CN108863736A - A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization - Google Patents
A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization Download PDFInfo
- Publication number
- CN108863736A CN108863736A CN201810840761.6A CN201810840761A CN108863736A CN 108863736 A CN108863736 A CN 108863736A CN 201810840761 A CN201810840761 A CN 201810840761A CN 108863736 A CN108863736 A CN 108863736A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acids
- aromatic carboxylic
- preparation
- carbonyl
- carbonyl functionalization
- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
Abstract
The invention discloses a kind of preparation methods of the aromatic carboxylic acids of carbonyl functionalization.The present invention passes through fragrant carboxylic acid halides and toluene carries out Friedel-Crafts reaction and generates aromatic ketone, then again by methyl oxidation at carboxyl, to obtain the aromatic carboxylic acids of carbonyl functionalization.This method novel and unique, experimental procedure is simple, and two-step reaction is achieved with required product, and reaction carries out in room temperature or ice-water bath, energy consumption is small, easy to operate, and yield is high, save the cost, while the presence of carbonyl group is also that the further Post functionalization of product is provided convenience, and is had great application prospect.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization.
Background technique
The aromatic carboxylic acids of carbonyl functionalization is easy to Post functionalization, is commonly used for polymer monomer or MOF ligand, and carbonyl therein can
Small molecule for identification, so widely used.But its structure is complex, is not easily-synthesized, therefore designs a kind of virtue of carbonyl functionalization
The preparation method of fragrant carboxylic acid becomes research hotspot.F. ChristopHer Pigge et al. utilizes 3- cyanobenzaldehyde and acetenyl
Alcohol needed for magnesium bromide reaction is made, then by itself and H2CrO43- propine acyl group benzonitrile is made in solution reaction, and it is anti-to carry out ring trimerization later
It answers, reaction is then hydrolyzed, so that a kind of aromatic carboxylic acids of carbonyl functionalization be made --- 4,4 ', 4 ' '-（Benzene -1,3,5-
Three carbonyls）Three benzoic acid.But the method reaction step is complicated, and raw material 3- cyanobenzaldehyde is difficult to synthesize, at high cost, to reaction
Condition and operator require also very high.So the simple preparation method for designing a kind of aromatic carboxylic acids of carbonyl functionalization very must
It wants.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of preparation of the aromatic carboxylic acids of carbonyl functionalization
Method.Preparation method novel and unique of the present invention, experimental procedure is simple, and two-step reaction is achieved with required product, and reacts in room
It is carried out in temperature or ice-water bath, energy consumption is small, and easy to operate, yield is high, save the cost, while also providing for its further Post functionalization
It is convenient, it has great application prospect.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization, includes the following steps：
1）In ice-water bath, 3 ~ 10 g fragrance carboxylic acid halides are dissolved in the toluene of 100 ~ 200 ml, it is anhydrous that 25 ~ 35 g are added portionwise
Alchlor, the subsequent mixture are stirred at room temperature 20 ~ 24 hours；
2）Reactant is poured into ice water, then repeatedly with methylene chloride and deionized water extraction, collects organic phase solution；
3）By gained organic phase solution after anhydrous magnesium sulfate is dry, revolving obtains crude product, and crude product is obtained with ethyl alcohol recrystallization
To aromatic ketone crystal；
4）By 50 ~ 80 ml acetic acid, 3 ~ 5 ml concentrated sulfuric acids and 1 ~ 3 g step 3）Aromatic ketone mixing obtained, and in≤40 DEG C of items
Constant temperature stirs under part；5 ~ 8 g chromium trioxides and 3 ~ 5 ml acetic anhydrides are added portionwise, become brownish black muddy to reaction mixture
After substance, continue stirring 20 ~ 24 hours；
5）Resulting product is poured into 200~300 ml ice water, is filtered after mixing evenly, the first filtrate is obtained；Filter residue gone from
It after sub- water washs repeatedly, is dissolved in 50~100 ml sodium hydroxide solutions, filters, filtrate is merged with the first filtrate；
6）Toward step 5）Filtrate in be added hydrochloric acid tune pH to 3 ~ 5, obtain crude product, crude product is recrystallized to give carbonyl through DMF
The aromatic carboxylic acids of functionalization.
Step 1）The carboxylic acid halides substituent group number of the fragrant carboxylic acid halides and position are unlimited, and contained halogen is in Cl, Br, I or F
One or more.Common aromas carboxylic acid halides includes m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride etc., but not only
It is limited to this.
