CN105037281A - Preparation method for 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid - Google Patents
Preparation method for 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid Download PDFInfo
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- CN105037281A CN105037281A CN201510404170.0A CN201510404170A CN105037281A CN 105037281 A CN105037281 A CN 105037281A CN 201510404170 A CN201510404170 A CN 201510404170A CN 105037281 A CN105037281 A CN 105037281A
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- XFTJASGXXRSKRG-UHFFFAOYSA-N 3-(3-fluorophenoxy)pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN=C1OC1=CC=CC(F)=C1 XFTJASGXXRSKRG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- INCSQLZZXBPATR-UHFFFAOYSA-N methyl 3-aminopyrazine-2-carboxylate Chemical compound COC(=O)C1=NC=CN=C1N INCSQLZZXBPATR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 230000033444 hydroxylation Effects 0.000 claims abstract description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000000640 hydroxylating effect Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 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
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 8
- 239000000203 mixture Substances 0.000 claims 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 4
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 229960001701 chloroform Drugs 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a preparation method for 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid. The method comprises the following steps: with 3-aminopyrazine-2-carboxylic acid methyl ester as an initial material, carrying out hydroxylation, chlorination, condensation and hydrolysis reactions so as to obtain a target product--the 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid. The 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid prepared in the invention is used as a template micromolecule to synthesize a variety of chemical compound libraries.
Description
Technical field
The present invention relates to a kind of preparation method of medicine intermediate, particularly the preparation method of 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid.
Technical background
Compound 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid, structural formula is:
This compound 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid and relevant derivative have widespread use in pharmaceutical chemistry and organic synthesis.The synthesis of current 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid 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 preparation method of 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid, with 3-Aminopyrazine-2-carboxylate methyl ester for starting raw material, obtain target product 5 through hydroxylation, chlorination, condensation, hydrolysis reaction, synthetic route as shown in Figure 1.Synthesis step is as follows:
(1) with 3-Aminopyrazine-2-carboxylate methyl ester for starting raw material, obtain 2 through hydroxylating,
(2) carry out chlorination reaction 2, obtain 3,
(3) carry out condensation reaction 3 and obtain 4,
(4) be hydrolyzed 4 and be obtained by reacting 5,
One preferred embodiment in, the reagent that described hydroxylating prepares compound 2 used is selected from Sodium Nitrite; The reagent that described chlorination reaction prepares compound 3 used is selected from phosphorus oxychloride; The alkali that described condensation reaction prepares compound 4 used is selected from salt of wormwood; The reagent that described hydrolysis reaction prepares compound 5 used is selected from sodium hydroxide.
One preferred embodiment in, the solvent that described hydroxylating prepares compound 2 used is selected from water; The solvent that described chlorination reaction prepares compound 3 used is selected from phosphorus oxychloride; The solvent that described condensation reaction prepares compound 4 used is selected from DMF; Described hydrolysis reaction prepares compound 5 solvent selected from methanol used.
One preferred embodiment in, it is 0 DEG C that described hydroxylating prepares compound 2 temperature of reaction used; Described chlorination reaction prepares the reflux temperature that compound 3 temperature used is solvent; The reflux temperature that compound 4 temperature used is solvent is prepared in described condensation reaction; It is room temperature that described hydrolysis reaction prepares compound 5 temperature used.
The present invention relates to the preparation method of 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid, there is no other Patents bibliographical informations at present.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of compound thing 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid.
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 3-HYDROXYPYRAZINE-2-methyl-formiate
18g3-Aminopyrazine-2-carboxylate methyl ester is joined in 50ml concentrated hydrochloric acid, add 80ml water, be cooled to 0 DEG C, slowly add 11g Sodium Nitrite, 0 DEG C is stirred 0.5 hour, add saturated aqueous sodium carbonate, continue stirring 1 hour, add extraction into ethyl acetate separatory, collect organic phase, drying, concentrated, obtain 13g3-HYDROXYPYRAZINE-2-methyl-formiate.
(2) synthesis of 3-chloropyrazine-2-methyl-formiate
13g3-HYDROXYPYRAZINE-2-methyl-formiate is joined in 150ml phosphorus oxychloride, and reflux stirs 3 hours, cooling, concentrated removing phosphorus oxychloride, adds water and extraction into ethyl acetate separatory, collects organic phase, drying, concentrated, cross post separation and obtain 10g3-chloropyrazine-2-methyl-formiate.
(3) synthesis of 3-(3-fluorophenoxy) pyrazine-2-methyl-formiate
10g3-chloropyrazine-2-methyl-formiate is joined 110mlN, in dinethylformamide, add 13g m fluorophenol and 12g salt of wormwood, reflux stirs 5 hours, is cooled to room temperature, adds water and extraction into ethyl acetate separatory, collect organic phase, drying, concentrated, obtain 12g3-(3-bromine phenoxy group) pyrazine-2-methyl-formiate.
