JP2002193945A - Method for producing imidazolecarboxylic acid - Google Patents
Method for producing imidazolecarboxylic acidInfo
- Publication number
- JP2002193945A JP2002193945A JP2000397188A JP2000397188A JP2002193945A JP 2002193945 A JP2002193945 A JP 2002193945A JP 2000397188 A JP2000397188 A JP 2000397188A JP 2000397188 A JP2000397188 A JP 2000397188A JP 2002193945 A JP2002193945 A JP 2002193945A
- Authority
- JP
- Japan
- Prior art keywords
- molecular oxygen
- producing
- formula
- bromide
- compound
- 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
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 bromine compound Chemical class 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 9
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 8
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CGWDABYOHPEOAD-VIFPVBQESA-N (2r)-2-[(4-fluorophenoxy)methyl]oxirane Chemical compound C1=CC(F)=CC=C1OC[C@@H]1OC1 CGWDABYOHPEOAD-VIFPVBQESA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- NKWCGTOZTHZDHB-UHFFFAOYSA-N 1h-imidazol-1-ium-4-carboxylate Chemical compound OC(=O)C1=CNC=N1 NKWCGTOZTHZDHB-UHFFFAOYSA-N 0.000 description 1
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- UADULFIZHZKEOP-UHFFFAOYSA-K cerium(3+);triformate Chemical compound [Ce+3].[O-]C=O.[O-]C=O.[O-]C=O UADULFIZHZKEOP-UHFFFAOYSA-K 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 description 1
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical class OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- OEERILNPOAIBKF-UHFFFAOYSA-J zirconium(4+);tetraformate Chemical compound [Zr+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O OEERILNPOAIBKF-UHFFFAOYSA-J 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イミダゾールカル
ボン酸の製造方法に関する。本発明により得られるイミ
ダゾールカルボン酸は、医薬、農薬等の合成中間体とし
て有用である。TECHNICAL FIELD The present invention relates to a method for producing imidazole carboxylic acid. The imidazolecarboxylic acid obtained according to the present invention is useful as a synthetic intermediate for pharmaceuticals, agricultural chemicals, and the like.
【０００２】[0002]
【従来の技術】従来、液相酸化による複素環カルボン酸
の製造法としては、例えば（１）ピリジン骨格またはキ
ノリン骨格を有する化合物を臭素および重金属化合物の
存在下で酸化する方法（特公昭３４−９８６８号公報参
照）、（２）アルキルピリジン誘導体をジルコニウム、
コバルト、マンガンおよび臭素化合物からなる触媒の存
在下、分子状酸素で液相酸化することによりピリジンカ
ルボン酸誘導体を得る方法（特公昭５０−１７０６８号
公報参照）、（３）アルキルチオフェン誘導体を臭素化
合物および重金属の存在下、分子状酸素または分子状酸
素を含有するガスにより液相酸化することによりチオフ
ェンカルボン酸誘導体を得る方法（特開平３−５６４７
８号公報参照）などが知られている。2. Description of the Related Art Conventionally, as a method for producing a heterocyclic carboxylic acid by liquid phase oxidation, for example, (1) a method of oxidizing a compound having a pyridine skeleton or a quinoline skeleton in the presence of bromine and a heavy metal compound (Japanese Patent Publication No. No. 9868), (2) Zirconium,
A method of obtaining a pyridinecarboxylic acid derivative by liquid phase oxidation with molecular oxygen in the presence of a catalyst comprising cobalt, manganese and a bromine compound (see Japanese Patent Publication No. 50-17068); And a method of obtaining a thiophene carboxylic acid derivative by liquid phase oxidation with molecular oxygen or a gas containing molecular oxygen in the presence of heavy metal (JP-A-3-5647)
No. 8) is known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、アルキ
ルイミダゾール誘導体を液相で酸化することによりイミ
ダゾールカルボン酸を得る方法は知られていない。However, there is no known method for obtaining an imidazole carboxylic acid by oxidizing an alkyl imidazole derivative in a liquid phase.
