CN108264456A - The synthetic method and its synthetic intermediate that 2,8- dibromos are bent - Google Patents
The synthetic method and its synthetic intermediate that 2,8- dibromos are bent Download PDFInfo
- Publication number
- CN108264456A CN108264456A CN201611257305.6A CN201611257305A CN108264456A CN 108264456 A CN108264456 A CN 108264456A CN 201611257305 A CN201611257305 A CN 201611257305A CN 108264456 A CN108264456 A CN 108264456A
- Authority
- CN
- China
- Prior art keywords
- dibromos
- bent
- bromo
- reaction
- synthetic
- 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
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
- C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
- C07C43/176—Unsaturated ethers containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to organic synthesis sciemtifec and technical spheres, and in particular to the synthetic method and its synthetic intermediate that 2,8 dibromos are bent.The synthetic method that 2,8 dibromo provided by the present invention is bent includes suzuki reaction step, phosphorus ylide reaction step and Friedel Crafts reaction steps.Provided by the present invention 2, the synthetic route end for the synthetic method that 8 dibromos are bent, gross production rate is up to 58.2%, can be effectively synthesized and amplify production.The reaction raw materials cost is relatively low, and reaction is mild controllable, and by optimizing the dosage of catalyst, especially with nickel chloride as catalyst, cost is controllable, can be produced on a large scale.Its product quality is stablized, and purity can reach more than 99%.The first synthetic intermediate 5 bromine 2 (6 bromine, the 2 naphthalene) benzaldehyde carried by the present invention can obtain the second synthetic intermediate that 2,8 dibromos are bent with a step, so as to which 2,8 dibromo of synthesis of high yield, short-circuit line is bent.
Description
Technical field
The invention belongs to organic synthesis sciemtifec and technical spheres, and in particular to the synthetic method and its synthesis that 2,8- dibromos are bent are intermediate
Body.
Background technology
Class compound is bent due to its distinctive conjugated structure, the extensive concern of organic semiconductor industry is caused, passes through bell
The coupling other groups such as wood reaction, the graceful reaction in Wall can obtain a variety of organofunctional materials.2,8 disubstituted in the wrong can be used as have
The functional forms organic semi-conductor weight such as organic electro luminescent, organic solar batteries, organic laser, organic photoswitch, ion detection
Synthetic intermediate is wanted, the compound after modification can be used as in organic electroluminescence device (OLED) shine Subjective and Objective material, current-carrying
The materials such as sub- transmission material, exciton-blocking material.
Class compound in the wrong is made a general survey of, decorating site is concentrated mainly on 6 and 12, and the synthesis in other sites is less, document
In related synthetic schemes it is comparatively laborious, Dann, O. et al. delivered 2,8- dibromos in 1973 and bend several synthetic schemes, but do not have
There is specific yield to report, and it is larger to synthesize difficulty, (Justus Liebigs Annalen der Chemie, 1973,1112-
1140)。
Invention content
To solve the deficiencies in the prior art, the synthetic method and its synthesis bent the present invention provides one kind 2,8- dibromos are intermediate
Body.
Technical solution provided by the present invention is as follows:
The present invention provides intermediate 5- bromo- 2- (the bromo- 2- naphthalenes of 6-) benzaldehyde of the first synthesis that 2,8- dibromos are bent, structures
Shown in formula such as formula (I):
Intermediate 5- bromo- 2- (the bromo- 2- naphthalenes of the 6-) benzaldehyde of the first synthesis bent by 2,8- dibromos provided by the present invention,
It can be bent with high yield, the synthesis 2 of short-circuit line, 8- dibromos.
The second synthesis that 2,8- dibromos are bent is intermediate, shown in structural formula such as formula (II):
The second synthesis bent by 2,8- dibromos provided by the present invention is intermediate, can with high yield, the synthesis 2 of short-circuit line,
8- dibromos are bent.
The first bromo- 2- of synthetic intermediate 5- (the bromo- 2- naphthalenes of the 6-) benzaldehyde carried by the present invention can be obtained with a step
The second synthetic intermediate that 2,8- dibromos are bent, so as to the synthesis 2 of high yield, short-circuit line, 8- dibromos are bent.
