CN104926775A - Preparation method of fluorine-containing pyran derivative - Google Patents
Preparation method of fluorine-containing pyran derivative Download PDFInfo
- Publication number
- CN104926775A CN104926775A CN201510228887.4A CN201510228887A CN104926775A CN 104926775 A CN104926775 A CN 104926775A CN 201510228887 A CN201510228887 A CN 201510228887A CN 104926775 A CN104926775 A CN 104926775A
- Authority
- CN
- China
- Prior art keywords
- xylol
- reaction
- compound
- prepares compound
- solvent
- 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 8
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 7
- 239000011737 fluorine Substances 0.000 title claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 title abstract 2
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000006266 etherification reaction Methods 0.000 claims abstract description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004176 ammonification Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 238000007363 ring formation reaction Methods 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 229940125898 compound 5 Drugs 0.000 claims description 6
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 3
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-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 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 6
- 239000000203 mixture Substances 0.000 claims 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims 4
- 238000000034 method Methods 0.000 claims 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- NBCIQSAGKNYXTQ-UHFFFAOYSA-N 5-fluoro-N-methyl-3,4-dihydro-2H-pyran-3-amine Chemical compound FC=1CC(COC=1)NC NBCIQSAGKNYXTQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005576 amination reaction Methods 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 dry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyrane Compounds (AREA)
Abstract
The invention discloses a preparation method of a fluorine-containing pyran derivative 5-fluoro-N-Methyl-3,4-dihydro-2H-pyran-3-amine. According to the invention, 2-(6-fluoro-2-hydroxyphenyl)methyl acetate is adopted as an initial raw material, and a target product 5 is obtained through etherification, ring-closing, decarboxylation, and amination reduction reactions. The product provided by the invention can be used as a template small molecule for synthesizing various compound libraries.
Description
Technical field
The present invention relates to a kind of novel processing step of medicine intermediate, particularly the preparation method of the preparation method of one fluorine-containing pyran derivate 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine.
Technical background
Compound 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine, structural formula is:
This compound 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine and relevant derivative have widespread use in pharmaceutical chemistry and organic synthesis.The synthesis of current 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine is comparatively difficult.Therefore, need exploitation raw material to be easy to get, easy to operate, reaction is easy to control, the synthetic method that overall yield is suitable.
Summary of the invention
The invention discloses the fluoro-N-methyl-3 of a kind of fluorine-containing pyran derivate 5-, the preparation method of 4-dihydro-2H-pyrans-3-amine, with 2-(6-fluoro-2-hydroxyphenyl) methyl acetate for starting raw material, obtain target product 5 through etherificate, Guan Huan, decarboxylation, ammonification reduction reaction, synthetic route as shown in Figure 1.Synthesis step is as follows:
(1) for starting raw material, 2 are obtained through etherification reaction with 2-(6-fluoro-2-hydroxyphenyl) methyl acetate,
(2) carry out ring closure reaction 2, obtain 3,
(3) carry out decarboxylic reaction 3 and obtain 4,
(4) carry out ammonification reduction reaction 4 and obtain 5,
One preferred embodiment in, the reagent that described etherification reaction prepares compound 2 used is selected from ethyl bromoacetate; The reagent that described ring closure reaction prepares compound 3 used is selected from sodium ethylate; The reductive agent that described decarboxylic reaction prepares compound 4 used is selected from sodium hydroxide; The reductive agent that described ammonification reduction reaction prepares compound 5 used is selected from methylamine hydrochloride.
One preferred embodiment in, the solvent that described etherification reaction prepares compound 2 used is selected from DMF; Described ring closure reaction prepares compound 3 solvent selected from ethanol used; The solvent that described decarboxylic reaction prepares compound 4 used is selected from DMF; Described ammonification reduction reaction prepares compound 5 solvent selected from methanol used.
One preferred embodiment in, described etherification reaction prepares the reflux temperature that compound 2 temperature of reaction used is solvent; It is 0 DEG C of reflux temperature to solvent that described ring closure reaction prepares compound 3 temperature used; Described decarboxylic reaction prepares the reflux temperature that compound 4 temperature used is solvent; It is room temperature that described ammonification reduction reaction prepares compound 5 temperature used.
The present invention relates to the preparation method of a kind of 5-fluorine pyran derivate 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine, there is no other Patents bibliographical informations at present.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of compound 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine.
The present invention is further described by the following embodiment, and these descriptions are not be further limited content of the present invention.One skilled in the art will understand that the equivalent replacement that technical characteristic of the present invention is done, or improve accordingly, still belong within protection scope of the present invention.
Specific embodiment mode
Embodiment 1
(1) synthesis of 2-(5-fluoro-2-phenoxyethanoic acid ethyl ester) ethyl acetate
17g 2-(6-fluoro-2-hydroxyphenyl) methyl acetate is joined 130ml N, in dinethylformamide, add 15g ethyl bromoacetate and 12g salt of wormwood, heated and stirred refluxes, and is cooled to room temperature, add water and ethyl acetate, extraction separatory, collects organic phase, dry, concentrated, obtain 10g 2-(5-fluoro-2-phenoxyethanoic acid ethyl ester) ethyl acetate.
