CN114106041A - Process for synthesizing triphenylphosphine halogenated salt by solvent-free reaction method - Google Patents
Process for synthesizing triphenylphosphine halogenated salt by solvent-free reaction method Download PDFInfo
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- CN114106041A CN114106041A CN202111481934.8A CN202111481934A CN114106041A CN 114106041 A CN114106041 A CN 114106041A CN 202111481934 A CN202111481934 A CN 202111481934A CN 114106041 A CN114106041 A CN 114106041A
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- triphenylphosphine
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 150000003839 salts Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000006561 solvent free reaction Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- -1 halogenated hydrocarbon carboxylic ester Chemical class 0.000 claims abstract description 24
- 239000012452 mother liquor Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 14
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical group Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 claims description 12
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 claims description 9
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical group [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- OAAGDVLVOKMRCQ-UHFFFAOYSA-N 5-piperidin-4-yl-3-pyridin-4-yl-1,2,4-oxadiazole Chemical compound C1CNCCC1C1=NC(C=2C=CN=CC=2)=NO1 OAAGDVLVOKMRCQ-UHFFFAOYSA-N 0.000 claims description 3
- IZZIPPQWYVRGRS-UHFFFAOYSA-N benzyl 2-bromopropanoate Chemical compound CC(Br)C(=O)OCC1=CC=CC=C1 IZZIPPQWYVRGRS-UHFFFAOYSA-N 0.000 claims description 3
- JEAVBVKAYUCPAQ-UHFFFAOYSA-N ethyl 2-chloropropanoate Chemical compound CCOC(=O)C(C)Cl JEAVBVKAYUCPAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000000706 filtrate Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- RSYXORMKBUFAMS-UHFFFAOYSA-M (1-ethoxy-1-oxopropan-2-yl)-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C(=O)OCC)C1=CC=CC=C1 RSYXORMKBUFAMS-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- KEVZIELRABBJEP-UHFFFAOYSA-M (1-methoxy-1-oxopropan-2-yl)-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C(=O)OC)C1=CC=CC=C1 KEVZIELRABBJEP-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for synthesizing triphenylphosphine halogenated salt by a solvent-free reaction method, which comprises the following steps of adding triphenylphosphine into alpha-halogenated hydrocarbon carboxylate, stirring at room temperature, detecting the reaction process by a central control mode until triphenylphosphine raw material points basically disappear, filtering to obtain a solid wet product of the triphenylphosphine halogenated salt, washing a filter cake by a small amount of alpha-halogenated hydrocarbon carboxylate, and drying the filter cake to obtain the triphenylphosphine halogenated salt. The preparation method has the advantages that the halophosphine salt is prepared by a solvent-free scheme, the reaction time is obviously shortened, the triphenylphosphine raw material can be reduced to about 2 percent (TLC) within 27 hours from the original 48 hours of incomplete reaction (the liquid phase can know that much triphenylphosphine remains), and the speed is increased; the reaction yield is obviously improved from 75 percent to about 90 percent, the effect is obvious, and the purity of the halogenated hydrocarbon carboxylic ester recovered from the mother liquor is also very high and reaches up to 99.4 percent.
Description
Technical Field
The invention relates to the technical field of production of triphenylphosphine halogenated salt, and particularly relates to a process for synthesizing triphenylphosphine halogenated salt by a solvent-free reaction method.
Background
Currently, the production of triphenylphosphine halogenated salts is carried out by a solvent reaction formula, the synthesis of the triphenylphosphine salt by the solvent is long in time and slow in speed, and the triphenylphosphine salt is not completely reacted within 48 hours (the liquid phase can show that much triphenylphosphine remains), for example, as described in patent document WO2006119125, 1-ethoxycarbonylethyl) triphenylphosphine bromide is prepared by the solvent, 1.6kg (6.10mol) triphenylphosphine is dissolved in 10L ethyl acetate, and then 1.0kg 2-ethyl bromopropionate is added dropwise, and the reaction is carried out for 2 days at room temperature. Suction filtration is carried out, and the obtained white solid is washed by a small amount of ethyl acetate, is dried by suction and is dried, and the yield is about 75 percent. The chemical formula of (1-ethoxycarbonylethyl) triphenyl phosphonium bromide is as follows:
the technical defects of the scheme exist, and research and improvement are needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a process for synthesizing triphenylphosphine halogenated salt by a solvent-free reaction method, which is complete and reasonable in process, fast in reaction and high in yield.