【０００４】本発明の目的は、安全に、かつ効率よくイ
ミダゾールカルボン酸を製造する方法を提供することに
ある。An object of the present invention is to provide a method for safely and efficiently producing imidazole carboxylic acid.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、上記の
目的は、式（Ｉ）According to the present invention, the above objects have been achieved by the formula (I)
【０００６】[0006]
【化３】 Embedded image
【０００７】で示されるイミダゾール誘導体〔以下、こ
れをイミダゾール誘導体（Ｉ）と称する〕を、重金属化
合物および臭素化合物の存在下、分子状酸素または分子
状酸素を含有するガスにより液相で酸化することを特徴
とする式（ＩＩ）(Hereinafter referred to as imidazole derivative (I)) in the liquid phase with molecular oxygen or a gas containing molecular oxygen in the presence of a heavy metal compound and a bromine compound. Formula (II) characterized by the following:
【０００８】[0008]
【化４】 Embedded image
【０００９】で示されるイミダゾールカルボン酸〔以
下、これをイミダゾールカルボン酸（ＩＩ）と称する〕
の製造方法を提供することにより達成される。Imidazole carboxylic acid [hereinafter referred to as imidazole carboxylic acid (II)]
Is achieved by providing a manufacturing method of
【００１０】[0010]
【発明の実施の形態】分子状酸素を含むガスとしては、
空気を使用してもよい。酸素の分圧は、１〜１００ｋｇ
／ｃｍ2の範囲が好ましく、１〜４０ｋｇ／ｃｍ2の範囲
がより好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As a gas containing molecular oxygen,
Air may be used. The partial pressure of oxygen is 1-100kg
/ Cm 2 , and more preferably 1 to 40 kg / cm 2 .
【００１１】重金属化合物としては、例えば、酢酸コバ
ルト、ギ酸コバルト、コバルトアセチルアセトナート、
塩化コバルト、臭化コバルト、ヨウ化コバルト、炭酸コ
バルトなどのコバルト塩；酢酸マンガン、ギ酸マンガ
ン、マンガンアセチルアセトナート、塩化マンガン、臭
化マンガン、ヨウ化マンガンなどのマンガン塩；酢酸
鉄、乳酸鉄、オクチル酸鉄、鉄アセチルアセトナート、
塩化鉄、臭化鉄、ヨウ化鉄などの鉄塩；ギ酸セリウム、
酢酸セリウム、セリウムアセチルアセトナート、塩化セ
リウム、臭化セリウム、ヨウ化セリウムなどのセリウム
塩；酢酸ジルコニウム、ギ酸ジルコニウム、ジルコニウ
ムアセチルアセトナート、塩化ジルコニウム、臭化ジル
コニウム、ヨウ化ジルコニウム等のジルコニウム塩など
が挙げられる。これらの重金属化合物は単独で使用して
も、複数を組み合わせて使用してもよい。重金属化合物
の使用量は、イミダゾール誘導体（Ｉ）１モルに対し
て、金属原子として０．０１〜０．５モルの範囲が好ま
しく、０．０１〜０．１モルの範囲がより好ましい。Examples of heavy metal compounds include cobalt acetate, cobalt formate, cobalt acetylacetonate,
Cobalt salts such as cobalt chloride, cobalt bromide, cobalt iodide, and cobalt carbonate; manganese salts such as manganese acetate, manganese formate, manganese acetylacetonate, manganese chloride, manganese bromide, and manganese iodide; iron acetate, iron lactate; Iron octylate, iron acetylacetonate,
Iron salts such as iron chloride, iron bromide and iron iodide; cerium formate,
Cerium salts such as cerium acetate, cerium acetylacetonate, cerium chloride, cerium bromide, and cerium iodide; zirconium salts such as zirconium acetate, zirconium formate, zirconium acetylacetonate, zirconium chloride, zirconium bromide, and zirconium iodide. No. These heavy metal compounds may be used alone or in combination of two or more. The amount of the heavy metal compound to be used is preferably 0.01 to 0.5 mol, more preferably 0.01 to 0.1 mol, as a metal atom, per 1 mol of the imidazole derivative (I).
