GB1583160A - Cationic naphtholactam dyes and the production and use thereof - Google Patents

Abstract

The novel naphtholactam dyestuffs of the formula (1) <IMAGE> in which R, Ar, R1, R2, Y and X have the meaning given in Claim 1, are prepared by reacting a naphtholactam of the formula (2) <IMAGE> with an amine of the formula (3) <IMAGE> in the presence of a condensing agent. They are especially suitable for dyeing fibres made from acylonitrile polymers and yield bright, intense blue shades. They are also suitable for spin-dyeing polymeric substances and for dyeing polymeric substances between the spinneret and drier.

Description

(54) CATIONIC NAPHTHOLACTAM DYES AND THE PRODUCTION AND USE THEREOF (71) We, CIBA-GEIGY AG, a Swiss body corporate, of Basle, Switzerland, 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 invention relates to cationic naphtholactam dyes of the formula

in which R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, e.g. an aralkyl radical, Ar represents an aryl radical, Z represents a hydrogen or halogen atom, Y represents the cyano group or a radical of the formula

wherein R,, R4 and R represent aliphatic, cycloaliphatic or aromatic radicals, R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, R2 represents an alkyl radical optionally substituted by nonionic substituents or represents an aryl radical, and Rl and R2 together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring, or one of the radicals R1 and R2 is linked with the carbon atom, in the o-position with respect to the amino group, of the radical Ar, and Xl3 is an anion.

If the radical R is an alkyl radical substituted by nonionic substituents, suitable substituents are, for example, the following: Hydroxyl, low-molecular alkoxy, phenoxy, low-molecular alkoxycarbonyl, cyano, chlorine, phenyl or phenyl subsctituted with nitro, chlorine, methyl or methoxy.

The radical A is in particular an alkyl radical having 1 to 8 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms, alkoxyalkyl having 3 to 8 carbon atoms, (3-chloroethyl, -cyanoethyl, alkoxycarbonylethyl having 1 to 4 carbon atoms in the alkoxy moiety, carbamoylethyl, N-mono- or N,N-disubstituted alkylcarbamoylethyl having 1 to 4 carbon atoms in the alkyl moiety, cyclohexyl, benzyl or phenylethyl.

The radical R is preferably an unsubstituted alkyl radical having 1 to 4 C atoms, in particular, the methyl or ethyl radical, or the benzyl radical.

The following may be given as examples of nonionic substituents on the radicals Ar, R1 and R2: halogen atoms such as chlorine, bromine or fluorine, low-molecular alkoxy, phenoxy, acyl, acylamino, acyloxy, hydroxy, cyano, N,N - di - C1-C4 - alkyl amino or C1-C4 - alkylarylamino or phenyl, or in the case of Ar also low-molecular alkyl. The term "acyl" denotes herein low-molecular alkanoyl and alkoxycarbonyl groups.

Preferably, Ar is an unsubstituted p-phenylene radical, R1 is a low-molecular hydroxyalkyl group such as fi-hydroxyethyl or fi-hydroxypropyl, and R2 is a lowmolecular alkyl radical which is optionally substituted with hydroxy, ClC4-alkoxy, chlorine or cyano.

R3, R4 and R, can herein represent optionally substituted alkyl, alkenyl, cycloalkyl, e.g. cyclohexyl, or aryl, e.g. phenyl, methylphenyl, chlorophenyl, nitrophenyl or methoxyphenyl. Preferably, however, they are low-molecular, optionally substituted alkyl radicals. Suitable substituents are, for example: hydroxy, low-molecular alkoxy or carbalkoxy, phenoxy, phenyl, phenyl substituted with nitro, chlorine, methyl or methoxy, cyano, carbonamido, acetoxy or halogen, particularly chlorine. R4 and R, can also form with the nitrogen atom, optionally with the inclusion of a further hetero atom, a ring, e.g. a piperidine, morpholine, piperazine or pyrrolidine ring.

The following may be mentioned as examples for Ra, R4 and R: methyl, butyl, propyl, ethyl, octyl, fi-cyanoethyl, )3-chloroethyl, -hydroxyethyl, ,3-hydroxypropyl, (3-hydroxy-y-chloropropyl, ss-carboxyethyl, ss-carbomethoxyethoxyethyl or p-carbo- methoxybutoxyethyl, ,ss-carbonamidoethyl and fi-acetoxyethyl; cycloaliphatic groups such as cyclopentyl, methylcyclohexyl or trimethylcyclohexyl, preferably cyclohexyl; phenyl, benzyl or phenethyl optionally substituted by C1-C4-alkyl such as methyl, lower alkoxy such as methoxy, or halogen such as chlorine.

The expression "low-molecular", when used in connection with definitions such as alkyl, alkoxy and carbalkoxy, denotes that the alkyl groups present in the radical contain no more than 4 carbon atoms.

The naphtholactam ring is unsubstituted in the 4-position or halo-substituted, e.g., by a chlorine atom or, in particular, a bromine atom.

Y is preferably a group of the formula COOR3 wherein R, represents, in particular, a C,4-alkyl radical which is optionally substituted with a Cl*C4-alkoxy group.

The anion X3 can be derived from strong organic acids, such as chloride, bromide, iodide, nitrate, sulphate especially hydrogen sulphate and phosgate, particularly dihydrogen phosphate. Also applicable however are anions of organic acids, among which are meant, for example, aryl- and alkylsulphonates, especially benzenesulphonate and benzene sulphonates substituted with nitro, chlorine, bromine, C1-C4-alkyl and C,4-alkoxy groups and C1-C4-alkyl-sulphonates, anions of aliphatic carboxylic acids having 1 to 4 carbon atoms, and benzoates, and the benzene ring tan carry the same substituents as in the case of the benzenesulphonates.Of particular importance are the anions of low-molecular alkylsulphuric acid semi-esters, i.e. those containing 1 to 4 carbon atoms. Furthermore, the dyes can be in the form of double salts with heavy-metal halides, especially with zinc and cadmium halides.

