JPS6338992B2 - - Google Patents
Info
- Publication number
- JPS6338992B2 JPS6338992B2 JP13612179A JP13612179A JPS6338992B2 JP S6338992 B2 JPS6338992 B2 JP S6338992B2 JP 13612179 A JP13612179 A JP 13612179A JP 13612179 A JP13612179 A JP 13612179A JP S6338992 B2 JPS6338992 B2 JP S6338992B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- butylthiopyrazole
- lower alkyl
- spectrum
- salt
- 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.)
- Expired
Links
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- -1 dicarbonyl compound Chemical class 0.000 description 29
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002429 hydrazines Chemical class 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 125000003277 amino group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- WYOGYWFSXNDUCT-UHFFFAOYSA-N chloroform;1,2-dimethoxyethane Chemical compound ClC(Cl)Cl.COCCOC WYOGYWFSXNDUCT-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は、新規な3―アミノピラゾール誘導体
に関するものである。詳しくは、トリチオシクロ
プロペニウム塩の環拡大反応により製造できる新
規な3―アミノピラゾール誘導体に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel 3-aminopyrazole derivatives. Specifically, the present invention relates to a novel 3-aminopyrazole derivative that can be produced by a ring expansion reaction of a trithiocyclopropenium salt.
ピラゾール骨格を有する化合物は、医薬、染料
またはカラー写真のカツプラーとして重要なもの
が数多く知られている。 Many compounds having a pyrazole skeleton are known to be important as pharmaceuticals, dyes, or couplers for color photography.
従来、ピラゾール骨格の製造法としては、β―
ジカルボニル化合物とヒドラジンまたはその置換
体とを縮合させる方法、アセチレンカルボニル化
合物にヒドラジンまたはその置換体を作用させる
方法、脂肪族ジアゾ化合物とβ―ジケトンまたは
アセチレン化合物を反応させる方法などが知られ
ているが、置換基が自由に選択できないなど必ず
しも十分な方法とは言えず、ピラゾールの製造法
の改良が望まれていた。 Conventionally, the method for producing pyrazole skeletons is β-
Known methods include condensing a dicarbonyl compound with hydrazine or a substituted product thereof, reacting an acetylene carbonyl compound with hydrazine or a substituted product thereof, and reacting an aliphatic diazo compound with a β-diketone or an acetylene compound. However, this method cannot necessarily be said to be sufficient as the substituents cannot be freely selected, and an improvement in the method for producing pyrazoles has been desired.
一方、本発明者は先にシクロプロペニウム塩と
ヒドラジン類を反応させることにより、3,4―
ジチオピラゾールまたは1―置換―3,4―ジチ
オピラゾールを製造する方法を提案した。(例え
ば、特開昭54―44667号公報参照)
しかしながら、本発明者が先に提案した方法で
も、未だ3位(または4位)にアミノ基を導入で
きなかつた。このようなピラゾール誘導体を得る
ことを目的に、鋭意研究した結果トリチオシクロ
プロペニウム塩をアミンまたはアンモニアと反応
させ、次いでヒドラジン類を反応させることによ
り、目的を達しうることを知り、本発明に到達し
た。 On the other hand, the present inventor first reacted a cyclopropenium salt with a hydrazine to create a 3,4-
A method for producing dithiopyrazole or 1-substituted-3,4-dithiopyrazole was proposed. (For example, see JP-A-54-44667.) However, even with the method previously proposed by the present inventor, it has not been possible to introduce an amino group into the 3-position (or 4-position). As a result of extensive research aimed at obtaining such pyrazole derivatives, it was discovered that the objective could be achieved by reacting trithiocyclopropenium salt with amine or ammonia and then reacting with hydrazines. Reached.
すなわち、本発明の要旨は一般式()
(式中、R1は低級アルキル基、R2およびR3は
水素原子、低級アルキル基またはアラルキル基、
R4は水素原子または低級アルキル基を表わす。)
で示される3―アミノピラゾール誘導体に存す
る。 That is, the gist of the present invention is the general formula () (In the formula, R 1 is a lower alkyl group, R 2 and R 3 are hydrogen atoms, lower alkyl groups or aralkyl groups,
R 4 represents a hydrogen atom or a lower alkyl group. ) It exists in the 3-aminopyrazole derivative shown by.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
一般式()においてR1は、メチル、エメル、
n―プロピル、iso―プロピル、n―ブチル、iso
―ブチル―、sec―ブチル、t―ブチル等の低級
アルキル基である。 In the general formula (), R 1 is methyl, emel,
n-propyl, iso-propyl, n-butyl, iso
-Butyl-, sec-butyl, t-butyl, and other lower alkyl groups.
