JPH0613475B2 - Method for producing 5-aminopyrazole compound - Google Patents
Method for producing 5-aminopyrazole compoundInfo
- Publication number
- JPH0613475B2 JPH0613475B2 JP7783885A JP7783885A JPH0613475B2 JP H0613475 B2 JPH0613475 B2 JP H0613475B2 JP 7783885 A JP7783885 A JP 7783885A JP 7783885 A JP7783885 A JP 7783885A JP H0613475 B2 JPH0613475 B2 JP H0613475B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- alkyl group
- represented
- examples
- 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 - Lifetime
Links
- -1 5-aminopyrazole compound Chemical class 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 150000002429 hydrazines Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 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
- FYTLHYRDGXRYEY-UHFFFAOYSA-N 5-Methyl-3-pyrazolamine Chemical compound CC=1C=C(N)NN=1 FYTLHYRDGXRYEY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZOHGOQJROHLKIB-UHFFFAOYSA-N 1h-pyrazol-5-ylhydrazine Chemical class NNC=1C=CNN=1 ZOHGOQJROHLKIB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- URZXWPWAIGOVFH-UHFFFAOYSA-N 2-iminoethyl 4,4-dimethyl-3-oxopentanoate hydrochloride Chemical compound CC(C)(C)C(=O)CC(=O)OCC=N.Cl URZXWPWAIGOVFH-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OPXYNEYEDHAXOM-UHFFFAOYSA-N 3-oxobutanenitrile Chemical compound CC(=O)CC#N OPXYNEYEDHAXOM-UHFFFAOYSA-N 0.000 description 1
- OLUAUWSAARAMSS-UHFFFAOYSA-N 3-tert-butyl-1,2-dihydropyrazol-3-amine Chemical compound CC(C)(C)C1(C=CNN1)N OLUAUWSAARAMSS-UHFFFAOYSA-N 0.000 description 1
- MXZMACXOMZKYHJ-UHFFFAOYSA-N 4,4-dimethyl-3-oxopentanenitrile Chemical compound CC(C)(C)C(=O)CC#N MXZMACXOMZKYHJ-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZHBXGHWSVIBUCQ-UHFFFAOYSA-N 5-tert-butyl-1h-pyrazol-3-amine Chemical compound CC(C)(C)C1=CC(N)=NN1 ZHBXGHWSVIBUCQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- NHOWLEZFTHYCTP-UHFFFAOYSA-N benzylhydrazine Chemical compound NNCC1=CC=CC=C1 NHOWLEZFTHYCTP-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【発明の詳細な説明】 ［技術分野］ 本発明は、５−アミノピラゾール系化合物の製造方法に
関し、更に詳しくはα−アシル酢酸イミノエステルを出
発原料として高収率に５−アミノピラゾール系化合物を
製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a 5-aminopyrazole-based compound, and more specifically, to a 5-aminopyrazole-based compound in high yield using α-acylacetic acid iminoester as a starting material. The present invention relates to a manufacturing method.
［従来技術］ ５−アミノピラゾール系化合物は写真用カプラー、特に
マゼンタカプラーの原料として有用な化合物である。す
なわち、この化合物をジアゾ化し還元して得られる５−
ヒドラジノピラゾール類を酸クロリドと反応させたアシ
ル体あるいはアルデヒドと反応させたヒドラゾーンを閉
環することにより１Ｈ−ピラゾロ［３，２−Ｃ］−１，
２，４−トリアゾール類が合成できるが、これは２次吸
収を持たないマゼンタカプラーとして近年注目されてい
る。[Prior Art] 5-Aminopyrazole compounds are useful compounds as starting materials for photographic couplers, particularly magenta couplers. That is, 5-
1H-pyrazolo [3,2-C] -1, by cyclization of an acyl derivative obtained by reacting hydrazinopyrazoles with an acid chloride or a hydrazone reacted with an aldehyde
Although 2,4-triazoles can be synthesized, they have recently attracted attention as magenta couplers having no secondary absorption.
