JPH01224365A - Production of 2-pyrazinecarboxamide 4-oxide - Google Patents
Production of 2-pyrazinecarboxamide 4-oxideInfo
- Publication number
- JPH01224365A JPH01224365A JP5117788A JP5117788A JPH01224365A JP H01224365 A JPH01224365 A JP H01224365A JP 5117788 A JP5117788 A JP 5117788A JP 5117788 A JP5117788 A JP 5117788A JP H01224365 A JPH01224365 A JP H01224365A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- oxide
- pyrazinecarboxamide
- formula
- hydrogen peroxide
- 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
- WWQPCELPPKZBJE-UHFFFAOYSA-N 4-oxidopyrazin-4-ium-2-carboxamide Chemical compound NC(=O)C1=C[N+]([O-])=CC=N1 WWQPCELPPKZBJE-UHFFFAOYSA-N 0.000 title description 29
- 238000004519 manufacturing process Methods 0.000 title description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229960005206 pyrazinamide Drugs 0.000 claims abstract description 21
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical compound NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical group O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- ACHIKYKJUATOBT-UHFFFAOYSA-N 4-oxidopyrazin-4-ium-2-carboxylic acid Chemical compound OC(=O)C1=C[N+]([O-])=CC=N1 ACHIKYKJUATOBT-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OYBQCUZBVHFPBU-UHFFFAOYSA-N 5-methylpyrazine-2-carboxamide Chemical compound CC1=CN=C(C(N)=O)C=N1 OYBQCUZBVHFPBU-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BTYKRSQVJNDFFF-UHFFFAOYSA-N 5-methyl-4-oxidopyrazin-4-ium-2-carboxamide Chemical compound CC1=CN=C(C(N)=O)C=[N+]1[O-] BTYKRSQVJNDFFF-UHFFFAOYSA-N 0.000 description 2
- DJQOOSBJCLSSEY-UHFFFAOYSA-N Acipimox Chemical compound CC1=CN=C(C(O)=O)C=[N+]1[O-] DJQOOSBJCLSSEY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- -1 and moreover Chemical compound 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 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
- 229940093915 gynecological organic acid Drugs 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
- 230000000055 hyoplipidemic effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は一般式（１）；
（式中、Ｒ，、Ｒ２及びＲ８は互いに同一であっても異
なっていてもよく、水素原子又は１〜６個の炭素原子を
含有するアルキル基を示す）で示される２−ピラジンカ
ルボキサミド４−オキシド（以下、「２−ピラジンカル
ボキサミド４−オキシド（Ｉ）」という）の製造方法に
関し、より詳細には、一般式（ＩＩ）；
（式中、Ｒ１、Ｒ２及びＲａは前記に同じ）で示される
２−ビラジルカルボキサミド（以下、［２−ピラジンカ
ルボキサミド（Ｉ）」という）の過酸化水素による酸化
によって、２−ピラジンカルボキサミド４−オキシド（
１）を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the general formula (1); 2-pyrazinecarboxamide 4-oxide (hereinafter referred to as "2-pyrazinecarboxamide 4-oxide (I)") represented by By oxidizing 2-virazylcarboxamide (hereinafter referred to as [2-pyrazinecarboxamide (I)) represented by formula (II) (wherein R1, R2 and Ra are the same as above) with hydrogen peroxide, 2 -pyrazinecarboxamide 4-oxide (
1).
本発明で得られる２−ピラジンカルボキサミド４−オキ
シド（１）は種々の医薬品、例えば低脂肪血症作用を有
する一般式（Ｉ）；
（式中、Ｒ１、Ｒ２及びＲａ は前記に同じ）で示さ
れる２−ピラジンカルボン酸４−オキシド（以下、１２
−ピラジンカルボン酸４−オキシド（ＩＩＤ Ｊという
）製造の中間体として有用な化合物である。2-Pyrazinecarboxamide 4-oxide (1) obtained in the present invention can be used as a variety of pharmaceuticals, such as those represented by the general formula (I) having hypolipidemic action; 2-pyrazinecarboxylic acid 4-oxide (hereinafter referred to as 12
- It is a compound useful as an intermediate in the production of pyrazinecarboxylic acid 4-oxide (referred to as IID J).