R2およびR3は、水素原子;メチル、エチル等
前記R1に例示した様な低級アルキル基;または
ベンジル等のアラルキル基である。 R 2 and R 3 are a hydrogen atom; a lower alkyl group as exemplified for R 1 above, such as methyl or ethyl; or an aralkyl group such as benzyl.
R4は、水素原子;またはメチル、エチル等前
記R1に例示した様な低級アルキル基である。 R 4 is a hydrogen atom; or a lower alkyl group such as methyl, ethyl, etc. as exemplified for R 1 above.
このような3―アミノピラゾール誘導体として
は、3―アミノ―4―エチルチオピラゾール、3
―アミノ―4―n―プロピルチオピラゾール、3
―アミノ―4―tブチルチオピラゾール、3―ジ
メチルアミノ―4―イソプロピルチオピラゾー
ル、3―ジメチルアミノ―4―t―ブチルチオピ
ラゾール、3―エチルアミノ―4―t―ブチルチ
オピラゾール、3―ジエチルアミノ―4―t―ブ
チルチオピラゾール、3―ベンジルアミノ―4―
t―ブチルチオピラゾール、3―アミノ―4―エ
チルチオ―1―メチルピラゾール、3―ジエチル
アミノ―4―t―ブチルチオ―1―メチルピラゾ
ール、3―ベンジルアミノ―4―t―ブチルチオ
―1―メチルピラゾール、3―アミノ―4―t―
ブチルチオ―1―エチルピラゾール、3―ジエチ
ルアミノ―4―t―ブチルチオ―1―エチルピラ
ゾール、3―ベンジルアミノ―4―t―ブチルチ
オ―1―エチルピラゾール等が挙げられる。 Such 3-aminopyrazole derivatives include 3-amino-4-ethylthiopyrazole, 3
-amino-4-n-propylthiopyrazole, 3
-amino-4-t-butylthiopyrazole, 3-dimethylamino-4-isopropylthiopyrazole, 3-dimethylamino-4-t-butylthiopyrazole, 3-ethylamino-4-t-butylthiopyrazole, 3-diethylamino -4-t-butylthiopyrazole, 3-benzylamino-4-
t-butylthiopyrazole, 3-amino-4-ethylthio-1-methylpyrazole, 3-diethylamino-4-t-butylthio-1-methylpyrazole, 3-benzylamino-4-t-butylthio-1-methylpyrazole, 3-amino-4-t-
Examples include butylthio-1-ethylpyrazole, 3-diethylamino-4-t-butylthio-1-ethylpyrazole, and 3-benzylamino-4-t-butylthio-1-ethylpyrazole.
一般式()で示されるアミノピラゾール誘導
体は、例えば一般式()
〔式中、R1は一般式()におけると同義と
し、Zは陰イオンを表わす。〕
で示されるトリチオシクロプロペニウム塩と、一
般式()
〔式中、R2およびR3は一般式()における
と同義とする。〕
で示されるアミンまたはアンモニアを反応させ
て、一般式〔〕
〔式中、R1,R2,R3およびZはそれぞれ一般
式()または()におけると同義とする。〕
で示される中間生成物(アルキルチオアンモニウ
ム塩)となし、次いでこれに一般式()
R4―NH―NH2 ()
〔式中、R4は一般式()におけると同義と
する。〕
で示されるヒドラジン類を反応させることにより
製造できる。原料である前記一般式()で示さ
れるトリチオシクロプロペニウム塩において、
Zは任意の陰イオンである。Zは、例えばハ
ロゲンイオン、過塩素酸イオン、フルオロホウ酸
イオン、六フツ化アンチモンイオン、六塩化アン
チモンイオン、塩化アルミニウムイオン等であ
る。 The aminopyrazole derivative represented by the general formula () is, for example, the general formula () [In the formula, R 1 has the same meaning as in the general formula (), and Z represents an anion. ] Trithiocyclopropenium salt represented by and general formula () [In the formula, R 2 and R 3 have the same meanings as in the general formula (). ] By reacting the amine or ammonia represented by the general formula [] [In the formula, R 1 , R 2 , R 3 and Z each have the same meaning as in the general formula () or (). ] An intermediate product (alkylthioammonium salt) represented by is prepared, and then the general formula () R 4 —NH—NH 2 () [wherein R 4 has the same meaning as in the general formula ()] is prepared. ] It can be produced by reacting the hydrazines shown below. In the trithiocyclopropenium salt represented by the general formula () which is a raw material,
Z is any anion. Z is, for example, a halogen ion, perchlorate ion, fluoroborate ion, antimony hexafluoride ion, antimony hexachloride ion, aluminum chloride ion, or the like.
