CN114539066A - Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid - Google Patents

Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid Download PDF

Info

Publication number
CN114539066A
CN114539066A CN202210131856.7A CN202210131856A CN114539066A CN 114539066 A CN114539066 A CN 114539066A CN 202210131856 A CN202210131856 A CN 202210131856A CN 114539066 A CN114539066 A CN 114539066A
Authority
CN
China
Prior art keywords
fecl
benzoyl
nitrobenzoic acid
alcl
mol
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
Application number
CN202210131856.7A
Other languages
Chinese (zh)
Inventor
付居标
袁忠义
李昕颖
黄国荣
刘良辉
刘晶
赵晓宏
曹威
曾德有
冯宇
鲍茹萍
梁世港
周江平
胡昱
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.)
Jiujiang Shanshui Technology Co ltd
Nanchang University
Original Assignee
Jiujiang Shanshui Technology Co ltd
Nanchang University
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 Jiujiang Shanshui Technology Co ltd, Nanchang University filed Critical Jiujiang Shanshui Technology Co ltd
Priority to CN202210131856.7A priority Critical patent/CN114539066A/en
Publication of CN114539066A publication Critical patent/CN114539066A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for green and efficient synthesis of 2-benzoyl-3-nitrobenzoic acid belongs to the technical field of anthraquinone dye intermediate synthesis. The method comprises the steps of dissolving 3-nitrophthalic anhydride and benzene in FeCl3‑AlCl3The compound catalyst is used for catalyzing reflux reaction to prepare the 2-benzoyl-3-nitrobenzoic acid. Using FeCl3‑AlCl3Compared with the traditional single Lewis acid catalyst, the composite catalyst has higher catalytic efficiency. In addition, the method is simple to operate, safe, environment-friendly and economic, has high product yield and purity of over 98 percent, and is suitable for industrial production of the 2-benzoyl-3-nitrobenzoic acid.