従来、２−ピラジンカルボキサミド（１）から２−ピラ
ジンカルボキサミド４−オキシド（１）を製造する方法
としては、２−ピラジンカルボキサミド（１）を氷酢酸
中で過酸化水素を反応させる方法がある（特公昭５５−
８５８８４）。しかしながら、この方法は２−ピラジン
カルボキサミド（Ｖの１０倍モル以上という大量の氷酢
酸を用い、氷酢酸の回収を必要とし、しかも２−ピラジ
ンカルボキサミド ４−オキシド（１）が６０〜７０％
にしかすぎず、工業的製法としては満足できるものでは
ない。Conventionally, as a method for producing 2-pyrazinecarboxamide 4-oxide (1) from 2-pyrazinecarboxamide (1), there is a method in which 2-pyrazinecarboxamide (1) is reacted with hydrogen peroxide in glacial acetic acid (especially Kosho 55-
85884). However, this method uses a large amount of glacial acetic acid, at least 10 times the mole of 2-pyrazinecarboxamide (V), requires recovery of glacial acetic acid, and moreover, 2-pyrazinecarboxamide 4-oxide (1) accounts for 60 to 70%
However, it is not satisfactory as an industrial manufacturing method.
本出願人は鋭意検討を重ねた結果、２−ピラジンカルボ
キサミド（１）を金属化合物触媒存在下、過酸化水素と
反応させることにより、２−ピラジンカルボン酸４−オ
キシドＩの重要な合成中間体である２−ピラジンカルボ
キサミド４−オキシド（１）を容易にかつ高収率に合成
することに成功し、さらにこのようにして得られる２−
ピラジンカルボキサミド４−オキシド（Ｉ）を加水分解
すれば高純度の２−ピラジンカルボン酸４−オキシド■
を製造できることをあわせて見出し本発明を完成するに
至った。As a result of extensive studies, the applicant has discovered that by reacting 2-pyrazinecarboxamide (1) with hydrogen peroxide in the presence of a metal compound catalyst, an important synthetic intermediate for 2-pyrazinecarboxylic acid 4-oxide I can be obtained. We have successfully synthesized a certain 2-pyrazinecarboxamide 4-oxide (1) easily and in high yield, and furthermore, we have succeeded in synthesizing a certain 2-pyrazinecarboxamide 4-oxide (1) easily and in high yield.
High purity 2-pyrazinecarboxylic acid 4-oxide can be obtained by hydrolyzing pyrazinecarboxamide 4-oxide (I).
The present invention has been completed based on the discovery that it is possible to produce the following.
本発明の目的は、２−ピラジンカルボキサミド４−オキ
シド（１）を高収率でかつ選択的に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 selectively producing 2-pyrazinecarboxamide 4-oxide (1) in high yield.
本発明の他の目的は、大量の有機酸の使用及び反応終了
時におけるこの有機酸の分離に係る欠点を避けることに
ある。Another object of the invention is to avoid the disadvantages associated with the use of large amounts of organic acids and their separation at the end of the reaction.
本発明の他の目的は、高純度を要求する医薬である２−
ピラジンカルボン酸４−オキシド■の原料として好適に
使用できる２−ピラジンカルボキサミド４−オキシド（
【）を製造する方法を提供することにあろう
課題を解決するための手段
本発明は２−ピラジンカルボキサミド（１） ヲ、モリ
ブデン、タングステン及びバナジウムからなる群より選
ばれる金属の酸化物、硫化物及び／又は塩化物からなる
触媒の存在下、過酸化水素と反応させることを特徴とす
る２−ピラジンカルボキサミド４−オキシド（Ｉ）の製
造方法に関するっ本発明の一般式（Ｉ）及び（厘）にお
けるＲ１．Ｒ２及びＲ３がアルキル基である場合の具体
例としては、メチル基、エチル基、プロピル基、ブチル
基、ペンチル基、ヘキシル基の炭素数１〜６の直鎮状ア
ルキル基、イソプロピル基、イソブチル基、ｔｅｒｔ−
ブチル基などの炭素数１〜６の分岐状アルキル基が挙げ
られる。Another object of the present invention is 2-
2-pyrazinecarboxamide 4-oxide (2-pyrazinecarboxamide 4-oxide) which can be suitably used as a raw material for pyrazinecarboxylic acid 4-oxide
The present invention provides a method for producing 2-pyrazinecarboxamide (1), an oxide or sulfide of a metal selected from the group consisting of molybdenum, tungsten, and vanadium. The general formulas (I) and (厘) of the present invention relate to a method for producing 2-pyrazinecarboxamide 4-oxide (I), which is characterized by reacting with hydrogen peroxide in the presence of a catalyst consisting of a chloride and/or a chloride. R1. Specific examples when R2 and R3 are alkyl groups include straight alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, isopropyl groups, and isobutyl groups. , tert-
Branched alkyl groups having 1 to 6 carbon atoms such as a butyl group can be mentioned.