５−アミノピラゾール系化合物の合成については、例え
ばジャーナル・オブ・ザ・ケミカル・ソサィァティ（J.
Chem.Soc.）、1941年、2857頁、ガゼッタ・キミカ・イ
タリアーナ（Gazz.Chim.Ital.）７７巻、１８２〜１９
８頁（1947年）、ジュルナール・オブスカイ・キミィ
（Zh.Obsch.Khim,）、３１巻、2307〜2310頁（1961
年）、米国特許2,975,188号、特公昭45-26082号など
に、３−メチル−５−アミノピラゾールが記載されてい
る。Regarding the synthesis of 5-aminopyrazole compounds, for example, Journal of the Chemical Society (J.
Chem. Soc.), 1941, p. 2857, Gazzetta Chimica Ital., 77, 182-19.
8 (1947), Journal of the Sky Kimi (Zh.Obsch.Khim,), Vol. 31, 2307-2310 (1961)
, U.S. Pat. No. 2,975,188, Japanese Patent Publication No. 45-26082, and the like, 3-methyl-5-aminopyrazole is described.
しかしながら、これ等の方法によって３位のメチル基を
２級あるいは３級のアルキル基（例えばイソプロピル
基、ｔ−ブチル基等）に替えようとすると全く合成でき
ないか、できても収率が著しく低いと云う問題があっ
た。However, if the methyl group at the 3-position is replaced with a secondary or tertiary alkyl group (for example, isopropyl group, t-butyl group, etc.) by these methods, it cannot be synthesized at all, or the yield is remarkably low. There was a problem called.
［発明の目的］ 本発明の目的は、上記問題点を解決するところにある。
すなわち、３位のアルキル基をはじめ置換基の影響な
く、いずれの場合にも高収率で５−アミノピラゾール系
化合物を製造する方法を提供することにある。[Object of the Invention] An object of the present invention is to solve the above problems.
That is, it is to provide a method for producing a 5-aminopyrazole-based compound in a high yield in any case without being affected by a substituent such as an alkyl group at the 3-position.
［発明の要旨］ 本発明の上記目的は、α−アシル酢酸イミノエステルと
ヒドラジン誘導体を反応させる５−アミノピラゾール系
化合物の製造方法によって達成される。α−アシル酢酸
イミノエステルは下記一般式[I]で、ヒドラジン誘導体
は下記一般式[II]で、５−アミノピラゾール系化合物は
下記一般式[III]で示される。SUMMARY OF THE INVENTION The above object of the present invention is achieved by a method for producing a 5-aminopyrazole compound by reacting an α-acyl acetic acid imino ester with a hydrazine derivative. The α-acyl acetic acid imino ester is represented by the following general formula [I], the hydrazine derivative is represented by the following general formula [II], and the 5-aminopyrazole compound is represented by the following general formula [III].
一般式[I] 式中Ｒ1は、それぞれ置換基を有してもよいアルキル
基、シクロアルキル基、アリール基またはヘテロ環基を
表し、Ｒ2は１級アルキル基を表す。Ａはｍ塩基プロト
ン酸を表し（ｍは１〜４の整数）、ｎは０または1/mを
表す。General formula [I] In the formula, R 1 represents an alkyl group which may have a substituent, a cycloalkyl group, an aryl group or a heterocyclic group, and R 2 represents a primary alkyl group. A represents an m-base protonic acid (m is an integer of 1 to 4), and n represents 0 or 1 / m.
一般式[II] Ｒ3−NHNH2 式中Ｒ3は水素原子、それぞれ置換基を有してもよいア
ルキル基、アリール基またはヘテロ環基を表す。General formula [II] R 3 -NHNH 2 formula in R 3 is a hydrogen atom, alkyl group which may have a substituent, an aryl group or a heterocyclic group.
一般式[III] 式中Ｒ1およびＲ3は前記Ｒ1およびＲ3と同義である。General formula [III] In the formula, R 1 and R 3 have the same meaning as the above R 1 and R 3 .