Step 1）Described is specially in batches：Points of 5 batches additions of aluminum trichloride (anhydrous), every time plus 5 ~ 7 g.
Step 4）Described is specially in batches：The 3 batches of additions of chromium trioxide and acetic anhydride point, add 1.7 ~ 3 g and 1 respectively every time
~2 ml。
The present invention has the following advantages that compared with the prior art：
1）The present invention passes through fragrant carboxylic acid halides and toluene carries out Friedel-Crafts reaction and generates aromatic ketone, then again by methyl oxidation at carboxyl,
To obtain the aromatic carboxylic acids of carbonyl functionalization；This method novel and unique, experimental procedure is simple, needed for two-step reaction is achieved with
Product, and reaction carries out in room temperature or ice-water bath, energy consumption is small, and easy to operate, yield is high；
2）The aromatic carboxylic acids of carbonyl functionalization is easy to Post functionalization, is commonly used for polymer monomer or MOF ligand, and carbonyl therein
It can be used to identify small molecule.
Detailed description of the invention
Fig. 1 is the reaction equation that embodiment 1 is related to；
Fig. 2 is the reaction equation that embodiment 2 is related to；
Fig. 3 is the reaction equation that embodiment 3 is related to.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
The preparation method of phenyl-diformyl dibenzoic acid between 4,4'-, the specific steps are：
1）In ice-water bath, 4.06g m-phthaloyl chloride is dissolved in the toluene of 150ml, the anhydrous tri-chlorination of 27g is added portionwise
Aluminium, the subsequent mixture are stirred at room temperature 24 hours；
2）Reactant is poured into ice water, the subsequent reaction mixture methylene chloride and deionized water extraction repeatedly, take organic
Phase solution；
3）By gained organic phase solution after anhydrous magnesium sulfate is dry, revolving obtains crude product, and crude product is obtained with ethyl alcohol recrystallization
It is double to 3.0 g 1,3- phenylenes（P-methylphenyl ketone）Crystal；
4）60ml acetic acid is added in the three-necked bottle of a 250ml, the 3.6ml concentrated sulfuric acid and 2.0g1,3- phenylene are double（To toluene
Base ketone）, and constant temperature stirs under the conditions of 30 DEG C；
5）6.4g chromium trioxide and 3.6ml acetic anhydride is added portionwise, after reaction mixture becomes brownish black muddy substance, continues
Stir about 24 hours；
6）Resulting product is poured into 200 ml ice water, is filtered after mixing evenly, the first filtrate is obtained；Filter residue is through deionized water
It is dissolved in after washing repeatedly in 80 ml sodium hydroxide solutions, filters, filtrate is merged with the first filtrate；
7）Toward step 6）Filtrate in be added hydrochloric acid tune pH to 3, obtain crude product, crude product is recrystallized to give between 4,4'- through DMF
Phenyl-diformyl dibenzoic acid.
Specifically：
The present embodiment step 1）Middle aluminum trichloride (anhydrous) divides 5 additions, every time 5.4 g, step 2）Middle reaction mixture extraction three
It is secondary, step 3）Gained 1,3- phenylene is double（P-methylphenyl ketone）Crystal yield is 56%, step 5）Middle chromium trioxide and acetic anhydride
It is added three times, step 6）The concentration of middle sodium hydroxide solution is 2 mol/L, and phenyl-diformyl dibenzoic acid is between 4 obtained, 4'-
White powder, yield 52%.
Reaction equation involved in testing is as shown in Figure 1.
