GB1585668A

GB1585668A - Aminonaphthalimide derivatives and their use as optical brightening agents

Info

Publication number: GB1585668A
Application number: GB3669777A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1976-09-03
Filing date: 1977-09-02
Publication date: 1981-03-11
Also published as: IT1086346B; DE2639649A1; FR2363558A1; JPS5331730A

Description

(54) NOVEL AMINONAPHTHALIMIDE DERIVATIVES 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 compounds of the aminonaphthalimide series and their use as optical brightening agents.

According to the invention there are provided novel compounds of the formula (I):

in which one R is identical to or different from the other R and each is C, to C4 alkyl or C, to C4 aloxyethyl; R' is hydrogen, C, to C,0 alkyl, (C1-C3) chloroalkyl, C2 to C6 alkenyl, styryl, C2 to C4 alkynyl, C, to C8 alkoxy, p-tert.butyl-cyclohexyloxy, C, to C8 alkylamino, C, to C8 dialkylamino, phenoxymethyl, phenyl, tolyl, benzyl or phenylethyl; and R2 is N.methylpiperidino-4, I-phenylethyl, 1 (hydroxyphenyll-ethyl or branched C3 to C,O alkyl optionally substituted by hydroxy, C, to C4 alkoxy, C, to C4 alkanoyloxy, C, to C4 dialkylamino, pyrrotidino, piperidino, morpholino, piperazino, N-methylpiperazino, N-p-hydroxyethyl- piperazino, phenyl, hydroxyphenyl, methoxyphenyl or dimethoxyphenyl.

The radical KZ containing amino groups may also be quaternized.

Examples of radicals R are: propyl, butyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxethyl and particularly methyl and ethyl because of the ease of production.

Examples of radicals R' are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, vinyl, allyl, propenyl, butenyl, styryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, n-heptyloxy, isoheptyloxy, n-octoyloxy, isooctoyloxy, dimethylamino, diethylamino and diisobutylamino.

Examples of radicals R are:

The compounds of the formula (I) may be prepared by the reaction of compound of the formula (II):

with a compound of the formula (III):

in which X is OH, Cl, Br or an acyl radical

The compounds of the formula (II) may be obtained by the reaction of a compound of the formula (IV):

which Hal is chloro or bromo, with a compound of the formula (V): ROMe (V) in which Me is sodium or potassium.

The reaction may be conveniently carried out in the corresponding alcohol of the formula ROH in the presence of from 2 toi 20% and preferably from 5 to 10% of a monoalkyl or dialkyl ether of a glycol or polyglycol. The ether group is preferably a C, to C4 alkoxy radical and the glycol chain preferably consists of from two to six ethylene groups.

In another preferred embodiment the reaction of the compound of the formula (IV) with that of the formula (V) is carried out in the corresponding alcohol of the formula ROH in the presence of from 5 to 95% and preferably from 10 to 50% of an inert organic solvent which has a boiling point higher than 80"C.

Examples of such solvents are: benzene, toluene, a xylene, trimethylbenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene.

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

Compounds of the formula (I) are suitable as optical brighteners for secondary cellulose acetate, cellulose triacetate and particularly synthetic linear polyesters and union fabrics of polyester and cotton. Owing to their high thermal stability they may be used for mass brightening and in the dope dyeing method.

Compounds of the formula (l) having basic groups, particularly when they have been quaternized, are also suitable for the optical brightening of acrylonitrile polymers.

The following should be emphasized; the very good fastness to light, the very high color strength and particularly the brilliance and high whiteness in a preferred reddish shade of the brightening and also the excellent tinctorial behavior.

Preferred compounds are those of the general formula (la):

in which B' is hydrogen or C, to C8 alkyl; B2 is branched C3 to C8 alkyl; and R has the meaning given above.

The following are particularly preferred radicals: for R: CH3, -C2H5, -C4H9, -C2H4OCH3 and -C2H4OC2H5; for B': H, -CH3, -C2H5, -C3H7 and C2H5-CH-C4H8; for B2: CH(CH3)2,

EXAMPLE 1.

12 parts of 4,5-dimethoxy-N-neopentylaminonaphthalim 40 parts of Nmethylpyrrolidone and 5.1 parts of potassium carbonate are placed in a reactor. 6 parts of acetyl chloride is then dripped in at 50"C while stirring and the whole is stirred for five hours at the same temperature. Then the mixture is poured onto ice and suction filtered. 13 parts of the compound of the formula:

is obtained. After it has been recrystallized from isobutanol it has a melting point of 228 to 2300C.

