CN103992225A - Salicylaldehyde derivatives and preparation method thereof - Google Patents
Salicylaldehyde derivatives and preparation method thereof Download PDFInfo
- Publication number
- CN103992225A CN103992225A CN201410120781.8A CN201410120781A CN103992225A CN 103992225 A CN103992225 A CN 103992225A CN 201410120781 A CN201410120781 A CN 201410120781A CN 103992225 A CN103992225 A CN 103992225A
- Authority
- CN
- China
- Prior art keywords
- preparation
- salicylaldehyde derivatives
- product
- salicylaldehyde
- derivatives
- 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.)
- Granted
Links
- 0 *C(*)(Cc1c(c(-c2ccccc2)c2C=O)C#Cc3ccccc3)Cc1c2O Chemical compound *C(*)(Cc1c(c(-c2ccccc2)c2C=O)C#Cc3ccccc3)Cc1c2O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides salicylaldehyde derivatives and a preparation method thereof. The preparation method comprises: a, precursor synthesis; b, target product synthesis; and c, purification. Compared with the salicylaldehyde derivative and the preparation method thereof in the prior art, the salicylaldehyde derivative and the preparation method thereof of the present invention have the following characteristics that: the completely-new poly-substituted salicylaldehyde derivative synthesis method is provided, a series of the new salicylaldehyde derivatives are produced, and compared with the ordinary salicylaldehyde derivative, the prepared salicylaldehyde derivative of the present invention has multiple rings so as to have the complex and diverse structure, and presents wide application prospects in chemical engineering production and clinical medicine.
Description
Technical field
The present invention relates to organic compound field, be specifically related to salicylaldehyde derivatives and preparation method thereof.
Background technology
Salicylic aldehyde and derivative thereof are widely used in industrial production and scientific research, and for example salicylic aldehyde and derivative thereof are the important intermediates of organic synthesis and fine chemistry industry, are widely used in the fields such as agricultural chemicals, medicine, spices, sequestrant, dyestuff intermediate.In view of the special significance of salicylic aldehyde and derivative thereof, how to go the synthesis path of expanding salicylic aldehyde and derivative thereof to cause that countless organic synthesis men and chemist actively think deeply, and drawn some effectively methods.
Common salicylic aldehyde synthetic method is seen and is mainly divided into four classes from raw material angle: respectively taking phenol, ortho-cresol, Whitfield's ointment and saligenol as raw material.
1, taking phenol as raw material
(1) phenol phase transfer catalysis process
The synthetic salicylic aldehyde of application Reimer-Tiemann method reaction is the industrial method more generally adopting, and because the productive rate of ortho position product is lower, therefore salicylic aldehyde yield is not high, and speed of reaction is slower, weak effect.Improved Reimer-Tiemann method is in reaction system, to add phase-transfer catalyst, and traditional inhomogeneous reaction is become to homogeneous reaction, to accelerate speed of reaction.
(2) formaldehyde method
Formaldehyde method is the same with Reimer-Tiemann method is all will realize on the hydroxyl ortho position of phenol, introducing an aldehyde radical, this method exist productive rate not too high, need noble metal catalyst, have the shortcomings such as phenolic wastewater, people had carried out some improvement afterwards, little and the product of its reaction volume of method after improvement is easily purified, but it exists noble metal catalyst and the disagreeableness problem of environment of using too.
2, taking ortho-cresol as raw material
(1) phosgenation
Phosgenation is taking ortho-cresol as raw material, and after the chlorination of phosgene side chain, hydrolysis obtains salicylic aldehyde, and this method is owing to there being the shortcoming such as phosgene, dangerous large, environment is extremely unfriendly, postprocessing working procedures trouble, therefore less employing.
(2) phosphorus oxychloride method (La Xigefa)
Ortho-cresol and phosphorus oxychloride are carried out esterification under magnesium oxide exists, and phosphorus oxychloride method is produced salicylic aldehyde stable operation, and equipment is simple, and quality product is high.But the method also exists, and production cost is higher, the critical process esterification degree of depth is wayward, equipment is caused to the shortcomings such as corrosion, exist compared with overall situation pollution problem.
