CN103936706B - A kind of synthetic method of lupinus luteus White's ketone - Google Patents
A kind of synthetic method of lupinus luteus White's ketone Download PDFInfo
- Publication number
- CN103936706B CN103936706B CN201410102351.3A CN201410102351A CN103936706B CN 103936706 B CN103936706 B CN 103936706B CN 201410102351 A CN201410102351 A CN 201410102351A CN 103936706 B CN103936706 B CN 103936706B
- Authority
- CN
- China
- Prior art keywords
- tlc
- milliliters
- ethyl acetate
- synthetic method
- product
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
- C07D311/36—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only not hydrogenated in the hetero ring, e.g. isoflavones
Abstract
The invention discloses the synthetic method of a kind of lupinus luteus White's ketone, the present invention, with genistein as raw material, is prepared for lupinus luteus White's ketone through four-step reaction.Second step of the present invention reaction uses bromo iso-amylene, potassium carbonate, DMF system to replace prenol, diethylazodicarboxylate, triphenyl phosphorus, THF system, cost is substantially reduced, and convenient post-treatment is a lot, yield has also brought up to 92% from 83%, present invention three-step reaction uses the high boiling solvents such as diethylaniline, dimethylaniline, decahydronaphthalene to be solvent, and the condition being heated to reflux completes the para-position Claisen rearangement of isopentene group and replaces original method to use Eu (fod)3The rearrangement of catalysis, eliminates valuable metallic catalyst, greatly reduces cost, and by original 68%, yield is brought up to 87%.
Description
Technical field
The present invention relates to chemosynthesis technical field, particularly relate to a kind of lupinus luteus White's ketone
Synthetic method.
Background technology
Isoamylene radical chromocor, especially prenyl isoflavones, show phytoalexin, elder brother
Worm takes food and antifungal activity.Additionally shown is the antiinflammatory of inside and outside, anticancer, lipotropism matter
Characteristic.5,7,4 '-trihydroxy-8-prenyl isoflavones (lupinus luteus White's ketone) is
Isolated from soybean pod and the seed of Lupinus albus, the root of lupinus luteus and the leaf of Glycyrrhiza glabra L.
's.In order to study the biological activity of lupinus luteus White's ketone, need a simple efficient chemistry
Synthetic method.
Current chemical synthesis process mainly has two, and one is the complete synthesis of Japanese scholars report
Method, the method has 15 steps, total recovery 7% (document 1:J.Chem.Res.Minipr. altogether
1998,5,1181).It will be apparent that this method is difficult to a large amount of preparation, more there is no industrialization
Value.Another one is the semisynthesis of British scholar, and this method utilizes the genistein to be
Initiation material, has obtained lupinus luteus White's ketone through 4 steps, total recovery 44% (document 2:
Tetrahedron, 2003,59,4,177 4181, following synthetic route).Our work
It it is the process modification for document 2 semisynthesis
Document 2 second step uses Mitsunobu reaction, has used diethylazodicarboxylate
And triphenyl phosphorus (PPh (DEAD)3), not only cost is high, and post processing trouble.
Document 2 the 3rd step has used the metallic catalyst Eu (fod) of costliness3, cost is the highest.
Summary of the invention
For solve existing lupinus luteus White's ketone synthesis present in problem, the invention provides
A kind of synthetic method of lupinus luteus White's ketone.