With this product brilliant brightenings of outstanding whiteness and reddish tinge are obtained particularly on cellulose acetate, polyester and blends of polyester and cotton. They very good fastness properties are emphasized.

4,5-dimethoxy-N-neopentylaminonaphthalimide is prepared by stirring 64 parts of 4,5-dichloro-N-neopentylaminonaphthalimide, 440 parts of methanol, 50 parts of butyl triglycol and 100 parts of a 30% solution of sodium methylate in methanol for eight hours at 650C. After the product has cooled it is suction filtered, washed with methanol and dried. The yield is 61 parts (98% of theory) and the melting point is 270 to 272"C.

4,5-dichloro-N-neopentylaminonaphthalimide is accessible by the reaction of 4,5-dichloronaphthalic anhydride with neopentylhydrazine. Melting point: 230 to 231 C.

EXAMPLE 2.

Reaction and working up are carried out as described in Example 1. 7 parts of propionyl chloride is used instead of acetyl chloride. 13.4 parts of the compound of the formula:

is obtained which has a melting point of 225 to 2260C after having been recrystallised from alcohol. The tinctorial properties are similar to those of the compound described in Example 1.

EXAMPLE 3.

The reaction and working up are carried out as described in Example 1. 8 parts of butyryl chloride is used instead of acetyl chloride. 13 parts of the compound of the formula:

is obtained; it has a melting point of 2030 to 2040C after it has been recrystallized from isobutanol. The tinctorial properties are similar to those of the compound described in Example 1.

EXAMPLE 4.

8 parts of 4,5-dimethoxy-N-neopentylaminonaphthalimide in 30 parts of formic acid is heated for four hours under reflux. The mixture is then poured into water. 8 parts of the compound of the formula:

is obtained (melting point 2400 to 2420C after recrystallisation from isobutanol).

The tinctorial properties are similar to those of the compound from Example I.

EXAMPLE 5.

60 parts of 4,5-dimethoxy-N-isopropylaminonaphthalimide, 200 parts of Nmethylpyrrolidone and 25 parts of potassium carbonate are placed in a reactor, 25 parts of acetyl chloride is dripped in at from 400 to 500C and the whole is stirred for five hours at 50 to 600 C. The mixture is then poured onto ice. 68 parts of the compound of the formula:

is obtained; it has a melting point of 266 to 267do after having been recrystallized from dimethylformamide. The tinctorial properties are similar to those of the compound from Example 1.

4,5-dimethoxy-N-isopropylaminonaphthalimide is prepared by placing 135 parts of 4,5-dichloro-N-isopropylaminonaphthalimide, 400 parts of methanol and 60 parts of o-dichlorobenzene in a.vessel adding 270 parts of a 30% solution of sodium methylate in methanol during two hours at refluxing temperature and stirring for seven hours at the same temperature. The product is cooled, suction filtered, washed with methanol and dried. The yield is 130 parts (98% of theory) and the melting point is 220 to 2230C.

4,5-dichloro-N-isopropylaminonaphthalimide having a melting point of 190 to 192"C is accessible by the reaction of 4,5-dichloronaphthalic anhydride with isopropylhydrazine.

EXAMPLE 6.

The reaction and working up are carried out as described in Example 5, 25 parts of butyryl chloride is used instead of acetyl chloride. 69 parts of the compound of the formula:

is obtained; it has a melting point of from 181" to 1820C after it has been recrystallized from isobutanol. It has similar tinctorial properties to the compound from Example 1.

EXAMPLE 7.

5 parts of 4,5-dimethoxy-N-isopropylaminonaphthalimide and 25 parts of methyl chlorocarbonate are stirred for eight hours at 600 C. The solid product is suction filtered after cooling. 5.5 parts of the compound of the formula:

is obtained. After it has been recrystallized from methanol it has a melting point of from 195 to 196"C.

The tinctorial properties are similar to those of the compound from Example 1.

EXAMPLE 8.

10 parts of 4,5-dimethoxy-N-isopropylaminonaphthalimide, 40 parts of dimethylformamide and 4 parts of potassium carbonate are placed in a reactor. 6 parts of dimethylcarbamyl chloride is then dripped in at 800 to 900C and the whole is stirred for seven hours at this temperature. After the mixture has been cooled it is poured onto ice and suction filtered. 11 parts of the compound of the formula:

is obtained; it has a melting point of from 256 to 2570C after it has been recrystallized from isobutanol. The tinctorial properties are comparable to those of the compound from Example I.

EXAMPLE 9.

The reaction and working up are carried out as described in Example 8. - chloropropionyl chloride is used instead of dimethylcarbamoyl chloride. 11 parts of the compound:

is obtained; it has a melting point of from 203 to 2040C after it has been recrystallized from isobutanol.