1,3- phenylene is double（P-methylphenyl ketone）：1H NMR (500MHz, chloroform-d) δ 8.40 (s, 1H),
8.21 (d, J = 7.75 Hz, 2H), 8.02 (d, J = 8.0 Hz, 4H), 7.83 (t, J = 7.86 Hz,
1H), 7.50 (d, J = 7.80 Hz, 4H), 2.80 (s, 6H)。
Phenyl-diformyl dibenzoic acid between 4,4'-：1H NMR (500 MHz, DMSO-d 6) δ 8.11 (d, J = 8.2
Hz, 4H), 8.09 – 8.04 (m, 3H), 7.89 (d, J = 8.2 Hz, 4H), 7.80 (t, J = 7.7 Hz,
1H)。
Embodiment 2
The preparation method of 4,4'- paraphenylene terephthalamide's dibenzoic acids, the specific steps are：
1）In ice-water bath, 4.03 g paraphthaloyl chlorides are dissolved in the toluene of 150 ml, 27 g anhydrous three are added portionwise
Aluminium chloride, the subsequent mixture are stirred at room temperature 24 hours；
2）Reactant is poured into ice water, repeatedly, collection has for the subsequent reaction mixture methylene chloride and deionized water extraction
Machine phase solution；
3）By gained organic phase solution after anhydrous magnesium sulfate is dry, revolving obtains crude product, and crude product is obtained with ethyl alcohol recrystallization
It is double to 3.0 g 1,4- phenylenes（P-methylphenyl ketone）Crystal；
4）60ml acetic acid is added in the three-necked bottle of a 250ml, the 3.5ml concentrated sulfuric acid and 2.0g1,4- phenylene are double（To toluene
Base ketone）, and constant temperature stirs under the conditions of 30 DEG C；
5）6.3g chromium trioxide and 3.5ml acetic anhydride is added portionwise, after reaction mixture becomes brownish black muddy substance, continues
Stirring 24 hours；
6）Resulting product is poured into 200 ml ice water, is filtered after mixing evenly, the first filtrate is obtained；Filter residue is through deionized water
It is dissolved in after washing repeatedly in 80 ml sodium hydroxide solutions, filters, filtrate is merged with the first filtrate；
7）Hydrochloric acid tune pH to 3 is added in filtrate, obtains crude product；Crude product is recrystallized to give 4,4'- paraphenylene terephthalamide's hexichol through DMF
Formic acid.
Specifically：
The present embodiment step 1）5 additions of middle aluminum trichloride (anhydrous) point, step 2）Middle reaction mixture extracts 3 times, step 3）Institute
It is double to obtain 1,4- phenylene（P-methylphenyl ketone）Crystal yield is 58%, step 5）Middle chromium trioxide and acetic anhydride are added three times,
Step 6）The concentration of middle sodium hydroxide solution is 2 mol/L, and obtained 4,4'- paraphenylene terephthalamide's dibenzoic acid is white powder,
Yield is 56%.
Reaction equation involved in testing is as shown in Figure 2.
1,4- phenylene is double（P-methylphenyl ketone）：1H NMR (500 MHz, chloroform-d) δ 7.88 (s, 1H),
7.77 (d, J = 8.2 Hz, 1H), 7.33 (d, J = 7.9 Hz, 1H), 2.48 (s, 2H)。
4,4'- paraphenylene terephthalamide's dibenzoic acid：1H NMR (500 MHz, DMSO-d 6) δ 8.13 (d, J = 8.4
Hz, 1H), 7.93 (s, 1H), 7.90 (d, J = 8.4 Hz, 1H)。
Embodiment 3
4,4',4'' -（Three carbonyl of benzene -1,3,5-）The preparation method of three benzoic acid, the specific steps are：
1）In ice-water bath, 4 g pyromellitic trimethylsilyl chlorides are dissolved in the toluene of 170 ml, the anhydrous trichlorine of 27 g is added portionwise
Change aluminium.The subsequent mixture is stirred at room temperature 24 hours；
2）Reactant is poured into ice water, the subsequent reaction mixture methylene chloride and deionized water extraction are multiple；
3）Gained organic phase solution revolving after anhydrous magnesium sulfate is dry obtains crude product, and crude product is obtained with ethyl alcohol recrystallization
3.8 g benzene -1,3,5- three（P-methylphenyl ketone）Crystal；
4）75 ml acetic acid, the 4.5 ml concentrated sulfuric acids and 2.84 g benzene -1,3,5- tri- are added in the three-necked bottle of 250 ml（It is right
Tolyl ketone）, and stir at room temperature；
5）7.2 g chromium trioxides and 4.8 ml acetic anhydrides are added portionwise, after reaction mixture becomes brownish black muddy substance, after
Continuous stirring 24 hours；
6）Resulting product is poured into 300 ml ice water, is filtered after mixing evenly, the first filtrate is obtained；Filter residue is anti-through deionized water
It is dissolved in after after backwashing in 100 ml sodium hydroxide solutions, filters, filtrate is merged with the first filtrate；
7）Hydrochloric acid tune pH to 4 is added in filtrate, obtains crude product；Crude product is recrystallized to give 4,4 ', 4 ' through DMF '-（Benzene -1,3,
Tri- carbonyl of 5-）Three benzoic acid.