The present invention adopts the following technical scheme that
The synthetic route of the synthetic method of lupinus luteus White's ketone of the present invention is as follows:
Specifically comprising the following steps that of the synthetic method of lupinus luteus White's ketone of the present invention
(1) every 8-12 gram of genistein is dissolved in 150 milliliters of DMF, adds 7 milliliters of acetic anhydride,
Back flow reaction 2-3 hour, then detects with TLC, and after reaction terminates, sucking filtration obtains white solid,
Solid washed with water, then dries and obtains product a;
(2) every 1-5 gram of product a is dissolved in 50 milliliters of dry DMF, adds 3.5g's
The bromo isoprene of potassium carbonate and 1.6ml, room temperature reaction 1h, then detect with TLC,
After reaction terminates, decompression boils off solvent, by petroleum ether, then uses acetone recrystallization 2-3 time,
Product b is obtained after drying;
(3) every 0.5-1.5 gram of product b is dissolved in 40 milliliters of N, N-diethylanilines, and reflux 0.5-1h,
Then detecting with TLC, after reaction terminates, reactant liquor is extracted with ethyl acetate, then with saturated
Ammonium chloride solution washs neutrality, washing, is dried, pours out solution, after removing solvent under reduced pressure,
Obtain white solid, add methanol and dissolve white solid, add excessive sodium hydrate, be stirred at room temperature
2h, then detects with TLC, reacts and solvent is evaporated off after terminating, sepia grease, petroleum ether:
Ethyl acetate=30:1 crosses column purification and obtains light yellow solid lupinus luteus White's ketone.
In step (1), preferably: every 10 grams of genistein are dissolved in 150 milliliters of DMF,
Add 7 milliliters of acetic anhydride, room temperature reaction 2-3 hour, then detect with TLC, after reaction terminates,
Sucking filtration obtains white solid, solid washed with water, then dries and obtains product a.
In step (1), in TLC detection, the weight ratio of petroleum ether and ethyl acetate is 20:1.
In step (2), preferably: every 3 grams of product a are dissolved in 50 milliliters of dry DMF,
Add the potassium carbonate of 3.5g and the bromo isoprene of 1.6ml, room temperature reaction 1h, then
Detecting with TLC, after reaction terminates, decompression boils off solvent, by petroleum ether, then uses acetone
Recrystallization 2-3 time, obtains product b after drying.
In step (2), DMF adds anhydrous sodium sulfate before using and is stirred overnight, and removes it
Middle moisture.
In step (2), in TLC detection, petroleum ether is 40:1 with the weight ratio of ethyl acetate.
In step (3), preferably: every 1 gram of product b is dissolved in 40 milliliters of N, N-diethylbenzenes
Amine, reflux 0.5-1h, then detects with TLC, after reaction terminates, reactant liquor acetic acid second
Ester extracts, and then washs neutrality with saturated ammonium chloride solution, washing, is dried, pours out solution,
After removing solvent under reduced pressure, obtain white solid, add methanol and dissolve white solid, add excessive hydrogen
Sodium oxide, is stirred at room temperature 2h, then detects with TLC, and reaction is evaporated off solvent after terminating, palm fibre
Brown oil, petroleum ether: ethyl acetate=30:1 crosses column purification and obtains light yellow solid Huang feather fan
Bean White's ketone.
In step (3), every 0.5-1.5 gram of product b is dissolved in 40 milliliters of N, N-diethylbenzenes
Amine, reflux 0.5-1h, then detects with TLC, during detection, petroleum ether and ethyl acetate
Weight ratio is 40:1.
In step (3), during hydrolysis, TLC detects, petroleum ether and the weight of ethyl acetate
Amount ratio is 30:1.
The positive effect of the present invention is as follows:
1, second step of the present invention reaction uses bromo iso-amylene, potassium carbonate, DMF system to replace iso-amylene
Alcohol, diethylazodicarboxylate, triphenyl phosphorus, THF system, cost is substantially reduced, and
Convenient post-treatment is a lot, and yield has also brought up to 92% from 83%
2, present invention three-step reaction uses diethylaniline, dimethylaniline, the contour boiling of decahydronaphthalene
Point solvent is solvent, and the condition being heated to reflux completes the para-position Claisen rearangement of isopentene group and replaces
Original method uses Eu (fod)3The rearrangement of catalysis, eliminates valuable metallic catalyst, significantly
Reduce cost, and yield is brought up to 87% by original 68%.