(4) synthesis of 3-(3-bromine phenoxy group) pyrazine-2-carboxylic acid
12g3-(3-bromine phenoxy group) pyrazine-2-methyl-formiate is joined in 110ml methyl alcohol, add 60ml water, add 9g sodium hydroxide again, stirring at room temperature 2 hours, adjusts pH=1 with hydrochloric acid, add ethyl acetate and water again, extraction separatory, collects organic phase, dry, concentrated, residuum is crossed post separation and is obtained 7g3-(3-bromine phenoxy group) pyrazine-2-carboxylic acid.
Claims (5)
1. a preparation method for 3-(3-fluorophenoxy) pyrazine-2-carboxylic acid, with 3-Aminopyrazine-2-carboxylate methyl ester for starting raw material, obtain target product 5 through hydroxylation, chlorination, condensation, hydrolysis reaction, synthetic route is as follows,
2. method according to claim 1, it is characterized by 4 described step reactions is,
(1) with 3-Aminopyrazine-2-carboxylate methyl ester for starting raw material, obtain 2 through hydroxylating,
(2) carry out chlorination reaction 2, obtain 3,
(3) carry out condensation reaction 3 and obtain 4,
(4) be hydrolyzed 4 and be obtained by reacting 5,
3. according to the method for claim 1-2, it is characterized in that, the reagent that described hydroxylating prepares compound 2 used is selected from Sodium Nitrite; Described chlorination reaction is prepared compound 3 reagent used and is selected from the mixture of one or more in phosphorus oxychloride, phosphorus trichloride, sulfur oxychloride; Described condensation reaction is prepared compound 4 alkali used and is selected from the mixture of one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, pyridine, triethylamine; Described hydrolysis reaction is prepared compound 5 reagent used and is selected from the mixture of one or more in sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood.
4. according to the method for claim 1-2, it is characterized in that, described hydroxylating prepares compound 2 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, triethylamine, pyridine, acetonitrile, water; Described chlorination 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, ammoniacal liquor, phosphorus oxychloride; Compound 4 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), dioxane, methylene dichloride, trichloromethane, toluene, o-Xylol, p-Xylol, m-xylene, N are prepared in described condensation reaction, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, acetonitrile, phosphorus oxychloride; Described hydrolysis reaction prepares compound 5 solvent selected from methanol used, ethanol, n-propyl alcohol, Virahol, 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, acetic acid, phosphorus oxychloride.
5. according to the method for claim 1-2, it is characterized in that, described hydroxylating prepares the reflux temperature that compound 2 temperature of reaction used is 0 DEG C ~ solvent; Described chlorination reaction prepares the reflux temperature that compound 3 temperature used is 0 DEG C ~ solvent; The reflux temperature that compound 4 temperature used is room temperature DEG C ~ solvent is prepared in described condensation reaction; Described hydrolysis reaction prepares the reflux temperature that compound 5 temperature used is 0 DEG C ~ solvent.
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| CN201510404170.0A CN105037281A (en) | 2015-07-11 | 2015-07-11 | Preparation method for 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid |
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| CN201510404170.0A CN105037281A (en) | 2015-07-11 | 2015-07-11 | Preparation method for 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid |
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| CN201510404170.0A Pending CN105037281A (en) | 2015-07-11 | 2015-07-11 | Preparation method for 3-(3-fluorophenoxyl)pyrazine-2-carboxylic acid |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418220A (en) * | 2000-02-16 | 2003-05-14 | 富山化学工业株式会社 | Novel pyrazine derivatives or salts thereof, containing the derives or the salts and intermediates for the preparation of both |
| WO2014113485A1 (en) * | 2013-01-15 | 2014-07-24 | Intermune, Inc. | Lysophosphatidic acid receptor antagonists |
-
2015
- 2015-07-11 CN CN201510404170.0A patent/CN105037281A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418220A (en) * | 2000-02-16 | 2003-05-14 | 富山化学工业株式会社 | Novel pyrazine derivatives or salts thereof, containing the derives or the salts and intermediates for the preparation of both |
| WO2014113485A1 (en) * | 2013-01-15 | 2014-07-24 | Intermune, Inc. | Lysophosphatidic acid receptor antagonists |
Non-Patent Citations (3)
| Title |
|---|
| ACS，STN REGISTRY数据库: "RN:1228552-82-6", 《ACS，STN REGISTRY数据库》 * |
| TOMOHIRO OKAWA等: "Methyl 3-(triphenylphosphoranylideneamino)pyrazine-2-carboxylate: synthesis, crystal structure and use in pteridin-4(3H)- ones synthesis", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
| 刘建华，等: "新型含甲氨甲酰苯基烟酰脲类化合物的设计、合成及生物活性研究", 《有机化学》 * |
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