The present invention also provides the synthetic methods that one kind 2,8- dibromos are bent, and include the following steps:
1) the bromo- 2- benzaldehyde iodines of 5- obtain the bromo- 2- of 5- (the bromo- 2- naphthalenes of 6-) with the bromo- 2- naphthalene boronic acids of 6- by suzuki reaction
Benzaldehyde;
2) the bromo- 2- of 5- (the bromo- 2- naphthalenes of 6-) benzaldehyde is reacted with chlorination methoxymethyl triphenylphosphonium microcosmic salt with phosphorus ylide
Alkene intermediates are obtained, shown in the structural formula such as above formula (II) of alkene intermediates;
3) 2,8- dibromos are obtained by the reaction by Friedel-Crafts with the alkene intermediates that step 2) obtains to bend.
The structural formula that 2,8- dibromos are bent is
Specifically, the phosphorus ylide in step 2) is
Specifically, using nickel chloride as catalyst in step 3).
Specifically, in step 3), the mass percent of alkene intermediates that nickel chloride is obtained with step 2) is 1~20%.
Specifically:
Step 1) is:The bromo- 2- benzaldehyde iodines of 5-, the bromo- 2- naphthalene boronic acids of 6- and Pd (PPh3)4According to molar ratio 1:0.9~1.5:
0.002~0.1 feeds intake, and lye is that either the solvent such as strontium carbonate is toluene and ethyl alcohol mixed system or four for sodium carbonate, potassium carbonate
Hydrogen furans, at 60~120 DEG C, the reaction time is 2~24 hours for reaction temperature control;
Step 2) is:The bromo- 2- of 5- (the bromo- 2- naphthalenes of 6-) benzaldehyde, methoxymethyl triphenylphosphonium phosphonium chloride and potassium tert-butoxide
According to molar ratio 1:1~2:1~2 feeds intake, solvent be tetrahydrofuran or Isosorbide-5-Nitrae-dioxane, control temperature -10 DEG C~0 DEG C into
Row stirring, 0.5~24 hour reaction time;
Step 3) is:In 1,2- dichloroethane solvents, control temperature is stirred at 0~60 DEG C, mixing time 1~12
Hour, 2,8- dibromos are obtained by the reaction under the catalysis of nickel chloride with the alkene intermediates that step 2) obtains and bend.
The synthetic route end for the synthetic method that 2,8- dibromos provided by the present invention are bent, gross production rate are up to 58.2%, can
It is effectively synthesized and amplifies production.
The present invention has the following advantages and effects:
1. synthesis 2,8- dibromos, which are bent, only needs three steps, ultimate yield can reach 58.2%.
2. reaction raw materials cost is relatively low, reaction is mild controllable, by optimizing the dosage of catalyst, especially with chlorine
Change nickel as catalyst, cost is controllable, can be produced on a large scale.
3. product quality is stablized, purity can reach more than 99%.
4. product 2,8- dibromos are bent as intermediate, can conveniently be modified by suzuki reaction, the graceful reaction in Wall etc.,
Obtain the material of potential commercial value.
Description of the drawings
Fig. 1 is the nuclear-magnetism figure that 2, the 8- dibromos that the embodiment of the present invention obtains are bent.
Fig. 2 is the mass spectrogram that 2, the 8- dibromos that the embodiment of the present invention obtains are bent.
Specific embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
Limit the scope of the present invention.
Embodiment 1:
The synthesis that 2,8- dibromos are bent
Toluene (80mL) in 500ml two mouth flasks, ethyl alcohol (40mL), 2M K2CO3Aqueous solution (80mL) mixed solution ultrasound
It is added in after 30 minutes, the bromo- 2- benzaldehyde iodines (3.10g, 10mmol) of 5-, 2- naphthalene boronic acids (2.8g, 11mmol) bromo- with 6-, Pd
(PPh3)4(230mg,0.2mmol),.It is heated to 80 DEG C to stir 24 hours, dichloromethane extraction, washing, anhydrous sodium sulfate drying,
Filtering, product 3.2g, yield 82% are obtained after concentration by column chromatography.
Addition methoxymethyl triphenylphosphonium phosphonium chloride (5.10g, 15mmol) in 100mL single port bottles, potassium tert-butoxide (1.23g,
15mmol), tetrahydrofuran 60mL is added in, temperature control is stirred at 0 DEG C, and reaction adds in the bromo- 2- of 5- (the bromo- 2- of 6- after 0.5 hour
Naphthalene) benzaldehyde (3.10g, 10mmol), it is stirred at room temperature 2 hours, adds water quenching reaction, be extracted with ethyl acetate, wash, it is anhydrous
Sodium sulphate is dried, and filtering obtains product 3.7g, yield 88% after concentration by column chromatography.