3, taking Whitfield's ointment as raw material
(1) Whitfield's ointment direct electrolysis method
Having report, is under 5.8-6.2 condition at aniline or salt acid for adjusting pH value, and salicylic aldehyde is manufactured in the acid of electrolytic reduction bigcatkin willow, and yield can reach 60% left and right.Anion-exchange membrane for Jiao Lifang etc., taking Hg as negative electrode, Pb alloy is anode, by Whitfield's ointment electrolytic reduction salicylic aldehyde processed, actual yield has reached more than 80%.But catholyte composition is complicated.
(2) Whitfield's ointment shortening method
Whitfield's ointment shortening method environmental friendliness, there is a kind of method of higher atom utilization, but the method is at present also in exploring and the experimental phase.
4, taking saligenol as raw material
Taking saligenol as raw material salicylic aldehyde processed, mainly contain saligenol liquid phase catalytic oxidation and electrooxidation method, still, liquid phase catalytic oxidation need to use noble metal catalyst, and electrooxidation method efficiency is not high.
In sum, prior art is prepared the method for salicylic aldehyde, has that cost is high, efficiency is low and the shortcoming such as environment is unfriendly.And make a general survey of scientific research history mirror, and salicylaldehyde derivatives is of a great variety especially, and it is prepared still in the stage of fumbling, the preparation system of neither one system.
Summary of the invention
The deficiency existing for prior art, the invention provides a kind of salicylaldehyde derivatives.
A further object of the invention, provides a kind of preparation method of salicylaldehyde derivatives.
A kind of salicylaldehyde derivatives provided by the invention, its structural formula is:
E in structural formula
1, E
2for identical CO
2r, R is straight chained alkyl, branched-chain alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group;
R
1, R
2for hydrogen, straight chained alkyl, branched-chain alkyl, halogen, alkoxyl group;
Further, described salicylaldehyde derivatives structural formula is:
Further, described salicylaldehyde derivatives is polysubstituted salicylaldehyde derivatives.
The preparation method of a kind of salicylaldehyde derivatives provided by the invention, comprises the following steps:
A, precursor compound synthesize;
B, target product synthesize;
C, purifying.
Wherein, step a, precursor compound synthesize, and comprise the following steps:
(1) diester malonate compounds and propargyl bromide are joined in solvent, add catalyzer, after reaction for some time, obtain product, washing, extraction, dry, column chromatography, obtain white solid product;
(2) in anhydrous and oxygen-free catalyst system, white solid product and phenylacetylene base bromine or derivatives thereof are joined in solvent, add after alkali reaction for some time, by product washing, extraction, dry, column chromatography, obtain light brown solid product, i.e. precursor compound.
Step (1) specifically comprises the steps: diester malonate compounds and propargyl bromide to join in anhydrous acetonitrile, taking sodium hydride as catalyzer, ice-water bath stirring reaction 8 hours, product adds water washing, be extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:80-100) obtains white solid product, and wherein diester malonate compounds and propargyl bromide mol ratio are 1:2.2-3.2;
The structural formula of described diester malonate compounds is
wherein, R is straight chained alkyl, branched-chain alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group;
Step (2) specifically comprises the steps: that white solid product and phenylacetylene base bromine or derivatives thereof that step (1) is obtained are blended in Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, make alkali with triethylamine, taking anhydrous acetonitrile as solvent, stirring reaction 12 hours under room temperature, product washes with water, is extracted with ethyl acetate, and decompression is spin-dried for, column chromatography (volume ratio ethyl acetate: sherwood oil=1:80-100) obtains light brown solid product, i.e. precursor compound; The mol ratio of wherein said white solid product and phenylacetylene base bromine or derivatives thereof is 1:2.2-3.2, described Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, mol ratio Pd (PPh
3)
2cl
2: CuI=3:1;
The structural formula of described phenylacetylene base bromine or derivatives thereof is
or both mixtures, wherein R
1, R
2for hydrogen, straight chained alkyl, branched-chain alkyl, halogen or alkoxyl group.