Examples of such anions are: benzenesulphonate, ,8-toluenesulphonate, p-methoxybenzenesulphonate, methanesulphonate, ethanesulphonate, formiate, acetate, chloroacetate, propionate, lactate, tartrate, benzoate, methylbenzoate, methyl sulphate, ethyl sulphate, ZnCIE, CdCI3'3, carbonate or dicarbonate.

Particularly interesting dyes correspond to the formula la

wherein Z represents hydrogen or a halogen atom, especially bromine, and R, R1, R,, R, and X3 have the given meanings; or to the formula ib

wherein R represents CH3 and in particular C2H:, R2 represents C2H5, CH2CH(OH)C2H and especially C,H, OH, Y represents COOCH,, CN, COOCH,CH,OCH, and particularly COOC2Hs, and X represents ZnC1, and especially Cl.

The new cationic naphtholactam dyes of the formula I are produced by reacting a naphtholactam of the formula

with an amine of the formula

in the presence of a condensation agent; and if the final product is to contain a hydroxyl group, this has to be present as an acyloxy group in the starting compounds and subsequent to the condensation reaction liberated by hydrolysis, As acyl radicals are used, e.g., low-molecular alkanoyl radicals, especially acetyl.

Suitable condensation agents are, e.g., the following reagents having an action resulting in the splitting off of water: phosphoric acid halides such as phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride, phosphorus trichloride, as well as sulphuryl chloride, thionyl chloride, zinc chloride, and aluminium chloride.

It is also possible to use mixtures of these compounds.

The reaction is performed with heating, generally at 50 to 1500C. Solvents are not necessary, but the reaction mixture can if required be diluted with an inert organic solvent, e.g. with a chlorinated hydrocarbon such as tetrachloroethane or chloro benzene Naphtholactams of the formula (2) to be mentioned are in particular: N - methyl - 5 - carbomethoxynaphtholactam - 1,8, N - methyl - 4 - bromo - 5- carbomethoxynaphtholactam - 1,8, N - benzyl - 5 - carbomethoxynaphtholactam - 1,8, N - ethyl - 4 - chloro - 5 - carboethoxynaphtholactam - 1,8, N - methyl - S - cyano- naphtholactam - 1,8 or N - ethyl - 5 - (p - methoxy- or -ethoxyethoxycarbonyl) naphtholactam-1,8.

Amines of the formula (3) are, in particular, anilines, and the aniline nucleus can be substituted with nonionic substituents. The following may be mentioned as examples of such compounds: N,N - dimethylaniline, N,N - diethylaniline, N butyl - N - ss - chloroethylaniline, 2 - ethoxy - N,N - dimethylaniline, N - ethyl - N p - acetoxyethylaniline, 3 - methyldimethylaniline, N - methyldiphenylamine, 17 dimethylaminonaphthalene, 1 - diethylaminonaphthalene, N - ethyl - N - (ss - phenyl- ethyl) - aniline, N - methyl - 4 - ethoxydiphenylamine, N - methyl - 1,2,3,4 - tetrahydroquinoline, 1 - ethyl - 3 - hydroxy - 1,2,3,4 - tetrahydroquinoline or 1,2 - dimethyl - 2,3 - dihydroquinoline.

The cationic naphtholactam dyes according to the invention are suitable for dyeing and printing the widest variety of fully-synthetic fibres, such as polyvinyl chloride fibres, polyamide fibres or polyurethane fibres; also fibres from polyesters of aromatic dicarboxylic acids, such as polyethylene glycol terephthalate fibres as well as, in particular, anionically modified polyester and polyamide fibres, especially however polymers and copolymers from acrylonitrile and asymmetrical dicyanoethylene. They are likewise suitable for solution dyeing, as well as for dyeing the said materials in the hydrated state, i.e. at a suitable point between spinning nozzle and dryer (gel dyeing).

The new dyes give brilliant, deeply coloured blue shades. They are characterised, in particular, by a good fastness to light. Furthermore, they have good fastness to washing, perspiration, sublimation, decatising, rubbing, carbonising, water, sea water, chlorine water, cross-dyeing and solvents, and they have good stability in a considerable pH range. A further advantage is their suitability for being combined with other cationic dyes.

The new dyes are suitable also for dyeing mixtures of the aforementioned materials with wool, with the wool constituent scarcely becoming dyed. They can also be used for the dyeing and printing of paper and mordanted cotton, and also for the production of inks and oil paints.

In the following Examples, 'parts' are parts by weight, percentages are per cent by weight and temperatures are in degrees Centrigrade. The relationship between parts by weight and parts by volume is the same as between g and cm3.

Example 1.

12.05 parts of N - methyl - 5 - carbomethoxynaphtholactam - 1,8, 7.5 parts of N,N-diethylaniline and 1 part of zinc chloride are mixed, and 20 parts of phosphorus oxytrichloride are added. The condensation reaction is finished after 18 hours at 800C.

The reaction mixture is poured onto ice and neutralised with sodium acetate, and the dye of the formula

is completely precipitated with zinc chloride. This dye dyes polyacrylonitrile fibres in a blue shade having a high degree of fasmess to light and to decatising.

