CN112250634A - Preparation method of 4-phenylimidazole - Google Patents

Preparation method of 4-phenylimidazole Download PDF

Info

Publication number
CN112250634A
CN112250634A CN202011139262.8A CN202011139262A CN112250634A CN 112250634 A CN112250634 A CN 112250634A CN 202011139262 A CN202011139262 A CN 202011139262A CN 112250634 A CN112250634 A CN 112250634A
Authority
CN
China
Prior art keywords
compound
phenylimidazole
reaction
preparation
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011139262.8A
Other languages
Chinese (zh)
Other versions
CN112250634B (en
Inventor
袁永坤
蒋玉贵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Yacoo Science Co ltd
Original Assignee
Suzhou Yacoo Science Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Yacoo Science Co ltd filed Critical Suzhou Yacoo Science Co ltd
Priority to CN202011139262.8A priority Critical patent/CN112250634B/en
Publication of CN112250634A publication Critical patent/CN112250634A/en
Application granted granted Critical
Publication of CN112250634B publication Critical patent/CN112250634B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention discloses a preparation method of 4-phenylimidazole, which comprises the following steps: reacting the compound 1A and the compound 1B with a nitrogen-containing compound to obtain an intermediate; and reacting the intermediate with a reducing agent to obtain a 4-phenylimidazole crude product, and purifying to obtain a 4-phenylimidazole refined product. According to the invention, a reagent with a low price is used as an initial raw material, a final product is obtained through two-step reaction, the reaction condition of each step is mild, the yield of the obtained 4-phenylimidazole is high, and the cost can be greatly reduced.