Wherein, step b, target product synthesize, and comprise the following steps:
Under the condition of 115 DEG C, the prepared light brown solid product of step a reacts 24 hours in DMF (DMF), obtains crude product, i.e. target product.
Wherein, step c, purifying, comprise the following steps:
Crude product prepared by step b washes with water, ethyl acetate extraction, and decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:40) separates and obtains light yellow solid, i.e. salicylaldehyde derivatives, column chromatography productive rate is about 46.9%.
Compared with prior art, the invention provides a kind of synthetic method of brand-new polysubstituted salicylic aldehyde, generate a series of new salicylaldehyde derivatives.With respect to common salicylaldehyde derivatives, salicylaldehyde derivatives prepared by the present invention has the existence of many rings, and its structure is more complicated various, in Chemical Manufacture, clinical medicine, also will show more wide purposes prospect.
Brief description of the drawings
Fig. 1 a is the structural formula of salicylaldehyde derivatives;
Fig. 1 b is the structural formula of preferred salicylaldehyde derivatives;
Fig. 2 a is the proton nmr spectra of the salicylaldehyde derivatives prepared of embodiment 1;
Fig. 2 b is the carbon-13 nmr spectra of the salicylaldehyde derivatives prepared of embodiment 1;
Fig. 3 a is the proton nmr spectra of the salicylaldehyde derivatives prepared of embodiment 2;
Fig. 3 b is the carbon-13 nmr spectra of the salicylaldehyde derivatives prepared of embodiment 2;
Fig. 4 a is the proton nmr spectra of the salicylaldehyde derivatives prepared of embodiment 3;
Fig. 4 b is the carbon-13 nmr spectra of the salicylaldehyde derivatives prepared of embodiment 3.
Embodiment
Embodiment 1
A kind of salicylaldehyde derivatives, described salicylaldehyde derivatives structural formula is:
A preparation method for salicylaldehyde derivatives, described preparation method comprises the following steps:
A, precursor compound synthesize;
B, target product synthesize;
C, purifying.
Wherein, a, precursor compound synthesize, and comprise the following steps:
(1) taking sodium hydride as catalyzer, 200mmol dimethyl malonate and 440mmol propargyl bromide are joined to ice-water bath in anhydrous acetonitrile, stirring reaction 8 hours, product adds water washing, be extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:100) obtains white solid product;
(2) 80mmol compound 1 and 240mmol phenylacetylene base bromine are blended in to Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, mol ratio Pd (PPh
3)
2cl
2: CuI=3:1, makes alkali with triethylamine, taking anhydrous acetonitrile as solvent, stirring reaction 12 hours under room temperature, product washes with water, is extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:100) obtains light brown solid product, i.e. precursor compound.
Wherein b, target product synthesize, and comprise the following steps:
Under the condition of 115 DEG C, the prepared light brown solid product of step a reacts 24 hours in DMF (DMF), obtains the crude product of salicylaldehyde derivatives, i.e. target product.
Wherein, c, purifying, comprise the following steps:
The crude product of salicylaldehyde derivatives prepared by step b washes with water, ethyl acetate extraction, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:40) separates and obtains light yellow solid product, be salicylaldehyde derivatives, column chromatography productive rate is about 46.9%.
Light yellow solid product structure passes through;
1h NMR;
13c NMR measures.