In 1,2- dichloroethane solvents, second step formed product 4.2g under the catalysis of nickel chloride 0.06g (5%),
Temperature control is stirred 2 hours at 25 DEG C, and finally obtaining 2,8- dibromos by column chromatography after concentration bends 3.83g, yield 81%.
1H-NMR(400MHz,CDCl3):δ=8.82 (2H), 8.32 (2H), 8.29 (2H), 8.05 (2H), 7.79 (2H),
MALDI-TOF-MS(m/z):It is calculated 385.9129;Actual measurement, 385.9133.C is calculated18H10Br2:C,56.00;H,
2.61 actual measurement:C,56.04;H,2.63.
Embodiment 2:
The synthesis that 2,8- dibromos are bent
Toluene (80mL) in 500ml two mouth flasks, ethyl alcohol (40mL), 2M Cs2CO3Aqueous solution (80mL) mixed solution ultrasound
It is added in after 30 minutes, the bromo- 2- benzaldehyde iodines (3.10g, 10mmol) of 5-, 2- naphthalene boronic acids (2.8g, 11mmol) bromo- with 6-, Pd
(PPh3)4(230mg,0.2mmol),.It is heated to 90 DEG C to stir 24 hours, dichloromethane extraction, washing, anhydrous sodium sulfate drying,
Filtering, product 3.5g, yield 90% are obtained after concentration by column chromatography.
Addition methoxymethyl triphenylphosphonium phosphonium chloride (5.10g, 15mmol) in 100mL single port bottles, potassium tert-butoxide (1.23g,
15mmol), tetrahydrofuran 60mL is added in, temperature control is stirred at 0 DEG C, and reaction adds in the bromo- 2- of 5- (the bromo- 2- of 6- after 0.5 hour
Naphthalene) benzaldehyde (3.10g, 10mmol), it is stirred at room temperature 3 hours, adds water quenching reaction, be extracted with ethyl acetate, wash, it is anhydrous
Sodium sulphate is dried, and filtering obtains product 3.7g, yield 89% after concentration by column chromatography.
In 1,2- dichloroethane solvents, second step formed product 4.2g nickel chloride 0.12g (510%) catalysis
Under, temperature control is stirred 1.5 hours at 25 DEG C, and finally obtaining 2,8- dibromos by column chromatography after concentration bends 3.92g, yield
83%.
MALDI-TOF-MS(m/z):It is calculated 385.9129;Actual measurement, 385.9131.Pass through thin-layer chromatography contact plate point
Analysis, product bend Rf value (R with 2, the 8- dibromos having been acknowledgedf) value is consistent, it was demonstrated that product 2,8- dibromos are bent.
Embodiment 3:
The synthesis that 2,8- dibromos are bent
Toluene (80mL) in 500ml two mouth flasks, ethyl alcohol (40mL), 2M Na2CO3Aqueous solution (80mL) mixed solution ultrasound
It is added in after 30 minutes, the bromo- 2- benzaldehyde iodines (3.10g, 10mmol) of 5-, 2- naphthalene boronic acids (2.8g, 11mmol) bromo- with 6-, Pd
(PPh3)4(135mg,0.1mmol),.It is heated to 85 DEG C to stir 16 hours, dichloromethane extraction, washing, anhydrous sodium sulfate drying,
Filtering, product 3.1g, yield 79% are obtained after concentration by column chromatography.
Addition methoxymethyl triphenylphosphonium phosphonium chloride (6.80g, 20mmol) in 100mL single port bottles, potassium tert-butoxide (1.64g,
20mmol), tetrahydrofuran 60mL is added in, temperature control is stirred at -5 DEG C, and reaction adds in the bromo- 2- of 5- after 0.5 hour, and (6- is bromo-
2- naphthalenes) benzaldehyde (3.10g, 10mmol), it is stirred at room temperature 2 hours, adds water quenching reaction, be extracted with ethyl acetate, wash, nothing
Aqueous sodium persulfate is dried, and filtering obtains product 3.6g, yield 85% after concentration by column chromatography.