The tinctorial properties are similar to those of the compound from Example 1.

EXAMPLE 10.

12 parts of 4,5-dimethoxy-N-isopentylaminonaphthalimide, 40 parts of dimethylformamide and 5 parts of potassium carbonate are placed in a reactor and then 6 parts of acetyl chloride is dripped in at 500C while stirring. The mixture is stirred for another four hours at this temperature, cooled, poured onto ice and suction filtered. 14 parts of the compound of the formula:

is obtained; it has a melting point of from 240 to 2410C after it has been recrystallized from ethyl glycol.

The tinctorial properties are similar to those of the compound from Example 1.

4,5-dimethoxy-N-isopentylaminonaphthalimide is prepared by placing 61 parts of 4,5-dichloro-N-isopentylaminonaphthalimide, 240 parts of o-dichlorobenzene and 60 parts of methanol in a reactor and adding 72 parts of sodium methylate over two hours. The whole is stirred for another five hours at refluxing temperature.

After cooling 400 parts of methanol is added and the product is suction filtered, washed and dried. The yield is 55 parts (93% of theory) and the melting point is from 272 to 2750C.

4,5-dichloro-N-isopropylaminonaphthalimide is obtained by the reaction of 4,5-dichloronaphthalic anhydride with isopentyl hydrazine. It has a melting point of 218 to 2220C.

EXAMPLE 11.

65 parts of 4,5-dimethoxy-N-isobutylaminonaphthalimide, 300 parts of dimethylformamide and 25 parts of potassium carbonate are placed in a reactor. 25 parts of acetyl chloride is dripped in at 50"C with stirring and stirring is continued for five hours at the same temperature. After the mixture has been cooled it is poured into water and suction filtered. 71 parts of the compound of the formula:

is obtained; it has a melting point of from 281 to 2820C after it has been recrystallized from dimethylformamide.

The tinctorial properties are similar to those of the compound from Example 1.

4,5-dimethoxy-N-isobutylaminonaphthalimide is obtained as described in Example 10 by the reaction of 4,5-dichloro-N-isobutylaminonaphthalimide with sodium methylate. It has a melting point of from 220 to 2210C.

4,5-dichloro-N-isobutylaminonaphthalimide is obtained by the reaction of 4,5dichloronaphthalic anhydride with isobutyl hydrazine. It has a melting point of from 1560 to 1600C.

The compounds set out in the following Tables may also be obtained by the method described in the foregoing Examples:

Example R Rl R2 CH3 12 CH3 H -CH-CH, 13 ,, C2H5 14 " CH2Cl 15 ,, C4H9 16 " C8 H1l C2H5 17 ,, -CH-C4H9 Cl 18 ,, -CH-CH3 19 ,, -CH-CH, 20 ,, -C=CH 21 " CH3 CH-C113 CH3 22 ,, CH2-CH-CH1 23 < " CH2OC6 H5 "

Example R R' R2 24 CH3 H CH=CH-C6Hs CH2 -CH-CH2 25 ,. C3H6CI 26 C2H5 CH3 27 C3H7 28 C, H, 29 C2H4OCH3 .. .. 30 C2H4OC2Hs .. .. 31 C2H5 C2H8 32 C4H6 ,, 33 C2H4OCH3 " ,. 34 CH3 C6H8 35 ,. CH2C6Hs 36 " C2 H4C6 H5 37 ,, C6H4CH3 38 " OC2H5 39 ,, OC4Hg CH3 40 .. OCHC2H8

Example R R' R2 C2H5 CH3 I I 41 CH3 OCH,-CH-C,H, CH-CH3 42 " OC2 H4 OCH3 ",, OC2H4OCH3 CH3 43 " sH3 " U 3 CH3 44 C2Hs N(CM, )2 45 CH3 N(C2Hs)2 CH3 46 ,, N(CH,-CH ) CH3 CH3 47 ,, H CH-C2 Ha 48 ,, C2H5 49 ,, C3H7 50 ,, C2H4Cl 51 ,, CH2CI C2H5 52 ,, CH-C4H9 53 " CH=CH2 CH3 54 " H CH-C3H7

Example R R1 R2 CH3 55 CH3 CH3 CH-C3 H7 56 ,, C2H5 57 ,, C3H7 58 ,' C2H4 Cl CH3 CH 59 ,, I H -CH-CH CH3 60 ,. CH3 61 ,, C2H8 62 ,, C3H7 63 .. C2 H4 Cl .. C2H8 64 .. H CH-C,H, 65 " CH3 66 ,, C2H8 67 ,, CH7 C2H5 68 ,, CH-C4H8 /CH3 69 " C2 H4 Cl -CH2-C- CH3 CH3