このようなシクロプロペニウム塩としては、例
えばトリエチルチオシクロプロペニウムパークロ
レート、トリ―n―プロピルチオシクロプロペニ
ウムパークロレート、トリ―iso―プロピルチオ
シクロプロペニウムパークロレート、トリ―t―
ブチルチオシクロプロペニウムパークロレート、
トリ―t―ブチルチオシクロプロペニウムテトラ
フルオロボレート等が挙げられる。 Examples of such cyclopropenium salts include triethylthiocyclopropenium perchlorate, tri-n-propylthiocyclopropenium perchlorate, tri-iso-propylthiocyclopropenium perchlorate, tri-t-
Butylthiocyclopropenium perchlorate,
Examples include tri-t-butylthiocyclopropenium tetrafluoroborate.
トリチオシクロプロペニウム塩は、例えば特開
昭48―96564号公報に記載された方法により、製
造すれば良い。 The trithiocyclopropenium salt may be produced, for example, by the method described in JP-A-48-96564.
一般式()で示されるものは、例えばメチル
アミン、エチルアミン、ブチルアミン、ベンジル
アミン、ジメチルアミン、ジエチルアミン、ベン
ジルメチルアミン等の一級または二級アミンもし
くはアンモニアである。 Those represented by the general formula () are, for example, primary or secondary amines such as methylamine, ethylamine, butylamine, benzylamine, dimethylamine, diethylamine, benzylmethylamine, or ammonia.
トリチオシクロプロペニウム塩とアミンまたは
アンモニアの反応は、通常適当な溶剤中で行われ
る。 The reaction of trithiocyclopropenium salt with amine or ammonia is usually carried out in a suitable solvent.
溶剤としては、塩化メチレン、クロロホルム、
ジメトキシエタン、ジメチルホルムアミドおよび
メタノール等が用いられる。 As a solvent, methylene chloride, chloroform,
Dimethoxyethane, dimethylformamide, methanol, etc. are used.
トリチオシクロプロペニウム塩とアミンまたは
アンモニアのモル比は、等モル程度とするのがよ
い。 The molar ratio of the trithiocyclopropenium salt to the amine or ammonia is preferably approximately equimolar.
反応温度は、通常−50〜+50℃付近である。 The reaction temperature is usually around -50 to +50°C.
反応時間は、通常0.5〜5時間、好ましくは1
〜2時間程度である。 The reaction time is usually 0.5 to 5 hours, preferably 1
It takes about 2 hours.
一般式()で示されるヒドラジン類として
は、例えばヒドラジン、メチルヒドラジン、エチ
ルヒドラジン等が挙げられる。 Examples of the hydrazines represented by the general formula () include hydrazine, methylhydrazine, and ethylhydrazine.
一般式()で示されるアルキルチオアンモニ
ウム塩とヒドラジン類との反応は、通常、適当な
溶剤中で行なわれる。 The reaction between the alkylthioammonium salt represented by the general formula () and hydrazines is usually carried out in a suitable solvent.
溶剤としては、塩化メチレン、クロロホルムジ
メトキシエタン、ジメチルホルムアミド、メタノ
ール等が用いられる。 As the solvent, methylene chloride, chloroform dimethoxyethane, dimethylformamide, methanol, etc. are used.
ヒドラジン類は、トリチオシクロプロペニウム
塩に対し1倍モル程度加えるのが望ましい。 It is desirable to add hydrazines in an amount of about 1 times the mole of the trithiocyclopropenium salt.
反応温度は−50〜+50℃、通常室温付近が選ば
れる。 The reaction temperature is -50 to +50°C, usually around room temperature.