Accompanying drawing explanation
Fig. 1 is the HNMR collection of illustrative plates of lupinus luteus White's ketone of embodiment 3 preparation.
Fig. 2 is the HPLC collection of illustrative plates of lupinus luteus White's ketone of embodiment 3 preparation.
Fig. 3 is the MS collection of illustrative plates of lupinus luteus White's ketone of embodiment 3 preparation.
Detailed description of the invention
The following examples are that the present invention is described in further detail.
Embodiment 1
(1) 8 gram of genistein is dissolved in 150 milliliters of DMF, adds 7 milliliters of acetic anhydride, backflow
Reacting 2-3 hour, then detect with TLC, after reaction terminates, sucking filtration obtains white solid, Gu
Body washes with water, then dries and obtains product a;
(2) 1 gram of product a is dissolved in 50 milliliters of dry DMF, adds the carbonic acid of 3.5g
The bromo isoprene of potassium and 1.6ml, room temperature reaction 1h, then detects with TLC, reaction
After end, decompression boils off solvent, by petroleum ether, then uses acetone recrystallization 2-3 time, dries
Product b is obtained after Gan;
(3) 0.5 grams of product b are dissolved in 40 milliliters of N, N-diethylanilines, and reflux 0.5-1h, so
Detecting with TLC afterwards, after reaction terminates, reactant liquor is extracted with ethyl acetate, and then uses saturated chlorine
Change ammonium salt solution and wash neutrality, washing, it is dried, pours out solution, after removing solvent under reduced pressure,
To white solid, add methanol and dissolve white solid, add excessive sodium hydrate, be stirred at room temperature
2h, then detects with TLC, reacts and solvent is evaporated off after terminating, sepia grease, petroleum ether:
Ethyl acetate=30:1 crosses column purification and obtains light yellow solid lupinus luteus White's ketone.
In step (1), in TLC detection, the weight ratio of petroleum ether and ethyl acetate is 20:1.
In step (2), DMF adds anhydrous sodium sulfate before using and is stirred overnight, and removes it
Middle moisture.
In step (2), in TLC detection, petroleum ether is 40:1 with the weight ratio of ethyl acetate.
In step (3), 0.5 gram of product b is dissolved in 40 milliliters of N, N-diethylanilines, backflow
0.5-1h, then detects with TLC, and during detection, petroleum ether with the weight ratio of ethyl acetate is
40:1.
In step (3), during hydrolysis, TLC detects, petroleum ether and the weight of ethyl acetate
Amount ratio is 30:1.
The reaction yield of the present embodiment is 87%.
Embodiment 2
(1) 12 gram of genistein is dissolved in 150 milliliters of DMF, adds 7 milliliters of acetic anhydride, backflow
Reacting 2-3 hour, then detect with TLC, after reaction terminates, sucking filtration obtains white solid, Gu
Body washes with water, then dries and obtains product a;
(2) 5 grams of product a are dissolved in 50 milliliters of dry DMF, add the carbonic acid of 3.5g
The bromo isoprene of potassium and 1.6ml, room temperature reaction 1h, then detects with TLC, reaction
After end, decompression boils off solvent, by petroleum ether, then uses acetone recrystallization 2-3 time, dries
Product b is obtained after Gan;
(3) 1.5 grams of product b are dissolved in 40 milliliters of N, N-diethylanilines, and reflux 0.5-1h, so
Detecting with TLC afterwards, after reaction terminates, reactant liquor is extracted with ethyl acetate, and then uses saturated chlorine
Change ammonium salt solution and wash neutrality, washing, it is dried, pours out solution, after removing solvent under reduced pressure,
To white solid, add methanol and dissolve white solid, add excessive sodium hydrate, be stirred at room temperature
2h, then detects with TLC, reacts and solvent is evaporated off after terminating, sepia grease, petroleum ether:
Ethyl acetate=30:1 crosses column purification and obtains light yellow solid lupinus luteus White's ketone.