［発明の構成］ 本発明において、出発原料として用いられるアシル酢酸
イミノエステルはベリヒテ(Ber.),44巻、2065〜2069頁
（1911年）に記載の方法により合成できる。すなわち、
アセトニトリルよりアシルアセトニトリルを合成し、更
にこれをアルコール中で塩酸ガスと反応させアシル酢酸
イミノエステルを合成することができる。その他、ジャ
ーナル・オブ・ザ・アメリカン・ケミカル・ソサイァテ
ィ（J.Am.Chem.Soc.）、５６巻、1171〜1173頁（1934
年）の方法によりアシルアセトニトリルを合成すること
もできる。[Structure of the Invention] In the present invention, the acylacetic acid iminoester used as a starting material can be synthesized by the method described in Berichte (Ber.), Vol. 44, 2065-2069 (1911). That is,
Acylacetonitrile can be synthesized from acetonitrile and further reacted with hydrochloric acid gas in alcohol to synthesize an acylacetic acid iminoester. Others, Journal of the American Chemical Society (J.Am.Chem.Soc.), 56, 1171-1173 (1934)
Acetoacetonitrile can also be synthesized by the method described in (1).
以下、本発明をより具体的に説明する。Hereinafter, the present invention will be described more specifically.
アシル酢酸イミノエステルとヒドラジン誘導体は、反応
に際して分散媒中に分散されて用いられる。用いること
のできる分散媒としては、ケトン類やアルデヒド類の如
くカルボニル基や酢酸エチルエステルの如くエステル結
合を有しない化合物、例えばアルコール類、ベンゼン
類、エーテル類、ハロゲン化炭素、アミド類等を代表的
に挙げることができる。このうち、好ましいものとして
はアルコール類、エーテル類であり、特に好ましいもの
はアルコール類である。The acyl acetic acid imino ester and the hydrazine derivative are used by being dispersed in a dispersion medium during the reaction. As a dispersion medium that can be used, a compound having no ester bond such as a carbonyl group or ethyl acetate such as ketones and aldehydes, for example, alcohols, benzenes, ethers, halogenated carbons, amides and the like are representative. I can list them. Among these, alcohols and ethers are preferable, and alcohols are particularly preferable.
ケトン類やアルデヒド類はカルボニル基がヒドラジン誘
導体のアミノ基と反応を起こすため好ましくない。また
酢酸エチルエステルはこのカルボニル基がヒドラジン誘
導体のアミノ基と結合してアミドを形成しアルコールが
脱離するので目的とする化合物を得ることができず好ま
しくない。Ketones and aldehydes are not preferred because the carbonyl group reacts with the amino group of the hydrazine derivative. Further, acetic acid ethyl ester is not preferable because the carbonyl group is bonded to the amino group of the hydrazine derivative to form an amide and the alcohol is eliminated, so that the desired compound cannot be obtained.
本発明において用いられるアルコール類としては、例え
ばメタノール、エタノール、ｎ−プロパノール、エチレ
ングリコール、エチレングリコールモノメチルエーテル
等を挙げることができる。また、ベンゼン類としては、
ベンゼン、ニトロベンゼン、トルエン、キシレン等が挙
げられる。さらにエーテル類としてはジエチルエーテ
ル、エチレングリコールジメチルエーテル、ジエチレン
グリコールジメチルエーテル、テトラヒドロフラン、ジ
オキサン等が挙げられる。ハロゲン化炭素としては、四
塩化炭素、クロロホルム、ブロモホルム等を挙げること
ができ、アミド類としてはホルムアミド、Ｎ，Ｎ−ジメ
チルホルムアミド等が挙げられる。その他ジメチルスル
ホオキサイド、アセトニトリル等も分散媒として用いる
ことができる。この分散媒は必ずしも無水である必要が
ない。Examples of alcohols used in the present invention include methanol, ethanol, n-propanol, ethylene glycol, and ethylene glycol monomethyl ether. Moreover, as benzenes,
Examples thereof include benzene, nitrobenzene, toluene and xylene. Further, examples of ethers include diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane and the like. Examples of the carbon halide include carbon tetrachloride, chloroform and bromoform, and examples of the amides include formamide and N, N-dimethylformamide. In addition, dimethyl sulfoxide, acetonitrile and the like can be used as the dispersion medium. This dispersion medium does not necessarily have to be anhydrous.
