JPH0743522B2 - Method for synthesizing photographic magenta coupler using 5-amino-1H-pyrazole compound - Google Patents
Method for synthesizing photographic magenta coupler using 5-amino-1H-pyrazole compoundInfo
- Publication number
- JPH0743522B2 JPH0743522B2 JP60148555A JP14855585A JPH0743522B2 JP H0743522 B2 JPH0743522 B2 JP H0743522B2 JP 60148555 A JP60148555 A JP 60148555A JP 14855585 A JP14855585 A JP 14855585A JP H0743522 B2 JPH0743522 B2 JP H0743522B2
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- Prior art keywords
- amino
- group
- compound
- pyrazole compound
- pyrazole
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/381—Heterocyclic compounds
- G03C7/382—Heterocyclic compounds with two heterocyclic rings
- G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
- G03C7/3835—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms four nitrogen atoms
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は新規な5−アミノ−1H−ピラゾール系化合物に
関し、更に詳しくは写真用カプラーの中間体として有用
な5−アミノ−1H−ピラゾール系化合物に関するもので
ある。TECHNICAL FIELD The present invention relates to a novel 5-amino-1H-pyrazole compound, and more specifically to a 5-amino-1H-pyrazole compound useful as an intermediate for a photographic coupler. Is.
5−アミノ−1H−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、本発明の化合物をジアゾ化し還元して
得られる5−ヒドラジノ−1H−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。The 5-amino-1H-pyrazole compounds are useful compounds as starting materials for photographic couplers, especially magenta couplers. That is, 5-hydrazino-1H-pyrazoles obtained by diazotizing and reducing the compound of the present invention are acylated by acid chloride or hydrazone reacted with aldehyde by ring closure to give 1H-pyrazolo
Although 2-c] -1,2,4-triazoles can be synthesized, they have recently attracted attention as magenta couplers having no secondary absorption.
5−アミノ−1H−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,182〜198
頁(1947年)、ジュルナール・オブスカイ・キミィ(Z
h.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。For the synthesis of 5-amino-1H-pyrazole compounds, see, for example, Journal of the Chemical Society (J. Chem. Soc.), 1941, p. 2857, Gazzetta Chimika Italiana. .), 77, 182-198
Page (1947), Journal of Sky Kimi (Z
h.Obsch.Khim.), 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
ないと云う問題があった。However, there is a problem in that no synthesis can be performed 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.
本発明の目的は、5−アミノ−1Hピラゾール系化合物を
提供することにあり、更に詳しくは写真用カプラーの中
間体として有用な5−アミノ−1H−ピラゾール系化合物
を提供することにある。An object of the present invention is to provide a 5-amino-1H-pyrazole compound, more specifically to provide a 5-amino-1H-pyrazole compound useful as an intermediate for a photographic coupler.
下記一般式〔I〕で表される5−アミノ−1H−ピラゾー
ル系化合物は、優れた写真用カプラーを広範囲にかつ高
収率で製造できる中間体として有用である。The 5-amino-1H-pyrazole type compound represented by the following general formula [I] is useful as an intermediate which can produce an excellent photographic coupler in a wide range and in a high yield.
一般式〔I〕 式中、R1は炭素原子数3〜30の3級アルキル基または3
級のシクロアルキル基を表し、Xは水素原子またはハロ
ゲン原子を表す。Aはプロトン酸を表しnは0または正
数を表す。General formula [I] In the formula, R 1 is a tertiary alkyl group having 3 to 30 carbon atoms or 3
Represents a primary cycloalkyl group, and X represents a hydrogen atom or a halogen atom. A represents a protonic acid and n represents 0 or a positive number.
以下、より具体的に本発明を説明する。Hereinafter, the present invention will be described more specifically.