If there are used, instead of N - methyl - 5 - carbomethoxynaphtholactam - 1,8, equivalent amounts of the naphtholactam compounds listed in the following Table I in column I, and, instead of N,N-diethylaniline, equivalent amounts of the amino components given in column II, with otherwise the same procedure, naphtholactam dyes having similar properties and producing on Orlon the shade shown in the last column are obtained.

(Orlon is the Registered Trade Mark for a brand of acrylic fibre produced by Du Pont.) Table I

w w Shade I Naphtholactam II Shade 1 No. Naphtholactam compound Amino component on Orlon H3C-N-C 1 H3C X =sO a sC2U40C}i3 blue COOCH3 H3C-N - II L/C2H5 blue 2 -N blue COOCH3 H3C-N-- C0 3 H3C-N - CH2 t NCH2CH2CH3 blue COOCH3 H,C-N CO 4 (y)) NH3 blue 2H40C2115 COOCH3 COOCH3 H3C-N-CO /C2Hs blue COOCH3 C?H40C?H5 H3C-N- C-N - blue 6 1 -N:/CH3 blue COOCH3

I II Shade No. Naphthoiactam compound Amino component j on Orlon 7 H3C-N--CO 7 H3C)C) NC blue C2H40CH? COOCH3 H C-N-C0 8 3 ( tN/C2N4C1 blue C2H5 COOCH3 H C-N - C= 9 3 3 r) blue C2H4Cl COOCH3 H CO tO 3 Q b NH 4 blue COOCH3 11 H3C-N-C0 H5 C0 blue 11 C2Hg COOCH3 H3C 12 j CzDOO3 j blue COOCH3 (inc))

6 I II Shade No. Naphtholactam compound Amino component on Orlon H3C-N--C0 C2H5 13 (w?i) blue COOCH3 H3C-N- C0 Cli i3 14 blue COOCH3 I C2H5 15 (A) I blue ON (WIoN)QI) H 5C2-NC 16 / CH3 blue COOCH3 C2H5 H5C2-N-C0 CH 17 NC22ll55 blue OCH3 .

H5C2-NC O .

18 N/CH3 3 blue C2H4OCH3 COOCH3

I II Shade No. Naphtholactam compound Amino component on Orlon H5C2-N-C0 l9 COOCH3 C2H4OCH3 blue COOCH, H5C2-NC O 20 (y) > ~ NWC2H4OCH3 blue COOCH3 2H40CH3 H5C2-N-C0 Cli3 21 C I 3P blue doocH ~. C2H5 22 | H C2-NC5*O | 5 blue 22 blue COOCH3 H5C2-N-C0 CH13 CH, COOCH3 ~ ~ ~ 24 125 blue COUCH3

I II Shade No. Naphtholactam compound Amino component on Orlon H5C2-N-CO CH3 25 g aO) blue INk oI COOCH3 C2115 26 b:3 ü C -NCh aCol2g3 blue COOCH3 II H3C-N - C-N-C0 3 e CH3 27 ()-' C2H5 blue COOC2H5 H | C-N-C0 3 \CH3 28 - CH3 blue COOC2H5 H3C-N- C0 29/C2Hg C2H5 COOC2H5 H3C-N- C.O 30 NCH;4o3 blue COOC2H5

I II Shade No. Naphtholactam compound Amino component on Orlon H3C-NCv C-N-C0 31 '-N.2115 blue - C2H4OC.H3 COOC2H5 COOC2H5 ~~ H3C-N-CO 32 3 ] < 3 zC2H40CH3 blue C2H4OCH3 COOC2H5 H3C-N-CO 33 C1H3 blue COOCZH -N H3C-N-C0 C2H5 34 ĭs blue (mo) C00C2H5 ~..~ 35 (#DI) blue CO0C2115 H 3C-N C2H5 36 COOC2H5 (3Ne blue COOC2H5

I II Shade No. Naphtholactam compound Amino component on Orion 0 CII H3C-NCv CH3 ( & ) COOC2H5 CO (\2H5 38 H (0N)Q) blue 380' H5C2-N-C 39 4) (3 XCH3 blue COOC2H5 CH3 H 5C2 O CH3 40 \C < t3 N H blue COOC 2H5 H C 41 52 - C i) bNzC2H5 blue 25 COOC2H5 H | 5C2-NCs O -N-C0 NCH3 42 C2H40CH3 COOC2H5

I II Shade No. Naphtholactam compound Amino component on ~ ~ Orlon ~ Orion H5C H5C2-N N CO 2H5 2Hg COOC2H5 H5C2 N C0 CHOCH 44 /C2H40CHJ C2H40CH3 COOC2H5 45 H5C21;0 CO blue COOC2H5 0 H5C2-N-C C2H5 46 I blue COOC2H5 J 47 | C 2-NCS j CH 47 52 i3 blue CooC.2H H5C2 N C0 C2H5 48 X ffi blue COOC2H5

I II Shade No. Naphtholactam compound Amino component on Orion H5C2 -N-C-0 CH3 49 (5)) 1 blue CO0C2H5 (Gi")Qi) H .C3-N--CO c,H, 000C2H5 H,C-N--CO 51 X (3~ ZCH3 blue COOCH2CH2-CH3 2 2'CH3 52 H3C-NC < O < 3~ C2H5 blue COOCH2CH2-CH3 H3C-N -CO 53 Q-L1/C2Hs blue COOCH2CH2-CH3 H3C-N-C0 54 u :-NC s'O l 5 sC2H4OCH3 blue COOCH2CH2-CH3

I II Shade No. Naphtholactam compound Amino component on Orion H3C-N- C0 H 55 QQ CH3 blue 55 C2H4OCH3 blue COOCH2CH2-CH3 H C-N-C0 56 3 X b / C2R4OCH3 blue COOCH2CH2-CH3 57 H3C)N- C0 C1H3 blue (si)) COOCH2CH2-CH3 H,C-N--CO 58 H3C-N - Ci 5 N 2115 blue COOCH2CH2-CH3 H3C-N- C5SO CH3 59 w (ŏN blue COOCH2CH2-CH3 ~ ~ ~.