In 1,2- dichloroethane solvents, second step formed product 4.2g nickel chloride 0.03g (2.5%) catalysis
Under, temperature control is stirred 2 hours at 25 DEG C, and finally obtaining 2,8- dibromos by column chromatography after concentration bends 3.54g, yield
75%.MALDI-TOF-MS(m/z):It is calculated 385.9129;Actual measurement, 385.9132.Pass through thin-layer chromatography point plate analysis, production
Object bends Rf value (R with 2, the 8- dibromos having been acknowledgedf) value is consistent, it was demonstrated that product 2,8- dibromos are bent.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (7)
- The first synthetic intermediate that 1.2,8- dibromos are bent, which is characterized in that shown in structural formula such as formula (I):
- The second synthetic intermediate that 2.2,8- dibromos are bent, which is characterized in that shown in structural formula such as formula (II):
- 3. one kind 2, the synthetic method that 8- dibromos are bent, which is characterized in that include the following steps:1) the bromo- 2- benzaldehyde iodines of 5- obtain the bromo- 2- of 5- (the bromo- 2- naphthalenes of 6-) benzene first with the bromo- 2- naphthalene boronic acids of 6- by suzuki reaction Aldehyde;2) the bromo- 2- of 5- (the bromo- 2- naphthalenes of 6-) benzaldehyde is obtained by the reaction with chlorination methoxymethyl triphenylphosphonium microcosmic salt with phosphorus ylide Alkene intermediates;3) 2,8- dibromos are obtained by the reaction by Friedel-Crafts with the alkene intermediates that step 2) obtains to bend.
- 4. the synthetic method that 2,8- dibromos according to claim 3 are bent, it is characterised in that:Phosphorus ylide in step 2) is
- 5. the synthetic method that 2,8- dibromos according to claim 3 are bent, it is characterised in that:Using nickel chloride to urge in step 3) Agent.
- 6. the synthetic method that 2,8- dibromos according to claim 5 are bent, it is characterised in that:In step 3), nickel chloride and step The mass percent of the rapid alkene intermediates 2) obtained is 1~20%.
- 7. the synthetic method that 2,8- dibromos according to claim 3 are bent, it is characterised in that:Step 1) is:The bromo- 2- benzaldehyde iodines of 5-, the bromo- 2- naphthalene boronic acids of 6- and Pd (PPh3)4According to molar ratio 1:0.9~1.5: 0.002~0.1 feeds intake, and lye is that either the solvent such as strontium carbonate is toluene and ethyl alcohol mixed system or four for sodium carbonate, potassium carbonate Hydrogen furans, at 60~120 DEG C, the reaction time is 2~24 hours for reaction temperature control;Step 2) is:The bromo- 2- of 5- (the bromo- 2- naphthalenes of 6-) benzaldehyde, methoxymethyl triphenylphosphonium phosphonium chloride and potassium tert-butoxides according to Molar ratio 1:1~2:1~2 feeds intake, and solvent is tetrahydrofuran or Isosorbide-5-Nitrae-dioxane, and control temperature is stirred at -10 DEG C~0 DEG C It mixes, 0.5~24 hour reaction time;Step 3) is:In 1,2- dichloroethane solvents, control temperature is stirred at 0~60 DEG C, and mixing time 1~12 is small When, 2,8- dibromos are obtained by the reaction under the catalysis of nickel chloride with the alkene intermediates that step 2) obtains and bend.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611257305.6A CN108264456A (en) | 2016-12-30 | 2016-12-30 | The synthetic method and its synthetic intermediate that 2,8- dibromos are bent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611257305.6A CN108264456A (en) | 2016-12-30 | 2016-12-30 | The synthetic method and its synthetic intermediate that 2,8- dibromos are bent |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108264456A true CN108264456A (en) | 2018-07-10 |
Family
ID=62754536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611257305.6A Pending CN108264456A (en) | 2016-12-30 | 2016-12-30 | The synthetic method and its synthetic intermediate that 2,8- dibromos are bent |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108264456A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114057655A (en) * | 2021-12-13 | 2022-02-18 | 郑州华赞医药科技有限公司 | Synthetic method of dibromo compound |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102083839A (en) * | 2008-02-06 | 2011-06-01 | 阿斯利康(瑞典)有限公司 | Compounds |