Description

Preparation method of 4-phenylimidazole
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4-phenylimidazole.
Background
4-phenylimidazole with CAS number of 670-95-1 and molecular structural formula of
Figure BDA0002737713700000011
Is an epoxy curing imidazole accelerator and an organic synthesis intermediate. 4-phenylimidazole is used as a basic raw material of medicines with central nervous system and metabolic disorder, is widely applied in the medical industry, but is relatively expensive, and at present, the literature reports on the synthesis of 4-phenylimidazole are few.
In patent CN103450089B, α -bromoacetophenone and formamidine acetate are subjected to substitution reaction in ethylene glycol, and then subjected to cyclization reaction with acid-binding agent potassium carbonate, and then post-treatment to obtain 4-phenylimidazole, but the yield is low.
Therefore, the method for preparing the 4-phenylimidazole has great significance for seeking a new method for preparing the 4-phenylimidazole, optimizing the preparation process, reducing the production cost and improving the yield.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the preparation method of the 4-phenylimidazole, which uses a reagent with lower price as an initial raw material, has mild reaction conditions, and can obtain the 4-phenylimidazole with high yield and greatly reduce the cost; the crude product of 4-phenylimidazole obtained by the preparation method is purified to obtain a refined product of 4-phenylimidazole.
The invention is realized by adopting the following technical scheme:
a preparation method of 4-phenylimidazole comprises the following preparation steps:
preparation step S1: reacting the compound 1A and the compound 1B with a nitrogen-containing compound to obtain an intermediate;
compound 1A is a compound of the general structure shown in formula i:
Figure BDA0002737713700000021
in the formula I, Z is one of hydrogen atom, hydroxyl, SH, OR, SR, OM, SM and halogen;
the compound 1B is a carbonyl reagent,
Figure BDA0002737713700000022
Triphosgene, N' -carbonyldiimidazole, (NH)4)2CO3、NH4HCO3One or more combinations of the above; x1、X2Are respectively halogen, hydroxyl and NH2SH, OR, SR, OM, SM;
wherein R in OR and SR is one of saturated OR unsaturated, straight-chain OR branched-chain, heteroatom-containing OR heteroatom-free C1-C30 hydrocarbon groups; m in OM and SM is metal element cation, inorganic ammonium salt cation, organic ammonium salt cation, phosphorus salt cation,
Figure BDA0002737713700000023
One of a salt positive ion and an onium salt positive ion;
preparation step S2: and (3) reacting the intermediate with a reducing agent to obtain the 4-phenylimidazole.
The reaction equation of the preparation step S1 is shown by the following formula (1):
Figure BDA0002737713700000031
the reaction equation of the preparation step S2 is shown in the following formula (2):
Figure BDA0002737713700000032
further, the intermediate is at least one structure of intermediate 2A, intermediate 2B, intermediate 2C and intermediate 2D;
wherein, the intermediate 2A is a compound with a general structure shown in a formula II:
Figure BDA0002737713700000033
intermediate 2B is a compound of the general structure shown in formula iii:
Figure BDA0002737713700000034
Figure BDA0002737713700000041
the intermediate 2C is a compound with a general structure shown in a formula IV:
Figure BDA0002737713700000042
intermediate 2D is a compound of the general structure shown in formula v:
Figure BDA0002737713700000043
further, the nitrogen-containing compound is one or a combination of a plurality of cyanide, ammonia gas, ammonia water and ammonium salt. Preferably, the nitrogen-containing compound is sodium cyanide, potassium cyanide, hydrocyanic acid, ammonia gas, ammonia water, (NH)4)2CO3、NH4HCO3One or a combination of several of them;
further, the reducing agent is one or more of hydrogen, lithium aluminum hydride, iron, zinc, magnesium, sulfite, ferrous salt, stannous salt, potassium borohydride, sodium borohydride, hydrazine, sulfur dioxide and hydrogen sulfide.
Further, the molar ratio of the compound 1A to the compound 1B is 1: 0.1-10; the molar ratio of the compound 1A to the nitrogen-containing compound is 1: 0.1-10; the molar ratio of the intermediate to the reducing agent is 1: 0.1-10.
Further, the reaction conditions in the preparation step S1 are: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72 h; the reaction conditions in the preparation step S2 were: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72 h.
Further, an auxiliary agent is added in the preparation step S1, wherein the auxiliary agent is POCl3、PCl5、P2S5、P2O5One or a combination of several of them.