Light yellow solid product:
1H?NMR(300MHz,CDCl
3)δ12.17(s,1H),9.60(s,1H),7.47（t,J=3.0Hz,3H）,7.40(t,J=4.5Hz,2H),7.23(m,2H),7.01(m,3H),3.84(s,2H),3.80(s,6H),3.71(s,2H)。
13C?NMR(75MHz,CDCl
3)δ197.1,171.7,158.5,152.2,149.27,135.6,131.2,130.7,129.3,129.1,128.2,126.9,123.1,118.1,111.7,109.9,95.2,85.4,77.5,77.1,76.6,75.0,59.0,53.2,42.1,37.4。
Embodiment 2
A kind of salicylaldehyde derivatives, described salicylaldehyde derivatives structural formula is:
A preparation method for salicylaldehyde derivatives, described preparation method comprises the following steps:
A, precursor compound synthesize;
B, target product synthesize;
C, purifying.
Wherein, a, precursor compound synthesize, and comprise the following steps:
(1) taking sodium hydride as catalyzer, 200mmol propanedioic acid dibenzyl ester and 600mmol propargyl bromide are joined to ice-water bath in anhydrous acetonitrile, stirring reaction 8 hours, product adds water washing, be extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:80) obtains white solid product;
(2) 80mmol compound 1 and 180mmol phenylacetylene base bromine are blended in to Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, mol ratio Pd (PPh
3)
2cl
2: CuI=3:1, makes alkali with triethylamine, taking anhydrous acetonitrile as solvent, stirring reaction 12 hours under room temperature, product washes with water, is extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:80) obtains brown solid product, i.e. precursor compound.
Wherein b, target product synthesize, and comprise the following steps:
Under the condition of 115 DEG C, the prepared white solid product of step a is reacted 24 hours in DMF (DMF), obtains the crude product of salicylaldehyde derivatives, i.e. target product.
Wherein, c, purifying, comprise the following steps:
The crude product of salicylaldehyde derivatives prepared by step b washes with water, ethyl acetate extraction, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:40) separates and obtains light yellow solid product, be salicylaldehyde derivatives, column chromatography productive rate is about 59.9%.
Light yellow solid product structure passes through;
1h NMR;
13c NMR measures.
Light yellow solid product:
1H?NMR(300MHz,CDCl
3)δ12.16(s,1H),9.60(s,1H),7.46(m,4H),7.39(m,3H),7.26(m,10H),7.13(m,3H),5.17(s,4H),3.85(s,2H),3.72(s,2H)。
13C?NMR(75MHz,CDCl
3)δ197.1,174.6,170.8,158.5,154.2,152.2,135.6,135.2,131.2,130.7,129.1,127.6,126.9,123.1,118.1,77.4,77.1,76.6,67.7,66.8,59.3,42.3,42.0,37.7,37.3,32.9。
Embodiment 3
A kind of salicylaldehyde derivatives, described salicylaldehyde derivatives structural formula is:
A preparation method for salicylaldehyde derivatives, described preparation method comprises the following steps:
A, precursor compound synthesize;
B, target product synthesize;
C, purifying.
Wherein, a, precursor synthesize, and comprise the following steps:
(1) taking sodium hydride as catalyzer, 200mmol propanedioic acid diisopropyl ester and 460mmol propargyl bromide are joined to ice-water bath in anhydrous acetonitrile, stirring reaction 8 hours, product adds water washing, be extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:80) obtains white solid product;
(2) 80mmol compound 1 and 200mmol4-fluorobenzene acetylenebromide are blended in to Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, mol ratio Pd (PPh
3)
2cl
2: CuI=3:1, makes alkali with triethylamine, taking anhydrous acetonitrile as solvent, stirring reaction 12 hours under room temperature, product washes with water, is extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:80) obtains brown solid product, i.e. precursor compound.
Wherein b, target product synthesize, and comprise the following steps:
Under the condition of 115 DEG C, the prepared white solid product of step a is reacted 24 hours in DMF (DMF), i.e. the crude product of salicylaldehyde derivatives, i.e. target product.
Wherein, c, purifying, comprise the following steps:
The crude product of salicylaldehyde derivatives prepared by step b washes with water, ethyl acetate extraction, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:40) separates and obtains light yellow solid product, be salicylaldehyde derivatives, column chromatography productive rate is about 69.5%.