反応時間は0.5〜5時間、通常1〜2時間程度
である。 The reaction time is 0.5 to 5 hours, usually about 1 to 2 hours.
生成したアミノピラゾール誘導体は有機化学合
成の常法に従いろ過、抽出、溶媒留去等の方法に
よつて反応液より粗生成物を分離し、カラムクロ
マトグラフイー、昇華、再結晶等の方法により単
離、精製することができる。 The produced aminopyrazole derivative is separated from the reaction solution by methods such as filtration, extraction, and solvent distillation according to conventional organic chemical synthesis methods, and then isolated by methods such as column chromatography, sublimation, and recrystallization. It can be separated and purified.
本発明に係わるアミノピラゾール誘導体は、農
園芸用殺菌剤および除草剤、もしくはそれらの中
間体として有用である。さらに、本発明に係るア
ミノピラゾール誘導体をラネーニツケル等の金属
触媒の存在下水素で処理すると―SR1基を脱離さ
せることができ、アミノピラゾールに導くことも
出来るので、アミノピラゾールの製造方法として
も有用である。 The aminopyrazole derivatives according to the present invention are useful as agricultural and horticultural fungicides and herbicides, or intermediates thereof. Furthermore, when the aminopyrazole derivative according to the present invention is treated with hydrogen in the presence of a metal catalyst such as Raney nickel, the -SR 1 group can be eliminated and it can be led to aminopyrazole, so it can also be used as a method for producing aminopyrazole. Useful.
以下に実施例を挙げて、本発明を更に具体的に
説明するが、本発明はその要旨を越えない限り、
実施例により限定を受けるものではない。 The present invention will be explained in more detail with reference to Examples below, but the present invention does not exceed the gist thereof.
The invention is not limited by the examples.
実施例 1
窒素置換下、室温においてメタノール15mlに溶
解せしめたトリ―t―ブチルチオシクロプロペニ
ウム、パークロレート(403mg、1ミリモル)に
ジエチルアミン(1ミリモル)をゆつくり滴下
し、1時間撹拌後、ヒドラジン(1ミリモル)を
加え、さらに1時間撹拌を行なつた。溶媒を減圧
留去後、アルミナカラムクロマトグラフイー処理
することにより、3―ジエチルアミノ―4―t―
ブチルチオピラゾールを53%の収率で得た。Example 1 Diethylamine (1 mmol) was slowly added dropwise to tri-t-butylthiocyclopropenium perchlorate (403 mg, 1 mmol) dissolved in 15 ml of methanol at room temperature under nitrogen substitution, and after stirring for 1 hour, Hydrazine (1 mmol) was added and stirring was continued for an additional hour. After distilling off the solvent under reduced pressure, 3-diethylamino-4-t-
Butylthiopyrazole was obtained with a yield of 53%.
b.d. 180℃/5mmHg
IRスペクトル(neat):3150(N―H)cm-1
NMRスペクトル(CCl4):δ1.06(t,6H,
NCH2CH3 )、1.20(s,9H,t―Bu)、
3.45(q,4H,NCH2 CH3)、7.28(s,
1H,H―5)、10.29(broad―s,1H,N
―H)ppm
マススペクトル m/e M+ 227
元素分析値(重量%) C H N S
C12H21N3Sとしての計算値
58.11 9.31 18.48 14.10
分 析 値 58.42 9.38 18.48 14.46
実施例 2
実施例1において、ヒドラジンをメチルヒドラ
ジンに代えた他は全く同様にして、3―ジエチル
アミノ―1―メチル―4―t―ブチルチオピラゾ
ールを63%の収率で得た。bd 180℃/5mmHg IR spectrum (neat): 3150 (NH) cm -1 NMR spectrum (CCl 4 ): δ1.06 (t, 6H,
NCH 2 CH 3 ), 1.20 (s, 9H, t-Bu),
3.45 (q, 4H, NC H 2 CH 3 ), 7.28 (s,
1H, H-5), 10.29 (broad-s, 1H, N
- H) ppm Mass spectrum m/e M + 227 Elemental analysis value (weight%) Calculated value as C H N S C 12 H 21 N 3 S
58.11 9.31 18.48 14.10 Analytical value 58.42 9.38 18.48 14.46 Example 2 In the same manner as in Example 1 except that hydrazine was replaced with methylhydrazine, 3-diethylamino-1-methyl-4-t-butylthiopyrazole was 63 % yield.