In step (1), in TLC detection, the weight ratio of petroleum ether and ethyl acetate is 2:1.
In step (2), DMF adds anhydrous sodium sulfate before using and is stirred overnight, and removes it
Middle moisture.
In step (2), in TLC detection, petroleum ether is 40:1 with the weight ratio of ethyl acetate.
In step (3), 1.5 grams of product b are dissolved in 40 milliliters of N, N-diethylanilines, return
Stream 0.5-1h, then detects with TLC, during detection, and petroleum ether and the weight ratio of ethyl acetate
For 40:1.
In step (3), during hydrolysis, TLC detects, petroleum ether and the weight of ethyl acetate
Amount ratio is 30:1.
The reaction yield of the present embodiment is 86%.
Embodiment 3
(1) 10 gram of genistein is dissolved in 150 milliliters of DMF, adds 7 milliliters of acetic anhydride, backflow
Reacting 2-3 hour, then detect with TLC, after reaction terminates, sucking filtration obtains white solid, Gu
Body washes with water, then dries and obtains product a;
(2) 3 grams of product a are dissolved in 50 milliliters of dry DMF, add the carbonic acid of 3.5g
The bromo isoprene of potassium and 1.6ml, room temperature reaction 1h, then detects with TLC, reaction
After end, decompression boils off solvent, by petroleum ether, then uses acetone recrystallization 2-3 time, dries
Product b is obtained after Gan;
(3) 1 grams of product b are dissolved in 40 milliliters of N, N-diethylanilines, and reflux 0.5-1h, then
Detecting with TLC, after reaction terminates, reactant liquor is extracted with ethyl acetate, and then uses saturated chlorination
Ammonium salt solution washs neutrality, washing, is dried, pours out solution, after removing solvent under reduced pressure, obtain
White solid, adds methanol and dissolves white solid, add excessive sodium hydrate, 2h is stirred at room temperature,
Then detecting with TLC, reaction is evaporated off solvent, sepia grease, petroleum ether: second after terminating
Acetoacetic ester=30:1 crosses column purification and obtains light yellow solid lupinus luteus White's ketone.
In step (1), in TLC detection, the weight ratio of petroleum ether and ethyl acetate is 20:1.
In step (2), DMF adds anhydrous sodium sulfate before using and is stirred overnight, and removes it
Middle moisture.
In step (2), in TLC detection, petroleum ether is 40:1 with the weight ratio of ethyl acetate.
In step (3), 1 gram of product b is dissolved in 40 milliliters of N, N-diethylanilines, backflow 0.5
-1h, then detects with TLC, and during detection, petroleum ether is 40 with the weight ratio of ethyl acetate:
1。
In step (3), during hydrolysis, TLC detects, petroleum ether and the weight of ethyl acetate
Amount ratio is 30:1.
The reaction yield of the present embodiment is 87%.
Although an embodiment of the present invention has been shown and described, for the ordinary skill of this area
For personnel, it is possible to understand that without departing from the principles and spirit of the present invention can be to this
A little embodiments carry out multiple change, revise, replace and modification, and the scope of the present invention is by appended power
Profit requires and equivalent limits.
Claims (9)
1. the synthetic method of lupinus luteus White's ketone, it is characterised in that: specifically comprising the following steps that of described method
(1) every 8-12 gram of genistein is dissolved in 150 milliliters of DMF, adds 7 milliliters of acetic anhydride, back flow reaction
2-3 hour, then detecting with TLC, after reaction terminates, sucking filtration obtains white solid, solid washed with water, then
Drying obtains product a;
(2) every 1-5 gram of product a is dissolved in 50 milliliters of dry DMF, adds potassium carbonate and the 1.6ml of 3.5g
Bromo isoprene, room temperature reaction 1h, then with TLC detect, reaction terminate after decompression boils off solvent,
By petroleum ether, then use acetone recrystallization 2-3 time, after drying, obtain product b;
(3) every 0.5-1.5 gram of product b is dissolved in 40 milliliters of N, N-diethylanilines, and reflux 0.5-1h, then
Detecting with TLC, after reaction terminates, reactant liquor is extracted with ethyl acetate, and then washs with saturated ammonium chloride solution
To neutrality, washing, it is dried, pours out solution, after removing solvent under reduced pressure, obtain white solid, add methanol molten
Solving white solid, add excessive sodium hydrate, 2h is stirred at room temperature, then detect with TLC, reaction is steamed after terminating
Except solvent, sepia grease, petroleum ether: ethyl acetate=30:1 crosses column purification and obtains light yellow solid Huang feather fan
Bean White's ketone.
