CN106496038A - A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity - Google Patents
A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity Download PDFInfo
- Publication number
- CN106496038A CN106496038A CN201610933001.0A CN201610933001A CN106496038A CN 106496038 A CN106496038 A CN 106496038A CN 201610933001 A CN201610933001 A CN 201610933001A CN 106496038 A CN106496038 A CN 106496038A
- Authority
- CN
- China
- Prior art keywords
- methyl
- acid
- ester
- preparation
- high selectivity
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention discloses a kind of preparation method of 3 methyl, 2 nitrobenzoic acid, adopts 3 methyl benzoic acid Arrcostabs to carry out nitration reaction for raw material, it is achieved that 2 high selectivities, high income, significantly reduces spent acid amount;And in nitration product only have 4 nitrobenzoyl acid alkyl ester of 3 methyl, 2 nitrobenzoyl acid alkyl ester and 3 methyl, separated after hydrolyze to obtain 4 nitrobenzoic acid of 3 methyl, 2 nitrobenzoic acid and 3 methyl again respectively;Technical process is simple, is suitable to industrialized production.
Description
Technical field
The invention belongs to organic synthesis field, specifically, is related to a kind of preparation side of 3- methyl -2- nitrobenzoic acids
Method.
Background technology
3- methyl -2- nitrobenzoic acids are the synthesis chloro- N of 2- amino -5-, the raw material of 3- dimethyl benzamides, agricultural chemicals,
Medical market is widely used.
At present it is known that with regard to 3- methyl -2- nitrobenzoic acids preparation method mainly have following several:
Qin Tao Master's thesis in document Institutes Of Technology Of Nanjing《Meta replaces methylbenzene nitration to select Journal of Sex Research》In, with 3- methylbenzenes
Methyl formate is raw material, and nitric acid-sulfuric acid nitration mixture has synthesized 3- methyl -2- nitrobenzene methyls, reacted as nitrating agent
Substantial amounts of spent acid is produced in journey, it is difficult to processed.
Document Tetrahedron Letters, 47(49):8651–8652;2006;With 3- methyl benzoic acids as raw material, urine
It is rough containing 3- methyl -2- nitrobenzoic acids, 3- methyl -4- nitrobenzene that plain single nitric acid salt or nitrourea are that nitrating agent synthesizes
Formic acid, the mixture of 3- methyl -6- nitrobenzoic acids, in based on 3- methyl -6- nitrobenzoic acids, and 3- methyl -2- nitros
Benzoic acid only accounts for the 23.4% ~ 24.5% of gross product, and reaction selectivity is poor.
Japan Patent JP 05132450A, with 1,3- dimethyl nitrobenzenes for raw material, prepared by oxidation in potassium chromate, sulfuric acid
3- methyl -2- nitrobenzoic acids, but yield only 40%, and have solid waste to produce.
Document Bulletin of the Chemical Society of Japan;60(10);3659-3662;1987;
With 3- methyl benzoic acids as raw material, nitrogen dioxide and nitric acid obtain 3- methyl -2- nitrobenzoic acids, yield as nitrating agent
49%, nitrogen dioxide limits which as nitrating agent and applies because of transport and vent gas treatment difficulty.
In order to meet 3- methyl -2- nitrobenzoic acids industrialization clean manufacturing, the present invention proposes a kind of 3- methyl -2- nitros
Benzoic preparation method.
Content of the invention
The object of the invention is just to provide a kind of preparation method of 3- methyl -2- nitrobenzoic acids, particular by following
Method is realized:
A kind of preparation method of the 3- methyl -2- nitrobenzoic acids of high selectivity, it be with 3- methyl benzoic acids as initiation material,
Including esterification, nitrification, recrystallization, esterolytic step, meanwhile, a small amount of 3- methyl -4- nitrobenzoic acids of by-product.
It is 0.5-2 that described esterification raw material is amount of substance ratio:1 3- methyl benzoic acids and the alkyl alcohol ester of C1 ~ C5,
Such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol etc., preferably C1 ~ C3 alkyl alcohol ester,
Under the conditions of 10~60 DEG C, reaction obtains the 3- methyl benzoic acid Arrcostabs of 2 high selectivity nitrifications.
