CN1253134A - 四甲基吡嗪的制备方法 - Google Patents
四甲基吡嗪的制备方法 Download PDFInfo
- Publication number
- CN1253134A CN1253134A CN 98124478 CN98124478A CN1253134A CN 1253134 A CN1253134 A CN 1253134A CN 98124478 CN98124478 CN 98124478 CN 98124478 A CN98124478 A CN 98124478A CN 1253134 A CN1253134 A CN 1253134A
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- CN
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- Prior art keywords
- tetramethylpyrazine
- preparation
- viii family
- metallic compound
- reaction
- 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.)
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- FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- 239000012967 coordination catalyst Substances 0.000 claims abstract description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910000765 intermetallic Inorganic materials 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- -1 Tetramethylpyrazine compound Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract 1
- 101150003085 Pdcl gene Proteins 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000009466 transformation Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RGPUSZZTRKTMNA-UHFFFAOYSA-N 1-benzofuran-7-carbaldehyde Chemical compound O=CC1=CC=CC2=C1OC=C2 RGPUSZZTRKTMNA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000112528 Ligusticum striatum Species 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 206010059245 Angiopathy Diseases 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010008132 Cerebral thrombosis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 201000001429 Intracranial Thrombosis Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 206010047115 Vasculitis Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036770 blood supply Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000000302 ischemic effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006476 reductive cyclization reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- MHNHYTDAOYJUEZ-UHFFFAOYSA-N triphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MHNHYTDAOYJUEZ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
实施例号 | 金属 | 金属化合物用量(mg) | DAM转化率(%) | TMP产率(%) |
1234567比较例 | PdCl2CoCl2H2PtCl4NiBr2RuCl3CoOAcFeCl3空白 | 2.912.135.563.583.402.902.310.00 | 94.6176.4776.6496.2543.6931.0425.04<1 | 85.5372.1049.2056.1841.6631.0413.24<1 |
实施例号 | 金属组分 | PPh3/M | 反应温度(℃) | 氢气压力(MPa) | DAM转化率(%) | TMP产率(%) |
891011比较例12131415161718192021222324 | CoCl2,PdCl2CoCl2,PdCl2CoCl2,PdCl2CoCl2,PdCl2PdCl2PdCl2PdCl2PdOAcPdOAcPdCl2CoCl2CoCl2CoCl2CoCl2NiCl2NiCl2NiCl2NiCl2 | 1.52.03.05.000.51.52.03.05.01.52.03.05.01.52.03.05.0 | 120120120120150150150150150150100100100100150150150150 | 4.04.04.04.02.42.42.42.42.42.44.04.04.04.04.04.04.04.0 | 96.5290.29100.0100.01.9378.6594.6175.9479.0869.0314.4249.8367.0644.0938.2126.2396.2573.98 | 94.4473.5479.2988.00.0843.6385.5352.9873.9859.6110.5640.1656.6535.1616.2512.7456.1825.57 |
实施例号 | 反应温度(℃) | DAM转化率(%) | TMP产率(%) |
2526271 | 3060120150 | 5.9614.1780.1494.61 | 3.2414.1751.4285.53 |
实施例号 | 氢气压力(MPa) | DAM转化率(%) | TMP产率(%) |
比较例28293031323334 | 00.61.11.32.03.04.04.6 | <1.040.7897.4697.2258.21100.087.2895.64 | <1.039.4776.9889.9054.7463.8952.6949.28 |
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN98124478A CN1100765C (zh) | 1998-11-11 | 1998-11-11 | 四甲基吡嗪的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CN98124478A CN1100765C (zh) | 1998-11-11 | 1998-11-11 | 四甲基吡嗪的制备方法 |
Publications (2)
Publication Number | Publication Date |
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CN1253134A true CN1253134A (zh) | 2000-05-17 |
CN1100765C CN1100765C (zh) | 2003-02-05 |
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Application Number | Title | Priority Date | Filing Date |
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CN98124478A Expired - Fee Related CN1100765C (zh) | 1998-11-11 | 1998-11-11 | 四甲基吡嗪的制备方法 |
Country Status (1)
Country | Link |
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CN (1) | CN1100765C (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1296409C (zh) * | 2003-10-15 | 2007-01-24 | 北京理工大学 | 川芎嗪聚乙二醇酯及其制备方法 |
CN100556895C (zh) * | 2006-10-18 | 2009-11-04 | 张锋 | 川芎嗪的制备方法 |
CN103664803A (zh) * | 2012-09-17 | 2014-03-26 | 王天桃 | 2,3,5,6-四甲基吡嗪新的合成方法 |
CN104341359A (zh) * | 2014-11-11 | 2015-02-11 | 武汉武药制药有限公司 | 一种四甲基吡嗪的制备方法 |
CN110156701A (zh) * | 2019-06-25 | 2019-08-23 | 吴赣药业(苏州)有限公司 | 一种2,3,5,6-四甲基吡嗪的合成方法 |
-
1998
- 1998-11-11 CN CN98124478A patent/CN1100765C/zh not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1296409C (zh) * | 2003-10-15 | 2007-01-24 | 北京理工大学 | 川芎嗪聚乙二醇酯及其制备方法 |
CN100556895C (zh) * | 2006-10-18 | 2009-11-04 | 张锋 | 川芎嗪的制备方法 |
CN103664803A (zh) * | 2012-09-17 | 2014-03-26 | 王天桃 | 2,3,5,6-四甲基吡嗪新的合成方法 |
CN104341359A (zh) * | 2014-11-11 | 2015-02-11 | 武汉武药制药有限公司 | 一种四甲基吡嗪的制备方法 |
CN110156701A (zh) * | 2019-06-25 | 2019-08-23 | 吴赣药业(苏州)有限公司 | 一种2,3,5,6-四甲基吡嗪的合成方法 |
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Publication number | Publication date |
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CN1100765C (zh) | 2003-02-05 |
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Owner name: ZHEJIANG UNIVERSITY Free format text: FORMER OWNER: ROOM #, YINGYONGHUAXUEZHONGDIANYANJIUSHIYAN, ZHEJIANG PROVINCE Effective date: 20020920 |
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Effective date of registration: 20020920 Address after: Hangzhou City, Zhejiang province 310027 Ancient Jade Road 20 Applicant after: Zhejiang University Address before: 310028, 34, Tianmu Road, Zhejiang, Hangzhou Applicant before: Key Laboratory of Applied Chemistry, Zhejiang Prov. |
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