atmosphere for formaldehyde (0.48ml, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml)
It answers 6 hours, filters, concentration removal solvent is added methylene chloride, washes, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography,
Obtain target product 1,2- bis- (4 '-aminomethyl phenyl) -2- hydroxyethanone, yield 72%.
Embodiment 3
In 50ml reaction flask, compound shown in formula (II-A) (0.5g contains imidazole salts 0.02mmol), methylbenzene is added
It is anti-to be heated to 70 DEG C of stirrings in nitrogen atmosphere for formaldehyde (0.48ml, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml)
It answers 6 hours, filters, concentration removal solvent is added methylene chloride, washes, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography,
Obtain target product 1,2- bis- (3 '-aminomethyl phenyl) -2- hydroxyethanone, yield 73%.
Embodiment 4
In 50ml reaction flask, compound shown in formula (II-A) (0.5g contains imidazole salts 0.02mmol), o-methyl-benzene is added
It is anti-to be heated to 70 DEG C of stirrings in nitrogen atmosphere for formaldehyde (0.47ml, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml)
It answers 6 hours, filters, concentration removal solvent is added methylene chloride, washes, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography,
Obtain target product 1,2- bis- (2 '-aminomethyl phenyl) -2- hydroxyethanone, yield 45%.
Embodiment 5
In 50ml reaction flask, compound shown in formula (II-A) (0.5g contains imidazole salts 0.02mmol) is added, to bromobenzene first
Aldehyde (0.74g, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml) are heated to 70 DEG C and are stirred to react 6 in nitrogen atmosphere
Hour, it filters, concentration removal solvent, methylene chloride is added, washing, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography is obtained
Target product 1,2- bis- (4 '-bromophenyl) -2- hydroxyethanone, yield 58%.
Embodiment 6
In 50ml reaction flask, compound shown in formula (II-A) (0.5g contains imidazole salts 0.02mmol), adjacent chlorobenzene first is added
Aldehyde (0.46ml, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml) are heated to 70 DEG C and are stirred to react 6 in nitrogen atmosphere
Hour, it filters, concentration removal solvent, methylene chloride is added, washing, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography is obtained
Target product 1,2- bis- (2 '-chlorphenyl) -2- hydroxyethanone, yield 57%.
Embodiment 7
In 50ml reaction flask, compound shown in formula (II-A) (0.5g contains imidazole salts 0.02mmol), m chlorobenzaldehyde
(0.46ml, 4mmol), NaOH (0.032g) and tetrahydrofuran (2.0ml), in nitrogen atmosphere, being heated to 70 DEG C, to be stirred to react 6 small
When, it filters, concentration removal solvent, methylene chloride is added, washing, using ethyl acetate/petroleum ether as eluant, eluent, column chromatography obtains mesh
Mark product 1,2- bis- (3 '-aminomethyl phenyl) -2- hydroxyethanone, yield 66%.
Embodiment 8: ionic liquid [SiPMIm] Cl preparation
.N in flask is added by feeding intake for 1:1 in 1- methylimidazole, 3- chloropropyl triethoxysilane2Under protection,
90 DEG C of back flow reaction 48h are heated to, after completion of the reaction, are extracted 3 times with ether, liquid separation, by lower layer 1- (three second
Oxysilane propyl) -3- methylimidazole villaumite [SiPMIm] Cl crude product Rotary Evaporators removing ether, it is dried in vacuo, obtains
To colorless and transparent viscous liquid.
Embodiment 9: ionic liquid [SiPMIm] [BF4] preparation
1- (triethoxysilane propyl) -3- methylimidazole villaumite [SiPMIm] Cl, sodium fluoborate are added by feeding intake for 1:1
Enter in flask, N2Under protection, 60 DEG C of back flow reaction 12h are heated to, after completion of the reaction, obtained liquid is revolved in filtering
Turn evaporimeter and remove acetone, vacuum drying obtains colorless and transparent viscous liquid.
Embodiment 10: ionic liquid [SiPMIm] [BF4] preparation
Mesopore film SBA-15 is to make template under oxalic acid effect with P123, make silicon source with ethyl orthosilicate (TEOS)
Synthesis.The amount ratio of each feedstock composition matter is n (P123): n (oxalic acid): n (TEOS): n (H in reaction2O)=0.0096:
20221:1:123.7.Step is to weigh a certain amount of oxalic acid, is dissolved in water, the magnetic agitation under the conditions of 40 DEG C, is added one
Quantitative P123 continues to stir 30min, and 5ml TEOS is then added, and stirring is added 0.74g ionic liquid [SiPMIm]
[BF4] after adding, is stirred for 30min, precursor liquid is poured into culture dish, is placed in baking oven under the conditions of 40 DEG C and stands film forming.
Ethyl alcohol extraction is taken in the removal of the non-surface-active agent P123 of mesopore film SBA-15, and the ratio 1:1 of ethyl alcohol and water is mixed,
The heating water bath under the conditions of 50 DEG C washs the mesoporous film SBA-15 of taking-up 3 times with ethanol water.Finally use Soxhlet extraction
Method (150ml dehydrated alcohol, 120 DEG C, 5 hours) removing template, obtains SBA-15-m material.
Claims (10)
1. a kind of preparation method of styrax class compound shown in formula (III), including compound shown in formula (I) are shown in formula (II)
Step is reacted to obtain under catalyst,
Wherein Ar is aryl perhaps heteroaryl preferably phenyl, halogen or C in compound shown in formula (I)1To C6Alkyl or C1
To C6Alkoxy replace phenyl.