Described nitration reaction is the 3- methyl benzoic acids Arrcostab and nitre of 2 high selectivity nitrifications in claim 2
Change reaction reagent is raw material, and temperature is -10 DEG C ~ 30 DEG C, the amount of substance of the 3- methyl benzoic acids Arrcostab in reaction and nitric acid it
Than for 1:0.8~4.
Nitration reaction reagent includes red fuming nitric acid (RFNA) of the concentration higher than 90%, preferably acetic anhydride-nitric acid, acetic anhydride-nitric acid.
Acetic anhydride is used after 5 DEG C ~ 20 DEG C premix 20min ~ 300min with nitric acid, and both amount of substance ratios are 1 ~ 5:1.
The solvent of nitration reaction can be acetic acid, nitrobenzene, ethyl acetate, dichloromethane, 1,2- dichloroethanes, tetrahydrochysene furan
Mutter, preferably acetic acid.
Nitration reaction obtains 3- methyl -2- nitrobenzoyl acid alkyl esters through recrystallization after terminating, for the organic of recrystallization
Solvent is:Methyl alcohol, ethanol, isopropanol, acetone, or its aqueous solution.
Described ester hydrolysis reaction is led in alcoholic solution by the 3- methyl -2- nitrobenzoyl acid alkyl esters of recrystallization gained
Cross ester basic hydrolysis or ester sour water solution is completed, wherein described alcoholic solution includes methyl alcohol, ethanol, isopropanol, or which combines, described
In ester basic hydrolysis, alkali used is NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, or its group
Close, its mass fraction is 5% ~ 30%.
It is 2-4 to add acid for adjusting pH after ester macromolecule alkali for hydrolysis again, separates out 3- methyl -2- nitrobenzoic acids, and acid used includes
Hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or its combination.
Acid used by ester acid hydrolytic reaction includes hydrochloric acid, sulfuric acid, nitric acid, glacial acetic acid, or which combines, and its mass fraction is 3%
~50%.
Compared with traditional handicraft, remarkable advantage is the method for the present invention:
(1)New method replaces sulfuric acid as catalyst using acetic anhydride, not only increases reaction selectivity and yield, and improves
The spatter property of commercial synthesis reaction, reduces environmental pollution.
(2)This method avoids producing substantial amounts of spent acid waste water in process of production.
(3)Reduce consuming, reduce production cost, the method reaction condition of invention is relatively mild, selective good, yield
Height, is suitable to industrialized production.
Specific embodiment
In order that those skilled in the art is better understood from the technical scheme that invents, some non-limits are disclosed further below
The present invention is described in detail for embodiment processed.
Embodiment 1
3- methyl benzoic acid 27.2g, methyl alcohol 50mL, concentrated sulfuric acid 4mL, back flow reaction 2h~3h is added in 250mL single port bottles.Instead
After should terminating, concentration removes methyl alcohol, organic phase saturated potassium hydrogen carbonate solution(30mL×3)Washing, purifies water washing(30mL),
Dry, obtain 28.82g yellow liquids, yield 96.08%, purity 98.64%.
65% nitric acid of 4.8mL is added in 100mL round-bottomed flasks(0.07moL), 7.6mL is added dropwise(0.08 moL)Acetic acid
Acid anhydride, drips off, after reaction 0.5h, by 7.6mL acetic anhydrides, 5.4mL acetic acid, 3.0g 3- methyl toluates(0.02moL)Mixing
Afterwards, it is slowly dropped in reaction system, above operation is carried out under condition of ice bath.After dripping off, 30 DEG C of reaction 3h are warming up to, are stopped
After only reacting, the glacial acetic acid of acetic anhydride, nitric acid and generation is steamed, concentrate is poured in frozen water, stirred, have yellow solid to analyse
Go out, add 20mL ethyl acetate to will be attached to the dissolving of the product in bottle wall, point liquid, concentration obtain light yellow liquid 3.83g, yield
98.21%.Analyze through HPLC, 3- methyl -2- nitrobenzene methyls with the content ratio of 3- methyl -4- nitrobenzene methyls are
72:28.Light yellow liquid mixture is recrystallized with absolute ethyl alcohol, 3- methyl -2- nitrobenzene methyls are obtained.