Further, in the preparation step S2, a catalyst is further added, where the catalyst is one or a combination of more of simple substances, oxides, and hydroxides containing platinum, palladium, ruthenium, rhodium, and nickel, or the catalyst is supported by activated carbon or Al2O3One or more of simple substances, oxides and hydroxides of loaded platinum, palladium, ruthenium, rhodium and nickel.
Further, the reaction of the preparation step S1 is carried out in a first reaction solvent; the first reaction solvent is one or a combination of more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water;
the reaction of preparation step S2 is carried out in a second reaction solvent; the second reaction solvent is one or a combination of more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
Preferably, the preparation method of the 4-phenylimidazole further comprises the following preparation steps:
under the drying condition, dissolving the crude 4-phenylimidazole obtained by the preparation method in a purification solvent, recrystallizing at low temperature, filtering to remove insoluble substances, and then performing rotary evaporation and drying on the filtrate to obtain refined 4-phenylimidazole; wherein the purifying solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a reagent with a low price is used as an initial raw material, a final product is obtained through two-step reaction, the reaction condition of each step is mild, the yield of the obtained 4-phenylimidazole is high, and the cost can be greatly reduced.
The whole preparation method is simple and easy to control, is favorable for enlarging production, shortens the reaction production period, can obtain the 4-phenylimidazole with higher purity through conventional recrystallization purification, and can effectively improve the yield of the product.
Detailed Description
The invention will now be further described with reference to specific embodiments, which are intended to illustrate the invention in more detail by way of some non-limiting examples. It should be noted that these examples should not be construed as limiting the scope of the invention, which can be implemented in any manner described in the summary of the invention. The pressure values mentioned in the patent of the invention are gauge pressures unless otherwise specified. The yield in the invention refers to the percentage ratio of the actual product quality to the theoretical product quality; wherein, the theoretical product quality is calculated by the raw materials which are not excessive in the reaction equation. The purification yield in the examples of the present invention refers to the number of moles of the purified 4-phenylimidazole divided by the number of moles of the crude 4-phenylimidazole before purification.
The following are specific examples of the present invention, and raw materials, equipment, and the like used in the following examples can be obtained by purchasing, unless otherwise specified.
Example 1
The preparation method of the 4-phenylimidazole comprises the following preparation steps:
106g of a benzaldehyde compound 1A and a benzaldehyde compound 1B (NH) were sequentially added to a stainless steel reaction vessel4)2CO3The molar ratio of the compound 1A to the compound 1B to the nitrogen-containing compound is 1:1.1:1.1, the mixture is uniformly stirred and reacts for 24 hours at the temperature of 100 ℃ and the pressure of 0.5MPa to obtain an intermediate;
introducing a reducing reagent sodium borohydride into the intermediate, reacting for 48 hours at the temperature of 60 ℃ and the pressure of 0MPa, wherein the molar ratio of the intermediate to the reducing reagent is 1:3, so as to obtain crude 4-phenylimidazole, and the total yield is about 78.6%;
under the drying condition, 100g of crude 4-phenylimidazole is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out again to remove insoluble substances, then the filtrate is added into a rotary evaporator, rotary evaporation is carried out for 1h at about 100 ℃, and then drying is carried out for 2h in a blast oven at 100 ℃ to obtain refined 4-phenylimidazole, wherein the purification yield is about 85.4%.
Example 2
The preparation method of the 4-phenylimidazole comprises the following preparation steps:
sequentially adding 122g of a mixture of a compound 1A benzoic acid, a compound 1B triphosgene, a nitrogen-containing compound hydrocyanic acid and ammonia water into a stainless steel reaction kettle, wherein the molar ratio of the compound 1A to the compound 1B to the nitrogen-containing compound is 1:1.3:1.3, uniformly stirring, and reacting for 24 hours at the temperature of 80 ℃ and the pressure of 0.3MPa to obtain an intermediate;
introducing a reducing reagent hydrogen into the intermediate, reacting for 48 hours at the temperature of 60 ℃ and the pressure of 0.6MPa, wherein the molar ratio of the intermediate to the reducing reagent is 1:8, and the total yield of the crude product 4-phenylimidazole is about 80.5%;