B is mesopore molecular sieve carrier in catalyst shown in formula (II), molten selected from molecular sieve SBA-15, molecular sieve MCM-41 or silicon
Glue Ludox HS, preferred molecular sieve SBA-15；
R1Selected from C1To C6Alkyl or alkenyl, preferably methyl；
N is selected from 0,1,2,3,4,5,6, preferably 4；
The X is selected from Cl-、Br-、AlCl4 -、Al2Cl4 -、BF4 -、PF6 -、CF3COO-、MeSO4 -、CF3SO3 -、AsF6 -、SbF6 -, excellent
Select BF4 -。
2. preparation method according to claim 1, it is characterised in that in catalyst shown in the formula (II)
The amount of part and the substance of compound shown in formula (I) shown in formula (IV) is 0.01:1-1:1, preferably 0.05:1-0.1:1, most
It is preferred that 0.05:1；
Wherein R1, X such as claim 1；
N is selected from 3 or 4.
3. the preparation method of compound shown in formula (III) according to claim 1, it is characterised in that the reaction is in alkalinity
Under the conditions of carry out, the alkaline condition by selected from triethylamine, n,N-diisopropylethylamine, n-BuLi, lithium diisopropylamine,
Lithium hexamethyldisilazide, potassium acetate, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium phosphate, sodium carbonate, potassium carbonate, acetic acid
One or more kinds of alkaline matters offer of potassium, cesium carbonate, sodium hydroxide and lithium hydroxide, preferably sodium hydroxide.
4. preparation method according to claim 1-3, it is characterised in that in catalyst shown in formula (II)
B is SBA-15；
R1For methyl；
N is 4；
The X is BF4 -；
Ar is phenyl, halogen or C in compound shown in formula (I)1To C6Alkyl-substituted phenyl, C1To C6Alkoxy replace
Phenyl.
5. the preparation method according to claim 4, it is characterised in that Ar is selected from phenyl, to first in compound shown in formula (I)
Base phenyl, o-methyl-phenyl, p-bromophenyl, chlorphenyl and Chloro-O-Phenyl.
6. according to the described in any item preparation methods of claim 5, reaction dissolvent be selected from methanol, ethyl alcohol, isopropanol, n-butanol,
Tetrahydrofuran, dioxane, acetone, n,N-Dimethylformamide, DMSO, preferably tetrahydrofuran.
7. preparation method according to claim 5, it is characterised in that the reaction temperature is selected from 40-80 DEG C, preferably 60-
80 DEG C, most preferably 70 DEG C；Reaction time is selected from 4-16h, preferably 5-7h, most preferably 6h.
8. the preparation method according to shown in claim 5, it is characterised in that the alkaline matter dosage is chemical combination shown in formula (I)
The 1%-30% of the amount of object substance, preferably 5%-20%, most preferably 10%-20%.
9. preparation method according to claim 1-8, it is characterised in that the preparation method is in inert gas
Protection is lower to be occurred, and the inert gas is selected from helium, argon gas, nitrogen, preferably nitrogen.
10. preparation method according to claim 9, it is characterised in that
Ar is selected from phenyl, p-methylphenyl, o-methyl-phenyl, p-bromophenyl, chlorphenyl and adjacent chlorine in compound shown in formula (I)
Phenyl；
In catalyst shown in formula (II)
B is SBA-15；
R1For methyl；
N is 4；
The X is BF4 -；
The amount of imidazole salts part and the substance of compound shown in formula (I) is 0.05:1 in catalyst shown in formula (II)；
The alkaline condition is provided by sodium hydroxide, and dosage is compound by weight 10%-20% shown in formula (I)；
Reaction dissolvent is tetrahydrofuran；
Reaction temperature is 70 DEG C；Reaction time is selected from 5-7h, preferably 6h；
The reaction carries out under nitrogen protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811571446.4A CN109665953B (en) | 2018-12-21 | 2018-12-21 | Method for preparing benzoin compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811571446.4A CN109665953B (en) | 2018-12-21 | 2018-12-21 | Method for preparing benzoin compounds |
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| CN109665953A true CN109665953A (en) | 2019-04-23 |
| CN109665953B CN109665953B (en) | 2022-09-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592449A (en) * | 2020-05-23 | 2020-08-28 | 绍兴佳英感光材料科技有限公司 | Production process of benzoin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153525A (en) * | 2011-03-07 | 2011-08-17 | 四川大学 | Preparation method and application of novel benzothiazole salt ionic liquid |
| CN103242153A (en) * | 2013-05-08 | 2013-08-14 | 南京大学 | Method for catalyzing preparation of benzoin from benzaldehyde by adopting imidazolium bicarbonate ionic liquid |
-
2018
- 2018-12-21 CN CN201811571446.4A patent/CN109665953B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153525A (en) * | 2011-03-07 | 2011-08-17 | 四川大学 | Preparation method and application of novel benzothiazole salt ionic liquid |
| CN103242153A (en) * | 2013-05-08 | 2013-08-14 | 南京大学 | Method for catalyzing preparation of benzoin from benzaldehyde by adopting imidazolium bicarbonate ionic liquid |
Non-Patent Citations (11)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592449A (en) * | 2020-05-23 | 2020-08-28 | 绍兴佳英感光材料科技有限公司 | Production process of benzoin |
| 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 |
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