Light yellow solid product structure passes through;
1h NMR;
13c NMR measures.
Light yellow solid product:
1H?NMR(300MHz,CDCl
3)δ12.16(s,1H),9.58(s,1H),7.28(ddd,J=54.9,43.7,8.3Hz,8H),5.09(dt,J=12.5,6.2Hz,2H),3.76(s,2H),3.65(s,2H),1.27(d,J=6.2Hz,12H)。
13C?NMR(75MHz,CDCl
3)δ196.4,170.7,158.7,152.6,147.7,134.6,134.2,132.3,132.0,128.6,128.2,127.7,121.3,117.8,111.3,94.2,86.1,77.8,76.8,76.6,69.6,41.8,37.2,22.6,21.5。
Claims (10)
1. a salicylaldehyde derivatives, is characterized in that, the structural formula of described salicylaldehyde derivatives is:
E in structural formula
1, E
2for identical CO
2r, R is straight chained alkyl, branched-chain alkyl, saturated hydrocarbons, unsaturated hydro carbons and arene group;
R
1, R
2for hydrogen, straight chained alkyl, branched-chain alkyl, halogen or alkoxyl group.
2. salicylaldehyde derivatives according to claim 1, is characterized in that, the structural formula of described salicylaldehyde derivatives is:
3. a preparation method for the salicylaldehyde derivatives described in claim 1 or 2, is characterized in that, the preparation method of described salicylaldehyde derivatives comprises the following steps:
A, precursor compound synthesize;
B, target product synthesize;
C, purifying.
4. the preparation method of salicylaldehyde derivatives according to claim 3, is characterized in that, step a, precursor compound synthesize, and comprise the following steps:
(1) diester malonate compounds and propargyl bromide are joined in solvent, add catalyzer, after reaction for some time, obtain product, washing, extraction, dry, column chromatography, obtain white solid product;
(2) in anhydrous and oxygen-free catalyst system, white solid product and phenylacetylene base bromine or derivatives thereof are joined in solvent, add after alkali reaction for some time, by product washing, extraction, dry, column chromatography, obtain light brown solid product, i.e. precursor compound.
5. the preparation method of salicylaldehyde derivatives according to claim 4, it is characterized in that, step (1) specifically comprises the steps: diester malonate compounds and propargyl bromide to join in anhydrous acetonitrile, taking sodium hydride as catalyzer, ice-water bath stirring reaction 8 hours, product adds water washing, is extracted with ethyl acetate, decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:80-100) obtains white solid product.
6. according to the preparation method of the salicylaldehyde derivatives described in claim 4 or 5, it is characterized in that, the structural formula of described diester malonate compounds is
wherein R is straight chained alkyl, branched-chain alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group, and diester malonate compounds and propargyl bromide mol ratio are 1:2.2-3.2.
7. the preparation method of salicylaldehyde derivatives according to claim 4, is characterized in that, step (2) specifically comprises the steps:
The white solid product that step (1) is obtained and phenylacetylene base bromine or derivatives thereof are blended in Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, make alkali with triethylamine, taking anhydrous acetonitrile as solvent, stirring reaction 12 hours under room temperature, product washes with water, is extracted with ethyl acetate, and decompression is spin-dried for, column chromatography (volume ratio ethyl acetate: sherwood oil=1:80-100) obtains light brown solid product, i.e. precursor compound.
8. the preparation method of salicylaldehyde derivatives according to claim 7, is characterized in that, the structural formula of described phenylacetylene base bromine or derivatives thereof is
or both mixtures, wherein R
1, R
2for hydrogen, straight chained alkyl, branched-chain alkyl, halogen or alkoxyl group, the mol ratio of described white solid product and phenylacetylene base bromine or derivatives thereof is 1:2.2-3.2, described Pd (PPh
3)
2cl
2in the anhydrous and oxygen-free catalyst system of/CuI, mol ratio Pd (PPh
3)
2cl
2: CuI=3:1.
