GB1585643A

GB1585643A - N - ammonium-alkylnaphthalimides and their use as optical brightening agents

Info

Publication number: GB1585643A
Application number: GB3770077A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1976-09-11
Filing date: 1977-09-09
Publication date: 1981-03-11
Also published as: DE2641001A1; JPS5335733A; FR2392977B3; FR2392977A1

Description

(54) N-AMMONIUMALKYLNAPHTHALIMIDES AND THEIR USE AS OPTICAL BRIGHTENING AGENTS (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us. and the method by which it is to be performed, to be particularly described in and by the following Statement: The present invention relates to novel N-ammoniumalkylnaphthalimides and their use as optical brightening agents.

The compounds of the invention have the general formula I

in which the radicals R are identical or different and each is alkyl of 1 to 4 carbon atoms or alkoxyethyl, where alkoxy is of l to 4 carbon atoms; R is methyl, ethyl. propyl or butyl; R2 and R3 independently of one another are alkyl of 1 to 8 carbon atoms, or alkyl of 1 to 4 carbon atoms which is substituted by hydroxyl, by alkoxy of 1 to 4 carbon atoms or by phenyl; R4 is hydrogen, alkyl of 1 to 4 carbon atoms, chloroethyl, hydroxyethyl, benzyl or allyl and XO is one equivalent of an anion.

Examples of radicals R are propyl. butyl, methoxyethyl, ethoxyethyl, propoxyethyl and butoxyethyl and especially methyl and ethyl. since with these meanings the compounds can be manufactured more advantageously.

Examples of radicals R2 and R3 are methyl. ethyl. n- and iso-propyl. -butyl. -pentyl.

-hexyl, -heptyl and -octyl. hydroxyethyl, hydroxypropyl. hydroxybutyl. methoxyethyl, ethoxyethyl. propoxyethyl. methoxypropyl. benzyl and phenylethyl.

Examples of radicals R4 are butyl, propyl and especially ethyl and methyl. since with these meanings the compounds can be manufactured more advantageously.

Examples of anions for XO are chloride, bromide, iodide tetrafluoborate, acetate, formate. zincate, tetrachlorozincate. sulfate, methosulfate. ethosulfate, phenylsulfonate. tolylsulfonate and perchlorate.

The compounds of the formula I may be manufactured by quaternizing a compound of the formula II

with a compound of the formula III X-R4 III where X is one equivalent of a radical which can be split off as an anion and is, in particular, chlorine, bromine, iodine, methosulfate, ethosulfate, phenylsulfonate or tolylsulfonate.

The compounds of the formula II may be obtained by reacting a compound of the formula IV

where Hal is chloride or bromine. with a compound of the formula V ROM V where M is sodium or potassium.

The reaction is advantageously carried out in the corresponding alcohol of the formula ROH in the presence of from 2 to 10ass, preferably from 3 to 6C/c, by weight of a monoalkyl ether or dialkyl ether of a glycol or polyglycol. Suitable ether groups are. in particular, those of alkyl of 1 to 4 carbon atoms; the glycol chains preferably comprise from 2 to 6 ethylene groups.

Details of the reactions may be found in the Examples, where parts and percentages are by weight. unless stated otherwise.

The compounds of the formula I are colourless to pale yellow. They give virtually colorless aqueous solutions which have an intense bluish violet fluorescence in daylight and very particularly under ultraviolet light. On acrylonitrile trans polymers or copolymers they give an intense brightening effect which can be further increased by the use of bleaching agents, eg. sodium chlorite. The compounds of the formula I may also be used with anionically modified polyesters and nylons.

Compounds of the formula I a

where Bl is alkyl of 2 to 4 carbon atoms. B2 and B independently of one another are alkyl of 1 to 8 carbon atoms. B4 is methyl. ethyl, hydroxyethyl or allyl. and R has the above meaning, are industrially particularly important.

EXAMPLE 1 44 parts of 4 ,5-dimethoxy-N-1 '-(N' ,N' -dibutylamino)-2'-butyl]-naphthalimide, 240 parts of acetone and 50 parts of dimethyl sulfate are stirred for 7 hours at 580C. The acetone is distilled off and the residue is taken up in 700 parts of water. The insoluble product is filtered off. 20 parts of zinc chloride are added to the filtrate. After salting out with sodium chloride, 54 parts of the compound of the formula

are obtained. The yield is 96% of theory; the product melts at 228-2290C.

The new product is readily water-soluble and the aqueous solutions have an intense blue fluorescence. Both without and with a chlorite bleach, the compound gives brilliantly brightened acrylonitrile polymers and copolymers of very high whiteness. The hue of the brightened material is a neutral white.