b.p. 112℃/3mmHg
IRスペクトル(neat):2930,1520,1440,116
cm-1
NMRスペクトル(CCl4):δ1.10(t,6H,
NCH2 CH3 )、1.22(s,9H,t―Bu)、
3.38(q,4H,NCH2 CH3)、3.68(s,
3H,N―CH3 )、7.07(s,1H,H―5)
ppm
マススペクトル m/e M+ 241
元素分析値(重量%) C H N S
C13H23N3Sとしての計算値
59.71 9.60 17.41 13.28
分 析 値 59.58 9.56 17.22 13.36
実施例 3
実施例1において、ジエチルアミンをベンジル
アミンに代えた他は全く同様にして、3―ベンジ
ルアミノ―4―t―ブチルチオピラゾールを96%
の収率で得た。bp 112℃/3mmHg IR spectrum (neat): 2930, 1520, 1440, 116
cm -1 NMR spectrum (CCl 4 ): δ1.10 (t, 6H,
NCH 2 CH 3 ), 1.22 (s, 9H, t-Bu),
3.38 (q, 4H, N CH 2 CH 3 ), 3.68 (s,
3H, N- CH 3 ), 7.07 (s, 1H, H-5)
ppm Mass spectrum m/e M + 241 Elemental analysis value (weight%) Calculated value as C H N S C 13 H 23 N 3 S
59.71 9.60 17.41 13.28 Analytical value 59.58 9.56 17.22 13.36 Example 3 Same as Example 1 except that diethylamine was replaced with benzylamine, but 3-benzylamino-4-t-butylthiopyrazole was 96%
It was obtained in a yield of .
b.p. 230℃/5mmHg
IRスペクトル(neat):3160(N―H)cm-1
NMRスペクトル(CCl4):δ1.18(s,9H,t―
ブチル)、4.30(s,2H,―CH2 ph)、6.90
〜7.21(m,5H,フエニル)、6.96(s,
1H,H―5)ppm
マススペクトル m/e M+ 261
元素分析(重量%) C H N S
C14H19N3Sとしての計算値
64.33 7.33 16.08 12.27
分 析 値 62.84 7.32 15.98 12.36
実施例 4
実施例3において、ヒドラジンをメチルヒドラ
ジンに代えた他は全く同様にして、3―ベンジル
アミノ―1―メチル―4―t―ブチルチオピラゾ
ールを88%の収率で得た。bp 230℃/5mmHg IR spectrum (neat): 3160 (NH) cm -1 NMR spectrum (CCl 4 ): δ1.18 (s, 9H, t-
butyl), 4.30 (s, 2H, -C H 2 ph), 6.90
~7.21 (m, 5H, phenyl), 6.96 (s,
1H, H-5) ppm Mass spectrum m/e M + 261 Elemental analysis (weight%) Calculated value as C H N S C 14 H 19 N 3 S
64.33 7.33 16.08 12.27 Analytical value 62.84 7.32 15.98 12.36 Example 4 In the same manner as in Example 3 except that hydrazine was replaced with methylhydrazine, 3-benzylamino-1-methyl-4-t-butylthiopyrazole was Obtained with a yield of 88%.
b.p. 160℃/3mmHg
IRスペクトル(neat):3350(N―H)cm-1
NMRスペクトル(CCl4):δ1.20(s,9H,t―
Bu)、3.58(s,3H,N―CH3 )、4.17
(broad―s,1H,N―H)、4.28(s,
2H,―CH2 ph)、6.94(s,1H,H―5)、
6.80〜7.23(m,5H,フエニル)ppm
マススペクトル m/e M+ 275
元素分析値(重量%) C H N S
C15H21N3Sとしての計算値
65.41 7.69 15.26 11.64
分 析 値 65.21 7.76 15.25 11.88
実施例 5
実施例1において、ジエチルアミンをアンモニ
アに代えた他は全く同様にして、3―アミノ―4
―t―ブチルチオピラゾールを81%の収率で得
た。bp 160℃/3mmHg IR spectrum (neat): 3350 (NH) cm -1 NMR spectrum (CCl 4 ): δ1.20 (s, 9H, t-
Bu), 3.58 (s, 3H, N-C H 3 ), 4.17
(broad-s, 1H, N-H), 4.28(s,
2H, -C H 2 ph), 6.94 (s, 1H, H-5),
6.80-7.23 (m, 5H, phenyl) ppm Mass spectrum m/e M + 275 Elemental analysis value (weight%) Calculated value as C H N S C 15 H 21 N 3 S
65.41 7.69 15.26 11.64 Analysis value 65.21 7.76 15.25 11.88 Example 5 3-Amino-4
-t-Butylthiopyrazole was obtained with a yield of 81%.