一般式〔I〕においてR1で表される炭素原子数3〜30の
3級アルキル基は置換されているものもよく、具体的に
はt−ブチル基、β−エチルスルホニル−α,α−ジメ
チルエチル基、γ−ベンジルスルホニル−α,α−ジメ
チルプロピル基、β−ドデシルスルホニル−α,α−ジ
メチルエチル基、γ−フェノキシ−α,α−ジメチルプ
ロピル基等が挙げられる。In the general formula [I], the tertiary alkyl group having 3 to 30 carbon atoms represented by R 1 may be substituted, and specifically, t-butyl group, β-ethylsulfonyl-α, α- Examples thereof include a dimethylethyl group, γ-benzylsulfonyl-α, α-dimethylpropyl group, β-dodecylsulfonyl-α, α-dimethylethyl group and γ-phenoxy-α, α-dimethylpropyl group.
R1で表される炭素原子数3〜12のシクロアルキル基とし
ては、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。Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R 1 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and a cyclododecyl group.
一般式〔I〕においてXで表されるハロゲン原子として
は、例えば塩素原子、臭素原子、沃素原子、弗素原子が
挙げられるが、塩素原子、臭素原子が好ましく、より好
ましくは塩素原子である。Examples of the halogen atom represented by X in the general formula [I] include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, but a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.
一般式〔I〕で示される5−アミノ−1H−ピラゾール系
化合物は、プロトン酸により塩を形成することができ
る。このことは本発明の重要構成要素ではなく、広範囲
の有機酸、無機酸が用いられる。代表的なものとして、
塩酸、臭化水素酸、硫酸、酢酸、メタンスルホン酸、p
−トルエンスルホン酸、ピクリン酸、ピロメリティック
酸等を挙げることができる。The 5-amino-1H-pyrazole compound represented by the general formula [I] can form a salt with a protic acid. This is not an important component of the present invention, and a wide range of organic and inorganic acids are used. As a typical one,
Hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid, p
-Toluenesulfonic acid, picric acid, pyromellitic acid and the like can be mentioned.
本発明の5−アミノ−1H−ピラゾール系化合物はα−ア
シル酢酸イミノエステルとヒドラジンとの反応によって
得られる。α−アシル酢酸イミノエステルは対応するア
シルアセトニトリルをアルコール中で塩酸ガスと反応さ
せることによって得られる。アシルアセトニトリル及び
α−アシル酢酸イミノエステルは、それぞれジャーナル
・オブ・ザ・アメリカン・ケミカル・ソサイァティー
(J.Am.Chem.Soc.),56巻,1171〜1173頁(1934年)及び
ベリヒテ(Ber.),44巻,2065〜2069頁(1911年)に記載
の方法及びその他の方法により合成することができる。The 5-amino-1H-pyrazole compound of the present invention can be obtained by the reaction of α-acyl acetic acid imino ester with hydrazine. The α-acyl acetic acid imino ester is obtained by reacting the corresponding acyl acetonitrile with hydrochloric acid gas in alcohol. Acylacetonitrile and α-acylacetic acid iminoesters are described in Journal of the American Chemical Society (J. Am. Chem. Soc.), 56, 1171-1173 (1934) and Berichte (Ber. ), 44, 2065-2069 (1911) and other methods.
本発明の5−アミノ−1H−ピラゾール系化合物を合成す
る代表的反応スキームを以下に示す。A typical reaction scheme for synthesizing the 5-amino-1H-pyrazole compound of the present invention is shown below.
(上記スキーム中、R1はいづれも一般式〔I〕で示した
基と同義でありXについては水素原子及び塩素原子の例
を代表例として示した。) アシル酢酸イミノエステルとヒドラジンは、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、ハロゲン化炭化水素、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。 (In the above scheme, R 1 has the same meaning as the group represented by the general formula [I], and X represents a hydrogen atom or a chlorine atom as a representative example.) Acylacetic acid iminoester and hydrazine react with each other. At that time, it is used by being dispersed in a dispersion medium. As the dispersion medium that can be used, compounds having no ester bond such as carbonyl groups and ethyl acetate such as ketones and aldehydes, such as alcohols, benzenes, ethers, halogenated hydrocarbons, amides, etc. It can be mentioned as a representative. 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のアミノ
基と結合し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 hydrazine. Further, ethyl acetate is not preferred because the carbonyl group is bonded to the amino group of hydrazine 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。ハロゲン化炭化水素として
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 halogenated hydrocarbon include carbon tetrachloride, chloroform and bromoform, and examples of the amides include formamide, N, N-
Examples thereof include 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 1-1000 parts by weight, preferably 5-100, per 1 part by weight of α-acyl acetic acid imino ester or hydrazine.