9. the preparation method of salicylaldehyde derivatives according to claim 4, is characterized in that, step b, target product synthesize, and comprise the following steps:
Under the condition of 115 DEG C, the prepared light brown solid product of step a reacts 24 hours in DMF (DMF), obtains crude product, i.e. target product.
10. the preparation method of salicylaldehyde derivatives according to claim 4, is characterized in that, step c, purifying, comprise the following steps:
Crude product prepared by step b washes with water, ethyl acetate extraction, and decompression is spin-dried for, and column chromatography (volume ratio ethyl acetate: sherwood oil=1:40) separates and obtains light yellow solid, i.e. salicylaldehyde derivatives, column chromatography productive rate is about 46.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410120781.8A CN103992225B (en) | 2014-03-26 | 2014-03-26 | A kind of salicylaldehyde derivatives and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410120781.8A CN103992225B (en) | 2014-03-26 | 2014-03-26 | A kind of salicylaldehyde derivatives and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103992225A true CN103992225A (en) | 2014-08-20 |
| CN103992225B CN103992225B (en) | 2016-01-13 |
Family
ID=51306596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410120781.8A Active CN103992225B (en) | 2014-03-26 | 2014-03-26 | A kind of salicylaldehyde derivatives and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103992225B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447599A (en) * | 2014-12-23 | 2015-03-25 | 安徽师范大学 | Tetrazole heterocyclic compound and preparation method thereof |
| CN104447337A (en) * | 2014-12-04 | 2015-03-25 | 安徽师范大学 | Cinnamic acid ester derivatives and preparation method thereof |
| CN104447336A (en) * | 2014-12-04 | 2015-03-25 | 安徽师范大学 | Triptycene derivative and preparation method thereof |
| CN105523981A (en) * | 2016-01-29 | 2016-04-27 | 安徽师范大学 | Diphenyl telluride derivative and preparation method thereof |
| CN105541684A (en) * | 2016-02-26 | 2016-05-04 | 安徽师范大学 | Oxidation reduction method of tetrayne compound and diphenylthiocarbazone |
| CN106588666A (en) * | 2016-12-14 | 2017-04-26 | 安徽师范大学 | Poly-substituted condensed aromatic derivative and preparation method thereof |
| CN106748769A (en) * | 2016-11-29 | 2017-05-31 | 安徽师范大学 | A kind of polysubstituted 3 phenyl phenol derivatives and preparation method thereof |
| CN106946704A (en) * | 2017-03-15 | 2017-07-14 | 安徽师范大学 | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof |
| CN108947828A (en) * | 2018-07-18 | 2018-12-07 | 安徽师范大学 | A kind of Multi substituted benzenes formaldehyde derivatives and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101772487A (en) * | 2007-06-06 | 2010-07-07 | 托伦特药物有限公司 | Novel cpd |
| CN103408445A (en) * | 2013-07-22 | 2013-11-27 | 安徽师范大学 | Arylamine derivatives and preparation method thereof |
-
2014
- 2014-03-26 CN CN201410120781.8A patent/CN103992225B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101772487A (en) * | 2007-06-06 | 2010-07-07 | 托伦特药物有限公司 | Novel cpd |
| CN103408445A (en) * | 2013-07-22 | 2013-11-27 | 安徽师范大学 | Arylamine derivatives and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAO ZHANG ET AL.: "Convenient one-step construction of yne-functionalized aryl halides through domino cyclization from tetraynes", 《CHEM. COMMUN.》 * |
| HAO ZHANG ET AL.: "Convenient one-step construction of yne-functionalized aryl halides through domino cyclization from tetraynes", 《CHEM. COMMUN.》, vol. 50, 13 January 2014 (2014-01-13), pages 3335 - 3337 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447337A (en) * | 2014-12-04 | 2015-03-25 | 安徽师范大学 | Cinnamic acid ester derivatives and preparation method thereof |