Specifically：
The present embodiment step 1）5 additions of middle aluminum trichloride (anhydrous) point, step 2）Middle reaction mixture extracts three times, step 3）Institute
Obtain benzene -1,3,5- three（P-methylphenyl ketone）Crystal yield is 60%, step 5）Middle chromium trioxide and acetic anhydride are added three times, step
Rapid 6）The concentration of middle sodium hydroxide solution be 2 mol/L, obtained 4,4 ', 4 ' '-（Three carbonyl of benzene -1,3,5-）Three benzoic acid are
White powder, yield 52%.
Reaction equation involved in testing is as shown in Figure 3.
Benzene -1,3,5- three（P-methylphenyl ketone）：1H NMR (500 MHz, chloroform-d) δ 8.33 (s, 1H),
7.75 (d, J = 8.2 Hz, 2H), 7.31 (d, J = 8.0 Hz, 3H), 2.45 (s, 4H)。
4,4',4'' -（Three carbonyl of benzene -1,3,5-）Three benzoic acid：1H NMR (500 MHz, DMSO-d 6) δ 13.38
(s, 1H), 8.29 (s, 1H), 8.10 (d, J = 8.3 Hz, 2H), 7.94 (d, J = 8.2 Hz, 2H)。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (9)
1. a kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization, it is characterised in that：Include the following steps：
1）The preparation of aryl ketones：In ice-water bath, 3 ~ 10 g fragrance carboxylic acid halides are dissolved in 100 ~ 200 ml toluene, are added portionwise
25 ~ 35 g aluminum trichloride (anhydrous)s are then stirred at room temperature 20 ~ 24 hours；Reactant is extracted, organic phase is dry, ties again
Crystalline substance obtains aromatic ketone crystal；
2）By 50 ~ 80 ml acetic acid, 3 ~ 5 ml concentrated sulfuric acids and 1 ~ 3 g step 1）Aromatic ketone obtained is permanent under the conditions of≤40 DEG C
Temperature stirring；5 ~ 8 g chromium trioxides and 3 ~ 5 ml acetic anhydrides are added portionwise, become brownish black muddy substance to reaction mixture
Afterwards, continue stirring 20-24 hours；Aromatic carboxylic acids that is product is purified, adjusting pH, be recrystallized to give carbonyl functionalization.
2. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 1）It is described
Fragrant carboxylic acid halides carboxylic acid halides substituent group number and position it is unlimited, contained halogen is one or more of Cl, Br, I or F.
3. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 2, it is characterised in that：Step 1）It is described
Fragrant carboxylic acid halides include one of m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride.
4. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 1）It is described
Extraction be：Reactant is poured into ice water, then repeatedly with methylene chloride and deionized water extraction, obtains organic phase solution.
5. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 1）It is described
Organic phase it is dry for by organic phase solution, after anhydrous magnesium sulfate is dry, revolving obtains crude product；The recrystallization is to adopt
Use ethyl alcohol recrystallization.
6. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 1）It is described
Be in batches：Points of 5 batches additions of aluminum trichloride (anhydrous), every time plus 5 ~ 7 g.
7. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 2）It is described
Purification be product is poured into 200~300 ml ice water, filter after mixing evenly, obtain the first filtrate, filter residue is through deionized water
It after washing repeatedly, is dissolved in 50~100 ml sodium hydroxide solutions, filters, filtrate is merged with the first filtrate.
8. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 2）It is described
Tune pH be into filtrate addition hydrochloric acid tune pH to 3~5, obtain crude product；The recrystallization is to tie crude product again through DMF
Crystalline substance obtains the aromatic carboxylic acids of carbonyl functionalization.