本発明における出発物質の２−ピラジンカルボキサミド
（１）としては、Ｒ１、Ｒ２及びＲ８の全てが水素原子
であるもの、またはＲ，、Ｒ２及びＲ３のうちの１個が
１〜６個の炭素原子を含有するアルキル基であり且つ残
りの２個の基が水素原子であるものを使用するのが好ま
しい。かかる２−ピラジンカルボキサミド（１）として
は具体的には２−ピラジンカルボキサミド、５−メチル
ピラジン−２−カルボキサミド等を挙げることができる
。The starting material 2-pyrazinecarboxamide (1) in the present invention is one in which R1, R2 and R8 are all hydrogen atoms, or one in which R, R2 and R3 is a carbon atom of 1 to 6. It is preferable to use an alkyl group containing , and the remaining two groups are hydrogen atoms. Specific examples of such 2-pyrazinecarboxamide (1) include 2-pyrazinecarboxamide, 5-methylpyrazine-2-carboxamide, and the like.
本発明における触媒としては、モリブデン、タングステ
ンまたはバナジウムの金属の酸化物、硫化物及び塩化物
が挙げられ、これらの１種又は２種以トを用いることが
できる。Examples of the catalyst in the present invention include metal oxides, sulfides, and chlorides of molybdenum, tungsten, and vanadium, and one or more of these can be used.
本発明における金属酸化物としては、モリブデン酸
ン酸、酸化モリブデン、ホモボ小ツデン酸、ヘテロポリ
モリブデン酸、タングステン酸、酸化タングステン、ホ
モポリタングステン酸、ヘテロポリタングステン酸、バ
ナジウム酸、酸化バナジウム、ホモポリバナジウム酸、
ヘテロポリバナジウム酸及び核酸のアルカリ金属塩また
はアンモニウム塩が挙げられる。Examples of the metal oxides in the present invention include molybdic acid, molybdenum oxide, homobobutudic acid, heteropolymolybdic acid, tungstic acid, tungsten oxide, homopolytungstic acid, heteropolytungstic acid, vanadate, vanadium oxide, and homopolyvanadium. acid,
Alkali metal or ammonium salts of heteropolyvanadate and nucleic acids are mentioned.
かかるモリブデン酸としては具体的にはＨ２ＭＯＯ４。Specifically, such molybdic acid is H2MOO4.
Ｍｏ０３−Ｒ２０、ＨｚＭＯＯ４・Ｒ２０、ＭＯＯ３−
２Ｈ２０等が挙げられる。酸化モリブデンとしては具体
的にはＭＯＯ２、Ｍｏ０Ｂ 、 ＭＯ２０１１、ＭＯ
２０５等が挙げられる。ホモポリモリブデン酸の塩とし
ては具体的にはモリブデン酸ナトリウムモリブデン酸ア
ンモニウム等が挙げられる。ヘテロポリモリブデン酸及
びその塩としては具体的にはリンモリブデン酸ナトリウ
ム、リンモリブデン酸アンモニウム、ケイソモリブデン
酸、チオモリブデン酸等が挙げられるっタングステン酸
としては具体的にはＨ２ＷＯ４，ｗｏ３・Ｒ２０、Ｈ，
ＷＯ，・Ｈ，Ｏ、ｗｏ８・２Ｈ２ｏ 。Mo03-R20, HzMOO4・R20, MOO3-
Examples include 2H20. Specifically, molybdenum oxides include MOO2, Mo0B, MO2011, MO
205 etc. are mentioned. Specific examples of the salt of homopolymolybdic acid include sodium molybdate and ammonium molybdate. Specific examples of heteropolymolybdic acid and its salts include sodium phosphomolybdate, ammonium phosphomolybdate, silicomolybdic acid, thiomolybdic acid, etc. Specific examples of tungstic acid include H2WO4, WO3・R20, H,
WO,・H,O, wo8・2H2o.