The technical scheme of the invention is as follows:
a process for synthesizing triphenylphosphine halogenated salt by a solvent-free reaction method comprises the following steps of adding triphenylphosphine into alpha-halogenated hydrocarbon carboxylate, stirring at room temperature, detecting the reaction process by a central control mode, completely converting the halogenated hydrocarbon carboxylate until triphenylphosphine raw material points basically disappear, filtering to obtain a triphenylphosphine halogenated salt solid wet product filter cake, then washing the filter cake by a small amount of alpha-halogenated hydrocarbon carboxylate, and drying the filter cake to obtain the triphenylphosphine halogenated salt.
A process for synthesizing 1-ethoxycarbonylethyl triphenyl phosphonium bromide comprises the steps of adding 100mL of 2-ethyl bromopropionate into a 250mL four-mouth reaction bottle, then adding 16g of triphenylphosphine, stirring at room temperature for 27 hours, and filtering to obtain the yield of about 90%; recovering ethyl 2-bromopropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-ethoxycarbonylethyl, and has a chemical formula as follows:
a synthesis process of triphenyl phosphine chloride of 1-ethoxycarbonylethyl comprises the steps of adding 100mL of 2-ethyl chloropropionate into a 250mL four-opening reaction bottle, then adding 16g of triphenyl phosphine, stirring for 28 hours at room temperature, and filtering to obtain a yield of about 88%; recovering ethyl 2-chloropropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine chloride of 1-ethoxycarbonylethyl, and has the following chemical formula:
a synthesis process of 1-methoxycarbonylethyl triphenyl phosphonium bromide comprises the steps of adding 100mL of 2-bromomethyl propionate into a 250mL four-mouth reaction bottle, then adding 16g of triphenylphosphine, stirring at room temperature for 27 hours, and filtering to obtain the yield of about 85%; recovering 2-bromomethyl propionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-methoxycarbonyl ethyl, and the chemical formula is as follows:
a synthesis process of triphenylphosphine bromide of 1-benzyloxycarbonylethyl comprises the steps of adding 100mL of 2-benzyl bromopropionate into a 250mL four-mouth reaction bottle, then adding 16g of triphenylphosphine, stirring at room temperature for 29 hours, and filtering to obtain the yield of about 84%; recovering benzyl 2-bromopropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-benzyloxycarbonylethyl, and the chemical formula is as follows:
recovering the mother liquor, filtering the mother liquor at about 35 ℃, concentrating under reduced pressure, receiving the positive fraction under the vacuum degree of about-0.085 to-0.095 MPa, wherein the recovery rate is up to 95 percent, and the purity is about 99.4 percent.
The invention has the advantages that the alpha-halogenated hydrocarbon carboxylate and triphenylphosphine are subjected to wittig reaction to generate the halogenated phosphonium salt, a solvent-free mode is adopted to replace a solvent to synthesize the halogenated phosphonium salt, the reaction time is obviously shortened, and the speed is increased; the reaction yield is improved. The halogenated phosphonium salt is prepared according to a solvent-free scheme, the reaction time is obviously shortened, the triphenylphosphine raw material can be reduced to about 2 percent (TLC) from the original 48 hours of incomplete reaction (the liquid phase can know that the triphenylphosphine has a lot of residues) to the reaction time of 27 hours, and the speed is increased; the reaction yield is obviously improved from 75 percent to about 90 percent, the effect is obvious, and the purity of the halogenated hydrocarbon carboxylic ester recovered from the mother liquor is also very high and reaches up to 99.4 percent.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an infrared spectrum of (1-ethoxycarbonylethyl) triphenylphosphine bromide according to the present invention.