9. the preparation method of the aromatic carboxylic acids of carbonyl functionalization according to claim 1, it is characterised in that：Step 2）It is described
Be added portionwise for：The 3 batches of additions of chromium trioxide and acetic anhydride point, add 1.7 ~ 3 g and 1 ~ 2 ml respectively every time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810840761.6A CN108863736A (en) | 2018-07-27 | 2018-07-27 | A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810840761.6A CN108863736A (en) | 2018-07-27 | 2018-07-27 | A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108863736A true CN108863736A (en) | 2018-11-23 |
Family
ID=64305566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810840761.6A Pending CN108863736A (en) | 2018-07-27 | 2018-07-27 | A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108863736A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51149201A (en) * | 1975-06-07 | 1976-12-22 | Bayer Ag | Preparation of gemmdiihalide |
| JPH05339204A (en) * | 1992-06-05 | 1993-12-21 | New Japan Chem Co Ltd | Production of aromatic dicarboxylic acid |
| JPH0625079A (en) * | 1991-03-01 | 1994-02-01 | New Japan Chem Co Ltd | Production of aromatic tetracarboxylic acid |
| CN102656165A (en) * | 2009-10-20 | 2012-09-05 | 诺瓦提斯公司 | Glycoside derivatives and uses thereof |
| CN104710367A (en) * | 2015-03-27 | 2015-06-17 | 中国药科大学 | Method for synthesizing enzalutamide |
-
2018
- 2018-07-27 CN CN201810840761.6A patent/CN108863736A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51149201A (en) * | 1975-06-07 | 1976-12-22 | Bayer Ag | Preparation of gemmdiihalide |
| JPH0625079A (en) * | 1991-03-01 | 1994-02-01 | New Japan Chem Co Ltd | Production of aromatic tetracarboxylic acid |
| JPH05339204A (en) * | 1992-06-05 | 1993-12-21 | New Japan Chem Co Ltd | Production of aromatic dicarboxylic acid |
| CN102656165A (en) * | 2009-10-20 | 2012-09-05 | 诺瓦提斯公司 | Glycoside derivatives and uses thereof |
| CN104710367A (en) * | 2015-03-27 | 2015-06-17 | 中国药科大学 | Method for synthesizing enzalutamide |
Non-Patent Citations (1)
| Title |
|---|
| J. R. PRATT等: "4,4’-Isophthaloyldiphthalic Anhydride Polyimides", 《POLYMER ENGINEERING AND SCIENCE》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114105859A (en) | Synthetic method of 6, 6-dimethyl-3-azabicyclo [3.1.0] hexane | |
| CN108947875A (en) | A kind of synthetic method of 2,4- diphenyl sulfone phenol | |
| CN106946650A (en) | A kind of hydrochloric acid A Lei replaces the synthetic method of Buddhist nun's intermediate | |
| CN108863736A (en) | A kind of preparation method of the aromatic carboxylic acids of carbonyl functionalization | |
| Wang et al. | Synthesis and crystal structure of the potassium ytterbium complex with triethylenetetraaminehexaacetic acid:[K3Yb (TTHA)(H2O) 5] | |
| Kirste et al. | EPR, proton and carbon-13 ENDOR studies of a quintet state 13C-labeled galvinoxyl-type tetraradical | |
| CN101239983A (en) | Chiral synthesis method for (-)-galantamin hydrobromide | |
| CN107445964A (en) | A kind of synthetic method of Vardenafil hydrochloric acid impurity | |
| CN104610046A (en) | Method for preparing 3-acenaphthylene butyric acid hapten | |
| CN109321939A (en) | The electrochemical method for synthesizing of thiazole compound | |
| CN104987310A (en) | Synthesis process of levosimendan | |
| RO121737B1 (en) | Process for preparing 5-carboxyphthalide and use thereof for producing citalopram | |
| Etter et al. | An enolized sulfonamide formed by strong hydrogen bonding to triphenylphosphine oxide | |
| CN106187855B (en) | A method of 2- (hetero) aryl indole class compound is prepared using deep eutectic solvent | |
| CN105669634B (en) | A kind of preparation method of rhodamine 110 | |
| CN101092377A (en) | Method for preparing 4 -methoxy - benzonitrile through 'one pot metho | |
| CN104402795A (en) | Synthetic method of substituted indol-2-formic acid | |
| CN109851563B (en) | Preparation method of bisphenol monomer containing phthalazinone structure | |
| CN100503567C (en) | Method for preparing-4-bromine-7-methyl isatin | |
| CN106187818A (en) | A kind of method preparing cancer therapy drug Vorinostat | |
| CN104341428A (en) | Pentamethyl pentacarbonyl cucurbit[5]uril and preparation method thereof | |
| CN109503339A (en) | A kind of preparation method of meta-methoxy phenol | |
| CN108911972A (en) | A kind of racemization recovery method for splitting by-product in mother liquor of sitafloxacin intermediate | |
| CN102887851A (en) | Compound 3,5-dimethyl-1H-pyrrole-2,4-diformaldehyde and preparation method thereof | |
| CN109535767B (en) | Preparation method of perylene pigment |
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 |
Application publication date: 20181123 |
|
| RJ01 | Rejection of invention patent application after publication |