To prepare 4,5-dimethoxy-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide, 43 parts of 4,5-dichloro-N-[1'-(N',N',-dibutylamino)-2'-butyl]-naphthalimide, 200 parts of methanol and 20 parts of butyltriglycol are mixed, and 50 parts of a 30% strength sodium methylate solution in methanol are added in the course of 2 hours at 65"C. The mixture is then stirred for 5 hours at this temperature and is allowed to cool, and the product is filtered off, washed with methanol and dried.

Yield: 39 parts (93% of theory), melting point = 140-141"C.

4,5-Dichloro-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide may be obtained by reacting 4,5-dichloronaphthalic anhydride with 2-amino- 1-dibutylamino-butane. Melting point = 128-130"C.

EXAMPLE 2 8.8 parts of 4,5-dimethoxy-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide, 30 parts of water and 10 parts of aqueous 50% strength HBF4 are stirred for 2 hours at room temperature. The product is filtered off, washed and dried, and 10 parts of the compound of the formula

are obtained. The yield is 95% of theory and the product melts at 179-182"C.

The tinctorial properties and color characteristics are comparable to those of the compound from Example 1.

EXAMPLE 3 8.8 parts of 4,5-dimethoxy-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide, 40 parts of acetone and 12 parts of diethyl sulfate are stirred for 10 hours at 40-50 C. The acetone is distilled off, the residue is taken up in 100 parts of water and the undissolved product is filtered off. The filtrate is then precipitated with 10 parts of aqueous 50% strength HBF4 and 10 parts of the compound of the formula

are isolated as a waxy material: the yield is 90% of theory.

EXAMPLE 4 9.4 parts of 4,5-diethoxy-N[1'-(N'.N'-dibutylamino)-2'-butyl]-naphthalimide. 60 parts of acetone and 10 parts of dimethylsulfate are stirred for 7 hours at 58"C. The acetone is distilled off and the residue is taken up in 150 parts of water. The undissolved product is filtered off and the mother liquor is precipitated with ZnCl,/NaCl.

11 parts (94% of theory) of the compound of the formula

are obtained: it melts at 98-110 C.

To prepare 4.5-diethoxy-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide. 22.4 parts of 4,5-dichloro-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide. 150 parts of ethanol.

10 parts of tetraglycol diethvl ether and 50 parts of 20% strength sodium ethylate solution in ethanol are heated for 10 hours under reflux. After the mixture has cooled. the product is filtered off, washed with ethanol and dried.

Yield: 21 parts (90% of theory). Melting point = 92-93 C.

EXAMPLE 5 The reaction and working up are carried out as described in Example 4. but instead of dimethyl sulfate/acetone. diethvl sulfate/dimethylformamide is used as the reaction medium.

10 parts (846Xc of theory) of the compound of the formula

are obtained in the form of a wax.

EXAMPLE 6 11.2 parts of 4,5-bis-ethoxy-ethoxy-N-[1'-(N',N'-dibutyl-amino)-2'-butyl]naphthalimide, 60 parts of acetone and 10 parts of dimethyl sulfate are stirred for 9 hours at 58 C. The acetone is distilled off and the residue is taken up in 150 parts of water. The undissolved product is filtered off, 10 parts of 50% strength HBF4 are added to the mother liquor and 12.5 parts (95% of theory) of the compound of the formula

are obtained as a wax.

To prepare 4,5-bis-ethoxy-ethoxy-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide, 22.4 parts of 4,5-dichloro-N-[1'-(N',N'-dibutylamino)-2'-butyl]-naphthalimide, 160 parts of ethylglycol and 20 parts of potassium tert.-butylate are stirred for 2 hours at 80 C. After the mixture has cooled, it is stirred into water, stirring is continued for 10 hours and the product is filtered off and dried.

Yield: 25 parts (90% of theory). Melting point = 50 - 51 C.

The compounds listed in the Table which follows can also be prepared by the method described in Examples 1 to 6.