Detailed Description
Referring to the attached figure 1, a process for synthesizing triphenylphosphine halogenated salt by a solvent-free reaction method comprises the following steps of adding triphenylphosphine into alpha-halogenated hydrocarbon carboxylate, stirring at room temperature, detecting the reaction process by a central control mode until triphenylphosphine raw material points basically disappear, filtering to obtain a filter cake of a triphenylphosphine halogenated salt solid wet product, washing the filter cake by a small amount of alpha-halogenated hydrocarbon carboxylate, and drying the filter cake to obtain triphenylphosphine halogenated salt; recovering halogenated hydrocarbon carboxylic ester from the mother liquor.
Example 1
A process for synthesizing 1-ethoxycarbonylethyl triphenyl phosphonium bromide comprises the steps of adding 100mL of 2-ethyl bromopropionate into a 250mL four-mouth reaction bottle, then adding 16g of triphenylphosphine, stirring at room temperature for 27 hours, and filtering to obtain the yield of about 90%; recovering ethyl 2-bromopropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-ethoxycarbonylethyl, and has a chemical formula as follows:
the infrared spectrum of (1-ethoxycarbonylethyl) triphenyl phosphonium bromide is shown in figure 2.
Nuclear magnetic analysis: 1H-NMR (500Hz CDCl3) delta 7.60-7.93 (m, 15H, ArH), 3.92(m,2H, OCH2),2.69(s,1H, CHP),1.60(dd,3H, CH3),0.92(t,3H, CH 3).
Example 2
A synthesis process of triphenyl phosphine chloride of 1-ethoxycarbonylethyl comprises the steps of adding 100mL of 2-ethyl chloropropionate into a 250mL four-opening reaction bottle, then adding 16g of triphenyl phosphine, stirring for 28 hours at room temperature, and filtering to obtain a yield of about 88%; recovering ethyl 2-chloropropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine chloride of 1-ethoxycarbonylethyl, and has the following chemical formula:
example 3
A synthesis process of 1-methoxycarbonylethyl triphenyl phosphonium bromide comprises the steps of adding 100mL of 2-bromomethyl propionate into a 250mL four-mouth reaction bottle, then adding 16g of triphenylphosphine, stirring at room temperature for 27 hours, and filtering to obtain the yield of about 85%; recovering 2-bromomethyl propionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-methoxycarbonyl ethyl, and the chemical formula is as follows:
example 4
A synthesis process of triphenylphosphine bromide of 1-benzyloxycarbonylethyl comprises the steps of adding 100mL of 2-benzyl bromopropionate into a 250mL four-mouth reaction bottle, then adding 16g of triphenylphosphine, stirring at room temperature for 29 hours, and filtering to obtain the yield of about 84%; recovering benzyl 2-bromopropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-benzyloxycarbonylethyl, and the chemical formula is as follows:
example 5
Recovery of ethyl 2-bromopropionate in the mother liquor of example 1: filtering the mother liquor, concentrating under reduced pressure at about 35 ℃, wherein the vacuum degree is about-0.085 to-0.095 MPa, receiving the positive fraction, the recovery rate is up to 95 percent, and the purity is about 99.4 percent; the chemical formula of the ethyl 2-bromopropionate is as follows:
Claims (6)
1. a process for synthesizing triphenylphosphine halogenated salt by a solvent-free reaction method is characterized by comprising the following steps of adding triphenylphosphine into alpha-halogenated hydrocarbon carboxylate, stirring at room temperature, detecting the reaction process by a central control mode until triphenylphosphine raw material points basically disappear, filtering to obtain a filter cake of a triphenylphosphine halogenated salt solid wet product, washing the filter cake by a small amount of alpha-halogenated hydrocarbon carboxylate, and drying the filter cake to obtain the triphenylphosphine halogenated salt.