分散媒は、α−アシル酢酸イミノエステルまたはヒドラ
ジン誘導体１重量部当り１〜1000重量部、好ましくは５
〜１００重量部の割合で含有せしめられる。The dispersion medium is 1 to 1000 parts by weight, preferably 5 parts by weight per 1 part by weight of α-acyl acetic acid imino ester or hydrazine derivative.
˜100 parts by weight.
本発明において一般式[I]のＲ1はアルキル基、アリール
基またはヘテロ環基を表すか、Ｒ1で表されるアルキル
基としては、好ましくは、炭素原子数１〜３０の直鎖ま
たは分岐のアルキル基、例えば、メチル基、エチル基、
イソプロピル基、ｔ−ブチル基、オクチル基、ドデシル
基、エイコシル基、トリアコンチル基等を挙げることが
できる。このアルキル基は置換基を有することができ、
置換基としては、ハロゲン原子、アリールオキシ基、ア
ルキルスルホニル基、アシルアミノ基、アルコキシ基、
ヒドロキシ基等を挙げることができ、このような置換基
を有するアルキル基の例としては、γ−（２，４−ジ−
ｔ−アミルフェノキシ）プロピル基、β−（ドデシルス
ルホニル）エチル基、フェノキシメチル基、メトキシエ
チル基等を挙げることができる。In the present invention, R 1 of the general formula [I] represents an alkyl group, an aryl group or a heterocyclic group, or the alkyl group represented by R 1 is preferably a straight chain or branched chain having 1 to 30 carbon atoms. An alkyl group of, for example, a methyl group, an ethyl group,
Examples thereof include isopropyl group, t-butyl group, octyl group, dodecyl group, eicosyl group and triacontyl group. The alkyl group can have a substituent,
As the substituent, a halogen atom, an aryloxy group, an alkylsulfonyl group, an acylamino group, an alkoxy group,
Examples thereof include a hydroxy group and the like, and examples of the alkyl group having such a substituent include γ- (2,4-di-
Examples thereof include t-amylphenoxy) propyl group, β- (dodecylsulfonyl) ethyl group, phenoxymethyl group and methoxyethyl group.
Ｒ1で表されるシクロアルキル基としては、好ましくは
炭素原子数３〜１２のシクロアルキル基、例えばシクロ
プロピル基、シクロペンチル基、シクロヘキシル基、シ
クロドデシル基等を挙げることができる。このシクロア
ルキル基は置換基を有してもよい。The cycloalkyl group represented by R 1 is preferably a cycloalkyl group having a carbon number of 3 to 12, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclododecyl group and the like. This cycloalkyl group may have a substituent.
Ｒ1で表されるアリール基としては、具体的にはフェニ
ル基が挙げられる。このフェニル基は置換基を有するこ
とができ、置換基としては、アルコキシ基、ハロゲン原
子、アルキル基、アミド基等を挙げることができ、この
ような置換基を有するフェニル基の例としては、ｐ−メ
トキシフェニル基、ドデシルオキシフェニル基、ｐ−
｛γ−（２，４−ジ−ｔ−アミルフェノキシ）ブチリル
アミノ｝フェニル基、ｏ−クロロフェニル基、ｐ−トリ
ル基、メシチル（トリメチルフェニル）基等を挙げるこ
とができる。Specific examples of the aryl group represented by R 1 include a phenyl group. The phenyl group may have a substituent, and examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, an amide group, and the like. Examples of the phenyl group having such a substituent include p -Methoxyphenyl group, dodecyloxyphenyl group, p-
Examples thereof include {γ- (2,4-di-t-amylphenoxy) butyrylamino} phenyl group, o-chlorophenyl group, p-tolyl group and mesityl (trimethylphenyl) group.