60 blue 60 blue COOCH2CH2-CH3

I II Shade No. Naphtholactam compound Amino component on Orlon H3C-N- C0 CH3 61 X a O B blue COOCH2CH2-CH3 H3C-N-0 62 H3Cj%1) / CH3 blue COOCH2- CII CH3 CH3 H3C-N-CO 63 X / CH3 5 N o CH3 blue COOCR2-CH - CH -O H3C-N - Ç55 64 \--J \C,H brue COOCH2- C2 5 -o H3C-N - Ç5= CH3 /CH3 COOCH2-CH C113 -O CH3 - Clf O 66 X / CH3 C2H4OCH3 blue COOCH2 CIICH3

No. Naphtholactam compound Amino component Sh de 67CH3"=:=5::: brue C2H40 CH3 COOCH2- CH COO H3C- -C0 68 H C g ;) ; J NCli3 blue I CR3 CR3 H3C- -C0 69 H3Cg < O i) SCH3 blue blue 'C2Hg CH3 H CO 3 70 3 X /C3H oC2H5 blue COOCH- C2H5 CR3 H C--CO 71 $i) ,CH, blue iOOCH-C2HS CR3

I E II Shade No. Naphtholactam compound Amino component on Orlon Orion H3C-N- C0 72 CH3 blue C2H4OCH3 CooClH-C2H5 CH3 H3C-p- Cffl6O NCC2H4OcH3 blue COOC11-C2Hg I CH3 ] H5 C,-N ,CO 75 H5C2 i b / CH3 blue 71i3N blue I H, C,-N--CO 76/C2H blue OOCH3 3

I it Shade No. Naphtholactam compound Amino component on Orlon Orion 77 Hs C2-N NCCR2H34OCH3 blue CH3 C2H 78 HS C2-N-C0 \C2H5 78 ')O0CH NC2H4OCH3 blue COOCH3 H5C2-N-C''O 79 g1$,/C2H40CH3 < C2 4 3 COOCH3 H5 \ toZ3 tCUUe C0 80 CR3 blue OO CH3 H5C2-NC= C H 81 < OO 12 5 blue CH3 . .. ~ H5C2-N - C=ZO CH3 82 tO)OCH3 CX blue ') 3

83 blue . II Shade No. Naphtholactam compound Amino component on 83 H5C2-N - C=s) CH3 blue 84 H3C)N CO NCH3 CH3 blue CN 85 H3C-N-C0 N$CH3S blue ; H3C-N--CB0 86/C2Hg blue C2Hs 87 --N blue 88 j 3C-N - C 'O j blue C2H4OCH3 CN

I II Shade No. Naphtholactam compound Amino component on Orion H,C-N-C"O 89 (N C2H40CH3 blue 90 XCN CIH3 blue CN H C0 C2H5 91 CN Cl2H5 blue N H 3C-N-C0 CR 92 (1) blue 11 . .

3 93 blue CN H C-N-C0 CR3 3 I 94 CN a N B blue

I II Shade No. Naphtholactam compound Amino component on Orlon 0 95 H5C2-N - C > *O con H5C2-N-C0 CH3 963/CH3 .. ~ 97/C2Hg C2H5 97 C2H'5 CN C2115 -C0 98 /\NC2H4OCH3 blue 99 I \C2H403 blue H5C2-N-CO 100 4 ; 9 C2H40CH3 blue

I II Shade No. Naphtholactam compound Amino component on Orion CH3 H,C,-N--CO 101 CN (3 < 3 blue CN H5C2-N--CO 102 I (t3Ne blue ThDN CN 0 R5C2-N-C CH3 103 CON < ) blue 103 I, H5C2-N-C0 C2H5 104 con :19 blue (MG) CN H5C,'N CO CH3 105 CN aN)I blue CN H3C-NC O /CK, 106 CH (3 XCH3 blue CON J blue CH3

I II Shade No. Naphtholactam compound Amino component on Orlon R3C-N- C0 107 CH3 b oCU3 blue C2R5 CON CH3 'CH3 C0 108 -NCh CH3 N / C2U5 blu CON H3C-N- CO 3 NCH2CH2CH3 109 < on - CH3 - C2R5 blue CON 1CH3 CO H3C-N 110 6 3Ns 2 2 blue CON 25 CH3 H3C-N-C0 111 t XON - CH3 5 \ C2u4 CU3 blue CON CR3 I $i) \ COO CON 2450C2R5 112 CR3 - C H blue NCR3

I II Shade No. Naphtholactam compound Amino component OronlOn 113 U :-N - C > b N < NOC2R blue H3C-N-- C) 0 114 CO 3 12R5 j blue CR3 0 I) C X C-N N CR3 1 3 blue CON CR3 116 IION)CH3 blue blue CON INCH3 H3C-N - CR 117 X C2R5 b \ CH3 blue C2HS . . ~~ .~ 118 3C;% CON O / $CCli2R35 blue CONC2RS

