CN103804150A - Preparation method of 3,4-dimethoxybenzyl bromide - Google Patents
Preparation method of 3,4-dimethoxybenzyl bromide Download PDFInfo
- Publication number
- CN103804150A CN103804150A CN201410071150.1A CN201410071150A CN103804150A CN 103804150 A CN103804150 A CN 103804150A CN 201410071150 A CN201410071150 A CN 201410071150A CN 103804150 A CN103804150 A CN 103804150A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- dimethoxy
- benzyl bromine
- molar equivalent
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- AKPSLMUFDIXDJJ-UHFFFAOYSA-N 4-(bromomethyl)-1,2-dimethoxybenzene Chemical compound COC1=CC=C(CBr)C=C1OC AKPSLMUFDIXDJJ-UHFFFAOYSA-N 0.000 title abstract description 10
- OEGPRYNGFWGMMV-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC OEGPRYNGFWGMMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000007069 methylation reaction Methods 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012141 vanillin Nutrition 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000001035 methylating effect Effects 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 230000011987 methylation Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N Tetrahydropalmatine Natural products C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- AEQDJSLRWYMAQI-KRWDZBQOSA-N tetrahydropalmatine Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3C[C@H]2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-KRWDZBQOSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- 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
- C07C45/64—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 introduction of functional groups containing oxygen only in singly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 3,4-dimethoxybenzyl bromide, and discloses a preparation method comprising the following steps: with vanillin as a starting raw material, under inorganic weak base, reacting the vanillin with a methylation reagent to generate veratraldehyde; reacting with sodium borohydride to reduce an aldehyde group into alcohol so as to obtain veratryl alcohol; brominating with boron tribromide to obtain a final product. The preparation method is higher in yield, simple in operation, and high in purity; the yield reaches up to 85 percent.
Description
Technical field
The invention belongs to organic synthesis technology, be specifically related to the preparation method of 3,4-dimethoxy-benzyl bromine.
Background technology
3,4-dimethoxy-benzyl bromine belongs to a kind of important medicine intermediate, is widely used, for the synthesis of tetrahydropalmatine (tetrahydropalmatine) at medicine industry.Mainly 3 for the synthesis of tetrahydropalmatine (tetrahydropalmatine) at present, 4-dimethoxy-benzyl chlorine, it is heated and easily decomposes, and the production to downstream technology product is unfavorable, carry out the study on the synthesis to 3,4-dimethoxy-benzyl bromine, can overcome these difficulties, and be conducive to improve yield etc., the research of its synthetic method is carried out significant.
The method of preparation 3,4-dimethoxy-benzyl bromine is more both at home and abroad at present, the larger shortcoming of most existence, the solution of still needing.(meter Shi La, the La Jieshikumaer such as meter Shi La; Sub-daf Tetrahedron letters, 2002, the first roll, 43, the 31 pages, 5419-5422) report raw material and carbon tetrabromide, triphenyl phosphorus reacts and generates product in methylene dichloride, yield 52%, the method yield is low, and triphenyl phosphorus is poisonous.
(TenBrink, Rose intestinal bacteria, MYCAL, John M. magazine heterocyclic chemistry, 1981, the first roll such as MYCAL.18, the 821-824) veratryl alcohol reacts and finally obtains 3,4-dimethoxy-benzyl bromine with hydrogen bromide ice bath in normal hexane, toluene, yield 68%, this reaction generates by product.
Zumbrunn etc. (Zumbrunn, Ah Er Buleixi top grade. synthetic, 1998, #9 page, 1357 to 1361) report take veratryl alcohol as raw material, in ether, first in ice-cooled next hour, 23 ℃ of next hours, obtain product, yield 95% with phosphorus tribromide.This route ether is polarity toxicity, is difficult for producing.
3,4-dimethoxy-benzyl bromine is a kind of important drugs intermediate, studies the synthesis techniques such as its high yield, low cost, safety and environmental protection significant.
Summary of the invention
For the problem of above-mentioned existing existence, the invention provides that a kind of income is high, the synthesis technique of safety and environmental protection.
Concrete technical scheme of the present invention is: vanillin food grade,1000.000000ine mesh is starting raw material, under inorganic weak bases, sends out and answers with methylating reagent, generates veratryl aldehyde; Be reduced into alcohol with sodium borohydride reaction aldehyde radical again, obtain veratryl alcohol; Obtain last product with boron tribromide bromination again.This process recovery ratio is higher, simple to operate, and purity is high, and yield is up to 85%.