２ＷＯ９・Ｒ２０等が挙げられる。酸化タングステンと
しては具体的にはＷＯ２、ＷＯＢ 、 Ｗ２Ｏ５等が
挙げられる。ホモポリタングステン酸の塩としては具体
的にはタングステン酸ナトリウム、タングステン酸アン
モニウム等が挙げられる。ヘテロポリタングステン酸及
びその塩としては具体的にはリンタングステン酸ナトリ
ウム、リンタングステン酸アンモニウム、ケイソタング
ステン酸、タングステン青銅等が挙げられるうバナジウ
ム酸としては具体（ｆＪ ニハＩ（ＶＯｓ 、 ＨＢ
ＶＯ４、ＨＶＯ４、Ｈ４Ｖ２０ｙ等が挙げられる。酸化
バナジウムとしては具体的にハｖｏ 、 Ｖ２Ｏ３、’
Ｖ’２０ｓ 、 ＶＯ２等カ挙Ｃｆ ラレル。ホモポリ
バナジウム酸の塩としては具体的にはバナジウム酸ナト
リウム、バナジウム酸アンモニウム等が挙げられる。ヘ
テロポリバナジウム酸及びその塩としては具体的にはリ
ンバナジウム酸ナトリウム、リンバナジウム酸アンモニ
ウム、ケイソバナジウム酸、チオバナジウム酸等が挙げ
られるう本発明における金属硫化物としては具体的には
ＭｏＳ２ 、 Ｍｏ５Ｂ 、 ＭＯ□ＳＢ 、 Ｍｏ２
５ｓ 、 ＷＳ２ ｒ ＷＳｇ 。Examples include 2WO9 and R20. Specific examples of tungsten oxide include WO2, WOB, W2O5, and the like. Specific examples of the salt of homopolytungstic acid include sodium tungstate and ammonium tungstate. Specific examples of heteropolytungstic acid and its salts include sodium phosphotungstate, ammonium phosphotungstate, silicotungstic acid, and tungsten bronze. Specific examples of vanadate include (fJ Niha I (VOs, HB)
Examples include VO4, HVO4, H4V20y, and the like. Specifically, vanadium oxide includes Havo, V2O3,'
V'20s, VO2 etc. Cf larel. Specific examples of the salt of homopolyvanadate include sodium vanadate, ammonium vanadate, and the like. Specific examples of heteropolyvanadate and its salts include sodium phosphovanadate, ammonium phosphovanadate, silicovanadate, thiovanadate, etc. Specific examples of the metal sulfide in the present invention include MoS2, Mo5B, MO□SB, Mo2
5s, WS2 r WSg.
Ｖ２Ｓ８ 、 Ｖ２Ｓ５ 等カ挙ケラｔＬ ル。V2S8, V2S5, etc.
本発明における金属塩化物としては具体的にはＭｏＣｚ
Ｂ 、 Ｍｏ０Ｃｚ２ 、 Ｍｏ０Ｃ４、ＭＯＣＬ４
． ＭｏＣｚ５ 。Specifically, the metal chloride in the present invention is MoCz
B, Mo0Cz2, Mo0C4, MOCL4
．． MoCz5.
ＷＣｔ、 、 ＷＣｔ４ 、 ＷＣｔ、、 ＷＣｔ６．
ＷＯＣｔ４ 、 ＶＣｔ 。WCt, , WCt4, WCt, WCt6.
WOCt4, VCt.
ＶＣＬＢ 、 ＶＣｌ４ 、 ＶＯＣＬｚ 、 ＶＯＣ
ＬＢ 等カ挙ケラレル。VCLB, VCl4, VOCLz, VOC
LB etc. Kelleral.
本発明はＭｏ０Ｂ 、 ＷＯＢ、モリブデン酸アンモニ
ウム、タングステン酸アンモニウムを用いるのが好まし
い。The present invention preferably uses Mo0B, WOB, ammonium molybdate, and ammonium tungstate.
本発明における触媒の使用量は、２−ピラジンカルボキ
サミド（［）１モル当りＭｏＯ２，ＷＯ８又はＭｏ２と
して０．００１〜１モルの範囲で使用するの応完結に長
時間がかかり工業上好ましくなく、１より多いと触媒が
２−ピラジンカルボキサミド４−オキシド（１）に残存
しやすいためである。The amount of catalyst used in the present invention is in the range of 0.001 to 1 mole as MoO2, WO8 or Mo2 per mole of 2-pyrazinecarboxamide ([), which is industrially undesirable because it takes a long time to complete the process. This is because if the amount is larger, the catalyst tends to remain in the 2-pyrazinecarboxamide 4-oxide (1).
本発明における過酸化水素の使用量は２−ピラジンカル
ボキサミド（１）に対するモル比が１．０〜１４５の範
囲、好ましくは１．１〜１．８の範囲で使用する。The amount of hydrogen peroxide used in the present invention is such that the molar ratio to 2-pyrazinecarboxamide (1) is in the range of 1.0 to 145, preferably in the range of 1.1 to 1.8.