under the drying condition, 100g of crude 4-phenylimidazole is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out again to remove insoluble substances, then the filtrate is added into a rotary evaporator and rotary evaporation is carried out for 1h at about 100 ℃, and then drying is carried out for 2h in a blast oven at 100 ℃ to obtain refined 4-phenylimidazole, wherein the purification yield is about 86.2%.
Example 3
The preparation method of the 4-phenylimidazole comprises the following preparation steps:
138g of a compound 1A benzaldehyde and a compound 1B NH are sequentially added into a stainless steel reaction kettle4HCO3The molar ratio of the compound 1A to the compound 1B to the nitrogen-containing compound is 1:1.1:1.1, the mixture is uniformly stirred and reacts for 24 hours at the temperature of 120 ℃ and the pressure of 0.3MPa to obtain an intermediate;
introducing a reducing reagent potassium borohydride into the intermediate, wherein the molar ratio of the intermediate to the reducing reagent is 1:3, and reacting for 48 hours at 50 ℃ and 0.1MPa to obtain crude 4-phenylimidazole, wherein the total yield is about 76.3%;
under the drying condition, 100g of crude 4-phenylimidazole is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out again to remove insoluble substances, then the filtrate is added into a rotary evaporator and rotary evaporation is carried out for 1h at about 100 ℃, and then drying is carried out for 2h in a blast oven at 100 ℃ to obtain refined 4-phenylimidazole, wherein the purification yield is about 82.1%.
Example 4
The preparation method of the 4-phenylimidazole comprises the following preparation steps:
139g of compound 1A methyl benzoate and compound 1B (NH) were sequentially added to a stainless steel reaction vessel4)2CO3A nitrogen-containing compound of sodium cyanide,the molar ratio of the compound 1A to the compound 1B to the nitrogen-containing compound is 1:1.5:1.5, the mixture is uniformly stirred and reacts for 24 hours at the temperature of 120 ℃ and the pressure of 0.8MPa to obtain an intermediate;
introducing a reducing reagent hydrogen into the intermediate, wherein the molar ratio of the intermediate to the reducing reagent is 1:6, reacting for 48 hours at the temperature of 550 ℃ and under the pressure of 0.6MPa to obtain crude 4-phenylimidazole, and the total yield is about 78.9%;
under the drying condition, 100g of crude 4-phenylimidazole is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out again to remove insoluble substances, then the filtrate is added into a rotary evaporator and rotary evaporation is carried out for 1h at about 100 ℃, and then drying is carried out for 2h in a blast oven at 100 ℃ to obtain refined 4-phenylimidazole, wherein the purification yield is about 81.4%.
Example 5
The preparation method of the 4-phenylimidazole comprises the following preparation steps:
2000ml of ethanol, 139g of compound 1A ammonium benzoate, compound 1B formamide, nitrogen-containing compound ammonium cyanide and 10g of PCl are added into a stainless steel reaction kettle in sequence5The molar ratio of the compound 1A to the compound 1B to the nitrogen-containing compound is 1:1.2:1.2, the mixture is uniformly stirred and reacts for 24 hours at the temperature of 120 ℃ and the pressure of 0.8MPa to obtain an intermediate;
uniformly mixing the intermediate with 5g of platinum catalyst loaded by active carbon and 1000ml of ethanol, introducing a reduction reagent hydrogen, reacting for 48 hours at the temperature of 120 ℃ and the pressure of 0.7MPa, wherein the molar ratio of the intermediate to the reduction reagent is 1:7, and the total yield of the 4-phenylimidazole is about 80.1%;
under the drying condition, 100g of crude 4-phenylimidazole is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out again to remove insoluble substances, then the filtrate is added into a rotary evaporator and rotary evaporation is carried out for 1h at about 100 ℃, and then drying is carried out for 2h in a blast oven at 100 ℃ to obtain refined 4-phenylimidazole, wherein the purification yield is about 84.5%.
The above embodiments are only a part of the preferred embodiments of the present invention, and the embodiments are described only for illustrating the principle of the present invention, and thus the scope of the present invention is not limited by the embodiments. As will be apparent to those skilled in the art, numerous changes, modifications and variations can be made in the present invention without departing from the spirit, principles and scope of the invention, the invention resides in the claims hereinafter appended, and the invention includes all such changes, modifications and variations.