【００１２】臭素化合物としては、例えば臭素、臭化ア
ンモニウム、臭化水素、臭化リチウム、臭化ナトリウ
ム、臭化カリウム、臭化コバルト、臭化マンガンなどが
挙げられる。臭素化合物の使用量は、イミダゾール誘導
体（Ｉ）１モルに対して、臭素原子として０．０１〜
０．５モルの範囲が好ましく、０．０１〜０．１モルの
範囲がより好ましい。Examples of the bromine compound include bromine, ammonium bromide, hydrogen bromide, lithium bromide, sodium bromide, potassium bromide, cobalt bromide and manganese bromide. The amount of the bromine compound to be used is from 0.01 to 0.01 as a bromine atom per 1 mol of the imidazole derivative (I).
A range of 0.5 mol is preferable, and a range of 0.01 to 0.1 mol is more preferable.
【００１３】本発明の反応は、溶媒の存在下で行うのが
好ましい。溶媒としては、安定であれば特に限定される
ものではないが、例えば酢酸、プロピオン酸、酪酸、無
水酢酸、無水プロピオン酸などを用いるのが好ましく、
酢酸を用いるのがより好ましい。溶媒の使用量に特に制
限はないが、イミダゾール誘導体（Ｉ）に対して０．５
〜１００重量倍の範囲であるのが好ましく、１〜１０重
量倍の範囲であるのがより好ましい。The reaction of the present invention is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it is stable.For example, acetic acid, propionic acid, butyric acid, acetic anhydride, and propionic anhydride are preferably used.
More preferably, acetic acid is used. The amount of the solvent to be used is not particularly limited, but may be 0.5 to the imidazole derivative (I).
The range is preferably from 100 to 100 times by weight, more preferably from 1 to 10 times by weight.
【００１４】反応温度は、２０〜３００℃の範囲が好ま
しく、４０〜２００℃の範囲がより好ましい。[0014] The reaction temperature is preferably in the range of 20 to 300 ° C, more preferably 40 to 200 ° C.
【００１５】反応は、イミダゾール誘導体（Ｉ）、重金
属化合物、臭素化合物および必要に応じて溶媒を混合
し、酸素ガスを所定の分圧まで圧入した後、所定の温度
まで加熱し、撹拌することにより行うのが好ましい。反
応後、溶媒を使用した場合は溶媒を留去し、アンモニア
水などの塩基性水溶液で反応混合物を中性または弱塩基
性とした後、水を除去することにより、反応混合物より
イミダゾールカルボン酸（ＩＩ）を単離することができ
る。なお、このようにして得られたイミダゾールカルボ
ン酸（ＩＩ）は、必要に応じて再結晶、カラムクロマト
グラフィーなどの通常の精製手段により、その純度をさ
らに高めることもできる。The reaction is carried out by mixing the imidazole derivative (I), the heavy metal compound, the bromine compound and, if necessary, a solvent, injecting oxygen gas to a predetermined partial pressure, heating to a predetermined temperature and stirring. It is preferred to do so. After the reaction, when a solvent is used, the solvent is distilled off, the reaction mixture is neutralized or weakly basic with a basic aqueous solution such as aqueous ammonia, and then the water is removed to remove imidazole carboxylic acid ( II) can be isolated. The imidazole carboxylic acid (II) thus obtained can be further increased in purity, if necessary, by ordinary purification means such as recrystallization and column chromatography.