過酸化水素量が１．０より少ないと未反応物が残るため
好ましくなく、１．５より多いと２−ビラジンカルボキ
サミド１．４−ジオキシド類が副成しやすいためである
。If the amount of hydrogen peroxide is less than 1.0, unreacted substances remain, which is not preferable, and if it is more than 1.5, 2-virazinecarboxamide 1,4-dioxides are likely to be formed as by-products.
過酸化水素は、通常水溶液で使用され、その濃度は特に
限定されるものではないが、安全性、容積効率、入手の
容易さ等から、８０〜５０重量％の水溶液を使用するの
が好ましい。Hydrogen peroxide is usually used in the form of an aqueous solution, and its concentration is not particularly limited, but from the viewpoint of safety, volumetric efficiency, ease of availability, etc., it is preferable to use an aqueous solution of 80 to 50% by weight.
２−ピラジンカルボキサミド（１）の酸化反応は、溶媒
中で行なうことが好ましく、かかる溶媒としては水、Ｄ
ＭＳＯ，ＤＭＦ、メタノール及びその混合溶液等を挙げ
ることができるが、その他、酸化反応を妨害する溶媒で
なければ、上記例示に限定されるものではない、本発明
は経済的な面から水を使用することが好ましいっ
溶媒の使用量は、２−ピラジンカルボキサミド（■）が
溶媒に対して１０〜１００重量％、好ましくは２０〜８
０重量％となるように使用する９１０重量％より少ない
と固体比が少なく、経済的に好ましくなく、１００重量
％より多いと均一な攪拌ができないからである。The oxidation reaction of 2-pyrazinecarboxamide (1) is preferably carried out in a solvent, such as water, D
Examples include MSO, DMF, methanol, and mixed solutions thereof, but the present invention is not limited to the above examples as long as the solvent does not interfere with the oxidation reaction.The present invention uses water from an economical point of view. The amount of solvent used is preferably 10 to 100% by weight, preferably 20 to 8% by weight of 2-pyrazinecarboxamide (■) based on the solvent.
If it is less than 910% by weight, which is used to obtain 0% by weight, the solids ratio will be low and is economically unfavorable, and if it is more than 100% by weight, uniform stirring will not be possible.
酸化反応の方法としては、２−ピラジンカルボキサミド
（ｉｆ）、触媒及び溶媒を仕込だ反応器内に過酸化水素
を滴下する方法、過酸化水素、触媒及び溶媒を仕込んだ
反応器内に２−ピラジンカルボキサミド（１）を添加す
る方法、さらには２−ピラジンカルボキサミド（１）、
過酸化水素、触媒及び溶媒を一度に混合して酸化反応さ
せる方法などが挙げられるが、これらに限定されるもの
ではない。Methods for the oxidation reaction include dropping hydrogen peroxide into a reactor containing 2-pyrazinecarboxamide (if), a catalyst, and a solvent, and dropping 2-pyrazine into a reactor containing hydrogen peroxide, a catalyst, and a solvent. A method of adding carboxamide (1), furthermore 2-pyrazine carboxamide (1),
Examples include, but are not limited to, a method of mixing hydrogen peroxide, a catalyst, and a solvent at the same time and causing an oxidation reaction.
酸化反応は酸性、中性及び塩基性のいずれの条件下でも
実施できるため、希鉱酸又は希塩基によって反応溶液の
ＰＨを調節する必要がない。Since the oxidation reaction can be carried out under any of acidic, neutral and basic conditions, there is no need to adjust the pH of the reaction solution with a dilute mineral acid or a dilute base.
酸化反応は、通常θ〜１００°Ｃの範囲の温度において
実施される。好ましくは約４０〜９５°Ｃ２より好まし
くは６０〜９５°Ｃにて行なう。また、通常は大気圧に
て行なうつ
反応時間は前記した反応温度、触媒の使用量等の種々の
反応条件を考慮して選定する必要があるが、通常ｏ、
ｉ〜１０時間、好ましくは０．５〜４時間、より好まし
くは１〜３時間行なう。The oxidation reaction is usually carried out at a temperature ranging from θ to 100°C. Preferably, the temperature is about 40-95°C, more preferably 60-95°C. In addition, the reaction time, which is usually carried out at atmospheric pressure, must be selected in consideration of various reaction conditions such as the reaction temperature and the amount of catalyst used, but usually o,
It is carried out for 1 to 10 hours, preferably 0.5 to 4 hours, more preferably 1 to 3 hours.