Description

Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid
Technical Field
The invention relates to a method for green and efficient synthesis of 2-benzoyl-3-nitrobenzoic acid, and belongs to the technical field of synthesis of anthraquinone dye intermediates.
Background
Anthraquinone dyes are the second most synthetic dyes in the world except azo dyes, have better performance compared with azo dyes, and do not use aromatic amine carcinogenic compounds in the production process, so the anthraquinone dyes are widely applied. The 2-benzoyl-3-nitrobenzoic acid is widely applied to the fields of dyes, medicines, pesticides, other fine chemicals and the like, is used as an important intermediate for producing anthraquinone series dyes, has an increasing demand year by year, and is popular in domestic and foreign markets.
Currently, 2-benzoyl-3-nitrobenzoic acid is synthesized mainly by reacting 3-nitrobenzoic anhydride with phenylmagnesium bromide. Japanese Fuji film company (Japanese Fuji film company, Japanese patent laid-open No. 59, 137945 (1984)) has studied the synthesis of 2-benzoyl-3-nitrobenzoic acid as intermediate by nitration of phthalic anhydride to 3-nitrobenzoic anhydride, which is then reacted with phenyl magnesium bromide in carbon-based addition reaction.
Figure 656948DEST_PATH_IMAGE001
In addition, the literature reports that 2-benzoyl-3-nitrobenzoic acid is synthesized by 3-nitrobenzoic anhydride and benzene under the catalysis of Lewis acid, but the method has the problems of poor reaction selectivity and low yield.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a method for synthesizing 2-benzoyl-3-nitrobenzoic acid in an environment-friendly and efficient manner.
The invention is realized by the following technical scheme:
a green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid comprises the following steps: mixing 3-nitrophthalic anhydride, benzene and FeCl3-AlCl3Mixing the composite catalysts, and heating to react to obtain the 2-benzoyl-3-nitrobenzoic acid, wherein the reaction formula is as follows:
Figure 308509DEST_PATH_IMAGE002
；
the FeCl3-AlCl3The composite catalyst comprises FeCl3And AlCl3。
Specifically, the method comprises the following reaction steps: mixing 3-nitrophthalic anhydride, benzene and FeCl3-AlCl3Mixing the composite catalyst, and heating for reaction. After the reaction is finished, cooling to room temperature, adding an HCl aqueous solution into the system, heating to reflux, removing unreacted benzene by steam distillation, filtering out a reaction mixture while the reaction mixture is hot, and cooling and separating out a crude product of the 2-benzoyl-3-nitrobenzoic acid. Finally, the crude product is purified to obtain a pure product of the 2-benzoyl-3-nitrobenzoic acid。
The 3-nitrophthalic anhydride, benzene and FeCl mentioned in step (a)3-AlCl3The mol ratio of the composite catalyst is 1:3: 1.7-1.8.
FeCl described in step (ii)3-AlCl3The composite catalyst comprises FeCl3And AlCl3Preferably, FeCl3-AlCl3FeCl in composite catalyst3The mole fraction of (B) is 10-100%, and more preferably FeCl3-AlCl3FeCl in composite catalyst3Is 50% to 100%, most preferably FeCl3-AlCl3FeCl in composite catalyst3The mole fraction of (A) is 90-98%.
Further preferably: the specific reaction step is to mix dry FeCl3-AlCl3Adding the composite catalyst into dry benzene, heating and refluxing for 0.5h, and then slowly adding 3-nitrophthalic anhydride into the reaction system to start reaction until the reaction is finished.
More preferably: in the step, the heating reflux reaction temperature is 70-90 ℃, and the reaction time is 3-4 h.
Further preferably: the HCl aqueous solution in the step (1) is a 2.5% HCl solution in volume fraction.
Further preferred is: the purification step in the step is to dissolve the crude product of the 2-benzoyl-3-nitrobenzoic acid in an anhydrous sodium carbonate solution, filter and acidify the crude product by hydrochloric acid, and separate the crude product to obtain a pure product of the 2-benzoyl-3-nitrobenzoic acid.
Compared with the prior art, the invention has the following remarkable advantages: (1) the method adopts two cheap and easily obtained reaction raw materials of 3-nitrophthalic anhydride and benzene, thereby reducing the production cost. (2) The method adopts FeCl3-AlCl3Compared with the traditional single Lewis acid catalyst, the composite catalyst has good selectivity and higher catalytic efficiency. (3) The method has the advantages of simple reaction conditions, convenient and safe operation, and environmental-friendly and economic post-treatment mode. (4) The 2-benzoyl-3-nitrobenzoic acid synthesized by the method has high yield and purity of more than 98 percent. (5) The method has the advantages of easily-accessible principle, simple reaction conditions, and simultaneous productionThe yield and purity are high, and the method is suitable for the industrial production of the 2-benzoyl-3-nitrobenzoic acid.
Detailed Description
The reaction equation for synthesizing 2-benzoyl-3-nitrobenzoic acid is as follows:
Figure 884984DEST_PATH_IMAGE003
example 1:
adding dry FeCl into a two-neck round-bottom flask in advance3(6.48 g, 0.04 mol), dried AlCl3(53.2 g, 0.40 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.44 mol, 1.7 eq, FeCl in it)3The molar fraction is 9 percent), dissolved in dry benzene (69 mL, 0.78 mol, 3 eq), heated to 80 ℃ and refluxed for 0.5h, then 3-nitrophthalic anhydride (50 g, 0.26mol, 1 eq) is slowly added under the condition of keeping the temperature, and the reaction is continued for 3h under stirring. After the reaction is finished, cooling to room temperature, adding an HCl aqueous solution (the volume fraction of HCl is 2.5%) which is equal to the volume of benzene into the reaction system, heating to reflux, distilling by using steam to remove unreacted benzene, filtering the reaction mixture while the reaction mixture is hot, and cooling and separating out the crude product of the 2-benzoyl-3-nitrobenzoic acid. Finally, the crude product was dissolved in anhydrous sodium carbonate solution, filtered and acidified with hydrochloric acid, and separated to give pure 2-benzoyl-3-nitrobenzoic acid (21.08g, 30%) with a purity of 98.5% (HPLC).