【００１６】[0016]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらの実施例により何ら限定されるも
のではない。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例１ 容量１００ｍｌのハステロイ製オートクレーブ中に、酢
酸５０ｍｌ、４−メチルイミダゾール１６．４０ｇ
（０．２ｍｏｌ）、酢酸コバルト０．９９ｇ（４ｍｍｏ
ｌ）、酢酸マンガン０．１２ｇ（１ｍｍｏｌ）および臭
化ナトリウム０．４１ｇ（４ｍｍｏｌ）を入れて、オー
トクレーブ内を酸素ガス５０ｋｇ／ｃｍ2で加圧した
後、１２０℃で５時間加熱攪拌した。室温まで冷却し、
常圧に戻した後、酢酸を減圧下に留去し、アンモニア水
１０ｍｌを加えて塩基性であることを確認した。これに
活性炭１ｇを加えて室温で１時間攪拌し、活性炭を濾過
して除き、濾液を希硫酸でｐＨ６に調整した。この水溶
液を５℃まで冷却し、析出した結晶を濾取し、これを乾
燥することにより４−イミダゾールカルボン酸１３．４
ｇを得た（収率７０％）。Example 1 In a Hastelloy autoclave having a capacity of 100 ml, 50 ml of acetic acid and 16.40 g of 4-methylimidazole were used.
(0.2 mol), 0.99 g of cobalt acetate (4 mmo
l), 0.12 g (1 mmol) of manganese acetate and 0.41 g (4 mmol) of sodium bromide were added, and the inside of the autoclave was pressurized with 50 kg / cm 2 of oxygen gas, followed by heating and stirring at 120 ° C. for 5 hours. Cool to room temperature,
After returning to normal pressure, acetic acid was distilled off under reduced pressure, and 10 ml of aqueous ammonia was added to confirm that the solution was basic. 1 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. The activated carbon was removed by filtration, and the filtrate was adjusted to pH 6 with diluted sulfuric acid. The aqueous solution was cooled to 5 ° C., and the precipitated crystals were collected by filtration and dried to give 4-imidazolecarboxylic acid 13.4.
g was obtained (70% yield).
【００１８】[0018]
【発明の効果】本発明の方法によれば、イミダゾールカ
ルボン酸を、安全に、かつ効率よく製造することができ
る。According to the method of the present invention, imidazole carboxylic acid can be produced safely and efficiently.
Claims (1)
臭素化合物の存在下、分子状酸素または分子状酸素を含
有するガスにより液相で酸化することを特徴とする式
（ＩＩ） 【化２】 で示されるイミダゾールカルボン酸の製造方法。1. A compound of the formula (I) Oxidizing the imidazole derivative represented by the formula (II) in the liquid phase with molecular oxygen or a gas containing molecular oxygen in the presence of a heavy metal compound and a bromine compound. A method for producing an imidazole carboxylic acid represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000397188A JP2002193945A (en) | 2000-12-27 | 2000-12-27 | Method for producing imidazolecarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000397188A JP2002193945A (en) | 2000-12-27 | 2000-12-27 | Method for producing imidazolecarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002193945A true JP2002193945A (en) | 2002-07-10 |
Family
ID=18862344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000397188A Pending JP2002193945A (en) | 2000-12-27 | 2000-12-27 | Method for producing imidazolecarboxylic acid |
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| Country | Link |
|---|---|
| JP (1) | JP2002193945A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002308854A (en) * | 2001-04-06 | 2002-10-23 | Nippon Synthetic Chem Ind Co Ltd:The | Production method for imidazolecarboxylic acid |
| CN110563728A (en) * | 2019-09-23 | 2019-12-13 | 南京奇可药业有限公司 | Preparation method of linagliptin intermediate |
-
2000
- 2000-12-27 JP JP2000397188A patent/JP2002193945A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002308854A (en) * | 2001-04-06 | 2002-10-23 | Nippon Synthetic Chem Ind Co Ltd:The | Production method for imidazolecarboxylic acid |
| CN110563728A (en) * | 2019-09-23 | 2019-12-13 | 南京奇可药业有限公司 | Preparation method of linagliptin intermediate |
| CN110563728B (en) * | 2019-09-23 | 2020-09-25 | 安庆奇创药业有限公司 | Preparation method of linagliptin intermediate |
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