CN102712558A (en) * | 2009-11-05 | 2012-10-03 | 出光兴产株式会社 | Asymmetric aromatic compound containing heterocyclic ring, compound for organic thin film transistor, and organic thin film transistor using same |
KR20150000967A (en) * | 2013-06-26 | 2015-01-06 | 최돈수 | Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device |
CN104703952A (en) * | 2012-10-02 | 2015-06-10 | 佳能株式会社 | Novel organic compound and organic light-emitting device and display apparatus having the same |
CN105418357A (en) * | 2015-11-20 | 2016-03-23 | 江苏三月光电科技有限公司 | Benzo spirofluorene compound and application thereof in OLED |
-
2016
- 2016-12-30 CN CN201611257305.6A patent/CN108264456A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102083839A (en) * | 2008-02-06 | 2011-06-01 | 阿斯利康(瑞典)有限公司 | Compounds |
CN102712558A (en) * | 2009-11-05 | 2012-10-03 | 出光兴产株式会社 | Asymmetric aromatic compound containing heterocyclic ring, compound for organic thin film transistor, and organic thin film transistor using same |
CN104703952A (en) * | 2012-10-02 | 2015-06-10 | 佳能株式会社 | Novel organic compound and organic light-emitting device and display apparatus having the same |
KR20150000967A (en) * | 2013-06-26 | 2015-01-06 | 최돈수 | Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device |
CN105418357A (en) * | 2015-11-20 | 2016-03-23 | 江苏三月光电科技有限公司 | Benzo spirofluorene compound and application thereof in OLED |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114057655A (en) * | 2021-12-13 | 2022-02-18 | 郑州华赞医药科技有限公司 | Synthetic method of dibromo compound |
CN114057655B (en) * | 2021-12-13 | 2023-10-27 | 郑州华赞医药科技有限公司 | Synthesis method of dibromo compound |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107936029B (en) | Method for synthesizing Ribociclib | |
CN106883207A (en) | A kind of preparation method of trimeric indenyl bicoumarin fluorescent dye | |
CN103274910B (en) | Synthesis method of benzenetricarboxaldehyde compound | |
Krebs et al. | Fluorinated molecules relevant to conducting polymer research | |
CN108264456A (en) | The synthetic method and its synthetic intermediate that 2,8- dibromos are bent | |
CN107778279A (en) | A kind of preparation method of Atorvastatin calcium intermediate | |
CN102633836B (en) | Method for synthesizing bis(diphenylphosphino)-alkane | |
CN105348249B (en) | A kind of synthetic method of the ketone of 4 chloromethyl, 5 methyl, 1,3 dioxole 2 | |
CN104262242B (en) | The in-situ preparation iodo reagent method synthesis iodo-4-aminopyridine of 3,5-bis- | |
CN102942444B (en) | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene | |
CN111170973B (en) | Synthetic method of benzofuranone | |
CN105753643A (en) | Synthesis method for 2,5-dibromo-iodobenzene | |
CN106518758A (en) | Preparation method of Betrixaban intermediate N-(5-chloro-2-pyridyl)-2-(4-cyanobenzeneformamido)-5-metoxybenzamide | |
CN108264447A (en) | The preparation method and its prepare intermediate that intermediate and 2,8- dibromos bend are bent and preparation method thereof and prepared to 3,9- dibromos | |
CN107954976B (en) | A method of synthesis 3,4- dimethoxy-thiophene | |
CN101293959B (en) | Hyperbranched conjugated polymer sensing material, preparation method and application thereof | |
CN105968013B (en) | A kind of π-copolymer and preparation method thereof | |
CN106397470B (en) | A kind of synthetic method of the fluorenes of 3,3 ' hypoboric acid pinacol ester, 9,9 ' spiral shell two | |
CN105330633A (en) | Preparation method for biphenyltetracarboxylic dianhydride mixture | |
CN109485550A (en) | The method for preparing styrene derivative with ionic liquid | |
CN102285878B (en) | Method for preparing 2-halo-4,5-dimethoxy benzoic acid | |
CN107827844A (en) | A kind of method for synthesizing butyrolactone derivative | |
CN103923102B (en) | Synthesis method of compound 5, 8-di (3, 4-ethylenedioxy-thienyl) -quinoline | |
CN102603777A (en) | Preparation method of nysted reagent | |
CN109970520B (en) | Preparation method of thermosensitive paper sensitizer benzyl-2-naphthyl ether |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180710 |