Ｒ1で表されるヘテロ環基としては、具体的にはフリル
基、ピラニル基、チェニル基、ピリジル基、２Ｈ−ピロ
リル基等を挙げることができる。Specific examples of the heterocyclic group represented by R 1 include a furyl group, a pyranyl group, a cenyl group, a pyridyl group and a 2H-pyrrolyl group.
前記Ｒ1で表されるそれぞれ置換基を有してもよいアル
キル基、シクロアルキル基、アリール基又はヘテロ環基
のうち、アルキル基が好ましい。アルキル基のうちでも
メチル基、エチル、イソプロピル基、ｔ−ブチル基等が
特に好ましい。Of the alkyl groups, cycloalkyl groups, aryl groups and heterocyclic groups each represented by R 1 , which may have a substituent, an alkyl group is preferable. Among the alkyl groups, methyl group, ethyl group, isopropyl group, t-butyl group and the like are particularly preferable.
Ｒ2は１級アルキル基を表すが、炭素原子数１〜１２の
アルキル基が好ましく、例えばメチル基、エチル基、ブ
チル基、オクチル基、ドデシル基などを挙げることがで
きる。中でもメチル基、エチル基、プロピル基が特に好
ましい。R 2 represents a primary alkyl group, but an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a butyl group, an octyl group and a dodecyl group. Of these, a methyl group, an ethyl group and a propyl group are particularly preferable.
プロトン酸としては塩酸、臭化水素酸、硫酸、酢酸、メ
タンスルホン酸、ピロメリティック酸等が代表的なもの
である。Typical examples of the protic acid are hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid, pyromellitic acid and the like.
本発明で用いられる一般式[I]で示されるアシル酢酸イ
ミノエステルの具体例を以下に示すが本発明はこれらに
限定されない。Specific examples of the acyl acetic acid imino ester represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.
Ｉ−１ Ｉ−２ Ｉ−３ Ｉ−４ Ｉ−５ Ｉ−６ Ｉ−７ Ｉ−８ 一般式[II]のＲ3は水素原子、それぞれ置換基を有して
もよいアルキル基、アリール基またはヘテロ環基を示す
が、Ｒ3で表されるアルキル基としては炭素原子数１〜
１２の直鎖または分岐のアルキル基、例えばメチル基、
エチル基、イソプロピル基、ブチル基、オクチル基、ド
デシル基、ベンジル基等を挙げることができる。I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-8 R 3 in the general formula [II] represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group or a heterocyclic group, and the alkyl group represented by R 3 has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups, such as methyl groups,
Examples thereof include ethyl group, isopropyl group, butyl group, octyl group, dodecyl group and benzyl group.
Ｒ3で表されるアリール基としては、具体的にはフェニ
ール基が挙げられる。このフェニール基は置換基を有し
てもよく例えばｐ−ニトロフェニル基、ｐ−トルル基が
ある。Specific examples of the aryl group represented by R 3 include a phenyl group. The phenyl group may have a substituent, and examples thereof include a p-nitrophenyl group and a p-toluru group.
Ｒ3で表されるヘテロ環基としては、具体的にはフリル
基、チェニル基、ピリジル基等を挙げることができる。Specific examples of the heterocyclic group represented by R 3 include a furyl group, a cenyl group and a pyridyl group.
前記Ｒ3で表される基のうち、水素原子またはベンジル
基が好ましく、水素原子が特に好ましい。Among the groups represented by R 3 , a hydrogen atom or a benzyl group is preferable, and a hydrogen atom is particularly preferable.
本発明で用いられる一般式[II]で示されるヒドラジン誘
導体の具体例を以下に示すが本発明はこれらに限定され
ない。Specific examples of the hydrazine derivative represented by the general formula [II] used in the present invention are shown below, but the present invention is not limited thereto.
II−１ NH2NH2 II−２ CH3NHNH2 II−３ (CH3)2CHNHNH2 II−４ C8H17NHNH2 II−５ II−６ II−７ II−８ 次に本発明の５−アミノピラゾール系化合物を生成する
ための代表的な反応経路を下記に示す。II-1 NH 2 NH 2 II-2 CH 3 NHNH 2 II-3 (CH 3 ) 2 CHNHNH 2 II-4 C 8 H 17 NHNH 2 II-5 II-6 II-7 II-8 Next, a typical reaction route for producing the 5-aminopyrazole compound of the present invention is shown below.