In the preparation method of veratryl aldehyde of the present invention, reaction solvent is tetrahydrofuran (THF), and methylating reagent includes but not limited to methyl iodide, sulfuric acid dimethyl, methylcarbonate etc., and methylating reagent molar equivalent is 1.3～1.5eq.
In the preparation method of veratryl aldehyde of the present invention, inorganic weak bases includes but not limited to sodium carbonate, salt of wormwood, sodium bicarbonate etc., molar equivalent 1.5～2.0eq.
In the preparation method of veratryl aldehyde of the present invention, methylation reaction temperature is preferable over 80～100 ℃, more preferably in 90～95 ℃.
In the preparation method of veratryl aldehyde of the present invention, the methylation reaction time is preferable over 15～25h, more preferably in 20～22h.
In the preparation method of veratryl alcohol of the present invention, in reduction reaction, selected reductive agent includes but not limited to sodium borohydride, POTASSIUM BOROHYDRIDE etc., molar equivalent 1.2～1.5.
In the preparation method of veratryl alcohol of the present invention, in upper step reaction, slowly add reductive agent, room temperature reaction 4～7h in batches.
Of the present invention 3, in the preparation method of 4-dimethoxy-benzyl bromine, boron tribromide molar equivalent 0.5～0.8, room temperature reaction time priority is in 4～7h, more preferably in 5～6h.
Synthesis technique cost of the present invention is low, it is little to pollute, yield is up to 85%, is conducive to expanding production.
Accompanying drawing explanation
Accompanying drawing is preparation method's route map of 3,4-dimethoxy-benzyl bromine.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided at length embodiment and process, but protection scope of the present invention is not limited to following embodiment.
The preparation of embodiment 1 veratryl aldehyde
Take vanillin food grade,1000.000000ine mesh 20g, salt of wormwood 27.2～36.3g in the single port bottle of configuration thermometer, ice bath stirs 30min, slowly drips methyl iodide 10.6～12.3ml, keeps thermotonus 1～2h, stirring at room temperature 20～22h, and reaction finishes, and is cooled to room temperature.
The preparation of embodiment 2 veratryl alcohols
Above-mentioned reaction solution ice bath stirs 30min, slowly adds sodium borohydride 6.0～7.5g, room temperature reaction 4～7h in batches.
Embodiment 33, the preparation of 4-dimethoxy-benzyl bromine
Above-mentioned reaction solution is cooled to-5～0 ℃, drips boron tribromide 6.1～9.8ml, room temperature reaction 5～6h, and reaction finishes, concentrating under reduced pressure, recrystallizing methanol, weight yield 80～85%.
Claims (6)
1. one kind 3, the preparation method of 4-dimethoxy-benzyl bromine, its special character is, vanillin food grade,1000.000000ine mesh is starting raw material, under inorganic weak bases, with methylating reagent send out should, generate veratryl aldehyde; Be reduced into alcohol with sodium borohydride reaction aldehyde radical again, obtain veratryl alcohol; Obtain last product with boron tribromide bromination again.
2. according to claim 13, the preparation method of 4-dimethoxy-benzyl bromine, it is characterized in that: in methylation reaction, reaction solvent is tetrahydrofuran (THF), methylating reagent includes but not limited to methyl iodide, sulfuric acid dimethyl, methylcarbonate etc., and methylating reagent molar equivalent is 1.3～1.5eq.
3. according to claim 13, the preparation method of 4-dimethoxy-benzyl bromine, is characterized in that: in methylation reaction, inorganic weak bases includes but not limited to sodium carbonate, salt of wormwood, sodium bicarbonate etc., molar equivalent 1.5～2.0eq.
4. according to claim 13, the preparation method of 4-dimethoxy-benzyl bromine, is characterized in that: in methylation reaction, methylation reaction temperature is preferable over 90～95 ℃, and the reaction times is preferable over 20～22h.
5. according to claim 13, the preparation method of 4-dimethoxy-benzyl bromine, is characterized in that: in reduction reaction, selected reductive agent includes but not limited to sodium borohydride, POTASSIUM BOROHYDRIDE etc., molar equivalent 1.2～1.5, room temperature reaction 4～7h.