(2) synthesis of 5-fluoro-3-oxo-3,4-dihydro-2H-chromene-4-ethyl formate
10g 2-(5-fluoro-2-phenoxyethanoic acid ethyl ester) ethyl acetate is joined in 70ml ethanol, be cooled to 0 DEG C, add 8g sodium ethylate, heated and stirred back flow reaction 3 hours, cooling room temperature, concentrated, add water and extraction into ethyl acetate separatory, collect organic phase, dry, concentrate and obtain 7g 5-fluoro-3-oxo-3,4-dihydro-2H-chromene-4-ethyl formate.
(3) synthesis of 5-fluoro-2H-chromene-3 (4H)-one
Fluoro-for 7g 6-3-oxo-3,4-dihydro-2H-chromene-4-ethyl formate joins 80mlN, in dinethylformamide, adds 5g sodium hydroxide, reflux stirs 24 hours, filter, then add water and ethyl acetate, extraction separatory, collect organic phase, drying, concentrated, on residuum, silicagel column is separated to obtain 4g 5 fluoro-2H-chromene-3 (4H)-one.
(4) synthesis of 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine
Bromo-for 4g 6-3-oxo-3,4-dihydro-2H-chromene-4-ethyl formate is joined in 30ml methyl alcohol, adds 3g methylamine hydrochloride, stirring at room temperature 20 hours, then add 4g sodium borohydride, stirring at room temperature 3 hours, filter, add water and ethyl acetate again, extraction separatory, collects organic phase, dry, concentrated, on residuum, silicagel column is separated to obtain 2.1g 5-fluoro-N-methyl-3,4-dihydro-2H-pyrans-3-amine.
Claims (5)
1. the fluoro-N-methyl-3 of fluorine-containing pyran derivate 5-, the preparation method of 4-dihydro-2H-pyrans-3-amine, with 2-(6-fluoro-2-hydroxyphenyl) methyl acetate for starting raw material, obtain target product 5 through etherificate, Guan Huan, decarboxylation, ammonification reduction reaction, synthetic route is as follows:
2. method according to claim 1, it is characterized by 4 described step reactions is,
(1) for starting raw material, 2 are obtained through etherification reaction with 2-(6-fluoro-2-hydroxyphenyl) methyl acetate,
(2) carry out ring closure reaction 2, obtain 3,
(3) carry out decarboxylic reaction 3 and obtain 4,
(4) carry out ammonification reduction reaction 4 and obtain 5,
3. according to the method for claim 1-2, it is characterized in that, the reagent that described etherification reaction prepares compound 2 used is selected from ethyl bromoacetate; The reagent that described ring closure reaction prepares compound 3 used is selected from sodium ethylate; Described decarboxylic reaction is prepared compound 4 reductive agent used and is selected from the mixture of one or more in sodium hydroxide, potassium hydroxide, salt of wormwood; The reductive agent that described ammonification reduction reaction prepares compound 5 used is selected from methylamine hydrochloride.
4. according to the method for claim 1-2, it is characterized in that, described etherification reaction is prepared compound 2 solvent used and is selected from tetrahydrofuran (THF), methylene dichloride, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile; Described ring closure reaction prepares compound 3 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), methylene dichloride, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile; Described decarboxylic reaction prepares compound 4 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, acetonitrile, tetrahydrofuran (THF), dioxane, methylene dichloride, trichloromethane, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide; Described ammonification reduction reaction prepares compound 5 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), methylene dichloride, toluene, o-Xylol, p-Xylol, m-xylene, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile.