2. The process for synthesizing triphenylphosphine halide salt according to claim 1, wherein 100mL 2-bromopropionic acid ethyl ester is added into a 250mL four-mouth reaction bottle, then 16g triphenylphosphine is added, the mixture is stirred for 27 hours at room temperature and filtered, and the yield is about 90%; recovering ethyl 2-bromopropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-ethoxycarbonylethyl, and has a chemical formula as follows:
3. the process for synthesizing triphenylphosphine halogenated salt according to claim 1, wherein 100mL 2-chloropropionic acid ethyl ester is added into a 250mL four-mouth reaction bottle, then 16g triphenylphosphine is added, stirring is carried out for 28 hours at room temperature, and the yield is about 88%; recovering ethyl 2-chloropropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine chloride of 1-ethoxycarbonylethyl, and has the following chemical formula:
4. the process for synthesizing triphenylphosphine halogenated salt according to claim 1, wherein 100mL 2-bromomethyl propionate is added into a 250mL four-mouth reaction bottle, then 16g triphenylphosphine is added, the mixture is stirred for 27 hours at room temperature and filtered, and the yield is about 85%; recovering 2-bromomethyl propionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-methoxycarbonyl ethyl, and the chemical formula is as follows:
5. the process for synthesizing triphenylphosphine halide salt according to claim 1, wherein 100mL 2-benzyl bromopropionate is added into a 250mL four-mouth reaction flask, then 16g triphenylphosphine is added, stirring is carried out at room temperature for 29 hours, and filtering is carried out, the yield is about 84%; recovering benzyl 2-bromopropionate from the mother liquor; the triphenylphosphine halogenated salt is triphenylphosphine bromide of 1-benzyloxycarbonylethyl, and the chemical formula is as follows:
6. the process for synthesizing triphenylphosphine halogenated salt according to claim 2, 3, 4 or 5, wherein the mother liquor is recovered, the mother liquor is filtered at about 35 ℃, and the filtrate is concentrated under reduced pressure, wherein the vacuum degree is about-0.085 to-0.095 MPa, the positive fraction is received, the recovery rate is as high as 95%, and the purity is about 99.4%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124570A (en) * | 2022-08-11 | 2022-09-30 | 万华化学集团股份有限公司 | Preparation method of C3 phosphonium salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB828999A (en) * | 1957-07-12 | 1960-02-24 | Hoffmann La Roche | Novel phosphorane compounds and a process for the manufacture thereof |
| CN103910759A (en) * | 2012-12-29 | 2014-07-09 | 安徽贝克生物制药有限公司 | Preparation method of (carbethoxyethylidene)triphenylphosphorane |
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2021
- 2021-12-07 CN CN202111481934.8A patent/CN114106041A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB828999A (en) * | 1957-07-12 | 1960-02-24 | Hoffmann La Roche | Novel phosphorane compounds and a process for the manufacture thereof |
| CN103910759A (en) * | 2012-12-29 | 2014-07-09 | 安徽贝克生物制药有限公司 | Preparation method of (carbethoxyethylidene)triphenylphosphorane |
Non-Patent Citations (2)
| Title |
|---|
| KEK FOO CHIN ET AL.: "Bisguanidinium-Catalyzed Epoxidation of Allylic and Homoallylic Amines under Phase Transfer Conditions", 《 ACS CATAL. 》, vol. 10, pages 2684 - 2691 * |
| SCOTT E. DENMARK ET AL/: "Total synthesis of (þ)-papulacandin D", 《TETRAHEDRON》, vol. 66, pages 4745, XP028211047, DOI: 10.1016/j.tet.2010.03.093 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124570A (en) * | 2022-08-11 | 2022-09-30 | 万华化学集团股份有限公司 | Preparation method of C3 phosphonium salt |
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