CN1391559A - 生产甲酰基咪唑的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 17
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical class O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 9
- ZOMATQMEHRJKLO-UHFFFAOYSA-N 1h-imidazol-2-ylmethanol Chemical compound OCC1=NC=CN1 ZOMATQMEHRJKLO-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal acetate Chemical class 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000003021 water soluble solvent Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- RRTJBIJAUFOAGW-UHFFFAOYSA-N 2-methyl-1h-imidazol-5-ol Chemical class CC1=NC=C(O)N1 RRTJBIJAUFOAGW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- UBPIRRORRFGPNE-UHFFFAOYSA-N benzoic acid;formic acid Chemical compound OC=O.OC(=O)C1=CC=CC=C1 UBPIRRORRFGPNE-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
叙述了羟甲基咪唑催化转化成甲酰基咪唑的一种新方法。催化作用在过氧化物存在下发生。甲酰基咪唑是药物的重要中间产物。
Description
本发明涉及生产通式(I)的甲酰基咪唑的一种新方法
其中R1意指一个烷基，通过在碱性介质中催化氧化通式(II)的羟甲基咪唑来生产通式(I)的甲酰基咪唑，其中R1具有如上给出的含义。
甲酰基咪唑是例如生产药物如利尿药或抗高血压药的重要中间产品(WO-A 92/20651)。以前已经知道生产甲酰基咪唑的几种方法。在CH-A 685496中介绍了一个方法，其中羟甲基咪唑催化氧化成甲酰基咪唑是在贵金属催化剂例如在活性炭上的铂/铋，铂黑，铂或钯存在下用氧气吹入来完成的。
因此，本发明的任务是提供一种生产甲酰基咪唑的经济的改进方法。
在本发明中，这个任务是通过权利要求1所定义的方法来完成的。在权利要求1中，通式(II)的羟甲基咪唑其中R1具有如上给出的含义，在碱性介质中，在一种贵金属催化剂和一种过氧化物存在下被催化氧化成通式(I)的甲酰基咪唑
其中R1具有如上给出的含义。
R1意指氢或一个烷基，和更具体的是一个直链或支链的1-6个碳原子的烷基。特别是甲基，乙基，丙基，异丙基，丁基，异丁基，特丁基，戊基及其异构体，以及己基及其异构体。优选的R1是丁基。
例如在WO-A 92/20651中或在E.F.Godefroi等人，Trav.Chim.Recueil Pays Bas.
91，1383(1992)中所详细说明的，作为起始化合物的羟甲基咪唑很容易生产。
铂，钯，铷或金可以用作贵金属催化剂。贵金属最好与作为第二组分的金属例如铋，铅，铈或铟一起使用。优选的催化剂是铂/铋或铂/铅。
贵金属可以其本身或结合于媒介物，例如活性炭，二氧化硅，氧化铝，氧化硅铝，氧化锆或氧化钛上被使用。优选结合于活性炭上。
结合于活性炭上的贵金属催化剂市面上可买到，例如从Degussa得到。
结合于媒介物的贵金属的适当百分比相对于媒介物为0.1和15％(重量计)之间，优选在0.5和7％(重量计)之间。
贵金属催化剂优选的使用量是相对于羟甲基咪唑的0.05至1.0摩尔％贵金属，特别优选的使用量是相对于羟甲基咪唑的0.1至0.4摩尔％。
有机的或无机的过氧化物都要用作过氧化物。例如过氧化氢，过硼酸盐，过羧酸，特丁基氢过氧化物，异丙苯氢过氧化物，过苯甲酸，间氯过苯甲酸，单过邻苯二甲酸或过乙酸都是适合的。以10％至30％水溶液使用的过氧化氢是特别适合的。
除了催化氧化外，通式(II)的羟甲基咪唑甲酯的水解会在碱性介质中发生。
碱性介质最好是通过将一种碱金属氢氧化物，碱金属碳酸盐或碱金属乙酸盐加到反应混合物中来产生。优选碱金属氢氧化物的使用量，相对于通式(II)的羟甲基咪唑所用的摩尔量的比例为1∶0.05-5，最好1∶3。
催化氧化最好在碱性介质中，在水，一种水溶性溶剂或其混合物的存在下进行。
特别适合的水溶性溶剂是，例如，含有1-6个C原子的醇或羧酸，或酮例如丙酮或甲乙酮。
优选使用水和水溶性溶剂的混合物。
催化氧化最好在20-120℃，优选50-100℃下进行。
在0.5-3小时的添加标准的过氧化物的时间之后，可用标准方法在足够的第二反应时间之后将通式(I)的化合物分离出来。
产品通过适当的结晶和过滤被分离出来。用过的催化剂因为没有失去活性，可以使用几次。
实施例
实施例1
4-[(2-丁基-5-甲酰基-1H-咪唑-1-基)甲基]苯甲酸的生产
在室温，将900mg(3mmol)4-[(2-丁基-5-羟甲基-1H-咪唑-1-基)甲基]苯甲酸甲酸，8ml苛性苏打溶液(1M)，0.5ml甲醇和107mg在含60％水的活性炭上的铂5％和铋5％放入25ml烧瓶中，并中热到60℃。
在60℃，30分钟内将0.8g(4.6mmol)20％H2O2水溶液加到该悬浮液中，然后在HPLC(分析)情况下，使该混合物反应。在10分钟内又加入另外的0.2g(1.1mmol)20％H2O2水溶液。然后加入0.2g(5mmol)20％NaOH。反应溶液在100℃加热2小时。该混合物冷至室温。在硅藻土上滤掉催化剂，并用5ml水洗涤。用HCl(15％)酸化到pH5.0后，产品沉淀析出。冷至2℃，过滤，用2×5ml水洗涤，在室温15mbar下干燥。得到410mg(48％)黄色的4-[(2-丁基-5-甲酰基-1H-咪唑-1-基)甲基]苯甲酸(HPLC含量96％)。