この反応は、例えば以下のように実施される：過酸化水
素及び触媒を含有する水溶液を調製し、この水溶液に２
−ピラジンカルボキサミド（１）を添加し、全体を激し
く攪拌しながら反応が完結するまで所望の温度にて処理
する。場合によっては反応終了までにすでに目的生成物
が沈殿し始めることがあり、反応が終了したときには、
大部分の目的生成物が常温沈殿する。This reaction is carried out, for example, as follows: an aqueous solution containing hydrogen peroxide and a catalyst is prepared, and this aqueous solution is
- Pyrazine carboxamide (1) is added and the whole is treated with vigorous stirring at the desired temperature until the reaction is complete. In some cases, the desired product may already begin to precipitate by the time the reaction is complete;
Most of the desired product precipitates at room temperature.
本発明で得られる２−ピラジンカルボキサミド４−オキ
シド（Ｉ）を加水分解することにより、容易に２−ピラ
ジンカルボン酸４−オキシド■を製造することができる
。By hydrolyzing 2-pyrazinecarboxamide 4-oxide (I) obtained in the present invention, 2-pyrazinecarboxylic acid 4-oxide (2) can be easily produced.
加水分解は通常アルカリ存在下、２−ピラジンカルボキ
サミド４−オキシド（１）水溶液を攪拌して行なう。か
かる、アルカリとしては具体的には水酸化ナトリウム、
水酸化カリウムなどの水酸化アルキル金属が挙げられる
。Hydrolysis is usually carried out by stirring an aqueous solution of 2-pyrazinecarboxamide 4-oxide (1) in the presence of an alkali. Specifically, the alkali includes sodium hydroxide,
Examples include alkyl metal hydroxides such as potassium hydroxide.
水の使用量は、２−ピラジンカルボキサミド４−オキシ
ド（ｆ）が水に対して１０〜１００重量％となるように
使用する。１０重量％より少ないと固体比が少なく、経
済的に好ましくなく、１００重量％より多いと均一な攪
拌ができないからである。The amount of water used is such that 2-pyrazinecarboxamide 4-oxide (f) is 10 to 100% by weight based on water. If it is less than 10% by weight, the solids ratio will be low, which is economically unfavorable, and if it is more than 100% by weight, uniform stirring will not be possible.
７７１／カリの使用量は、２−ピラジンカルボキサミド
４−オキシド（ｆ） １モル当り、通常１〜１．５モル
の範囲で使用する。The amount of 771/potassium used is usually in the range of 1 to 1.5 mol per 1 mol of 2-pyrazinecarboxamide 4-oxide (f).
加水分解は、通常θ〜１００°Ｃの範囲の温度において
実施される。好ましくは約４０〜９５°Ｃ１より好まし
くは６０〜９５゛Ｃにて行なうつまた、通常は大気圧に
て行なう。Hydrolysis is usually carried out at temperatures ranging from θ to 100°C. It is preferably carried out at a temperature of about 40-95°C, more preferably 60-95°C, and usually at atmospheric pressure.
加水分解の反応時間は、反応温度、アルカリの使用量等
の種々の反応条件を考慮して選定する必要があるが、通
常０．１〜１時間程度行なう。The reaction time for hydrolysis must be selected in consideration of various reaction conditions such as the reaction temperature and the amount of alkali used, but it is usually about 0.1 to 1 hour.
加水分解後、反応水溶液に塩酸、硫酸等の鉱酸を添加し
、水溶液をＰＨ約１〜２の酸性にすることにより、容易
に高純度の２−ピラジンカルボン酸４−オキシド（２）
が沈殿結晶として得られる。After hydrolysis, high purity 2-pyrazinecarboxylic acid 4-oxide (2) can be easily obtained by adding a mineral acid such as hydrochloric acid or sulfuric acid to the reaction aqueous solution and making the aqueous solution acidic with a pH of about 1 to 2.
is obtained as precipitated crystals.
実施例
以下、本発明を実施例に基いてより詳細に説明攪拌機、
還流冷却器及び温度計を備えた１００−フラスコ内でＷ
Ｏｇ Ｏ，４７ｆｌ （２ミリモル）を水４（Ｍｌに
溶解させた。この溶液に８５％過酸化水素水１１．７ｇ
（１２０Ｅリモル）を添加した。Examples Hereinafter, the present invention will be explained in more detail based on examples.
W in a 100-flask equipped with a reflux condenser and thermometer.