It is contained in a ratio of parts by weight.
α−アシル酢酸イミノエステルとヒドラジンは、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0〜1
00℃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。α-acyl acetic acid imino ester and hydrazine are 1: 0.5
It is used in a molar ratio of ˜1: 15, preferably in the range of 1: 2 to 1: 5. The reaction temperature is preferably −20 to 200 ° C., particularly 0 to 1
The range of 00 ° C is preferred. Further, in order to complete the reaction, the temperature is preferably once 40 ° C. or higher.
次に本発明の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。Next, representative compounds of the present invention are exemplified below, but the present invention is not limited thereto.
本発明の5−アミノ−1H−ピラゾール系化合物より写真
用マゼンタカプラー1H−ピラゾロ〔3,2−c〕−1,2,4−
トリアゾール系化合物に至る合成経路は次の如くであ
る。 From the 5-amino-1H-pyrazole compound of the present invention, a photographic magenta coupler 1H-pyrazolo [3,2-c] -1,2,4-
The synthetic route leading to the triazole-based compound is as follows.
(上記経路中、R1、X、nおよびAは一般式〔I〕で説
明したものと同義であり、R2はアルキル基、Yは塩素原
子またはヒドロキシ基を表す。) このようにして得られる1H−ピラゾロ〔3,2−c〕−1,
2,4−トリアゾール系化合物は、カラー写真感光材料に
用いられるマゼンタカプラーとして従来最も多く使用さ
れてきた5−ピラゾロン系カプラーにみられる430nm近
辺の2次吸収がない、或いは長波長部の切れがシャープ
な点で近年注目されているカプラーである。 (In the above route, R 1 , X, n and A have the same meanings as those described in the general formula [I], R 2 represents an alkyl group, and Y represents a chlorine atom or a hydroxy group.) 1H-pyrazolo [3,2-c] -1,
The 2,4-triazole-based compound does not have the secondary absorption around 430 nm or the long-wavelength cut-off, which is observed in the 5-pyrazolone-based coupler which has been most often used as a magenta coupler used in a color photographic light-sensitive material. It is a coupler that has been attracting attention in recent years due to its sharpness.
本発明の化合物より誘導される6位に3級アルキル基ま
たは3級のシクロアルキル基を有する1H−ピラゾロ〔3,
2,c〕−1,2,4−トリアゾール系カプラーは、特に耐光性
に優れたマゼンタ色素を形成する有用な写真用カプラー
である。これらのカプラーを従来の製造法により合成し
ようとしても、非常に低収率であるか或いは全然得られ
ず工業化が困難であった。1H-pyrazolo [3, having a tertiary alkyl group or a tertiary cycloalkyl group at the 6-position derived from the compound of the present invention
2, c] -1,2,4-triazole couplers are useful photographic couplers which form magenta dyes having particularly excellent light resistance. Even if these couplers were attempted to be synthesized by conventional production methods, the yields were very low or they were not obtained at all, and industrialization was difficult.
次に本発明の5−アミノ−1H−ピラゾール系化合物より
誘導される1H−ピラゾロ〔3,2−c〕−1,2,4−トリアゾ
ール系化合物の代表的具体例を以下に示す。Next, typical examples of 1H-pyrazolo [3,2-c] -1,2,4-triazole compounds derived from the 5-amino-1H-pyrazole compounds of the present invention are shown below.