Claims (10)

1. The preparation method of 4-phenylimidazole is characterized by comprising the following preparation steps:
preparation step S1: reacting the compound 1A and the compound 1B with a nitrogen-containing compound to obtain an intermediate;
compound 1A is a compound of the general structure shown in formula i:
Figure FDA0002737713690000011
in the formula I, Z is one of hydrogen atom, hydroxyl, SH, OR, SR, OM, SM and halogen;
the compound 1B is a carbonyl reagent,
Figure FDA0002737713690000012
Triphosgene, N' -carbonyldiimidazole, (NH)4)2CO3、NH4HCO3One or more combinations of the above; x1、X2Are respectively halogen, hydroxyl and NH2SH, OR, SR, OM, SM;
wherein R in OR and SR is one of saturated OR unsaturated, straight-chain OR branched-chain, heteroatom-containing OR heteroatom-free C1-C30 hydrocarbon groups; m in OM and SM is metal element cation, inorganic ammonium salt cation, organic ammonium salt cation, phosphorus salt cation,
Figure FDA0002737713690000013
Salt positive ionOne kind of onium salt positive ion;
preparation step S2: and (3) reacting the intermediate with a reducing agent to obtain the 4-phenylimidazole.
2. The method for preparing 4-phenylimidazole according to claim 1, wherein the intermediate is at least one structure selected from intermediate 2A, intermediate 2B, intermediate 2C, and intermediate 2D;
wherein, the intermediate 2A is a compound with a general structure shown in a formula II:
Figure FDA0002737713690000014
Figure FDA0002737713690000021
intermediate 2B is a compound of the general structure shown in formula iii:
Figure FDA0002737713690000022
the intermediate 2C is a compound with a general structure shown in a formula IV:
Figure FDA0002737713690000023
intermediate 2D is a compound of the general structure shown in formula v:
Figure FDA0002737713690000024
3. the method for preparing 4-phenylimidazole according to claim 1, wherein the nitrogen-containing compound is one or a combination of several of cyanide, ammonia gas, ammonia water and ammonium salt.
4. The method for preparing 4-phenylimidazole according to claim 1, wherein the reducing agent is one or more of hydrogen, lithium aluminum hydride, iron, zinc, magnesium, sulfite, ferrous salt, stannous salt, potassium borohydride, sodium borohydride, hydrazine, sulfur dioxide, and hydrogen sulfide.
5. The method for producing 4-phenylimidazole according to claim 1, wherein the molar ratio of the compound 1A to the compound 1B is 1:0.1 to 10; the molar ratio of the compound 1A to the nitrogen-containing compound is 1: 0.1-10; the molar ratio of the intermediate to the reducing agent is 1: 0.1-10.
6. The process for producing 4-phenylimidazole according to claim 1, wherein the reaction conditions in the production step S1 are: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72 h; the reaction conditions in the preparation step S2 were: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72 h.
7. The method according to claim 1, wherein an auxiliary agent is further added in step S1, wherein the auxiliary agent is POCl3、PCl5、P2S5、P2O5One or a combination of several of them.
8. The method according to claim 1, wherein a catalyst is further added in step S2, and the catalyst is one or more of platinum, palladium, ruthenium, rhodium, and nickel, or an oxide or hydroxide thereof, or the catalyst is supported on activated carbon or Al2O3One or more of simple substances, oxides and hydroxides of loaded platinum, palladium, ruthenium, rhodium and nickel.
9. The process for producing 4-phenylimidazole according to claim 1, wherein the reaction of production step S1 is carried out in a first reaction solvent; the first reaction solvent is one or a combination of more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water;
the reaction of preparation step S2 is carried out in a second reaction solvent; the second reaction solvent is one or a combination of more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
10. The process for the preparation of 4-phenylimidazole according to claims 1 to 9, further comprising the steps of:
under the drying condition, dissolving the crude 4-phenylimidazole obtained in the preparation step S2 in a purification solvent, recrystallizing at low temperature, filtering to remove insoluble substances, and then performing rotary evaporation and drying on the filtrate to obtain refined 4-phenylimidazole; wherein the purifying solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
CN202011139262.8A 2020-10-22 2020-10-22 Preparation method of 4-phenylimidazole Active CN112250634B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011139262.8A CN112250634B (en) 2020-10-22 2020-10-22 Preparation method of 4-phenylimidazole

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011139262.8A CN112250634B (en) 2020-10-22 2020-10-22 Preparation method of 4-phenylimidazole

Publications (2)

Publication Number Publication Date
CN112250634A true CN112250634A (en) 2021-01-22
CN112250634B CN112250634B (en) 2022-08-12

Family

ID=74264687

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011139262.8A Active CN112250634B (en) 2020-10-22 2020-10-22 Preparation method of 4-phenylimidazole

Country Status (1)

Country Link
CN (1) CN112250634B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892554A (en) * 2020-08-10 2020-11-06 苏州亚科科技股份有限公司 Preparation method of 2,2' -biazonitrogen-bis (3-alkylbenzothiazoline-6-sulfonic acid) salt