例−１ 例−２ 本発明の出発原料である一般式[I]で示される化合物と
一般式[II]で示される化合物は、１：0.5〜１：１５の
モル比で用いられ、好ましくは１：２〜１：５の範囲で
ある。反応温度は-20〜200℃が好ましく、特に０〜１０
０℃の範囲が好ましい。また反応を完結させるために一
度は４０℃以上とすることが好ましい。Example-1 Example-2 The compound represented by the general formula [I] and the compound represented by the general formula [II], which are the starting materials of the present invention, are used in a molar ratio of 1: 0.5 to 1:15, preferably 1: 2 to 1: 1. The range is 5. The reaction temperature is preferably -20 to 200 ° C, particularly 0 to 10
The range of 0 ° C is preferred. Further, in order to complete the reaction, the temperature is preferably once 40 ° C. or higher.
本発明の方法によれば前記一般式[III]で示される化合
物が得られる。代表的化合物を以下に例示するが、本発
明はこれらに限定されない。According to the method of the present invention, the compound represented by the above general formula [III] can be obtained. Representative compounds are exemplified below, but the present invention is not limited thereto.
［実施例］ 以下に本発明の具体的実施例を記載するが、本発明はこ
れに限定されない。 [Examples] Specific examples of the invention are described below, but the invention is not limited thereto.
実施例−１（例示化合物III−３の合成） 20.8ｇのα−ピバロイル酢酸イミノエチルエステル塩酸
塩に、２５０mlのヒドラジン・アルコール溶液（１モル
／濃度）を氷冷下に滴下する。内温は５℃以下に保
つ。３０分攪拌した後１時間還流する。反応液に１０ml
の水を加えてから濃縮し、クロロホルムで抽出、水で洗
浄後、硫酸マグネシウムで乾燥し濃縮する。濃縮物はカ
ラムクロマトグラフィーで分離精製し、12.8ｇ（92.1
％）の３−ｔ−ブチル−５−アミノ−１Ｈ−ピラゾール
を得た。 融点７２〜７４℃ C7H13N3としての元素分析値 計算値（％） Ｃ：60.40 Ｈ：9.41 Ｎ：30.19 実測値（％） Ｃ：60.26 Ｈ：9.58 Ｎ：30.24 比較例−１（例示化合物III−３の別途合成） 12.5ｇのピバロイルアセトニトリルと１００mlのヒドラ
ジン・アルコール溶液（１モル／濃度）に濃塩酸２０
mlを加え、１時間攪拌下に還流する。反応液は２０％水
酸化ナトリウム水溶液で中和し濃縮後エーテルで抽出す
る。エーテル層を濃縮しカラムクロマトグラフィーで分
離精製し、2.4ｇ（19.3％）の３−ｔ−ブチル−３−ア
ミノ−１Ｈ−ピラゾールを得た。Example-1 (Synthesis of Exemplified Compound III-3) To 20.8 g of α-pivaloyl acetic acid iminoethyl ester hydrochloride, 250 ml of a hydrazine / alcohol solution (1 mol / concentration) was added dropwise under ice cooling. Keep the internal temperature below 5 ° C. After stirring for 30 minutes, the mixture is refluxed for 1 hour. 10 ml in the reaction solution
After adding water, the mixture is concentrated, extracted with chloroform, washed with water, dried over magnesium sulfate and concentrated. The concentrate was separated and purified by column chromatography to give 12.8 g (92.1
%) Of 3-t-butyl-5-amino-1H-pyrazole. Melting point 72 to 74 ° C. Elemental analysis value as C 7 H 13 N 3 Calculated value (%) C: 60.40 H: 9.41 N: 30.19 Measured value (%) C: 60.26 H: 9.58 N: 30.24 Comparative example-1 (exemplification) Separate synthesis of compound III-3) 12.5 g of pivaloylacetonitrile and 100 ml of hydrazine / alcohol solution (1 mol / concentration) were added with concentrated hydrochloric acid 20.