113C- N- /\ 2R5 I II Shade No. Naphtholactam compound Amino component Orlon 119 ; tCOs zC2 5 p ff xC2U5 j 120 - N. blue 121 \C v NC9O t NC2H4OCR3 CON C2115 ----- ---------------- CR '\N25 121 C2R5 - C2H40C2R5 blue CONC2R5 H3C-N-C0 122 C2R5 t2e' blue CON C2R5 H3C-N-C 10 C2H5 123 wC wC2H5 b 4 blue CON R3C-N-C0 (H3 124 (5) C2H5 N blue CON C2H5

= &verbar; I Naphtholactam compound II Shade No. Naphtholactam compound Amino compound on Orlon ll3C-N-C0 125 CON CjS5 (ȯR3j) blue I 126 j C4Hg bNXCH3 blue H3C-fJ-CO CR3 C4Hs C4H9 Cols R3C-N-C0 /C2Hg CONR9 'C4Hs 129 i %) tNz blue r J H3C-N-CbO 130 Q- blue 130 C4R9 C2R4OCH3 blue CONC4R9

1 2 II Shade No. Naphtholactam compound Amino component on Or ion HC-N--C O 131 C4R9 /C2Hs blue CONC4R9 H3C-N - C *O 132 - C4Hg t N%CC2R4OCH3 blue CON 2H40CR3 ~ C-N CR3 133 N blue I blue CON C4R9 H3C-N - C5sO 134 C12R5 blue CON C4R9 - C4R9 .C-N H COO 135 N CR3 blue CON H,C-N--CO 136 N3 blue CON 3

II Shade No. Naphtholactam compound Amino component on Orlon H C-N - C > O 137 3 con 9 b / C2R5 blue COI'3 N3C-N-C0 138 N2$45OCH3 blue COb'3 H3C-N- C0 C2H4OCR3 139 oC2H4oCH3 CON J H3C-N - C CR 140 CON 3 > / CH3 blue CONj N3C-N- C CR 141 CON C2H5 blue H3C-N - C0 142 X -\ b / C2Hs blue coN, p

I II Shade No. Naphtholactam compound Amino component on Orlon 143 H3C-N - C0 C2H40CH3 blue /C2Hg H3C-N-CO 143 C2R4OCR3 blue CONu) 113C-N- C0 CR 144 N blue CONY CON C0 C12115 145 N blue S 4 A i C12R5 H3C-N-C 146 X b / CH3 blue blue CooC2H4ocH3 Hg N CR3 147 C2115 i blue COOC2H4OCR3 H C-N - C-sst 148 3 X b N / C2H5 blue COOC2H40CH3

I II Shade No. Naphtholactam compound Amino component on Orlon 0 H3C-N - C)t CR 149 X b N & N' blue COCC2H40CH3 H3C-N--C//0 150 (5)) N C)* b \ CH3 blue CH3 C0OC2H40C2H5 H3C-N- ~ 151 H3C-N - C q t \ C/CH3 blue COOC2H40C2H5 0 R3C-N-C CII 152 H3C gg b N / C2H5 blue ~ COOC2H40C2H5 H3C-N-C0 CH3 153 X b l N1 blue COOC2H40C2R5 O H5C2-N- C0 154 X X / CH3 blue COOC2H40CH3

I II Shade No. Naphtholactam compound Amino component on Orlon H5C2-N--C0 155 X t / CH3 blue COOC2H40CH3 H,C,-N-CO /C2Hi 156 H5C2-N - C O b N / C2U5 blue CooC2H4OCH3 H5C2-NC O 157 CR13 blue CooC2H4OCH3 H5C2-N-C0 158 9 > \ CH blue COOCclH,OC U i 1 L -; 25 H5C,-N-CO C C2H4 C2H5 2 5 159 3 160 X H b / C2R5 blue COOC2H4OC2R5 2 5

I II Shade No. Naphtholactam compound Amino component on Orlon H C -N - C*O /C2Hg 161 C2H403 blue CooC2H4oC2 5 H5C2-N-C0 (\R3 162 CooC2H4oC2 5 blue blue H3C- N - C//O e/CH3 163 0OC2H4- Cl CH3 blue C,H,-C1CH3 blue H3C- N- CO 164 < ~ t \ C H blue Cl R3C-N-C L2R4 C1 2H4-Cl 16 166 C2R4OCR3 blue 0OC2R4- Cl

II Shade No. Naphtholactam compound Amino component on R3C-N-C0 N.2R5 3C2Hq- C1 )CH3 I 168 > b ",C2H4OCH3 blue (5$)) w C2H40CH3 C0OC2H4- Cl 12H4-COOCH3 N-C=O ' 169 X - o b \ CH3 blue COOCH3 C2H4-COOCH3 N-C=O ;; 170 N /\NC22RSS blue 3 sC2H4-COOCH3 N-C=O b zC2R5 N2 171 X C2H4OCH3 blue COOCH3 C2H4-COOC2H5 N-C=O 4 172 N - C =O 5 N vC * 5 blue 2H5

I II Shade No. Naphtholactam compound Amino component on Orlon C2H4-0CH3 N-C=O ' 173 X o t \ CH3 blue CR3 COOCH3 C2R4-OCH3 N-C=O CR N--C=O 1R3 C2R5 3 C2H4-OCH3 N-C=O 175 N%C113 blue CR3 COOC2H5 C2N4-0CH N-C=O CII 176 N%25 blue 1 \-JC2H5 C N--C=O 177 1N CH3 blue 3 COOCH3 J C2H4-0C2H5 N-C=O 178 t 5 / C2u5 blue C2Hg

No. I II Shade Naphtholactam compound Amino component on Orion C2Hq-OC2Hg/CH3 I COOC,H1 C2H4-0C2H5 18C t O /\C2R5 N--C=O NC2HS blue OC2H5 C12R4- 04 N-C=O CR 181 X CR3 \ CH3 blue COOCH3 I C2H4 e --0 C2R5 182 < CR3 /NC2R blue 182 Q .