The liquid phase detection method of the 2-benzoyl-3-nitrobenzoic acid comprises the following steps: mobile phase of methanol-waterV:V=3:2), and additionally 0.5% by mass of anhydrous Na each was added2SO4And 1.6% phosphoric acid; chromatographic column with octadecylsilane chemically bonded silica as filler (C18, 4.6X 250 mm, 5 μm); the detection wavelength is 254 nm; the flow rate is 1.0 mL/min; the column temperature is 30 ℃; test solution: about 50mg of sample was taken and taken into a 10mL volumetric flask, dissolved in methanol and diluted to the mark.
Example 2:
the synthesis method is as in example 1, except that FeCl is added3(14.27 g, 0.088 mol)，AlCl3(46.81 g, 0.352 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.44 mol, 1.7 eq, FeCl in it)3Molar fraction of 20%), to give pure 2-benzoyl-3-nitrobenzoic acid (24.57g, 35%) with a purity of 98.4% (HPLC).
Example 3:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(21.38g, 0.132 mol)，AlCl3(40.96 g, 0.308 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.44 mol, 1.7 eq, FeCl in it)3Mole fraction of 30%) to obtain pure 2-benzoyl-3-nitrobenzoic acid (25.27 g, 36%) with purity of 98.6% (HPLC).
Example 4:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(35.68g, 0.22 mol)，AlCl3(29.26 g, 0.22 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.44 mol, 1.7 eq, FeCl in it)3Mole fraction of 50%), and the final product was 98.3% (HPLC) pure 2-benzoyl-3-nitrobenzoic acid (32.30 g, 46%).
Example 5:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(37.26 g, 0.23 mol)，AlCl3(30.59 g, 0.23 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it3Mole fraction of 50%), and finally pure 2-benzoyl-3-nitrobenzoic acid (36.51 g, 52%) with a purity of 98.2% (HPLC).
Example 6:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(38.07g, 0.235 mol)，AlCl3(31.26 g, 0.235 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.47 mol, 1.8 eq, FeCl in it)3The mole fraction is 50 percent), and finally the pure 2-benzoyl-3-nitrobenzoic acid (33 g) is obtained47%) and 98.6% purity (HPLC).
Example 7:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(52.23 g, 0.322 mol)，AlCl3(18.35 g, 0.138 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it3Mole fraction of 70%), and the final product was 98.4% pure 2-benzoyl-3-nitrobenzoic acid (39.32 g, 56%).
Example 8:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(67.15 g, 0.414 mol)，AlCl3(6.12 g, 0.046 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it390% by mole fraction) to obtain pure 2-benzoyl-3-nitrobenzoic acid (49.14g, 70%) with a purity of 98.2% (HPLC).
Example 9:
the synthesis method is as in example 1, except that FeCl is added3(68.64 g, 0.423 mol)，AlCl3(4.92 g, 0.037 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it392% by mole fraction) to obtain pure 2-benzoyl-3-nitrobenzoic acid (50.55 g, 72%) with a purity of 98.3% (HPLC).
Example 10:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(70.13 g, 0.432 mol)，AlCl3(3.72 g, 0.028 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl among them394% mole fraction) to obtain pure 2-benzoyl-3-nitrobenzoic acid (52.66 g, 75%) with 98.4% purity (HPLC).
Example 11:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(70.88 g, 0.437 mol)，AlCl3(3.06 g, 0.023 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it395% mole fraction) to obtain pure 2-benzoyl-3-nitrobenzoic acid (53.36 g, 76%) with purity of 98.6% (HPLC).
Example 12:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(73.12g, 0.451 mol)，AlCl3(1.20 g, 0.009 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it398% by mole fraction) to obtain pure 2-benzoyl-3-nitrobenzoic acid (45.63 g, 65%) with a purity of 98.3% (HPLC).
Example 13:
the synthesis method is as in example 1, and differs from example 1 in that FeCl is contained therein3(73.87g, 0.455 mol)，AlCl3(0.665 g, 0.005 mol), FeCl obtained by mixing the two3-AlCl3Composite catalyst (0.46 mol, 1.75 eq, FeCl in it3Molar fraction 99%), and finally pure 2-benzoyl-3-nitrobenzoic acid (42.78 g, 61%) with a purity of 98.5% (HPLC).
Example 14:
adding dry FeCl into a two-neck round-bottom flask in advance3(74.61g, 0.46 mol, 1.75 eq) was dissolved in dry benzene (69 mL, 0.78 mol, 3 eq), heated to 80 ℃ and refluxed for 0.5h, then 3-nitrophthalic anhydride (50 g, 0.26mol, 1 eq) was added slowly under constant temperature, and the reaction was continued for 3h with stirring. After the reaction is finished, cooling to room temperature, adding an HCl aqueous solution (the volume fraction of HCl is 2.5%) which is equal to the volume of benzene into the reaction system, heating to reflux, distilling by using steam to remove unreacted benzene, filtering the reaction mixture while the reaction mixture is hot, and cooling and separating out the crude product of the 2-benzoyl-3-nitrobenzoic acid. Finally, the crude product was dissolved in anhydrous sodium carbonate solution, filtered and acidified with hydrochloric acid, and isolated to give pure 2-benzoyl-3-nitrobenzoic acid (39.28g, 56%) with a purity of 98.5% (HPLC).
The specific examples set forth above illustrate only preferred embodiments of the invention and are not intended to limit the scope of the invention. It should be noted that any variations, modifications and substitutions may be made without departing from the spirit of the present invention, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (7)