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560533A (en) * 2009-05-21 2009-10-21 苏州立新制药有限公司 Preparation method of S-(+)-o-chlorobenzoyl glycine
CN109776424A (en) * 2019-01-22 2019-05-21 浙江云涛生物技术股份有限公司 A kind of MIC reactor prepares the new method of L-Phenylglycine precursor benzene glycolylurea
CN110105222A (en) * 2019-05-15 2019-08-09 南开大学 A kind of novel processing step of 4- aminoidan class compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560533A (en) * 2009-05-21 2009-10-21 苏州立新制药有限公司 Preparation method of S-(+)-o-chlorobenzoyl glycine
CN109776424A (en) * 2019-01-22 2019-05-21 浙江云涛生物技术股份有限公司 A kind of MIC reactor prepares the new method of L-Phenylglycine precursor benzene glycolylurea
CN110105222A (en) * 2019-05-15 2019-08-09 南开大学 A kind of novel processing step of 4- aminoidan class compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A.H.COOK等: "Studies in the azole series. Part II. The interaction ofα-amino nitriles and carbon disulfide", 《JOURNAL OF THE CHEMICAL SOCIETY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892554A (en) * 2020-08-10 2020-11-06 苏州亚科科技股份有限公司 Preparation method of 2,2' -biazonitrogen-bis (3-alkylbenzothiazoline-6-sulfonic acid) salt
CN111892554B (en) * 2020-08-10 2022-08-16 苏州亚科科技股份有限公司 Preparation method of 2,2' -biazonitrogen-bis (3-alkylbenzothiazoline-6-sulfonic acid) salt

Also Published As

Publication number Publication date
CN112250634B (en) 2022-08-12

Similar Documents

Publication Publication Date Title
CN109092309B (en) Preparation method of catalyst for preparing 5-hydroxymethylfurfural from cellulose
CN112250634B (en) Preparation method of 4-phenylimidazole
CN104496943A (en) Method for preparing dihydroxymethyl tetrahydrofuran
CN112125826B (en) Preparation method of 2,4, 6-toluene triisocyanate
CN112479890B (en) Preparation method of nitro compound
CN111087274A (en) Method for preparing bis (norbornadiene) rhodium tetrafluoroborate
CN112778250A (en) Preparation method of 5-hydroxymethyl furoic acid
WO2023039940A1 (en) Method for preparing n,n,n-tripivaloyl-1,3,5-triaminobenzene
CN114933535A (en) Preparation method of membrane reactor and method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene
CN114426502B (en) Process for the preparation of nitriles
CN114653378A (en) Novel catalyst for synthesizing dimethyl carbonate
CN113072539A (en) Chemical synthesis method of pantoprazole dimer
KR20200024577A (en) Method of manufacturing bio-adipic acid derived from glucose
CN114907415B (en) Preparation method of bis (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride
CN109053785A (en) One kind is for being catalyzed CO2Hydrogenation reaction prepares homogeneous catalyst and its preparation method and the application of formates
CN111302962A (en) Rapid method for reducing nitro in aliphatic nitro compound into amino
CN117624110B (en) Synthetic method of fluoroethylene carbonate
CN110878020B (en) Method for directly preparing dimethyl carbonate under low pressure
CN113233985B (en) Method for synthesizing asymmetric N-isopropyl propylamine and method for preparing catalyst
CN103626667B (en) A kind of method that catalytic hydrogenation prepares 3,3', 4,4'-tetramino diphenyl ether hydrochlorate
CN111909047B (en) Preparation process of 2- [ (2-amino-2-oxyethyl) - (carboxymethyl) amino ] acetic acid
CN113480415B (en) Process for synthesizing glyoxal by hydroformylation of acrolein
CN115894372B (en) Pyrazoline derivative synthesis method based on ketone and mono-hydrazine salt
CN117417262B (en) Preparation method of diglycolamine
CN114082442B (en) Succinimidyl ionic liquid and method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by using same as catalyst

Legal Events

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