47 fl (2 mmol) of Og O was dissolved in 4 Ml of water. To this solution was added 11.7 g of 85% hydrogen peroxide.
(120E mol) was added.
次いで、５−メチルピラジン−２−カルボキサミド１８
．７ｆ（１００Ｅリモル）を添加した。Then, 5-methylpyrazine-2-carboxamide 18
．． 7f (100E remol) was added.
得られた水懸濁液を攪拌下で３時間８０°Ｃに加熱して
反応させた。The resulting aqueous suspension was heated to 80° C. for 3 hours under stirring to react.
反応終了後、冷却して生成物の沈殿を結晶状て得た。生
成物を沖過し、少量の氷水で洗浄し、乾燥させて純度９
５．７％の５−メチルピラジン−２−カルボキサミド４
−オキシドｉａ、ｓｇを得た。After the reaction was completed, it was cooled to obtain a crystalline product precipitate. The product was filtered, washed with a small amount of ice water, and dried to a purity of 9.
5.7% 5-methylpyrazine-2-carboxamide 4
-Oxide ia,sg was obtained.
収率８６．８％。Yield 86.8%.
礪２〜３）
実施例１で使用した５−メチルピラジン−２−カルボキ
サミドを表１に示した他の２−ピラジンカルボキサミド
に変えた以外は、実施例１と同様の操作を行なった。結
果を表１に示した。2-3) The same operation as in Example 1 was performed except that 5-methylpyrazine-2-carboxamide used in Example 1 was replaced with another 2-pyrazinecarboxamide shown in Table 1. The results are shown in Table 1.
注１）２−ピラジンカルボキサミドの使用量は１００ミ
リモルである。Note 1) The amount of 2-pyrazinecarboxamide used is 100 mmol.
実施例１で使用したＷ２Ｂを表２に示した他の触媒に変
えた以外は、実施例１と同様の操作を行なった。結果を
表２に示した。The same operation as in Example 1 was performed except that W2B used in Example 1 was replaced with another catalyst shown in Table 2. The results are shown in Table 2.
比較例
実施例１で使用した５−メチルピラジン−２−カルボキ
サミドＬ８．７１１の代りに５−メチルピラジン−２−
カルボン酸１８．８ｆを使用した以外は１、実施例１と
同様の操作を行ない、５−メチルピラジン−２−カルボ
ン酸４−オキシドを８．Ｏｆ！（収率５２％）得たが純
度は８９．９％であった。Comparative Example 5-methylpyrazine-2-carboxamide L8.711 used in Example 1 was replaced with 5-methylpyrazine-2-
1. The same operation as in Example 1 was carried out except that 18.8f of carboxylic acid was used, and 5-methylpyrazine-2-carboxylic acid 4-oxide was added to 8.8f. Of! (yield: 52%), but the purity was 89.9%.
参考例
攪拌機、還流冷却器及び温度計を備えた１００にして得
られた５−メチルピラジン−２−カルボキサミド４−オ
キシド１５．８１ （１００Ｅ ’Ｊ−Ｅル）を添加し
た。REFERENCE EXAMPLE 15.81 liters of 5-methylpyrazine-2-carboxamide 4-oxide (100E'JE) obtained in 100 was added, equipped with a stirrer, a reflux condenser and a thermometer.
得られた水懸濁液を攪拌下で３０分間８０″Ｃに加熱し
、これによって水溶液としたつこの水溶液に濃塩酸を添
加してＰｆ（を１．５にしたのち、冷却して生成物の沈
殿を結晶状で得た。生成物を沖過し、少量の氷水で洗浄
し、乾燥、ｌｔ”ｌｔ１度９９．９％の５−メチルピラ
ジン−２−カルボン酸４−オキシド１４．８Ｆ（９６ｉ
：リモル）を得た。収率９６．１％。The resulting aqueous suspension was heated to 80"C for 30 minutes under stirring to form an aqueous solution. Concentrated hydrochloric acid was added to the aqueous solution to bring Pf to 1.5, and then cooled to form the product. A precipitate of 5-methylpyrazine-2-carboxylic acid 4-oxide 14.8F (1°C, 99.9%) was obtained by filtering the product, washing with a small amount of ice water, and drying. 96i
: Rimol) was obtained. Yield 96.1%.
特許出願人 広栄化学工業株式会社Patent applicant: Koei Chemical Industry Co., Ltd.