H3C-N-CO COOCH3 CH3 H3C-N-C C2H5 184 t OO O oC2H5 blue CH2CH20CH3

II Shade No. Naphtholactam compound Amino component on Orlon H3C-N- C0 H H 185 $i) 1N1 H blue COOCH3 CH3 cur3 H3C-N-CO H o DL 2N5 J XH COOC2R5 CR3 CR3 3 H H 187 (5) $lNICRR3 blue COOC2H40CH3 CH3 H .C-N--C O 188 blue COOCH3 CH, NOC2R5 blue COOC2H5 H3C-N- C-NC < O 190 3 X C2H44 blue COOCH3

No. I II Shade Naphtholactam compound Amino component on Orlon H3C-N-C0 \NC2 H5 191 H3C-NC < C2H44 blue COOC2H40CH3 R3C-N-C0 192 (5) I blue COOCH3 CR3 H3C-N-- C -f\ 193 (5) blue cOOC2H4OCR3 3 H3C-N- C0 194 blue C2Hg 0NC2115 blue 3 H ,C-N--CO 196 10 blue COOCH3

I II Shade No. Naphtholactam compound Amino component on Orlon H .C-N--CO 197 blue COOC2H5 0 5 9 6, 0 198 H5C2 X < > N~O blue COOC2R5 H3C-N - C < $ 199 X 5 4 blue COOCH3 0 --NHH- blue 200 5 2 X 5 4 blue COOC2H5 H C-N - C-sstO .

201 3 X 5 NH 4 blue COOC2HOCHR HRC-N-CO 1CH, 202 C I " COOCH3

203 blue COOCH3 C2R5 0 6, II Shade No. Naphtholactam compound Amino component Or lnon 204 it C-N-C - C 6,6, blue 6, N CooC2H40CH3 L 5 20i'C-PI--C S NS blue 6, jO I CR3 COOC2H40CH3 H3C-N-CO 206 6, C H C2H5 blue 25 Cl COOCH3

No. I II Shade Naphtholactam compound Amino component on On-on 0 R3C-N-C C2R5 207 H3CgtO CF- zC2H5 blue C1 COOC2H4OCH3 H3C-N N- N C2R5 208 H3C;g O bNzC2H5 blue Br COOCH3 R5C2-N-C0 Q C2H5 b C H blue 209 C,H C1 COOC2H5 H5C2 .C-N-C C2R5 210 H5C2 -NC < O > N C2H 5 blue H3C-N-C=O 211 O-rF'ou blue Example 2.

6.6 parts of N - ethyl - N - (2 - hydroxyethyl) - aniline are completely acetylated, in 30 minutes at 70 to 750, with 4.5 parts of acetic acid anhydride. There are then successively added 9.65 parts of N - methyl - 5 - carbomethoxynaphtholactam1,8, 0.6 part of zinc chloride, 10 parts of 1,2-dichloroethane and 12.3 parts of phosphorus oxytrichloride. The mixture is condensed for 18 hours at 800; it is then diluted with 50 parts of methyl ethyl ketone; 50 parts of water are added dropwise at 60 and hydrolysis is performed at 60 for 30 minutes. The mixture is subsequently neutralised at 20 to 25" with sodium hydroxide solution. The product of the formula

precipitates at pH 6 in good yield and is filtered off with suction and dried.The dye thus obtained dyes polyacrylonitrile fibres in a blue shade having a high degree of fastness to light and good fastness to decatising.

If there are used, instead of N - methyl - 5 - carbomethoxy - naphtholactam1,8, equivalent amounts of the naphtholactam compounds listed in the following Table II in column I, and, instead of N - ethyl - N - (2 - hydroxyethyl) - aniline, equivalent amounts of the oxyalkyl anilines given in column II, with otherwise the same procedure, dyes having similar properties and producing on Orlon the shade given in the last column cn the Table are obtained.

Table II

I II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon H C-N-C0 3 CR3 1 0-NC H OR blue COOCH3 H C-N - C;;O 3 CR 2 3 X CH21CH CH3 blue OCH3 OH H3C-N-CO 30 ---N C2H5 3 3 Q CH2lU CH3 blue 3 COOCH LJ 4 H3C-N - C > blue OH H3C-N C0 C2H4OH 5 H3C 4 Ó t C2R4 H blue COOCH3 1 .CO 6 H3C-N-C0 CH2ICH CH3 blue COOCH3 OH

~ II Shade No. Naptholactam compound oxyalkyl-anilines on Or lon H3C-NC < O I H CR2CR-C113 blue COOCH3 2OH 3 OR H H3C)N COC-NC < O 3 &num; o~NzC2H4 OH 8 be ~ CH2CH-C2H5 COOCH3 3 OH 113C-N OH 011 3 {US CH2CH-C2H5 9 16, NNCR2CR1C2HS blue COOCH3 OH H5C2-NC9O 10 &commat; CR blue blue COOCH3 H5C2-N-C0 C2H5 11 blue C2H4OH blue COOCH3 HiC2-N--CO 6,'6,CR3 6, 12 2l3 blue OH COOCH3

I II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon H 3C2-N-C0 C2H5 13 i) CR2CR-CH3 blue COOCH3 OH '3 14 H5C2-N H- Cur3 blue I OR H5C2-N-C0 )-NC2H4-OH 15 < CH2CH-C2H5 blue COOCH3 OR íC2H4 CN N-C=O 16 X t oCH3 blue COO CH3 C12114- CN 17N C2fI5 blue 17 X C2U4OH COOCH3 C12114- CN N-C=O '\N C2115 18 - blue CR2CR-CH3 OR COOCR3

I II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon l 19 X \CH.OH blue 1// 6,6,C2H5 6, N 20 6, - N CO0C2H5 C21140H blue 21 blueH3C-N-C0 COOC2H5 blue COOC2H5 OH blue CH,CH- CH3 COOC2H5 OH H C0 CR 23C2HI blue 23 C2H4OH blue COOC2H5 H5C2-N CO ,6,6,C2H5 24 (5)6, NN blue COOC2R5 C2H4OH

I II Shade No. Naphtholactam Shade No. Naphtholactam compound 0xyalkyl-anilines on H5C,-N- CO 25 (5)6, - Cç 5 ~ C2H4OH blue COOC2H5 COOC,H .