Example R R1 R2 R3 R4 XO 7 CH3 C2H5 CH3 CH3 CH3 BF4# 8 CH3 C2H5 C2H5 C2H5 CH3 BF4# 9 CH3 C2H5 C2H5 C2H5 C2H5 BF4# 10 CH3 C2H5 C3H7 C3H7 CH3 BF4# 11 CH3 C2H5 C2H5 C2H5 CH2C6H5 Br# 12 CH3 C2H5 C2H5 C2H5 CH2-CH=CH2Br# 13 CH3 C2H5 C2H5 C2H5 C4H9 Br# 14 CH3 C2H5 C5H9 C5H9 CH3 C104# 15 CH3 C2H5 C6H13 C6H13 CH3 1/2 ZnCl42# 16 CH3 C2H5 C8H17 C8H17 CH3 1/2 ZnCl42# 17 CH3 C2H5 C4H9 CH2 CH3 1/2 ZnCI42(3 18 CH3 C2H5 C4H9 CH3 C2H5 BF4# 19 CH3 C2H5 C8H17 CH3 CH3 BF4# 20 CH3 C2H5 C4H9 C2H5 CH3 1/2 ZnCl42# 21 CH3 C2H5 C2H4OH C2H4OH CH3 BF4# 22 CH3 C2H C2H4'OH CH3 CH3 CH3SO4# 23 CH3 C3H7 CH3 CH3 CH3 CH3SO4# 24 CH3 C3H7 C2H5 C2H5 CH3 1/2 ZnCl428 25 CH3 C3H7 C3H7 C3H7 CH3 1/2 ZnCl42# 26 CH3 C3H7 C4H9 C4H9 CH3 BF4# 27 CH3 C3H7 C6H13 C6H13 CH3 BF4# 28 CH3 C3H7 C8H17 C8H17 CH3 BF4# 29 CH3 C4H9 CH3 CH3 CH3 BF4# 30 CH3 C4H9 C4H9 C4H9 CH3 1/2 ZnCl42# 31 CH3 C4H9 C6H13 C6H13 CH3 CH3SO4# 32 CH3 CH3 C4H9 C4H9 CH3 1/2 ZnCl42# 33 CH3 CH3 C6H13 C6H13 CH3 C104# 34 CH3 C2H5 C4H9 C4H9 C2H4Cl #OSO2C6H4CH3 35 CH3 C2H5 C4H9 C4H9 C2H5 #OSO2C6H4CH3 36 CH3 C2H5 C4H9 C4H9 CH2-CH=CH2 Br# 37 CH3 C2H5 C4H9 C4H9 C3H7 Br# 38 C2H4OC2H5 C2H5 C4H9 C4H9 C2H5 C2H5SO4# 39 C2H4OCH3 C2H5 C4H9 C4H9 CH3 1/2 ZnCl42# 40 C2H4OCH3 C2H5 C4H9 C4H9 C2H5 1/2 ZnCl42# 41 C3H7 C2H5 C4H9 C4H9 CH3 BF4# 42 C3H7 C2H5 C4H9 C4H9 C2H5 BF4# 43 C4H9 C2H5 C4H9 C4H9 CH3 1/2 ZnCl42# 44 C4H9 C2H5 C4H9 C4H9 C2H5 ClO4# All the compounds as described in Examples l to 44 have blue fluorescence in aqueous solution.

Claims

WHAT WE CLAIM IS:

1. A compound having the general formula:

where the radicals R are identical or different and each is alkyl of 1 to 4 carbon atoms or alkoxyethyl of which alkoxy is of 1 to 4 carbon atoms; R' is methyl, ethyl, propyl or butyl; R2 and R independently of one another are alkyl of 1 to 8 carbon atoms or alkyl of 1 to 4 carbon atoms which is substituted by hydroxyl, by alkoxy of 1 to 4 carbon atoms or by phenyl; R4 is hydrogen, alkyl of 1 to 4 carbon atoms, chloroethyl, hydroxyethyl, benzyl or allyl; and XO is one equivalent of an anion.

2. A compound as claimed in claim 1 and having the general formula:

where B' is alkyl of 2 to 4 carbon atoms, B2 and B3 independently of one another are alkyl of 1 to 8 carbon atoms. B4 is methyl, ethyl, hydroxyethyl or allyl, and R and XO are as defined in claim 1.

3. A compound as claimed in claim 1 or 2 wherein XO is chloride, bromide, iodide, methosulfate. ethosulfate, phenylsulfonate, tolylsulfonate, tetrafluoroborate, tetrachlorozincate or perchlorate.

4. A compound as claimed in claim 1 and as hereinbefore specifically identified.

5. A process for the manufacture of a compound as claimed in claim 1, in which process a compound of the general formula:

in which R. Rl, R2 and R3 are each as defined in claim 1 is quaternized with a compound of the general formula:- X-R4 where X is one equivalent of a radical which can be split off as an anion.

6. A process as claimed in claim 5 and substantially as described in anv one of the foregoing Examples.

7. A compound as claimed in claim 1 whenever obtained by a process as claimed in claim 5 or claim 6.

8. A textile polvmer whenever optically brightened by means of a compound as claimed in any one of claims 1 to 4 and 7.

9. An acrylonitrile homopolymer or copolymer optically brightened by means of a compound as claimed in any one of claims 1 to 4 and 7.