Example R R1 R2 CH3 70 CH3 Ca H6 Cl -CH2-C-CH3 CH3 71 C2H8 CH3 72 C4Hg " " CH3 CH3 73 CH3 H CH-CH2-CH3 CH3 74 " CH3 75 " C2 Hs " CHa 76 ,, H CH-C4H9 77 " CH3 CHa 78 ,, C2H5 CH-C4H8 79 ,, C3H7 80 C2Ha CH3 81 C4H8 ,, CH3 / CH3 82 CH3 ,, CH-C2 H4-CH CH3

Example R R1 R2 83 CH3 CH3 CH3 CH-C5H11 CHa 84 ,, ,, CH-C6H13 C2H8 85 ,, ,, CH2-CH-C4H8 86 ,, H 87 C2H8 CII, C2H8 88 CH3 C2H8 CH2-CH-C4H8 89 ,, C3H7 CH3 90 " CH3 CH-C7H15 CH3 91 ,, ,, CH-C8H17 CH3 92 ,, CH-C6H5 93 ,, C2H3 CH3 94 ,, CH3 CH~CH2C6 Hs 95 ,, C2Hs

Example R R1 R2 CH3 96 CH3 CH3 CH-C6 H4 OH CH3 97 ,, CHCH2C6H4OCHa CH3 98 ,, ., CH-CH2-C6Ha(OCH)a CH3 99 ., -CH2-C-CH2OH CH3 100 ,, -CH-(CH2)2CH3 CH3 0 II 101 ,, ,, -CH-(CH2)2-O-C-CH3 CH3 102 " " ~CN~CH3 103 ,, -CH CH2-N 104 ,, -CH-CH2-N(n But)2 CH3

The fluorescences of the compounds from Examples I to 104 in dimethylformamide solution are bluish violet.

Claims

WHAT WE CLAIM IS:-

I. A compound of the general formula (1):

in which one R is identical to or different from the other R and each is C, to alkyl or C, to C4 alkoxyethyl; R' is hydrogen, C1 to C,0 alkyl, C,--C, chloroalkyl, C2 ta C8 alkenyl, styryl, C2 to C4 alkynyl, C, to C8 alkoxy, p-tert.butyl-cyclohexyloxy, C, to C8 alkylamino, C, to C8 dialkylamino, phenoxymethyl, phenyl, tolyl, benzyl or phenylethyl; and R2 is N-methylpiperidino-4, I-phenylethyl, I-(hydroxyphenyl)- ethyl or branched C3 to C,0 alkyl optionally substituted by hydroxy, C, to C4 alkyl, C, to C4 alkanoyloxy, C, to C4 dialkylamino, pyrrolidino, piperidino, morpholino, piperazino, N-methylpiperazine, N-A-hydroxyethylpiperazino, phenyl, hydroxyphenyl, methoxyphenyl or dimethoxyphenyl.
2. A compound as claimed in claim 1, wherein R' is hydrogen, C, to C,O alkyl, C2 to C8 alkenyl, C2 to C4 alkynyl, C, to C8 alkoxy, C, to C8 alkylamino, C, to C8 dialkylamino, phenoxymethyl, phenyl, tolyl, benzyl or phenylethyl; and R2 is branched C2 to C,0 alkyl optionally substituted by phenyl, hydroxyphenyl, methoxyphenyl or dimethoxyphenyl.
3. A compound as claimed in claim 1 and having the general formula (Ia):-

in which B' is hydrogen or C, to C8 alkyl; B2 is branched C2 to C8 alkyl; and R has the meaning given in claim 1.
4. A quaternized derivative of a compound claimed in claim 1 and having a basic nitrogen atom.
5. An N-amidocarbonyl-substituted naphthalimide identified in any one of the foregoing Examples.
6. A process for the production of a compound as claimed in claim 1 wherein a compound of the formula (II):

is reacted with a compound of the formula (III):

in which X is OH, Cl, Br or an acyl radical

and R, R' and R2 have the meanings given in claim 1.
7. A process as claimed in claim 6 carried out substantially as described in any one of the foregoing Examples.
8. A compound as claimed in claim I or claim 2 whenever obtained by a process as claimed in claim 6 or claim 7.
9. A process for the optical brightening of a secondary cellulose acetate, cellulose triacetate, synthetic linear polyester or polyester/cotton fabric, wherein a compound as claimed in claim 1, 2, 3, 5 or 8 is used as optical brightener.

10; A process for the optical brightening of an acrylonitrile polymer wherein a compound as claimed in claim 4 is used as optical brightener.