1. A green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid is characterized in that 3-nitrophthalic anhydride, benzene and FeCl are added3-AlCl3Mixing the composite catalysts, and heating to react to obtain the 2-benzoyl-3-nitrobenzoic acid, wherein the reaction formula is as follows:
Figure 614758DEST_PATH_IMAGE001
；
the FeCl3-AlCl3The composite catalyst comprises FeCl3And AlCl3。
2. The method for green high-efficiency synthesis of 2-benzoyl-3-nitrobenzoic acid according to claim 1, wherein the 3-nitrophthalic anhydride, benzene, FeCl3-AlCl3The mol ratio of the composite catalyst is 1:3: 1.7-1.8.
3. The method for green high-efficiency synthesis of 2-benzoyl-3-nitrobenzoic acid according to claim 1, wherein the FeCl is3-AlCl3FeCl in composite catalyst3The mole fraction of (A) is 50% -100%.
4. The method for green high-efficiency synthesis of 2-benzoyl-3-nitrobenzoic acid according to claim 3, wherein the FeCl is3-AlCl3FeCl in composite catalyst3The mole fraction of (A) is 90-98%.
5. According to any one of claims 1 to 4The method for green and efficient synthesis of 2-benzoyl-3-nitrobenzoic acid is characterized in that dry FeCl is added3-AlCl3Adding the composite catalyst into dry benzene, heating and refluxing for 0.5h, adding 3-nitrophthalic anhydride, and continuing heating and reacting until the reaction is finished.
6. The method for green high-efficiency synthesis of 2-benzoyl-3-nitrobenzoic acid according to any one of claims 1 to 4, characterized in that the reaction temperature is 70-90 ℃.
7. The method for green high-efficiency synthesis of 2-benzoyl-3-nitrobenzoic acid according to any one of claims 1 to 4, characterized in that: the reaction time is 3-4 h.
CN202210131856.7A 2022-02-14 2022-02-14 Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid Pending CN114539066A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210131856.7A CN114539066A (en) 2022-02-14 2022-02-14 Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210131856.7A CN114539066A (en) 2022-02-14 2022-02-14 Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid

Publications (1)

Publication Number Publication Date
CN114539066A true CN114539066A (en) 2022-05-27

Family

ID=81673994

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210131856.7A Pending CN114539066A (en) 2022-02-14 2022-02-14 Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid

Country Status (1)

Country Link
CN (1) CN114539066A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500636A (en) * 1983-01-27 1985-02-19 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
CN1827587A (en) * 2005-11-24 2006-09-06 东华大学 Process for synthesizing 2-(4'-amino benzoyl) benzoic acid
CN106008187A (en) * 2016-06-04 2016-10-12 江阴市长江化工有限公司 Preparation method of synthetic anthraquinone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500636A (en) * 1983-01-27 1985-02-19 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
CN1827587A (en) * 2005-11-24 2006-09-06 东华大学 Process for synthesizing 2-(4'-amino benzoyl) benzoic acid
CN106008187A (en) * 2016-06-04 2016-10-12 江阴市长江化工有限公司 Preparation method of synthetic anthraquinone

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LAWRENCE, WALTER A.，等: "Fridel and Crafts\' reaction-nitrophthalic anhydrides and acetylaminophthalic anhydrides with benzene and aluminium chloride", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 42, pages 1871 - 9 *
李树安;李润莱;张珍明;葛洪玉;齐家娟;: "FeCl_3/ZnCl_2加压催化酰化制备4-氯二苯甲酮工业化技术", 精细化工, no. 06, pages 708 - 711 *
钱圣利;: "2-苯甲酰基-3-氯苯甲酸的合成工艺条件研究", 浙江化工, no. 02, pages 14 - 17 *
雷春华, 李承志: "一步法合成5, 12-(二苯乙炔基)丁省化学发光染料", 化学工程师, no. 10, pages 1 - 3 *

Similar Documents

Publication Publication Date Title
CN101757950B (en) Catalyst system and application for leading poly-fluorine phenyl in organic synthesis thereof
CN108047036A (en) A kind of synthetic method of Ergol
CN103228611B (en) 3,4-dialkyl group diphenyldicarboxylic acid compound, 3,4-dialkoxy carbonyl biphenyl bases-3 ', 4 '-dicarboxylic acid and corresponding acid anhydrides, and the preparation method of these compounds
CN111423304B (en) Synthetic method of 1,1-difluoroolefin compound
CN111718372B (en) Axial chiral phosphine-alkene ligand and preparation method and application thereof
CN114516817B (en) Chemical intermediate and preparation method thereof
CN112300073B (en) Preparation method of isoquinoline derivative
CN114539066A (en) Green and efficient method for synthesizing 2-benzoyl-3-nitrobenzoic acid
CN101781222A (en) Method for preparing enamine ketone compound
CN113980028B (en) Preparation method of chiral spiro indolone compound
CN113698276B (en) Synthesis method of 2, 6-dihydroxytoluene
CN113105301B (en) Method for preparing conjugated diyne compound by using copper complex
CN113443950A (en) Method for reducing carbonyl into methylene under illumination
CN101148402A (en) Process for preparing 2-bromofluorenone
CN110818620A (en) Preparation method of meta-aromatic aldehyde
CN111100042A (en) Preparation method of 2-methoxy-5-sulfonamide benzoic acid
KR102632488B1 (en) Synthetic method for 3,3-bis(bromomethyl)oxetane via continuous flow chemistry
CN116514711A (en) New synthesis process of key intermediate of montelukast sodium
CN114773206B (en) Synthesis method of o-tert-butylaniline
CN100357245C (en) Prepn process of 2,5-dihalogeno benzoic acid
CN115286609B (en) Preparation method of 2-trifluoromethyl substituted dihydrobenzochromene
CN111763198B (en) Preparation method of 5-substituted cyclopropyl formylaminoindole derivative
CN111808021B (en) Preparation method of indacaterol and salt thereof
CN116606250A (en) Preparation method of key intermediate of montelukast sodium
JPH0529215B2 (en)

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