5. according to the method for claim 1-2, it is characterized in that, described etherification reaction prepares the reflux temperature that compound 2 temperature of reaction used is solvent; It is 0 DEG C of reflux temperature to solvent that described ring closure reaction prepares compound 3 temperature used; It is the reflux temperature of room temperature to solvent that described decarboxylic reaction prepares compound 4 temperature used; It is room temperature that described ammonification reduction reaction prepares compound 5 temperature used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510228887.4A CN104926775A (en) | 2015-05-07 | 2015-05-07 | Preparation method of fluorine-containing pyran derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510228887.4A CN104926775A (en) | 2015-05-07 | 2015-05-07 | Preparation method of fluorine-containing pyran derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104926775A true CN104926775A (en) | 2015-09-23 |
Family
ID=54114229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510228887.4A Pending CN104926775A (en) | 2015-05-07 | 2015-05-07 | Preparation method of fluorine-containing pyran derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104926775A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831681A (en) * | 2017-01-17 | 2017-06-13 | 湖南华腾制药有限公司 | A kind of preparation method of 5 nitro pyran derivate |
| CN106905282A (en) * | 2017-02-26 | 2017-06-30 | 长沙深橙生物科技有限公司 | A kind of preparation method of benzo oxa- ring derivatives |
| CN106995426A (en) * | 2017-05-31 | 2017-08-01 | 湖南华腾制药有限公司 | A kind of preparation method of 5 chlorine pyran derivate |
| CN107400106A (en) * | 2016-05-20 | 2017-11-28 | 湖南华腾制药有限公司 | A kind of preparation method of 5- fluorine pyran derivate |
| CN107698547A (en) * | 2016-08-08 | 2018-02-16 | 湖南华腾制药有限公司 | A kind of preparation method of pyran derivate |
| CN108129434A (en) * | 2016-12-01 | 2018-06-08 | 湖南华腾制药有限公司 | A kind of preparation method of 5- cyano chroman derivatives |
| CN108610318A (en) * | 2016-12-12 | 2018-10-02 | 湖南华腾制药有限公司 | A kind of preparation method of trifluoromethyl pyran derivate |
-
2015
- 2015-05-07 CN CN201510228887.4A patent/CN104926775A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| A DANAN ET AL.: "Les chroman-3-ones", 《BULL SOC CHIM FR》 * |
| DERVILLA M. X. DONNELLY ET AL.: "Synthesis of neoflavenes by ligand coupling reactions with aryllead triacetates", 《TETRAHEDRON》 * |
| MAGNUS BRISANDER ET AL.: "Alkylation of Tricarbonylchromium-Stabilized Benzylic Anions of 3-(Dipropylamino)chroman", 《J. ORG. CHEM.》 * |
| REGISTRY: "RN 1545084-35-2", 《STN ON THE WEB》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400106A (en) * | 2016-05-20 | 2017-11-28 | 湖南华腾制药有限公司 | A kind of preparation method of 5- fluorine pyran derivate |
| CN107698547A (en) * | 2016-08-08 | 2018-02-16 | 湖南华腾制药有限公司 | A kind of preparation method of pyran derivate |
| CN108129434A (en) * | 2016-12-01 | 2018-06-08 | 湖南华腾制药有限公司 | A kind of preparation method of 5- cyano chroman derivatives |
| CN108610318A (en) * | 2016-12-12 | 2018-10-02 | 湖南华腾制药有限公司 | A kind of preparation method of trifluoromethyl pyran derivate |
| CN106831681A (en) * | 2017-01-17 | 2017-06-13 | 湖南华腾制药有限公司 | A kind of preparation method of 5 nitro pyran derivate |
| CN106905282A (en) * | 2017-02-26 | 2017-06-30 | 长沙深橙生物科技有限公司 | A kind of preparation method of benzo oxa- ring derivatives |
| CN106995426A (en) * | 2017-05-31 | 2017-08-01 | 湖南华腾制药有限公司 | A kind of preparation method of 5 chlorine pyran derivate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104926775A (en) | Preparation method of fluorine-containing pyran derivative | |
| CN104230853B (en) | A kind of preparation method of (p-methylphenyl) methylamine-N-ethylmorpholine hydrochloride | |
| CN104829581A (en) | Preparation method of 6-bromo pyran derivative | |
| CN104262257A (en) | Preparation method of pyrazole derivative | |
| CN104844528A (en) | Preparation method of triazole derivative | |
| CN104860910A (en) | Preparation method of 8-fluoropyran derivative | |
| CN104829576A (en) | Preparation method of 7-fluoropyran derivatives | |
| CN104829575A (en) | Preparation method of 6-fluoropyran derivative | |
| CN104829574A (en) | 8-bromo pyran derivative preparation method | |
| CN104844549A (en) | Preparation method of 7 - bromine pyran derivatives | |
| CN104817515A (en) | Preparation method of benzene substituent oxadiazole compound | |
| CN104277042A (en) | Preparation method of imidazopyridine derivative | |
| CN104387367A (en) | Method for preparing disubstituted benzimidazole derivative | |
| CN104829547A (en) | Substituted triazole compound preparation method | |
| CN104402880A (en) | Preparation method of imidazopyridine derivative | |
| CN105001117A (en) | Method for synthesizing chlorine-containing azide compound | |
| CN104326977A (en) | Preparation method of 6,7-diethyl-4-hydroxyquinoline | |
| CN106831681A (en) | A kind of preparation method of 5 nitro pyran derivate | |
| CN106905282A (en) | A kind of preparation method of benzo oxa- ring derivatives | |
| CN108129434A (en) | A kind of preparation method of 5- cyano chroman derivatives | |
| CN107698547A (en) | A kind of preparation method of pyran derivate | |
| CN105061253A (en) | Preparation method of bromine-containing azide | |
| CN104592109A (en) | Method for preparing 8-bromoquinoline derivative | |
| CN104725331A (en) | Method for preparing 5-fluorobenzo[d]oxazole-2-nitrile | |
| CN104876918A (en) | Preparation method of pyrazinyl substituted oxadiazole compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150923 |