5-氧代-1-苯基-2,5-二氢-1H-吡唑-3-羧酸 | 49597-17-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 5-氧代-1-苯基-2,5-二氢-1H-吡唑-3-羧酸
• 英文名称: 5-oxo-1-phenyl-2,5-dihydro-1H-pyrazole-3-carboxylic acid
• 英文别名: 1-phenylpyrazol-5-one-3-carboxylic acid；1-Phenyl-3-carboxy-pyrazol-5-on；1-phenyl-5-pyrazolone-3-carboxylic acid；1-phenyl-3-carboxypyrazol-5-one；1-phenyl-3-carboxy-5-pyrazolone；5-Oxo-1-phenyl-2,5-dihydro-1H-pyrazol-3-carbonsaeure；1-Phenyl-pyrazolon-(5)-carbonsaeure-(3)；3-carboxy-1-phenyl-5-pyrazolone；5-oxo-1-phenyl-2,5-dihydro-1H-pyrazole-3-carboxylic acid；3-oxo-2-phenyl-1H-pyrazole-5-carboxylic acid
• CAS: 49597-17-3
• 化学式: C₁₀H₈N₂O₃
• mdl: MFCD02929824
• 分子量: 204.185
• InChiKey: SIVDWYOIVRKZPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  69.6
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 海关编码：
  2933199090
• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P305+P351+P338,P330,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  5-氧代-1-苯基-2,5-二氢-1H-吡唑-3-羧酸 在 氯化亚砜 、 乙醇 作用下， 生成 5-oxo-1-phenyl-2,5-dihydro-1H-pyrazole-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Koike et al., Kogyo Kagaku zasshi / Journal of the Society of Chemical Industry, 1954, vol. 57, p. 123

  摘要：

  DOI：
• 作为产物：
  描述：

  5-oxo-1-phenylpyrazolidine-3-carboxylic acid 以93.5%的产率得到5-氧代-1-苯基-2,5-二氢-1H-吡唑-3-羧酸
  参考文献：
  名称：

  Process for the manufacture of pyrazolones from pyrazolidones

  摘要：

  一种制备式为：##STR1## 其中R为芳香基团，R.sup.1为烷基，羧酸，氨基甲酰基或羧酸酯基的吡唑酮的方法，包括在碱的存在下用过氧化氢处理式为：##STR2## 其中R和R.sup.1具有上述所述含义的吡唑酮。这种新工艺提供了一种制备吡唑酮的方法，避免了使用β-酮酸酯。在许多情况下，它提供了一条比工业中已建立的方法更便宜的途径来制备这些有价值的化合物。

  公开号：

  US04081597A1

文献信息

• Pigment compositions for solvent and water-based ink systems and the methods for producing them
  申请人：HOECHST CELANESE CORPORATION

  公开号：EP0592907A1

  公开（公告）日：1994-04-20

  This invention is an azo pigment composition containing a water insoluble metal salt of a water soluble polymer; a method of preparing said composition and ink compositions prepared from said azo pigment compositions.

  这项发明是一种含有水不溶性金属盐的水溶性聚合物的偶氮颜料组合物；一种制备该组合物的方法以及由该偶氮颜料组合物制备的油墨组合物。
• 1-Hexzl-1H-Pyrazole-4,5-Diamine Hemisulfate, and Its Use in Dyeing Compositions
  申请人：The Procter & Gamble Company

  公开号：US20130212810A1

  公开（公告）日：2013-08-22

  1-hexyl-1H-pyrazole-4,5-diamine hemisulfate, as represented in formula (IX-a), and its use in oxidative dyeing composition. This pyrazole salt was found to combine good stability as raw material and good shade intensity with a range of common couplers when formulated in hair dyeing composition.

  1-己基-1H-吡唑-4,5-二胺硫酸半盐，如式（IX-a）所示，并其在氧化染料组合物中的应用。这种吡唑盐在头发染料组合物中配方时，发现它既具有良好的原料稳定性，又能与一系列常见的偶联剂结合，呈现出良好的色泽强度。
• Stable Yellow Imidazolium Compounds
  申请人：NOXELL COPRORATION

  公开号：US20180079907A1

  公开（公告）日：2018-03-22

  Described herein is a yellow imidazolium chromophore having a structure according to Formula V.

  本文描述了一种具有如下V式结构的黄色咪唑铵色团。
• [EN] CATIONIC DIRECT DYES<br/>[FR] COLORANTS DIRECTS CATIONIQUES
  申请人：BASF SE

  公开号：WO2016146813A1

  公开（公告）日：2016-09-22

  The invention relates to cationic direct dyes of the formula I (1), wherein m and n are independently from each other 0 or 1, D is an aromatic or a cationic heteroaromatic group, which are further specified, K is an aromatic or heteroaromatic group, E1 and E2 are independently from each other =CH- or =N-, An is an anion and a is a number from 1 to 6 and R1 and R2 are independently from each other and further specified. The compounds show washfastness at hair-dying.

  这项发明涉及公式I（1）的阳离子直接染料，其中m和n分别独立于0或1，D是芳香或阳离子杂芳基，进一步具体说明，K是芳香或杂芳基，E1和E2分别独立于=CH-或=N-，An是阴离子，a是1到6之间的数字，R1和R2分别独立于彼此并进一步具体说明。这些化合物在染发时表现出良好的耐洗性。
• Production of pyrazole-5-ones
  申请人：ILFORD LTD

  公开号：US02459226A1

  公开（公告）日：1949-01-18

  Pyrazole-5-ones are manufactured by reacting a diazonium compound with a compound of the formula wherein R1 and R2 represent the same or different groups -COOR, -CN, -COR or -CONHR, and R and R3 represent hydrogen or hydrocarbon or substituted hydrocarbon groups and may be the same or different, the reaction being effected in the presence of a weak base and completed, if necessary, by heating in the presence of a stronger base, or being effected with a quantity of diazonium compound less than two molecular equivalents (calculated with regard to the number of diazo groups present) per molecular equivalent of the other reactant and in the presence of a strong base, separating the product obtained and allowing it to stand at room temperature or elevated temperature to permit molecular rearrangement and ring-closure. The diazonium compound may be derived from a monoamine, in which case it is preferable to use equimolecular proportions of the reactants and the reaction takes place in accordance with the equation wherein R4 is an aryl, substituted aryl or heterocyclic residue and Y is an acid grouping. Alternatively, diazonium compounds containing more than one diazo group may be employed, in which case the maximum molar porportion thereof when using strong alkali is correspondingly reduced and the products contain more than one pyrazolone residue in the molecule. When the group R2 in the product is an ester or nitrile group it may be subsequently hydrolysed to a carboxylic acid group -COOH. Small quantities of azo dyestuffs with which the products may be contaminated may be removed by filtering an alkali solution of the product and reprecipitating the pyrazolone by the addition of acid. The products may be used as dyestuff intermediates, e.g. for the production of azo dyes (by reaction with diazonium compounds, which may be the same as or different from those used in making the pyrazolones), of azo-methine dyestuffs (e.g. in processes of colour photography) or of merocyanine dyes. In examples: (1) aniline is diazotized and treated with an equimolecular proportion ethyl acetosuccinate in the presence of sodium hydroxide solution, or (2) in alcoholic solution in the presence of sodium acetate, sodium carbonate or borax, or (3) in aqueous pyridine solution-yielding in each case 1-phenyl 3-carbethoxypyrazole-5-one; (4) and (5) benzidine is tetrazotized and treated as in (1) or (3) to give 4 : 41 - diphenylene - bis - (3-carbethoxy-pyrazole-5-one-1); (6) the ethyl acetosuccinate in (2) is replaced by ethyl methyl acetosuccinate, producing 1 - phenyl - 3 - carbomethoxypyrazole-5-one; (7) the ethyl acetosuccinate in (3) is replaced by ethyl b : b -diacetylpropionate, yielding 1-phenyl-3-acetylpyrazole-5-one; (8) the ethyl acetosuccinate in (3) is replaced by ethyl cyanosuccinate and the product is heated with sodium hydroxide solution to effect ring closure and hydrolysis and acidified to liberate 1-phenylpyrazole-5-one-3-carboxylic acid; (9) ethyl ethane-a : a : b -tricarboxylate similarly yields the same product; (10) the ethyl acetosuccinate in (2) is replaced by ethyl acetosuccinate-o-chloranilide, producing 1-phenylpyrazole-5-one-3-carboxylic acid o-chloranilide; (11) a -naphthylamine is diazotized and treated with ethyl acetosuccinate in ethyl alcohol in the presence of sodium acetate, and the product is heated with sodium hydroxide solution and acidified to yield 1-a -naphthylpyrazole-5-one-3-carboxylic acid; (12) b -naphthylamine is similarly treated; (13) the aniline in (3) is replaced by p-aminobenzenesulphonamide, producing 1-p-sulphonamidophenyl-3-carbethoxypyrazole-5-one; (14) dehydrothio-p-toluidine is diazotized and treated with ethyl acetosuccinate in aqueous pyridine solution, and the product is heated with sodium carbonate solution; (15) p-aminobenzoic acid is treated as in (3) to give 1-p-carboxyphenyl-3-carbethoxypyrazole-5-one; (16) sulphanilic acid is similarly treated and the product is heated with sodium hydroxide to yield the di-sodium salt of 1-p-sulphophenylpyrazole-5-one-3-carboxylic acid; (17) p-nitraniline is diazotized and treated as in (14), producing 1 - p - nitrophenyl - 3 - carboxy - pyrazole-5-one. Additional starting materials specified are, on the one hand, the diazo and tetrazo compounds of toluidines, xylidines, naphthionic acid, p - aminobenzyldimethyl - amine, m-aminophenyldimethylamine, m-nitraniline, p-aminophenol, aminonaphtholsulphonic acids, aminoazobenzene and its sulphonic acids, tolidines, p : p1-diaminostilbene, p : p1-diaminodiphenylamine, 2 : 7 - diaminocarbazole, 2 : 7 - diaminofluorene, p : p1 - diaminoazobenzene, p - phenylenediamine, 1 : 4- and 1 : 5-diaminonaphthalenes and dehydrothio-p-toluidinesulphonic acid, and, on the other hand, ethyl acetosuccinate-anilide. Acids and esters of the general formula are obtainable by the interaction of an alkali metal derivative (which may be formed in situ) of a reactive methylene compound R1-CH2-R2 with a monohalogen acetic acid or ester XCH2.COOR3 (where X represents a halogen atom), e.g. by the action of ethyl chloracetate on diethyl malonate, ethyl or methyl acetoacetate, ethyl cyanacetate, acetylacetone or acetoacetanilide in the presence of an alkali metal (e.g. sodium) ethoxide, or on sodio acetoacet-o-chloranilide in ethyl alcohol. The ethyl chloracetate may be replaced by the corresponding bromo or iodo derivatives or by the free acids. Specifications 544,647, 549,202, 553,144, 555,936 and 585,781 are referred to.

  吡唑酮-5-酮通过将重氮化合物与式的化合物反应制备，其中R1和R2代表相同或不同的基团-COOR、-CN、-COR或-CONHR，R和R3代表氢或烃或取代烃基团，可以相同也可以不同，反应在弱碱存在下进行，并在必要时通过在强碱存在下加热来完成，或者在使用不超过另一反应物的每分子当量对应的两分子当量以下（根据存在的重氮基团数量计算）的重氮化合物的情况下，在强碱存在下进行，分离得到的产物并使其在室温或升高温度下静置，以促使分子重排和环闭合。重氮化合物可以源自单胺，此时最好使用等分子比例的反应物，并且反应按照方程式进行，其中R4是芳基、取代芳基或杂环残基，Y是酸基团。另外，也可以使用含有多个重氮基团的重氮化合物，此时在使用强碱时其最大摩尔比例相应减少，并且产物分子中含有多个吡唑酮残基。当产物中的R2基团是酯基或腈基时，可以随后水解为羧基-COOH。产物可能受到的少量偶氮染料污染可以通过过滤产物的碱性溶液并通过加酸重新沉淀吡唑酮来去除。这些产物可以用作染料中间体，例如用于制备偶氮染料（通过与重氮化合物反应，这些重氮化合物可能与制备吡唑酮时使用的相同或不同），偶氮-亚甲染料（例如在彩色摄影过程中）或梅洛氰染料。在示例中：（1）苯胺经重氮化处理，并与等分子比例的乙酰琥珀酸乙酯在氢氧化钠溶液存在下反应，或者（2）在醇溶液中在存在钾醋酸钠、碳酸钠或硼砂的情况下处理，或者（3）在水合吡啶溶液中，每种情况下产生1-苯基-3-羧乙氧基吡唑酮-5-酮；（4）和（5）联苯二胺经四重重氮化处理并如同（1）或（3）中处理以得到4：41-二苯基-双-(3-羧乙酰基吡唑酮-5-酮-1)；（6）（2）中的乙酰琥珀酸乙酯被乙基乙酸琥珀酸乙酯替换，产生1-苯基-3-羧甲氧基吡唑酮-5-酮；（7）（3）中的乙酰琥珀酸乙酯被乙基b:b-二乙酰丙酸酯替换，产生1-苯基-3-乙酰基吡唑酮-5-酮；（8）（3）中的乙酰琥珀酸乙酯被乙基氰基琥珀酸乙酯替换，并且产物与氢氧化钠溶液加热以实现环闭合和水解，并加酸使其游离出1-苯基吡唑酮-5-酮-3-羧基；（9）乙基乙烷-a:a:b-三羧酸酯类似地产生相同的产物；（10）（2）中的乙酰琥珀酸乙酯被乙酰琥珀酸乙酯-o-氯醌酰胺替换，产生1-苯基吡唑酮-5-酮-3-羧基氯醌酰胺；（11）α-萘胺经重氮化处理，并与醇溶液中的乙酰琥珀酸乙酯在存在钾醋酸钠的情况下反应，产物与氢氧化钠溶液加热并加酸得到1-α-萘基吡唑酮-5-酮-3-羧基；（12）β-萘胺类似地处理；（13）（3）中的苯胺被p-氨基苯磺酰胺替换，产生1-p-磺酰胺基苯基-3-羧乙氧基吡唑酮-5-酮；（14）脱氢硫代-p-甲基苯胺经重氮化处理，并与水合吡啶溶液中的乙酰琥珀酸乙酯反应，产物与碳酸钠溶液加热；（15）对氨基苯甲酸如同（3）中处理得到1-p-羧基苯基-3-羧乙氧基吡唑酮-5-酮；（16）磺酸胺基甲酸类似处理，产物与氢氧化钠加热得到1-p-磺基苯基吡唑酮-5-酮-3-羧基的二钠盐；（17）对硝基苯胺经重氮化处理并如同（14）处理，产生1-p-硝基苯基-3-羧基吡唑酮-5-酮。其他指定的起始材料包括一方面是甲苯胺、二甲苯胺、萘甲酸、p-氨基苯乙基二甲基胺、m-氨基苯基二甲基胺、m-硝基苯胺、p-氨基苯酚、氨基偶氮苯和其磺酸、甲苯胺、p:p1-二氨基亚基联苯、p:p1-二氨基二苯胺、2:7-二氨基咔唑、2:7-二氨基萘、p:p1-二氨基偶氮苯、p-苯二胺、1:4-和1:5-二氨基萘和脱氢硫代-p-甲基苯胺磺酸，另一方面是乙酰琥珀酸乙酰胺。一般式的酸和酯可由反应性亚甲基化合物R1-CH2-R2的碱金属衍生物（可以原位形成）与单卤代乙酸或酯XCH2.COOR3（其中X代表卤素原子）相互作用而得到，例如通过乙氯乙酸乙酯作用于二乙酸二乙酯、乙酸酯或甲基乙酸酯、氰基乙酸酯、乙酰丙酮或乙酰乙酰苯胺在碱金属（例如钠）乙醇酸盐存在下，或在醇中作用于乙酰乙酸酯-氯醌酰胺中。乙氯乙酸乙酯可以被相应的溴或碘衍生物或自由酸替换。参见规范544,647、549,202、553,144、555,936和585,781。