3- methyl -2- nitrobenzene methyl 19.5g, methyl alcohol 50mL are added in 250mL single port bottles, is added after dissolving
12% watery hydrochloric acid 40mL, 5.0~6.0h of room temperature reaction, concentration remove methyl alcohol, filter, and dry, obtain 10.8g white solids, yield
59.67%, purity 98.61%.
Embodiment 2
3- methyl benzoic acid 109g, methyl alcohol 300mL, concentrated sulfuric acid 8mL, back flow reaction 2h~3h is added in 250mL single port bottles.Instead
After should terminating, concentration removes methyl alcohol, organic phase saturated sodium carbonate solution(120mL×3)Washing, purifies water washing(120mL),
Dry, obtain 86.56g yellow liquids, yield 72.72%, purity 96.94%.
65% nitric acid of 2.7mL is added in 100mL round-bottomed flasks(0.04moL), 3.8mL is added dropwise(0.04 moL)Acetic acid
Acid anhydride, drips off, after reaction 0.5h, by 3.8mL acetic anhydrides, 2.7mL dichloromethane, 3.0 g 3- methyl toluates
(0.02moL)After mixing, it is slowly dropped in reaction system, above operation is carried out under condition of ice bath.After dripping off, it is warming up to
40 DEG C ~ 50 DEG C reaction 15min, after stopping reaction, steam acetic anhydride and glacial acetic acid, concentrate are poured in frozen water, stir, have Huang
Color solid is separated out, and adds 20mL ethyl acetate to will be attached to the dissolving of the product in bottle wall, and point liquid, concentration obtain light yellow liquid
3.66g, yield 93.85%.Through HPLC analyses, 3- methyl -2- nitrobenzene methyls and 3- methyl -4- nitrobenzene methyls
Content ratio about 66:34.The light yellow liquid mixture is recrystallized with absolute ethyl alcohol, 3- methyl -2- nitros are obtained
Methyl benzoate.
3- methyl -2- nitrobenzene methyl 19.5g, methyl alcohol 50mL are added in 250mL single port bottles, is added after dissolving
10.1% NaOH 50mL, 4.0~6.0h of room temperature reaction, concentration remove methyl alcohol, plus watery hydrochloric acid regulation PH is 2~3, filters, does
Dry, obtain 14.65g white solids, yield 80.96%, purity 98.35%.
Embodiment 3
Addition 3- methyl benzoic acid 109g in 250mL single port bottles, n-butanol 370mL, concentrated sulfuric acid 80mL, back flow reaction 2h~
3h.After reaction terminates, concentration removes n-butanol, organic phase saturated sodium bicarbonate solution(80mL×3)Washing, purifies water washing
(80mL), dry, obtain 127.6g yellow liquids, yield 75.92%, purity 97.34%.
95% nitric acid of 4.8mL is added in 100mL round-bottomed flasks(0.11moL), 8.6mL is added dropwise(0.011moL)Acetic acid
Acid anhydride, drips off, after reaction 1.0h, by 5.2mL acetic anhydrides, 5.5mL 1,2- dichloroethanes, 6.72 g 3- methyl benzoic acid N-butyls
After mixing, it is slowly dropped in reaction system, above operation is carried out under condition of ice bath.After dripping off, 15 DEG C ~ 20 DEG C are warming up to
Reaction, after stopping reaction, steams the glacial acetic acid of acetic anhydride, nitric acid and generation, concentrate is poured in frozen water, stirs, has yellow
Oily liquids, adds the extraction of 30mL ethyl acetate, concentration to obtain yellow liquid 7.81g, yield 95.38%.Analyze through HPLC, 3- first
Base -2- nitrobenzoic acids N-butyl is 75 with the content ratio of 3- methyl -4- nitrobenzoic acid N-butyls:25.By the light yellow liquid
Body mixture is recrystallized with absolute ethyl alcohol, obtains 3- methyl -2- nitrobenzoic acid N-butyls.
In 100mL single port bottles, add 3- methyl -2- nitrobenzoic acid N-butyls 7.8g, ethanol 30mL to add after dissolving
12% watery hydrochloric acid 15mL, 6.0~7.0h of room temperature reaction, concentration remove ethanol, filter, and dry, obtain 4.34g white solids, yield
78.62%, purity 97.55%.
Claims (9)
1. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity, it is characterised in that it is with 3- methylbenzene first
Acid is initiation material, including esterification, nitrification, recrystallization, esterolytic step, meanwhile, a small amount of 3- methyl -4- nitrobenzene of by-product
Formic acid.
2. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity according to claim 1, its feature exist
In it is 0.5-2 that described esterification raw material is amount of substance ratio:1 3- methyl benzoic acids and the alkyl alcohol ester of C1 ~ C5, such as first
Alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol etc., preferably C1 ~ C3 alkyl alcohol ester, 10~
Under the conditions of 60 DEG C, reaction obtains the 3- methyl benzoic acid Arrcostabs of 2 high selectivity nitrifications.
3. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity according to claim 1, its feature exist
In described nitration reaction is the 3- methyl benzoic acids Arrcostab of 2 high selectivity nitrifications in claim 2 and nitration reaction
Reagent is raw material, and temperature is -10 DEG C ~ 30 DEG C, and the 3- methyl benzoic acids Arrcostab in reaction is 1 with the ratio of the amount of substance of nitric acid:
0.8~4.
4. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity according to claim 1, its feature exist
In described nitration reaction reagent includes red fuming nitric acid (RFNA) of the concentration higher than 90%, preferably acetic anhydride-nitric acid, acetic anhydride-nitric acid, described
The preparation method of acetic anhydride-nitric acid be, at 5 DEG C ~ 20 DEG C by acetic anhydride, nitric acid premix 20min ~ 300min after use, two
The amount of substance ratio of person is 1 ~ 5:1.
5. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity according to claim 1, its feature exist
In the solvent of described nitration reaction can be acetic acid, nitrobenzene, ethyl acetate, dichloromethane, 1,2- dichloroethanes, tetrahydrochysene
Furans, preferably acetic acid.
6. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity according to claim 1, its feature exist
In nitration reaction obtains 3- methyl -2- nitrobenzoyl acid alkyl esters through recrystallization after terminating, for the organic solvent for recrystallizing
For:Methyl alcohol, ethanol, isopropanol, acetone, or its aqueous solution.
7. the preparation method of the 3- methyl -2- nitrobenzoic acids of a kind of high selectivity according to claim 1, its feature exist
In described ester hydrolysis reaction is to recrystallize the 3- methyl -2- nitrobenzoyl acid alkyl esters of gained in alcoholic solution by claim 6
In completed by ester basic hydrolysis or ester sour water solution, wherein described alcoholic solution includes methyl alcohol, ethanol, isopropanol, or which combines, institute
In the ester basic hydrolysis that states, alkali used is NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, or
Which combines, and its mass fraction is 5% ~ 30%.
8. ester basic hydrolysis according to claim 7, it is characterised in that it is 2-4 to add acid for adjusting pH after ester macromolecule alkali for hydrolysis again,
3- methyl -2- nitrobenzoic acids are separated out, acid used includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or which combines.
9. ester ester hydrolysis according to claim 7, it is characterised in that the acid used by ester acid hydrolytic reaction includes hydrochloric acid, sulphur
Acid, nitric acid, glacial acetic acid, or its combination, its mass fraction is 3% ~ 50%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610933001.0A CN106496038A (en) | 2016-11-01 | 2016-11-01 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610933001.0A CN106496038A (en) | 2016-11-01 | 2016-11-01 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106496038A true CN106496038A (en) | 2017-03-15 |
Family
ID=58319682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610933001.0A Pending CN106496038A (en) | 2016-11-01 | 2016-11-01 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106496038A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108129322A (en) * | 2017-12-13 | 2018-06-08 | 江西科苑生物药业有限公司 | A kind of synthetic method of 2- nitros -3- methyl benzoic acids |
CN108218710A (en) * | 2017-12-13 | 2018-06-29 | 江西科苑生物药业有限公司 | A kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste |
CN113897322A (en) * | 2021-06-29 | 2022-01-07 | 迪嘉药业集团有限公司 | Engineering bacterium of 3-methyl-4-nitrobenzoic acid and preparation method thereof |
CN114560772A (en) * | 2022-02-14 | 2022-05-31 | 南昌大学 | Synthetic method of 3-methyl-2-nitrobenzoic acid |
CN115784893A (en) * | 2022-11-09 | 2023-03-14 | 西安近代化学研究所 | Method for continuously synthesizing 3-methyl-2-nitrobenzoic acid |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105820054A (en) * | 2016-04-26 | 2016-08-03 | 合肥工业大学 | Preparation method of 3-methoxy-2-nitrobenzoate |
-
2016
- 2016-11-01 CN CN201610933001.0A patent/CN106496038A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105820054A (en) * | 2016-04-26 | 2016-08-03 | 合肥工业大学 | Preparation method of 3-methoxy-2-nitrobenzoate |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108129322A (en) * | 2017-12-13 | 2018-06-08 | 江西科苑生物药业有限公司 | A kind of synthetic method of 2- nitros -3- methyl benzoic acids |
CN108218710A (en) * | 2017-12-13 | 2018-06-29 | 江西科苑生物药业有限公司 | A kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste |
CN108129322B (en) * | 2017-12-13 | 2020-09-18 | 江西科苑生物药业有限公司 | Synthetic method of 2-nitro-3-methylbenzoic acid |
CN108218710B (en) * | 2017-12-13 | 2020-10-20 | 江西科苑生物药业有限公司 | Comprehensive utilization method of m-methylbenzoic acid nitration solid waste |
CN113897322A (en) * | 2021-06-29 | 2022-01-07 | 迪嘉药业集团有限公司 | Engineering bacterium of 3-methyl-4-nitrobenzoic acid and preparation method thereof |
CN113897322B (en) * | 2021-06-29 | 2023-01-17 | 迪嘉药业集团股份有限公司 | Engineering bacterium of 3-methyl-4-nitrobenzoic acid and preparation method thereof |
CN114560772A (en) * | 2022-02-14 | 2022-05-31 | 南昌大学 | Synthetic method of 3-methyl-2-nitrobenzoic acid |
CN115784893A (en) * | 2022-11-09 | 2023-03-14 | 西安近代化学研究所 | Method for continuously synthesizing 3-methyl-2-nitrobenzoic acid |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106496038A (en) | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity | |
CN106146379B (en) | A kind of synthetic method of Oxiracetam | |
CN113651866B (en) | Novel method for synthesizing cholesterol by taking 21-hydroxy-20-methyl pregna-4-en-3-one as raw material | |
CN112079848A (en) | Synthesis method of baroxavir key intermediate | |
CN105330582A (en) | Preparation method for (R)-4-hydroxy-2-oxo-1-pyrrolidine acetamide | |
CN105330581A (en) | Preparation method for (S)-oxiracetam | |
US8754256B2 (en) | Process for preparation of L-Arginine α-ketoglutarate 1:1 and 2:1 | |
CN107033210B (en) | A kind of preparation method of fulvestrant and its intermediate | |
CN102898328B (en) | Synthesis method of diethyl azodicarboxylate and intermediate of diethyl azodicarboxylate | |
CN111116424B (en) | Method for preparing trifluoromethanesulfonic acid by continuous hydrolysis | |
CN105820054A (en) | Preparation method of 3-methoxy-2-nitrobenzoate | |
CN105315184B (en) | A kind of fertile Preparation Method And Their Intermediate for Xi Ting | |
CN103113254B (en) | Technology for directly synthesizing acetaminophen from nitrobenzene | |
CN102617461A (en) | Novel method for refining aripiprazole | |
CN102702037B (en) | The preparation method of ethylenediamino ethyl sulfonate | |
CN103804373A (en) | Synthesis process of azasetron hydrochloride | |
CN110330422B (en) | Preparation method of 2, 6-diethyl-4-methylphenylacetic acid | |
CN104926660B (en) | The green synthesis method of a kind of trinitrophloroglucinol and application | |
CN101704788A (en) | Improved preparation process of 2-Butyl-1,3-diazapira[4,4]nonane-1-en-4-one | |
CN104402721A (en) | Synthetic method of 4-aldehyde butyrate | |
CN108069866A (en) | The method of asymmetric synthesis that a kind of isobutyl adds bar | |
CN104557604B (en) | Synthetic method for 5-acetylsalicylamide | |
CN107721832A (en) | A kind of preparation method of the fluorobenzene ether of 4 chlorine 3 | |
CN104356155B (en) | Preparation method of (S)-tert-butyldimethylsilyloxy-glutaramate | |
CN103755545B (en) | Preparation method of glutaric acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170315 |
|
RJ01 | Rejection of invention patent application after publication |