b.p. 205℃/10mmHg
IRスペクトル(neat):3440〜3200(N―H)cm
-1
NMRスペクトル(CCl4):δ1.18(s,9H,t―
Bu)、6.58(brcad―s,3H,N―H)、
7.30(s,1H,H―5)ppm
マススペクトル m/e M+ 171
元素分析(重量%) C H N S
C7H13N3Sとしての計算値
49.09 7.65 24.54 18.72
分 析 値 49.29 7.74 24.35 18.84
実施例 6
実施例5において、ヒドラジンをメチルヒドラ
ジンに代えた他は全く同様にして、3―アミノ―
1―メチル―4―t―ブチルチオピラゾールを76
%の収率で得た。bp 205℃/10mmHg IR spectrum (neat): 3440-3200 (N-H) cm
-1 NMR spectrum (CCl 4 ): δ1.18 (s, 9H, t-
Bu), 6.58 (brcad-s, 3H, N-H),
7.30 (s, 1H, H-5) ppm Mass spectrum m/e M + 171 Elemental analysis (wt%) Calculated value as C H N S C 7 H 13 N 3 S
49.09 7.65 24.54 18.72 Analytical value 49.29 7.74 24.35 18.84 Example 6 In exactly the same manner as in Example 5 except that hydrazine was replaced with methylhydrazine, 3-amino-
76 1-methyl-4-t-butylthiopyrazole
% yield.
b.p. 155℃/15mmHg
IRスペクトル(neat):3300(N―H)cm-1
NMRスペクトル(CCl4):δ1.21(s,9H,t―
Bu)、3.63(s,3H,N―CH3)、3.75
(broad―s,2H,N―H)、7.03(s,
1H,H―5)ppm
マススペクトル m/e M+ 185
元素分析(重量%) C H N S
C8H15N3Sとしての計算値
51.86 8.16 22.68 17.31
分 析 値 51.60 8.29 22.60 17.16bp 155℃/15mmHg IR spectrum (neat): 3300 (NH) cm -1 NMR spectrum (CCl 4 ): δ1.21 (s, 9H, t-
Bu), 3.63 (s, 3H, N-CH 3 ), 3.75
(broad-s, 2H, N-H), 7.03(s,
1H, H-5) ppm Mass spectrum m/e M + 185 Elemental analysis (weight%) Calculated value as C H N S C 8 H 15 N 3 S
51.86 8.16 22.68 17.31 Analysis value 51.60 8.29 22.60 17.16
Claims (1)
水素原子、低級アルキル基またはアラルキル基、
R4は水素原子または低級アルキル基を表わす。) で示される3―アミノピラゾール誘導体。[Claims] 1 General formula () (In the formula, R 1 is a lower alkyl group, R 2 and R 3 are hydrogen atoms, lower alkyl groups or aralkyl groups,
R 4 represents a hydrogen atom or a lower alkyl group. ) A 3-aminopyrazole derivative represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13612179A JPS5659760A (en) | 1979-10-22 | 1979-10-22 | 3-aminopyrazole derivative |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13612179A JPS5659760A (en) | 1979-10-22 | 1979-10-22 | 3-aminopyrazole derivative |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5659760A JPS5659760A (en) | 1981-05-23 |
JPS6338992B2 true JPS6338992B2 (en) | 1988-08-03 |
Family
ID=15167787
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13612179A Granted JPS5659760A (en) | 1979-10-22 | 1979-10-22 | 3-aminopyrazole derivative |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5659760A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01166020U (en) * | 1988-05-12 | 1989-11-21 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3606476A1 (en) * | 1986-02-28 | 1987-09-03 | Bayer Ag | 1-ARYLPYRAZOLE |
-
1979
- 1979-10-22 JP JP13612179A patent/JPS5659760A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01166020U (en) * | 1988-05-12 | 1989-11-21 |
Also Published As
Publication number | Publication date |
---|---|
JPS5659760A (en) | 1981-05-23 |
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