〔実施例〕 以下に本発明の化合物の合成および本発明の化合物から
誘導される写真用カプラーの合成について具体例を挙げ
て説明する。 [Examples] Hereinafter, the synthesis of the compound of the present invention and the synthesis of a photographic coupler derived from the compound of the present invention will be described with reference to specific examples.
合成例−1(例示化合物1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/l
濃度)を5℃以下で滴下する。同濃度で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、水洗後、硫酸マグネシウムで
クロロホルム層を乾燥し濃縮する。濃縮物はカラムクロ
マトグラフィーで分離精製し、5−アミノ−3−t−ブ
チル−1H−ピラゾールを得た。Synthesis Example-1 (Synthesis of Exemplified Compound 1) 20.8 g of α-pivaloyl acetic acid iminoethyl ester hydrochloride was added to 250 ml of a hydrazine alcohol solution (1 mol / l).
(Concentration) is added dropwise at 5 ° C or lower. The mixture is stirred at the same concentration for 30 minutes and then refluxed for 1 hour. 10 ml of water is added to the reaction solution, which is then concentrated, extracted with chloroform, washed with water, dried over magnesium sulfate to concentrate the chloroform layer. The concentrate was separated and purified by column chromatography to obtain 5-amino-3-t-butyl-1H-pyrazole.
合成例−2(例示化合物2の合成) 13.9gの5−アミノ−3−t−ブチル−1H−ピラゾール
を300mlのクロロホルムに溶解し、5℃以下に保ちなが
らN−クロロコハク酸イミド13.3gを徐々に添加した。3
0分攪拌後、反応液を100mlの水で2回水洗する。クロロ
ホルム層を硫酸マグネシウムで乾燥後クロロホルムを減
圧留去する。残渣をクロロホルム−n−ヘキサン混液よ
り再結晶し5−アミノ−3−t−ブチル−4−クロロ−
1H−ピラゾールを得た。Synthesis Example-2 (Synthesis of Exemplified Compound 2) 13.9 g of 5-amino-3-t-butyl-1H-pyrazole was dissolved in 300 ml of chloroform, and 13.3 g of N-chlorosuccinimide was gradually added while keeping the temperature below 5 ° C. Was added to. 3
After stirring for 0 minutes, the reaction solution is washed twice with 100 ml of water. The chloroform layer is dried over magnesium sulfate and chloroform is distilled off under reduced pressure. The residue was recrystallized from a mixed solution of chloroform-n-hexane to give 5-amino-3-t-butyl-4-chloro-.
1H-pyrazole was obtained.
上記合成例からも明らかなように、従来合成できなかっ
た5−アミノ−3−分岐アルキル又はシクロアルキル−
1H−ピラゾール系化合物が好ましい収率で得られる。As is clear from the above Synthesis Examples, 5-amino-3-branched alkyl or cycloalkyl-which could not be conventionally synthesized.
The 1H-pyrazole compound is obtained in a favorable yield.
その他の例示化合物も同様の方法で得ることができた。
それらの特性値を表−1に示す。Other exemplified compounds could be obtained by the same method.
The characteristic values are shown in Table 1.
合成例−3 17.4gの例示化合物2を150mlの6N塩酸に溶解し、−5〜
0℃で7gの亜硝酸ナトリウムを含む水溶液20gを滴下す
る。30分後、更に50gの塩化錫・2水塩を35mlの濃塩酸
に溶解した溶液を−5〜0℃で滴下する。その後、同温
度で30分攪拌し析出する結晶を濾取、6N塩酸より再結晶
し、結晶を得、得られた結晶11.2gを100mlのアセトニト
リルに分散し、−5℃を保ちながら16gのトリエチルア
ミンを加える。更に8.1gのオクタノイルクロリドを20ml
のアセトニトリルに溶解した液を−5℃以下で滴下す
る。反応液を濃縮したのちカラムクロマトグラフィーで
分離精製し、カラメル状の目的物を得た。 Synthesis example-3 17.4 g of Exemplified Compound 2 was dissolved in 150 ml of 6N hydrochloric acid,
20 g of an aqueous solution containing 7 g of sodium nitrite is added dropwise at 0 ° C. After 30 minutes, a solution of 50 g of tin chloride dihydrate in 35 ml of concentrated hydrochloric acid is added dropwise at -5 to 0 ° C. After that, the mixture was stirred at the same temperature for 30 minutes, and the precipitated crystals were collected by filtration and recrystallized from 6N hydrochloric acid to obtain crystals. 11.2 g of the obtained crystals were dispersed in 100 ml of acetonitrile, and 16 g of triethylamine was maintained at -5 ° C. Add. 20 ml of 8.1 g of octanoyl chloride
The solution dissolved in acetonitrile of is added dropwise at -5 ° C or lower. The reaction solution was concentrated and then purified by column chromatography to obtain a caramel-like target product.
CH15H27ClN4Oとしての元素分析値 計算値(%)C:57.22 H:8.65 N:17.80 Cl:11.26 実測値(%)C:57.18 H:8.59 N:17.83 Cl:11.25 FDマススペクトル値は314を示した。CH 15 H 27 ClN 4 O Elemental analysis value Calculated value (%) C: 57.22 H: 8.65 N: 17.80 Cl: 11.26 Measured value (%) C: 57.18 H: 8.59 N: 17.83 Cl: 11.25 FD Mass spectrum value Showed 314.
核磁気共鳴スペクトル(溶媒CDCl3)のδ値が0.85(3H,
t) 1.22(8H,m) 1.32(9H,s) 1.51(2H,m) 2.0
8(2H,t) 6.57(1H,d) 8.73(1H,d)を示し、FDマ
ススペクトルと共に上記の構造を支持した。The δ value of the nuclear magnetic resonance spectrum (solvent CDCl 3 ) is 0.85 (3H,
t) 1.22 (8H, m) 1.32 (9H, s) 1.51 (2H, m) 2.0
8 (2H, t) 6.57 (1H, d) 8.73 (1H, d) was shown, supporting the above structure with FD mass spectrum.
合成例−4(例示カプラーM−1の合成) 6.2gの3−t−ブチル−4−クロロ−5−オクタノイル
ヒドラジノ−1H−ピラゾール(合成例−6で得られた化
合物)を60mlのベンゼン、3.2gのオキシ塩化燐と共に攪
拌下に3時間還流する。反応液をカラムクロマトグラフ
ィーで分離精製し、4.1g(69%)の6−t−ブチル−7
−クロロ−3−ヘプチル−1H−ピラゾロ〔3,2−c〕−
1,2,4−トリアゾールを得た。Synthesis Example-4 (Synthesis of Exemplified Coupler M-1) 6.2 g of 3-t-butyl-4-chloro-5-octanoylhydrazino-1H-pyrazole (the compound obtained in Synthesis Example-6) was added to 60 ml. Reflux with benzene and 3.2 g of phosphorus oxychloride for 3 hours with stirring. The reaction solution was separated and purified by column chromatography to give 4.1 g (69%) of 6-t-butyl-7.
-Chloro-3-heptyl-1H-pyrazolo [3,2-c]-
1,2,4-triazole was obtained.
融点46〜49℃ CH15H25N4Clとしての元素分析値 計算値(%)C:60.69 H:8.49 Cl:11.94 N:18.88 実測値(%)C:60.61 H:8.52 Cl:11.89 N:18.84 FDマススペクトル値は296を示した。Melting point 46-49 ° C Elemental analysis value as CH 15 H 25 N 4 Cl Calculated value (%) C: 60.69 H: 8.49 Cl: 11.94 N: 18.88 Measured value (%) C: 60.61 H: 8.52 Cl: 11.89 N: 18.84 The FD mass spectrum value was 296.
核磁気共鳴スペクトル(溶媒CDCl3)のδ値が0.86(3H,
t) 1.26(8H,m) 1.43(9H,s) 1.85(2H,m) 2.9
3(2H,t) 9.68(1H,s)を示しFDマススペクトルと共
に上記構造を支持した。The δ value of the nuclear magnetic resonance spectrum (solvent CDCl 3 ) is 0.86 (3H,
t) 1.26 (8H, m) 1.43 (9H, s) 1.85 (2H, m) 2.9
3 (2H, t) 9.68 (1H, s) was shown to support the above structure with FD mass spectrum.
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 (56)参考文献 特開 昭56−158768(JP,A) 特開 昭59−29669(JP,A) 特開 昭60−100581(JP,A) 欧州公開49071(EP,A) Tetrahedron Lett. (13),1101〜1104(1975) J.Chem.Soc.,Perkin Trans.1(12)2997〜3001 (1981)Continuation of the front page (72) Inventor Kenzo Nakayama 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Co., Ltd. Examiner Naoko Tsukanaka (56) Reference JP-A-56-158768 (JP, A) JP 59-29669 (JP, A) JP 60-100581 (JP, A) European publication 49071 (EP, A) Tetrahedron Lett. (13), 1101 to 1104 (1975) J. Chem. Soc. , Perkin Trans. 1 (12) 2997-3001 (1981)
Claims (1)
1H−ピラゾール系化合物を用いる写真用マゼンタカプラ
ーの合成方法。 一般式〔I〕 〔式中、R1は炭素原子数3〜30の3級アルキル基または
炭素原子数3〜12の3級のシクロアルキル基を表す。X
は水素又はハロゲンを表し、Aはプロトン酸を表し、n
は0または正数を表す。〕1. A 5-amino-represented by the following general formula [I]:
A method for synthesizing a magenta coupler for photography using a 1H-pyrazole compound. General formula [I] [In the formula, R 1 represents a tertiary alkyl group having 3 to 30 carbon atoms or a tertiary cycloalkyl group having 3 to 12 carbon atoms. X
Represents hydrogen or halogen, A represents a protic acid, and n
Represents 0 or a positive number. ]
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JPS6210069A JPS6210069A (en) | 1987-01-19 |
JPH0743522B2 true JPH0743522B2 (en) | 1995-05-15 |
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JPS56158768A (en) * | 1980-05-09 | 1981-12-07 | Nissan Chem Ind Ltd | Substituted pyrazole derivative and industrial antimicrobial and antifungal agent containing the same |
MA19269A1 (en) * | 1980-09-16 | 1982-04-01 | Lilly Co Eli | IMPROVEMENT RELATING TO N-ARYLBENZAMIDE DERIVATIVES. |
JPS5929669A (en) * | 1982-08-13 | 1984-02-16 | Showa Denko Kk | Aminopyrazole derivative |
JPS59171956A (en) * | 1983-03-18 | 1984-09-28 | Fuji Photo Film Co Ltd | Formation of color image |
JPS6033552A (en) * | 1983-08-04 | 1985-02-20 | Fuji Photo Film Co Ltd | Color image forming method |
JPS60100581A (en) * | 1983-11-07 | 1985-06-04 | S D S Baiotetsuku:Kk | Pyrazolo(1,5-a)pyrimidine derivative, agricultural and horticultural fungicide containing the same, and its preparation |
JPS60197688A (en) * | 1984-03-22 | 1985-10-07 | Fuji Photo Film Co Ltd | Preparation of pyrazolo(1,5-b)(1,2,4)triazole derivative |
JPS60215687A (en) * | 1984-04-10 | 1985-10-29 | Fuji Photo Film Co Ltd | Production of pyrazolo(1,5-b)(1,2,4)triazole derivative |
JPS6165245A (en) * | 1984-09-06 | 1986-04-03 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JPS61145163A (en) * | 1984-12-19 | 1986-07-02 | Fuji Photo Film Co Ltd | Production of n-pyrazolylamidoxime compound |
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1985
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Non-Patent Citations (2)
Title |
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J.Chem.Soc.,PerkinTrans.1(12)2997〜3001(1981) |
TetrahedronLett.(13),1101〜1104(1975) |
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