Add ml and reflux with stirring for 1 hour. The reaction solution is neutralized with a 20% aqueous sodium hydroxide solution, concentrated and extracted with ether. The ether layer was concentrated and separated and purified by column chromatography to obtain 2.4 g (19.3%) of 3-t-butyl-3-amino-1H-pyrazole.
実施例−２（例示化合物III−６の合成） 16.5ｇのアセト酢酸イミノエチルエステル塩酸塩を２０
０mlのエタノールに溶解し、これに12.2ｇのベンジルヒ
ドラジンを含むアルコール溶液３０mlを０〜５℃で滴下
する。更に１５ｇのトリエチルアミンを滴下した後３０
分攪拌する。その後１時間還流し反応液を濃縮、カラム
クロマトグラフィーで分離精製し、１−ベンジル−３−
メチル−５−アミノピラゾール16.9ｇ（90.4％）を得
た。 融点６９〜７０℃ C11H13N3としての元素分析値 計算値（％） Ｃ：70.56 Ｈ：7.00 Ｎ：22.44 実測値（％） Ｃ：70.58 Ｈ：7.02 Ｎ：22.38Example-2 (Synthesis of Exemplified Compound III-6) 16.5 g of acetoacetic acid iminoethyl ester hydrochloride was added to 20
It is dissolved in 0 ml of ethanol, and 30 ml of an alcohol solution containing 12.2 g of benzylhydrazine is added dropwise at 0-5 ° C. After dropping an additional 15 g of triethylamine, 30
Stir for a minute. After refluxing for 1 hour, the reaction solution is concentrated, separated and purified by column chromatography, and 1-benzyl-3-
16.9 g (90.4%) of methyl-5-aminopyrazole was obtained. Melting point 69 to 70 ° C. Elemental analysis value as C 11 H 13 N 3 Calculated value (%) C: 70.56 H: 7.00 N: 22.44 Measured value (%) C: 70.58 H: 7.02 N: 22.38
フロントページの続き (72)発明者 中山 憲卓 東京都日野市さくら町１番地 小西六写真 工業株式会社内 審査官 塚中 直子Front Page Continuation (72) Inventor Kenzoku Nakayama No. 1 Sakura-cho, Hino City, Tokyo Konishi Roku Photo Industry Co., Ltd. Examiner Naoko Tsukanaka
Claims (2)
酸塩も含む）とヒドラジン誘導体とを反応させることを
特徴とする５−アミノピラゾール系化合物の製造方法。1. A process for producing a 5-aminopyrazole compound, which comprises reacting an α-acyl acetic acid imino ester (including a proton acid salt) with a hydrazine derivative.