熔点：144-146℃
1H-NMR(DMSO-d6，400Mhz)δ：12.9(1H，s)；
9.65(1H，s)；
7.94(1H，s)；
7.90(2H，d)；
7.11(2H，d)；
5.65(2H，s)；
2.63(2H，t)；
1.54(2H，五峰)；
1.36(2H，六峰)
0.79(3H，t)。
Claims (7)
1.在贵金属催化剂存在下通过催化氧化通式(II)的羟甲基咪唑生产通式(I)的甲酰基咪唑的方法，
其中R1意指一个烷基，
其中R1具有如上给出的含义，
该方法的特征在于催化氧化在一种过氧化物存在下在碱性介质中进行。
2.权利要求1的方法，其特征在于R1是一个丁基。
3.权利要求1或2的方法，其特征在于贵金属催化剂是铂/铋催化剂或铂/铅催化剂。
4.权利要求1至3任一项的方法，其特征在于过氧化物是过氧化氢。
5.权利要求1至4任一项的方法，其特征在于碱性介质是通过将碱金属氢氧化物，碱金属碳酸盐或碱金属乙酸盐加到反应混合物中产生的。
6.权利要求1至5中任一项的方法，其特征在于催化氧化是在水，水溶性溶剂或其混合物存在下在碱性介质中完成的。
7.权利要求1至6中任一项的方法，其特征在于该反应是在20°-120℃完成的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98110868.1 | 1998-06-15 | ||
| EP98110868 | 1998-06-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1391559A true CN1391559A (zh) | 2003-01-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99807463A Pending CN1391559A (zh) | 1998-06-15 | 1999-06-11 | 生产甲酰基咪唑的方法 |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US6258958B1 (zh) |
| EP (1) | EP1087944A1 (zh) |
| JP (1) | JP2002518376A (zh) |
| KR (1) | KR100569775B1 (zh) |
| CN (1) | CN1391559A (zh) |
| AR (1) | AR019659A1 (zh) |
| AU (1) | AU4513299A (zh) |
| BR (1) | BR9911172A (zh) |
| CA (1) | CA2334901C (zh) |
| HU (1) | HUP0102771A3 (zh) |
| IL (1) | IL140170A0 (zh) |
| MY (1) | MY119854A (zh) |
| NO (1) | NO20006351L (zh) |
| NZ (1) | NZ508693A (zh) |
| PL (1) | PL344597A1 (zh) |
| TR (1) | TR200003693T2 (zh) |
| TW (1) | TW568906B (zh) |
| WO (1) | WO1999065879A1 (zh) |
| ZA (1) | ZA200007345B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978257A (zh) * | 2020-08-26 | 2020-11-24 | 武汉药明康德新药开发有限公司 | 含有醛基和羧基的1-甲基芳烃-1h-咪唑系列化合物的合成方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01151534A (ja) * | 1987-12-09 | 1989-06-14 | Nippon Shirika Kogyo Kk | アルデヒドの製造方法 |
| JP3168079B2 (ja) * | 1992-10-08 | 2001-05-21 | 日本合成化学工業株式会社 | ２−アルキルホルミルイミダゾールの製造法 |
| JP3391837B2 (ja) * | 1993-02-16 | 2003-03-31 | 日本合成化学工業株式会社 | ５−ホルミルイミダゾール類の製造方法 |
| US5336779A (en) * | 1992-10-08 | 1994-08-09 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Method of producing formylimidazoles |
| JP3391836B2 (ja) * | 1993-02-16 | 2003-03-31 | 日本合成化学工業株式会社 | ５−ホルミルイミダゾール類の製造法 |
| US6008417A (en) * | 1997-10-20 | 1999-12-28 | Roche Vitamins Inc. | Process for making metabolites of lycopene |
| KR100587187B1 (ko) * | 1997-10-29 | 2006-10-24 | 론자 아게 | 포르밀이미다졸의제조방법 |
| KR100567183B1 (ko) * | 1997-11-14 | 2006-06-13 | 론자 아게 | 포르밀이미다졸의제조방법 |
