Phosphonophenylaminonaphthalene compounds

Abstract

Naphthalene compounds of the formula: ##STR1## WHEREIN M IS 0, 1 OR 2n 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 groupX is a divalent alkylene, aralkylene or arylene radical, which may be substituted andp 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 2n 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 groupX is a divalent alkylene, aralkylene or arylene radical, which may be substituted, andp 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-sulphonicacid 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- sulphonicacid 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 acid1,5-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 acid2-aminoethylphosphonic acid3-aminopropylphosphonic4-aminobutylphosphonic acid5-aminopentylphosphonic acid6-aminohexylphosphonic acid-amino-1-methylethylphosphonic acid2-amino-1-methylethylphosphonic acid1-amino-3-methylbutylphosphonic acid2-amino-1-hydroxypropylphosphonic acid3-amino-2-hydroxypropylphosphonic acid.alpha.-aminobenzylphosphonic acid.alpha.-aminophenylethylphosphonic acid3- or 4-aminobenzylphosphonic acid2, 3- or 4-aminophenylphosphonic acid3-amino-4-methylphenylphosphonic acid4-amino-2-fluorophenylphosphonic acid2-amino-5-chlorophenylphosphonic acid3-amino-4-chlorophenylphosphonic acid4-amino-2-bromophenylphosphonic acid4-amino-3-nitrophenylphosphonic acid4-n-butylamino-3-nitrophenylphosphonic acid1-naphthylamine-6-phosphonc acid1-naphthylamine-7-phosphonic acid7-phosphono-2-naphthylamine-5-sulphonic acid2-naphthylamine-7-phosphonic acid8-sulpho-2-naphthylamine-3-phosphonic acid6,8-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 acids1-hydroxy-4-naphthoic acid6- and 8-sulpho-2-hydroxy-3-naphthoic acids4- 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.

Description

Claims

1. A naphthalene compound of the formula ##STR37## 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 OH or NH.sub.2 in m position to a SO.sub.3 H group,

p is 1 or 2,

q is 0 or 1 and

the benzene ring can be further substituted by OCH.sub.3 or CH.sub.3.

2. A naphthalene compound of the formula ##STR38## 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 phenylene, tolylene or anisylene, and p is 1 or 2.

3. The naphthalene compound of claim 2 having the formula ##STR39##

4. The naphthalene compound of claim 2 having the formula ##STR40##

5. The naphthalene compound of claim 2 having the formula ##STR41##