Claims (1)
ても異なっていてもよく、水素原子又は１〜６個の炭素
原子を含有するアルキル基を示す）で示される２−ピラ
ジンカルボキサミドを、モリブデン、タングステン及び
バナジウムからなる群より選ばれる金属の酸化物、硫化
物及び／又は塩化物からなる触媒の存在下、過酸化水素
と反応させることを特徴とする一般式（ I ）； ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１、Ｒ＿２及びＲ＿３は互いに同一であっ
ても異なっていてもよく、水素原子又は１〜６個の炭素
原子を含有するアルキル基を示す）で示される２−ピラ
ジンカルボキサミド４−オキシドの製造方法。 ２、基Ｒ＿１、Ｒ＿２及びＲ＿３の全てが水素原子であ
ることを特徴とする請求項１記載の方法。 ３、基Ｒ＿１、Ｒ＿２及びＲ＿３のうちの１個が１〜６
個の炭素原子を含有するアルキル基であり、かつ残りの
２個の基が水素原子であることを特徴とする請求項１記
載の方法。４、１〜６個の炭素原子を含有するアルキル
基がメチル基であることを特徴とする請求項３記載の方
法。 ５、金属酸化物がモリブデン酸、酸化モリブデン、ホモ
ポリモリブデン酸、ヘテロポリモリブデン酸、タングス
テン酸、酸化タングステン、ホモポリタングステン酸、
ヘテロポリタングステン酸、バナジウム酸、酸化バナジ
ウム、ホモポリバナジウム酸、ヘテロポリバナジウム酸
並びに該酸のアルカリ金属塩及びアンモニウム塩よりな
る群から選択されることを特徴とする請求項１記載の方
法。[Claims] 1. General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2 and R_3 may be the same or different, and each represents a hydrogen atom or 2-pyrazinecarboxamide (indicating an alkyl group containing ~6 carbon atoms) is reacted with a catalyst consisting of an oxide, sulfide and/or chloride of a metal selected from the group consisting of molybdenum, tungsten and vanadium. General formula (I), which is characterized by reacting with hydrogen peroxide in the presence of a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms). 2. The method according to claim 1, wherein all of the groups R_1, R_2 and R_3 are hydrogen atoms. 3, one of the groups R_1, R_2 and R_3 is 1-6
2. The method according to claim 1, wherein the remaining two groups are hydrogen atoms. 4. Process according to claim 3, characterized in that the alkyl group containing 1 to 6 carbon atoms is a methyl group. 5. The metal oxide is molybdic acid, molybdenum oxide, homopolymolybdic acid, heteropolymolybdic acid, tungstic acid, tungsten oxide, homopolytungstic acid,
2. The method of claim 1, wherein the acid is selected from the group consisting of heteropolytungstic acid, vanadate acid, vanadium oxide, homopolyvanadate acid, heteropolyvanadate acid, and alkali metal and ammonium salts of said acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5117788A JPH01224365A (en) | 1988-03-03 | 1988-03-03 | Production of 2-pyrazinecarboxamide 4-oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5117788A JPH01224365A (en) | 1988-03-03 | 1988-03-03 | Production of 2-pyrazinecarboxamide 4-oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01224365A true JPH01224365A (en) | 1989-09-07 |
Family
ID=12879559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5117788A Pending JPH01224365A (en) | 1988-03-03 | 1988-03-03 | Production of 2-pyrazinecarboxamide 4-oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01224365A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479710B2 (en) | 1995-06-08 | 2002-11-12 | Nippon Shokubai Co., Ltd. | Method of catalyzing a gas phase reaction using an acid-base catalyst composed of vanadium pentoxide hydrate |
| US7153965B2 (en) | 2004-05-18 | 2006-12-26 | Isp Investments Inc. | Pharmaceutically acceptable inorganic and organic salts of 5-methylpyrazine-2-carboxylic acid-4-oxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535384A (en) * | 1978-09-06 | 1980-03-12 | Nippon Musical Instruments Mfg | Electronic musical instrument |
-
1988
- 1988-03-03 JP JP5117788A patent/JPH01224365A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535384A (en) * | 1978-09-06 | 1980-03-12 | Nippon Musical Instruments Mfg | Electronic musical instrument |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479710B2 (en) | 1995-06-08 | 2002-11-12 | Nippon Shokubai Co., Ltd. | Method of catalyzing a gas phase reaction using an acid-base catalyst composed of vanadium pentoxide hydrate |
| US7153965B2 (en) | 2004-05-18 | 2006-12-26 | Isp Investments Inc. | Pharmaceutically acceptable inorganic and organic salts of 5-methylpyrazine-2-carboxylic acid-4-oxide |
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