6. according to claim 13, the preparation method of 4-dimethoxy-benzyl bromine, is characterized in that: in bromination reaction, and boron tribromide molar equivalent 0.5～0.8, room temperature reaction time priority is in 5～6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410071150.1A CN103804150A (en) | 2014-03-01 | 2014-03-01 | Preparation method of 3,4-dimethoxybenzyl bromide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410071150.1A CN103804150A (en) | 2014-03-01 | 2014-03-01 | Preparation method of 3,4-dimethoxybenzyl bromide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103804150A true CN103804150A (en) | 2014-05-21 |
Family
ID=50701593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410071150.1A Pending CN103804150A (en) | 2014-03-01 | 2014-03-01 | Preparation method of 3,4-dimethoxybenzyl bromide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804150A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459444A (en) * | 2017-07-11 | 2017-12-12 | 山东理工大学 | A kind of preparation method of veratryl alcohol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU217542B (en) * | 1995-12-22 | 2000-02-28 | EGIS Gyógyszergyár Rt. | Process for producing veratrumaldehyde |
| WO2006128142A2 (en) * | 2005-05-27 | 2006-11-30 | Wyeth | Inhibitors of cytosolic phospholipase a2 |
-
2014
- 2014-03-01 CN CN201410071150.1A patent/CN103804150A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU217542B (en) * | 1995-12-22 | 2000-02-28 | EGIS Gyógyszergyár Rt. | Process for producing veratrumaldehyde |
| WO2006128142A2 (en) * | 2005-05-27 | 2006-11-30 | Wyeth | Inhibitors of cytosolic phospholipase a2 |
Non-Patent Citations (3)
| Title |
|---|
| JOELLE D.PELLETIER，ET AL.: "Bromination of Alcohols by Boron Tribromide", 《TETRAHEDRON LETTERS》 * |
| LIANSHUN FENG，ET AL.: "Synthesis and in vitro antibacterial activity of gemifloxacin derivatives containing a substituted benzyloxime moiety", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》 * |
| 徐冰凌: "藜芦醛的合成及应用", 《湖南化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459444A (en) * | 2017-07-11 | 2017-12-12 | 山东理工大学 | A kind of preparation method of veratryl alcohol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105367557B (en) | A kind of preparation method of epoxy quinoline | |
| CN104262442B (en) | The preparation method of Progesterone | |
| CN103864588B (en) | A kind of preparation method of 2,3-dimethoxybenzaldehyde | |
| CN105693470A (en) | Continuous 3-methyl-3-buten-1-ol production method | |
| CN102070421A (en) | Method for synthesizing veratraldehyde | |
| CN103724327A (en) | High-efficiency and green method for preparing pymetrozine | |
| CN106946707B (en) | Polysubstituted hydrogenation indene derivative of one kind and preparation method thereof | |
| CN104230853A (en) | Preparation method of (p-methylphenyl) methylamine-N-morpholinoethyl hydrochloride | |
| CN103833560A (en) | Preparation method of (S)-5-chloro-alpha-cyclopropinyl-2-amino-alpha-trifluoromethyl phenylcarbinol | |
| CN103804150A (en) | Preparation method of 3,4-dimethoxybenzyl bromide | |
| CN107216298A (en) | A kind of preparation method of butylphenyl phthaleine | |
| CN110343056A (en) | A kind of preparation method of N- tertbutyloxycarbonyl-N- methyl-2-amino -4,4- dimethyl valeric acid | |
| CN110218189B (en) | Abelide intermediate and simple preparation method of Abelide | |
| CN103265428B (en) | Method for preparing 4-[(3-halogenate-4-oxo) butyl] benzoic acid | |
| CN103044356A (en) | New method for synthesizing levocetirizine and key intermediate thereof | |
| CN108129260B (en) | Synthesis method of phenyl ethylene glycol | |
| CN102675036B (en) | Method for preparing 7-bromine-1-heptylene | |
| CN103373973A (en) | Novel synthetic process for levocetirizine and key intermediates | |
| CN104447355A (en) | Novel method for preparing bromhexine hydrochloride | |
| CN103724196A (en) | Dimethyl malonate preparation method | |
| CN106478422A (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN103435439A (en) | Preparation method of bromomethyl cyclobutane | |
| CN104649994B (en) | A kind of preparation method of 4-methyl-5-alkoxy-oxazole | |
| CN103896903A (en) | Method for preparing and purifying 2,3-O-isopropylidene threitol | |
| CN108191633A (en) | A kind of method for synthesizing homoanisic 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140521 |
|
| RJ01 | Rejection of invention patent application after publication |