| CN104447336A (en) * | 2014-12-04 | 2015-03-25 | 安徽师范大学 | Triptycene derivative and preparation method thereof |
| CN104447336B (en) * | 2014-12-04 | 2016-03-30 | 安徽师范大学 | A kind of three dish ene derivatives and preparation method thereof |
| CN104447599A (en) * | 2014-12-23 | 2015-03-25 | 安徽师范大学 | Tetrazole heterocyclic compound and preparation method thereof |
| CN105523981A (en) * | 2016-01-29 | 2016-04-27 | 安徽师范大学 | Diphenyl telluride derivative and preparation method thereof |
| CN105541684A (en) * | 2016-02-26 | 2016-05-04 | 安徽师范大学 | Oxidation reduction method of tetrayne compound and diphenylthiocarbazone |
| CN106748769A (en) * | 2016-11-29 | 2017-05-31 | 安徽师范大学 | A kind of polysubstituted 3 phenyl phenol derivatives and preparation method thereof |
| CN106588666A (en) * | 2016-12-14 | 2017-04-26 | 安徽师范大学 | Poly-substituted condensed aromatic derivative and preparation method thereof |
| CN106946704A (en) * | 2017-03-15 | 2017-07-14 | 安徽师范大学 | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof |
| CN108947828A (en) * | 2018-07-18 | 2018-12-07 | 安徽师范大学 | A kind of Multi substituted benzenes formaldehyde derivatives and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103992225B (en) | 2016-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103992225B (en) | A kind of salicylaldehyde derivatives and preparation method thereof | |
| Zhu et al. | Formal fluorine atom transfer radical addition: silver-catalyzed carbofluorination of unactivated alkenes with ketones in aqueous solution | |
| CN104447337B (en) | A kind of cinnamate analog derivative and preparation method thereof | |
| CN103408445B (en) | Arylamine derivatives and preparation method thereof | |
| CN103896815B (en) | A kind of ortho position mercapto-phenol derivative and preparation method thereof | |
| CN111519204B (en) | Method for preparing N- (5-chloro-8-quinolyl) benzamide compound by adopting electrochemical microchannel reaction device | |
| CN105523981A (en) | Diphenyl telluride derivative and preparation method thereof | |
| CN108164475B (en) | Method for catalytic synthesis of difluoromethyl-substituted linear aryl hetero-ketone | |
| CN109320489A (en) | A kind of color alkyl compound and preparation method thereof | |
| CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
| CN113529110B (en) | Electrochemical-promoted substituted aromatic meta-nitration method | |
| CN111269129B (en) | Method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by continuous flow oxidation coupling method | |
| CN109651367B (en) | Method for preparing 1, 4-dihydroquinoline and pyrrolo [1,2-a ] quinoline compounds | |
| CN106117225A (en) | The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound | |
| CN104447336B (en) | A kind of three dish ene derivatives and preparation method thereof | |
| CN110950778A (en) | Process and catalyst system for preparing aromatic malononitrile | |
| CN101585783B (en) | Preparing method of ortho-nitrobenzonitrile series compound | |
| CN103992261A (en) | Industrial process for preparing 2-bromo-carbazole | |
| CN109836383B (en) | Method for preparing 3, 4-dihydroquinoline-2 (1H) -ketone compound | |
| CN106349170A (en) | Preparation method of 1,3-dimethyl-5-phenyluracil | |
| CN110683949B (en) | Method for preparing 9, 10-phenanthrene dicarboxylic ester compound | |
| CN106187779B (en) | A kind of method for synthesizing aromatic nitro compound | |
| CN104860880A (en) | Method for synthesizing 8-(nitro methyl) quinoline compounds | |
| CN113980055B (en) | Cyclic phosphonamide derivative with biaryl framework, synthesis method and application | |
| CN104230926A (en) | Preparation method of minodronic acid key intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |