5-(3-Phosphonoanilino)naphthalene-2-sulfonic acid | 61892-33-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5-(3-Phosphonoanilino)naphthalene-2-sulfonic acid
• CAS: 61892-33-9
• 化学式: C₁₆H₁₄NO₆PS
• 分子量: 379.3
• InChiKey: AGJXYNOXTMYUDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  132
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  sodium hydrogensulfite 、 sodium hydroxide 、 5-氨基-2-萘磺酸 、 (3-氨基苯基)膦酸 、 盐酸 、 二氧化硫 、 在 Congo Red 、 氯化钠 作用下， 反应 29.0h， 以to give 7 parts of 1-(3-phosphonophenylamino)-6-sulphonaphthalene的产率得到5-(3-Phosphonoanilino)naphthalene-2-sulfonic acid
  参考文献：
  名称：

  Phosphonophenylaminonaphthalene compounds

  摘要：

  本发明涉及新的萘化合物，特别是用于合成染料的有用偶联组分的新的萘化合物。根据本发明，提供了下式化合物： 其中M为0、1或2，n为0或者如果m为1或2，则可以为1，此时X1为NH2或者OH，位于SO3H基团的m位置，X为二价的烷基、芳基烷基或芳基烃基，可以被取代，p为1或2。在公式（1）中所表示的烷基由直链或支链组成，可以含有OH。它通常含有少于6个碳原子，例如亚甲基、三亚甲基、四亚甲基、丙烯基、己亚甲基或羟基丙烷基，但是首选的烷基是乙烯基。在公式X中表示的芳基烷基首选为m-或p-苯基，其中NH基团首选连接到苯环上，磷原子首选连接到亚甲基上。在公式X中表示的芳基烃基首选为苯基或萘基，其中在第一种情况下，首选的是m-或p-苯基，可以选择由CH3、F、Cl、Br或NO2取代；在萘基的情况下，首选的是1,3-、1,6-、1,7-或2,7-萘基，可以选择由SO3H取代。本发明还提供了一种用于制造新的萘化合物的方法，该方法包括在碱性亚硫酸盐水溶液存在下，加热下式化合物： 其中X1、m、n和p具有上述含义，X2为OH、NH2或NHR，其中R为1至4个碳原子的烷基，不位于SO3H的间位，以及下式胺： 其中X具有上述含义，以制造新的萘化合物。新化合物可以通过酸化和沸腾以分解亚硫酸盐，然后过滤来分离。在某些情况下，可能需要盐析或喷雾干燥。本发明提供的新萘化合物可用作染料中间体，例如大多数情况下可用作合成偶氮染料的偶联组分，类似于其他N-取代萘胺。具有1-氨基-4-苯胺基或1,4-二苯胺萘基结构的新化合物，苯环含有磷酸基团，可用作合成硫染料的中间体。具有2,6-或2,7-二苯胺萘基结构的化合物可用于合成偶氮染料。

  公开号：

  US04051175A1

文献信息

• Phosphonophenylaminonaphthalene compounds
  申请人：Imperial Chemical Industries Limited

  公开号：US04051175A1

  公开（公告）日：1977-09-27

  Naphthalene compounds of the formula: ##STR1## WHEREIN M IS 0, 1 OR 2 n is 0 or can be 1 if m is 1 or 2, in which case X.sub.1 is NH.sub.2 or OH in m position to a SO.sub.3 H group X is a divalent alkylene, aralkylene or arylene radical, which may be substituted and p is 1 or 2. The new compounds are useful dyestuff intermediates, especially as coupling components for the manufacture of azo dyestuffs. This invention relates to new naphthalene compounds and more particularly to new naphthalene compounds valuable for use in the synthesis of dyestuffs. According to the invention, there are provided compounds of the formula: ##STR2## WHEREIN M IS 0, 1 OR 2 n is 0 or can be 1 if m is 1 or 2, in which case X.sub.1 is NH.sub.2 or OH in m position to a SO.sub.3 H group X is a divalent alkylene, aralkylene or arylene radical, which may be substituted, and p is 1 or 2. An alkylene group represented by X in formula (1) may be straight chain or branched, and may contain OH. It preferably contains less than 6 carbon atoms, e.g. methylene, trimethylene, tetramethylene, propylene, hexamethylene or hydroxypropylene, but the preferred alkylene radical is ethylene. An aralkylene radical represented by X is preferably m- or p-benzylene, having the NH group preferably attached to the benzene nucleus and the phosphorus atom preferably attached to the methylene group. An arylene radical represented by X is preferably a phenylene or naphthylene radical, and in the first case is preferably m- or p-phenylene, optionally substituted by CH.sub.3, F, Cl, Br or NO.sub.2 ; in the case of naphthylene is preferably a 1,3-, 1,6-, 1,7- or 2,7-naphthylene radical, optionally substituted by SO.sub.3 H. The invention also provides a process for manufacture of the new naphthalene compounds which comprises heating together a naphthalene compound of the formula: ##STR3## WHEREIN X.sub.1, m, n and p have the meanings stated above and X.sub.2 is OH, NH.sub.2 or NHR, where R is an alkyl group of 1 to 4 carbon atoms, which is not in meta position to SO.sub.3 H, and an amine of the formula: NH.sub.2 -- X -- PO(OH).sub.2 ( 3) wherein X has the meaning stated above, in the presence of an aqueous solution of an alkali metal bisulphite. The process can be carried out under a variety of conditions according to the ease with which the group X.sub.2 is replaced by the group NH -- X -- PO(OH).sub.2. As a general rule, compounds in which X.sub.2 is NH.sub.2 react more readily than the corresponding OH or NHR compound; also the presence of SO.sub.3 H in ortho position to X.sub.2 lowers the reactivity of the latter so that higher reaction temperatures are desirable. As a general rule also, the compounds of formula (3) in which X is alkylene or aralkylene are more reactive than those in which X is arylene. Within these broad limitations it is sometimes possible to effect the reaction at from 90.degree. C upwards, but it is usually more practical to operate within the range of 100.degree.-200.degree. C in order to achieve a satisfactory rate of reaction. It is usually preferable to use a small excess of the compound of formula (3) over the theoretical amount required for reaction. The new compounds can be isolated by acidification and boiling to decompose sulphites followed by filtration. In some cases salting or spray drying may be necessary. The following table gives examples of naphthalene compounds which can be used in the above process, together with an indication of the kinds of product obtained therefrom; as can be seen from the table, there is frequently a choice of starting material for preparing a class of the new naphthalene compounds. __________________________________________________________________________ Starting material __________________________________________________________________________ 1-naphthol 1-naphthylamine ##STR4## (4) 2-naphthol 2-naphthylamine ##STR5## (5) 1,2-dihydroxynaphthalene 1-amino-2-naphthol ##STR6## (6) 1,4-dihydroxynaphthalene 1-amino-4-naphthol ##STR7## (7) and ##STR8## (8) 1,5-dihydroxynaphthalene 1-amino-5-hydroxynaphthalene ##STR9## (9) and ##STR10## (10) 1-amino-8-naphthol ##STR11## (11) 2,7-dihydroxynaphthalene ##STR12## (12) and ##STR13## (13) 1-naphthol-4-sulphonic acid 1-aminonaphthalene-4-sulphonic acid 1-methylaminonaphthalene-4- sulphonic acid ##STR14## (14) 2-naphthol-1-sulphonic acid Tobias acid N-methyl Tobias ##STR15## (15) 2-naphthol-6-sulphonic acid 2-aminonaphthalene-6- sulphonic acid 2-methylaminonaphthalene- 6-sulphonic acid ##STR16## (16) 2-naphthol-7-sulphonic acid 2-aminonaphthalene-7- sulphonic ##STR17## (17) 2-naphthol-8-sulphonic acid 2-aminonaphthalene-8- sulphonic ##STR18## (18) 2-naphthol-5,7-disulphonic acid ##STR19## (19) 2-naphthol-6,8-disulphonic acid 2-aminonaphthalene-6,8- disulphonic ##STR20## (20) 1-aminonaphthalene-6- sulphonic acid ##STR21## (21) 1-aminonaphthalene-7- sulphonic acid ##STR22## (22) 1,5-dihydroxynaphthalene-4- sulphonic acid 1-amino-5-naphthol-4- sulphonic acid ##STR23## (23) and ##STR24## (24) 1,5-diaminonaphthalene-4- Formula (24) sulphonic acid 1,5-dihydroxynaphthalene-7- sulphonic acid 1-amino-5-naphthol-7- sulphonic acid ##STR25## (25) 1-amino-5-naphthol-2- sulphonic acid ##STR26## (26) and ##STR27## (27) 1,7-dihydroxynaphthalene- 4-sulphonic acid 1-amino-7-naphthol-4- sulphonic acid 1-methylamino-7-naphthol- 4-sulphonic acid ##STR28## (28) and ##STR29## (29) 1-amino-5-naphthol-8- sulphonic acid ##STR30## (30) 2,5-dihydroxynaphthalene-7- sulphonic acid 2-amino-5-naphthol-7- sulphonic acid 2-methylamino-5-naphthol-7- sulphonic acid ##STR31## (31) 2-amino-5-naphthol-1- sulphonic acid ##STR32## (32) and ##STR33## (33) 2,5-diaminonaphthalene-1- sulphonic acid Formula (33) 2,8-dihydroxynaphthalene-6- sulphonic acid 2-amino-8-naphthol-6- sulphonic acid 2-methylamino-8-naphthol-6- sulphonic acid ##STR34## (34) 1-amino-8-naphthol-5- sulphonic acid ##STR35## (35) __________________________________________________________________________ as examples of compounds of formula (3) which can be used, there may be mentioned: 1-aminomethylphosphonic acid 2-aminoethylphosphonic acid 3-aminopropylphosphonic 4-aminobutylphosphonic acid 5-aminopentylphosphonic acid 6-aminohexylphosphonic acid -amino-1-methylethylphosphonic acid 2-amino-1-methylethylphosphonic acid 1-amino-3-methylbutylphosphonic acid 2-amino-1-hydroxypropylphosphonic acid 3-amino-2-hydroxypropylphosphonic acid .alpha.-aminobenzylphosphonic acid .alpha.-aminophenylethylphosphonic acid 3- or 4-aminobenzylphosphonic acid 2, 3- or 4-aminophenylphosphonic acid 3-amino-4-methylphenylphosphonic acid 4-amino-2-fluorophenylphosphonic acid 2-amino-5-chlorophenylphosphonic acid 3-amino-4-chlorophenylphosphonic acid 4-amino-2-bromophenylphosphonic acid 4-amino-3-nitrophenylphosphonic acid 4-n-butylamino-3-nitrophenylphosphonic acid 1-naphthylamine-6-phosphonc acid 1-naphthylamine-7-phosphonic acid 7-phosphono-2-naphthylamine-5-sulphonic acid 2-naphthylamine-7-phosphonic acid 8-sulpho-2-naphthylamine-3-phosphonic acid 6,8-disulpho-1-naphthylamino-3-phosphonic acid. As alkali-metal bisulphite, there may be used potassium bisulphite, but it is preferred to use sodium bisulphite. As a general rule, the amount of alkali metal bisulphite used is greater than 1 mole per mole of naphthalene compound. The naphthalene compounds of formula (1) in which n is 0 and p is 1, can alternatively be obtained by heating together a compound of the formula: ##STR36## in which m has the meaning stated above preferably 0 or 1, and one X.sub.3 is H and the other is CO.sub.2 H, and an amine of formula (3) wherein X has the meaning stated above, in the presence of an aqueous solution of an alkali metal bisulphite. This alternative process can be carried out in a similar manner to the process described above, with the proviso that it is usually possible to effect the reaction at slightly lower temperatures, e.g. from 80.degree. C upwards, than is the case when using compounds of formula (2) as a reactant. The preferred range of reaction temperature is 80.degree.-150.degree. C. As examples of compounds of formulae (36) and (37), there may be mentioned: 2-hydroxy-1 and 3-naphthoic acids 1-hydroxy-4-naphthoic acid 6- and 8-sulpho-2-hydroxy-3-naphthoic acids 4- and 7-sulpho-2-hydroxy-1-naphthoic acids. The new naphthalene compounds can be used as dyestuff intermediates, e.g. in most cases as coupling components for the manufacture of azo dyes by coupling with aromatic diazonium salts in similar manner to other N-substituted naphthylamines. The new compounds having a 1-amino-4-anilino- or 1,4-dianilinonaphthalene structure, the benzene ring containing a phosphonic acid group, are useful as intermediates for the synthesis of sulphur dyes. Those having a 2,6- or 2,7-dianilinonaphthalene structure are useful for the synthesis of azine dyes.

  本发明涉及新的萘化合物，特别是用于合成染料的有用偶联组分的新的萘化合物。根据本发明，提供了下式化合物： 其中M为0、1或2，n为0或者如果m为1或2，则可以为1，此时X1为NH2或者OH，位于SO3H基团的m位置，X为二价的烷基、芳基烷基或芳基烃基，可以被取代，p为1或2。在公式（1）中所表示的烷基由直链或支链组成，可以含有OH。它通常含有少于6个碳原子，例如亚甲基、三亚甲基、四亚甲基、丙烯基、己亚甲基或羟基丙烷基，但是首选的烷基是乙烯基。在公式X中表示的芳基烷基首选为m-或p-苯基，其中NH基团首选连接到苯环上，磷原子首选连接到亚甲基上。在公式X中表示的芳基烃基首选为苯基或萘基，其中在第一种情况下，首选的是m-或p-苯基，可以选择由CH3、F、Cl、Br或NO2取代；在萘基的情况下，首选的是1,3-、1,6-、1,7-或2,7-萘基，可以选择由SO3H取代。本发明还提供了一种用于制造新的萘化合物的方法，该方法包括在碱性亚硫酸盐水溶液存在下，加热下式化合物： 其中X1、m、n和p具有上述含义，X2为OH、NH2或NHR，其中R为1至4个碳原子的烷基，不位于SO3H的间位，以及下式胺： 其中X具有上述含义，以制造新的萘化合物。新化合物可以通过酸化和沸腾以分解亚硫酸盐，然后过滤来分离。在某些情况下，可能需要盐析或喷雾干燥。本发明提供的新萘化合物可用作染料中间体，例如大多数情况下可用作合成偶氮染料的偶联组分，类似于其他N-取代萘胺。具有1-氨基-4-苯胺基或1,4-二苯胺萘基结构的新化合物，苯环含有磷酸基团，可用作合成硫染料的中间体。具有2,6-或2,7-二苯胺萘基结构的化合物可用于合成偶氮染料。