| JP2000053651A (ja) * | 1998-06-18 | 2000-02-22 | Lonza Ag | ホルミルイミダゾ―ル類の製造方法 |
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1999
- 1999-06-11 NZ NZ508693A patent/NZ508693A/en unknown
- 1999-06-11 JP JP2000554706A patent/JP2002518376A/ja active Pending
- 1999-06-11 BR BR9911172-1A patent/BR9911172A/pt not_active Application Discontinuation
- 1999-06-11 TR TR2000/03693T patent/TR200003693T2/xx unknown
- 1999-06-11 HU HU0102771A patent/HUP0102771A3/hu unknown
- 1999-06-11 KR KR1020007014165A patent/KR100569775B1/ko not_active IP Right Cessation
- 1999-06-11 PL PL99344597A patent/PL344597A1/xx not_active Application Discontinuation
- 1999-06-11 CN CN99807463A patent/CN1391559A/zh active Pending
- 1999-06-11 AR ARP990102810A patent/AR019659A1/es active IP Right Grant
- 1999-06-11 MY MYPI99002399A patent/MY119854A/en unknown
- 1999-06-11 US US09/719,380 patent/US6258958B1/en not_active Expired - Fee Related
- 1999-06-11 CA CA002334901A patent/CA2334901C/en not_active Expired - Fee Related
- 1999-06-11 EP EP99927979A patent/EP1087944A1/en not_active Withdrawn
- 1999-06-11 WO PCT/EP1999/004107 patent/WO1999065879A1/en active IP Right Grant
- 1999-06-11 IL IL14017099A patent/IL140170A0/xx unknown
- 1999-06-11 AU AU45132/99A patent/AU4513299A/en not_active Abandoned
- 1999-08-18 TW TW088114068A patent/TW568906B/zh not_active IP Right Cessation
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2000
- 2000-12-11 ZA ZA200007345A patent/ZA200007345B/en unknown
- 2000-12-13 NO NO20006351A patent/NO20006351L/no not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978257A (zh) * | 2020-08-26 | 2020-11-24 | 武汉药明康德新药开发有限公司 | 含有醛基和羧基的1-甲基芳烃-1h-咪唑系列化合物的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ508693A (en) | 2002-06-28 |
| AU4513299A (en) | 2000-01-05 |
| NO20006351D0 (no) | 2000-12-13 |
| TW568906B (en) | 2004-01-01 |
| AR019659A1 (es) | 2002-03-13 |
| HUP0102771A3 (en) | 2002-05-28 |
| MY119854A (en) | 2005-07-29 |
| CA2334901C (en) | 2009-03-17 |
| US6258958B1 (en) | 2001-07-10 |
| JP2002518376A (ja) | 2002-06-25 |
| CA2334901A1 (en) | 1999-12-23 |
| NO20006351L (no) | 2000-12-13 |
| KR20010071472A (ko) | 2001-07-28 |
| ZA200007345B (en) | 2002-01-22 |
| BR9911172A (pt) | 2001-03-13 |
| HUP0102771A2 (hu) | 2002-03-28 |
| KR100569775B1 (ko) | 2006-04-11 |
| PL344597A1 (en) | 2001-11-05 |
| TR200003693T2 (tr) | 2001-06-21 |
| EP1087944A1 (en) | 2001-04-04 |
| WO1999065879A1 (en) | 1999-12-23 |
| IL140170A0 (en) | 2002-02-10 |
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