一般式[I]で、ヒドラジン誘導体が下記一般式[II]で、
５−アミノピラゾール系化合物が下記一般式[III]で示
される特許請求の範囲第１項記載の５−アミノピラゾー
ル系化合物の製造方法。 一般式[I] ［式中Ｒ1は、それぞれ置換基を有してもよいアルキル
基、シクロアルキル基、アリール基またはヘテロ環基を
表し、Ｒ2は１級アルキル基を表す。Ａはｍ塩基プロト
ン酸を表し（ｍは１〜４の整数）、ｎは０または1/mを
表す。］ 一般式[II] Ｒ3−NHNH2 ［式中Ｒ3は水素原子、それぞれ置換基を有してもよい
アルキル基、アリール基またはヘテロ環基を表す。］ 一般式[III] ［式中Ｒ1およびＲ3は前記Ｒ1およびＲ3と同義であ
る。］2. The α-acyl acetic acid imino ester has the following general formula [I] and the hydrazine derivative has the following general formula [II]:
The method for producing a 5-aminopyrazole compound according to claim 1, wherein the 5-aminopyrazole compound is represented by the following general formula [III]. General formula [I] [In the formula, R 1 represents an alkyl group which may have a substituent, a cycloalkyl group, an aryl group or a heterocyclic group, and R 2 represents a primary alkyl group. A represents an m-base protonic acid (m is an integer of 1 to 4), and n represents 0 or 1 / m. General formula [II] R 3 -NHNH 2 [wherein R 3 represents a hydrogen atom, respectively an optionally substituted alkyl group, an aryl group or a heterocyclic group. ] General formula [III] [In the formula, R 1 and R 3 have the same meaning as the above R 1 and R 3 . ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7783885A JPH0613475B2 (en) | 1985-04-11 | 1985-04-11 | Method for producing 5-aminopyrazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7783885A JPH0613475B2 (en) | 1985-04-11 | 1985-04-11 | Method for producing 5-aminopyrazole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61236768A JPS61236768A (en) | 1986-10-22 |
| JPH0613475B2 true JPH0613475B2 (en) | 1994-02-23 |
Family
ID=13645185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7783885A Expired - Lifetime JPH0613475B2 (en) | 1985-04-11 | 1985-04-11 | Method for producing 5-aminopyrazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613475B2 (en) |
-
1985
- 1985-04-11 JP JP7783885A patent/JPH0613475B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61236768A (en) | 1986-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6431088B2 (en) | Process for producing 3,5-bis (haloalkyl) pyrazole derivatives from α, α-dihaloamines and ketimines | |
| JPH0613475B2 (en) | Method for producing 5-aminopyrazole compound | |
| Hovakimyan et al. | Synthesis of pyridazinone derivatives | |
| JPH0672142B2 (en) | Method for producing 4-amino-1,2,4-triazoline-5-thione compound | |
| JPS61249968A (en) | 5-hydrazino-1h-pyrazole based compound | |
| Hassaneen et al. | Functionally substituted enamines as building blocks in heterocyclic synthesis: reactivity of glyoxal diphenylhydrazone toward electrophilic reagents | |
| Smith et al. | Amidrazones 13. A Convenient Method for the Preparation of 1-Alkyl-1-methylhydrazines | |
| US5235058A (en) | 3(5)-hydrazinopyrazole compounds | |
| JPH07267932A (en) | 5-amino-1h-pyrazole compound | |
| JPH0743522B2 (en) | Method for synthesizing photographic magenta coupler using 5-amino-1H-pyrazole compound | |
| JPH07109260A (en) | Production of 5-amino-2-nitropyridine derivative and 5-diamond-3-hydroxypyridine derivative | |
| JP2563231B2 (en) | Method for synthesizing 1H-pyrazolo [1,5-b] -1,2,4-triazole derivative | |
| EP0464736B1 (en) | A process for producing 5-amino-4-halogeno-1H-pyrazole compounds | |
| Collins et al. | Dihydro-1, 2, 4-triazin-6 (1 H)-ones. II Synthesis of Several Methylated 3-Phenyl-4, 5-dihydro-1, 2, 4-triazin-6 (1 H)-ones | |
| JPH0637477B2 (en) | 5-hydrazino-1H-pyrazole compound | |
| WO1997047608A1 (en) | Process for producing 2-(1h-1,2,4-triazol-1-yl)acetophenones | |
| JPH01190668A (en) | Production of 5-amino-1-phenyl-4-nitropyrazole | |
| US6562979B1 (en) | Process for the preparation of substituted benzisothiazole compounds | |
| JPH01287073A (en) | Production of 5-amino-1h pyrazole compound | |
| JP2003300963A (en) | Method for producing 5-amino-4-nitrosopyrazole derivative | |
| JPS61251684A (en) | Production of 1h-pyrazolo(3,2-c)-1,2,4-triazole compound | |
| JPH04253964A (en) | Production of 5-amino-1h-pyrazoles | |
| JPH0442397B2 (en) | ||
| JPH0655726B2 (en) | 4-Halo-pyrazolone-5 imino derivative and process for producing the same | |
| JPS63101386A (en) | Production of 1h-pyrazolo(3,2c)-1,2,4-triazole compound |