2. synthetic method as claimed in claim 1, it is characterised in that: in step (1), every 10 grams of goldspinks are different
Flavin is dissolved in 150 milliliters of DMF, adds 7 milliliters of acetic anhydride, back flow reaction 2-3 hour, then uses TLC
Detection, after reaction terminates, sucking filtration obtains white solid, solid washed with water, then dries and obtains product a.
3. synthetic method as claimed in claim 1, it is characterised in that: in step (1), in TLC detection, stone
The weight ratio of oil ether and ethyl acetate is 20:1.
4. synthetic method as claimed in claim 1, it is characterised in that: in step (2), by every 3 grams of product a
It is dissolved in 50 milliliters of dry DMF, adds the potassium carbonate of 3.5g and the bromo isoprene of 1.6ml,
Room temperature reaction 1h, then detects with TLC, and after reaction terminates, decompression boils off solvent, by petroleum ether, so
Use acetone recrystallization 2-3 time afterwards, after drying, obtain product b.
5. synthetic method as claimed in claim 1, it is characterised in that: in step (2), DMF adds before using
Enter anhydrous sodium sulfate to be stirred overnight, remove wherein moisture.
6. synthetic method as claimed in claim 1, it is characterised in that: in step (2), in TLC detection, stone
Oil ether is 40:1 with the weight ratio of ethyl acetate.
7. synthetic method as claimed in claim 1, it is characterised in that: in step (3), every 1 gram of product b
Being dissolved in 40 milliliters of N, N-diethylanilines, reflux 0.5-1h, then detects with TLC, after reaction terminates,
Reactant liquor is extracted with ethyl acetate, and then washs neutrality with saturated ammonium chloride solution, washing, is dried, and falls
Go out solution, after removing solvent under reduced pressure, obtain white solid, add methanol and dissolve white solid, add excessive hydrogen
Sodium oxide, is stirred at room temperature 2h, then detects with TLC, reacts and solvent is evaporated off after terminating, sepia grease,
Petroleum ether: ethyl acetate=30:1 crosses column purification and obtains light yellow solid lupinus luteus White's ketone.
8. synthetic method as claimed in claim 1, it is characterised in that: in step (3), every 0.5-1.5 gram
Product b is dissolved in 40 milliliters of N, N-diethylanilines, and reflux 0.5-1h, then detects with TLC, during detection,
Petroleum ether is 40:1 with the weight ratio of ethyl acetate.
9. synthetic method as claimed in claim 1, it is characterised in that: in step (3), during hydrolysis,
TLC detects, and petroleum ether is 30:1 with the weight ratio of ethyl acetate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410102351.3A CN103936706B (en) | 2014-03-19 | 2014-03-19 | A kind of synthetic method of lupinus luteus White's ketone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410102351.3A CN103936706B (en) | 2014-03-19 | 2014-03-19 | A kind of synthetic method of lupinus luteus White's ketone |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103936706A CN103936706A (en) | 2014-07-23 |
CN103936706B true CN103936706B (en) | 2016-08-17 |
Family
ID=51184618
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410102351.3A Expired - Fee Related CN103936706B (en) | 2014-03-19 | 2014-03-19 | A kind of synthetic method of lupinus luteus White's ketone |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103936706B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110179785B (en) * | 2019-05-15 | 2021-06-29 | 江苏康缘药业股份有限公司 | Application of widmanone in preparation of medicine for treating or preventing hand-foot-and-mouth disease |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004069774A2 (en) * | 2003-02-04 | 2004-08-19 | The University Court Of The University Of St Andrews | Synthesis of 13c-labelled estrogen analogues |
-
2014
- 2014-03-19 CN CN201410102351.3A patent/CN103936706B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004069774A2 (en) * | 2003-02-04 | 2004-08-19 | The University Court Of The University Of St Andrews | Synthesis of 13c-labelled estrogen analogues |
Non-Patent Citations (3)
Title |
---|
Anti-AGEs and antiparasitic activity of an original prenylated isoflavonoid and flavanones isolated from Derris ferruginea;Sylvie Morel et al.,;《Phytochemistry Letters》;20130629;第6卷;第498-503页 * |
Masao Tsukayama et al.,.Regioselective Synthesis of Prenylisoflavones.Syntheses of Lupiwighteone, Lupiwighteone Hydrate and Related Compounds.《J. CHEM. RESEARCH 》.1998,(第5期),第238-239页. * |
Synthesis of lupiwighteone via a para-Claisen–Cope rearrangement;Nawaf Al-Maharik and Nigel P. Botting;《Tetrahedron》;20030510;第59卷(第23期);第4177-4181页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103936706A (en) | 2014-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103724261B (en) | A kind of industrialized process for preparing of hydroxychloroquine sulfate quinoline | |
CN103467547A (en) | Novel method for extracting hesperidin from orange peel | |
CN106278964B (en) | The preparation method of Florfenicol | |
CN103896855B (en) | The synthetic method of the fluoro-6-chlorine of a kind of 4-(1-bromoethyl)-5-pyrimidine | |
CN103694294A (en) | Method for extracting baicalin by use of flash extraction technology | |
CN106674044A (en) | Method for preparing 3-cyano-4-isopropoxybenzoic acid | |
CN103936706B (en) | A kind of synthetic method of lupinus luteus White's ketone | |
CN104402696A (en) | Oxidoreduction method of benzoin organic matter | |
CN103333359B (en) | A kind of method of solvent recovery in polyphenylene sulfide synthesis technique | |
CN104370745B (en) | The preparation method of rosin acid derivative | |
CN101768165B (en) | Ellagic acid preparation method employing tara powder | |
CN103145527B (en) | Process for synthesizing p-methoxy benzaldehyde or p-tertbutyl benzaldehyde | |
CN101973991A (en) | Preparation method of fibrauretine | |
CN105820145A (en) | Method for preparing 5-nitro-2-furaldehyde and nifuratel | |
CN103880683A (en) | Chemical synthesis method of 3-bromo-2-nitrobenzaldehyde | |
CN104193701B (en) | A kind of synthetic method of 3-hydroxymethyl tetrahydrofuran | |
CN106008449A (en) | Cheap synthetic method of watermelon ketone | |
CN101875649A (en) | Synthesis process for industrially producing daidzein | |
CN109694311B (en) | Method for synthesizing isoliquiritigenin | |
CN106674046A (en) | Preparation method of 3-cyano-4-isopropyloxybenzoic acid | |
CN114163316A (en) | Method for preparing 4-bromo-2-methoxy-5-trifluoromethylbenzaldehyde | |
CN106674053A (en) | Preparation method of 3-cyano-4-isopropoxy methyl benzoate | |
CN108640842B (en) | Synthetic method of 2-bromo-5-fluoronitrobenzene | |
CN112079775A (en) | Synthesis method of 5-trifluoromethyl isoquinoline-8-formic acid | |
CN106674047A (en) | Method for preparing 3-cyano-4-isopropoxybenzoic acid |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20210319 |
|
CF01 | Termination of patent right due to non-payment of annual fee |