H3C)N-C0 C2H4OH 26 g C2R4OR blue COOCH2CH2-CH3 COOCHZCH-CH, H QC-N- C0 27 PIC2H blue CooCH2CH2-cH3 COOCH,CH,-CH, H3C-N 28 X & CR3 blue COOCH2-CH C2R4OR COC H3C-N C' CH3NIC2Hs COOCH2-CH C2H4OH CH3 H,C-N--CO 30 Q3 NC2H4OR blue COOCH2CH2CH2' CH3 COOCH2CH2CH2 CH3

I II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon H3C-N- C0 31 g /C,H blue COOCH2CH2CR2- Cli3 C2H4OR .. ~~ 6, - CR3 32 6, NN blue COOCIH-C2H5 4 CR3 H3C-N- C0 33 X b / C2R5 blue COOCIH-C2H5 C2H4OH CH3 H ,C-N C CH3 34 XN 5 C2H4 U blue CN H3C-N-C0 NCR3 6, NCR2C1RCR3 X f blueblue CN OR H3C-N-C0 6,6,C2H5 36 6, 1\N blue C2R4OH

I II Shade No. Naphtholactam compound Oxyalkyl anilines on H3C-N CO 3C-N-C0 blue 37 X \ CH2fH-CH3 blue OR CN H?C-N-CBO /\ CH3 38 X - CH2CH-C2H5 blue CN OR H C-N- CaO 39 3 X N t ~ C2H4OH blue H3C-N - /\NC2H4OR 40 X ~ CH2CH-CH3 blue CN OH OH H3C-N-C I 41 (; CR-CR3 blue 0 42 H C2-N - C *O O ",CH3 blue

I II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon 0 H5C2-NC * 5 / CH3 LI=H-CH, X f blue blue OH CON 0 H5C2-N-C CII 44 5C2-NChO ()) zC2R5 blu \--J blue 45 5C2 CH,CH-CH3 blue 'I CN blue 46CH,CH-C,H, blue CN OR 0 47 5C20 | b / C2U40U CN 0 C2H40H 1N blue CR2CR1-CR3 48 i) - blue OH

II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon 0 OH R5C2 H5C2-NC < * 5 ~ N-CO CH3 49 6, N CR2CH-CR3 blue 49 CH2C1R- blue CN OH H3C-N-C0 SO 6,6,CR 50 N blue I - CH C2R4OH CON H5C2-NCOO C2H 51 CON / 4 9 C2H4OH blue C4Hs H C-N - C 9 6,6,CR 52 3 X 5 / C2H5 blue CON 2 C2R4OH R5C2-N-C0 6,6,C2R5 C2Hg COND C2H4OR H3C-' OH 54 H3C X c O Q blue COOCH3 CR3

R3C-N- C0 II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon 55 g 6, COOC2H5 CH3 56 0 OR blue R3C-N-) G(MNH COOCH3 C2R5 H3C-N-- OR 57 3 X X OH blue COOC2H5 C2H5 58 X xsso S N C2ii5 blue C1 COOCH3 C2R4OH blue 59 H,C-N--, CR2C1H-CH3 Ci COOCH3 OH

I II Shade No. Naphtholactam compound Oxyalkyl-anilines on Orlon 60 \ 3C-N - C > i b / blue 16, L/ Br COOCH3 H ~~~.

61 H3C-N C$ C2H4OH blue 6,j \--J - \ C2R4OR Br COOCH3 HSC ,-N- cho 62 H5C2-N--C O b N / C2 5 blue C H OR Br COOC2R5 H5C2'N--C,,0 C2R4OH C1 C1 COOC2R5 HSC2-N--CO 64 HsC2;;$O t C21140H blue Br COOC2R5 Dyeing instruction I 1 part of the dye obtained according to Example 1 is dissolved in 2000 parts of water with the addition of 4 parts of 40% acetic acid, 1 part of crystallised sodium acetate and 10 parts of anhydrous sodium sulphate. Into this dye bath at 600C are introduced 100 parts of dried yarn made from polyacrylcnitrile staple fibres; the temperature is raised within half an hour to 1000C and the material is dyed for one hour at boiling temperature. The dyeing is then well rinsed and dried Polyacrylonitrile staple fibres dyed in a blue shade are obtained.

Dyeing instruction II A polyacrylonitrile copolymer consisting of 93% of acrylonitrile and 7% of vinyl acetate is dissolved in dimethylacetamide to the extent of 15%. The spinning solution is extruded into a spin bath composed of 40% of dimethylacetamide and 60% of water. The resulting tow is subsequently stretched by known methods and freed from dimethylacetamide by rinsing with hot and cold water. This wet tow is dyed by immersion in a bath at 420C which contains per litre 9 g of dye according to Example 2 and which has been adjusted to pH 4.5 with acetic acid. The contact time tow/dye liquor is 2 seconds. The excess dye liquor is afterwards squeezed out and the tow is fed to the dryer. There is obtained a tow dyed in a deep-blue shade having good fastness properties.

WHAT WE CLAIM IS: 1. Cationic naphtholactam dyes of the formula

in which R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, Ar represents an aryl radical, Z represents a hydrogen or halogen atom, Y represents the cyano group or a radical of the formula

wherein R,, R4 and R5 represent aliphatic, cycloaliphatic or aromatic radicals, R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, R2 represents an alkyl radical optionally substituted by nonionic substituents or represents an aryl radical, and R1 and R2 together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring, or one of the radicals R1 and R2 is linked with the carbon atom, in the o-position with respect to the amino group, of the radical Ar, and X'~ is an anion.

2. Cationic naphtholactam dyes according to Claim 1, wherein R3, R4 and R represent optionally substituted, low-molecular alkyl radicals, and R4 and R together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring.

3. Cationic naphtholactam dyes according to Claims 1 and 2, wherein R represents C1-C4-alkyl or benzyl.

4. Cationic naphtholactam dyes according to Claim 3, wherein R represents ethyl or methyl.

5. Cationic naphtholactam dyes according to Claims 1 to 4, wherein R, represents a C1-C4-alkyl radical optionally substituted with low-molecular alkoxy.

6. Cationic naphtholactam dyes according to Claims 1 to 5, wherein R1 represents a low-molecular hydroxyalkyl group, and R2 represents a low-molecular alkyl radical optionally substituted with hydroxy, C1-C4-alkoxy, chlorine or cyano.

7. Cationic naphtholactam dyes according to any preceding claim wherein Z represents a halogen atom and Y represents COOR,.

8. Cationic naphtholactam dyes according to Claim 7, wherein Z represents a bromine atom.

9. Cationic naphtholactam dyes according to Claim 1 of the formula ib

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (27)

**WARNING** start of CLMS field may overlap end of DESC **. Polyacrylonitrile staple fibres dyed in a blue shade are obtained. Dyeing instruction II A polyacrylonitrile copolymer consisting of 93% of acrylonitrile and 7% of vinyl acetate is dissolved in dimethylacetamide to the extent of 15%. The spinning solution is extruded into a spin bath composed of 40% of dimethylacetamide and 60% of water. The resulting tow is subsequently stretched by known methods and freed from dimethylacetamide by rinsing with hot and cold water. This wet tow is dyed by immersion in a bath at 420C which contains per litre 9 g of dye according to Example 2 and which has been adjusted to pH 4.5 with acetic acid. The contact time tow/dye liquor is 2 seconds. The excess dye liquor is afterwards squeezed out and the tow is fed to the dryer. There is obtained a tow dyed in a deep-blue shade having good fastness properties. WHAT WE CLAIM IS:

1. Cationic naphtholactam dyes of the formula

in which R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, Ar represents an aryl radical, Z represents a hydrogen or halogen atom, Y represents the cyano group or a radical of the formula

wherein R,, R4 and R5 represent aliphatic, cycloaliphatic or aromatic radicals, R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, R2 represents an alkyl radical optionally substituted by nonionic substituents or represents an aryl radical, and R1 and R2 together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring, or one of the radicals R1 and R2 is linked with the carbon atom, in the o-position with respect to the amino group, of the radical Ar, and X'~ is an anion.

2. Cationic naphtholactam dyes according to Claim 1, wherein R3, R4 and R represent optionally substituted, low-molecular alkyl radicals, and R4 and R together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring.

3. Cationic naphtholactam dyes according to Claims 1 and 2, wherein R represents C1-C4-alkyl or benzyl.

4. Cationic naphtholactam dyes according to Claim 3, wherein R represents ethyl or methyl.

5. Cationic naphtholactam dyes according to Claims 1 to 4, wherein R, represents a C1-C4-alkyl radical optionally substituted with low-molecular alkoxy.

6. Cationic naphtholactam dyes according to Claims 1 to 5, wherein R1 represents a low-molecular hydroxyalkyl group, and R2 represents a low-molecular alkyl radical optionally substituted with hydroxy, C1-C4-alkoxy, chlorine or cyano.

7. Cationic naphtholactam dyes according to any preceding claim wherein Z represents a halogen atom and Y represents COOR,.

8. Cationic naphtholactam dyes according to Claim 7, wherein Z represents a bromine atom.

9. Cationic naphtholactam dyes according to Claim 1 of the formula ib

wherein R represents CH3 or C,H; R2 represents C2Hs, C2H4OH or CH2CH(OH)C,H; Y represents COOCH,, COOC2H5 CN or COOCH2CH2OCH,; and X9 represents Cl or ZnCl3.

10. Cationic naphtholactam dye according to Claim 9 wherein R represents C2H; R2 represents C2H4OH; Y represents COOC2Hs and X represents Cl.

11. Process for the production of cationic naphtholactam dyes of the formula

in which R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, Ar represents an aryl radical, Z represents a hydrogen or halogen atom, Y represents the cyano group or a radical of the formula

wherein R,, R4 and R represent aliphatic, cycloaliphatic or aromatic radicals, R represents an alkyl or cycloalkyl radical optionally substituted by nonionic substituents, R2 represents an alkyl radical optionally substituted by nonionic substituents or represents an aryl radical, and R1 and R2 together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring, or one of the radicals R, and R2 is linked with the carbon atom, in the o-position with respect to the amino group, of the radical Ar, and X is an anion, in which process a naphtholactam of the formula

is reacted with an amine of the formula

in the presence of a condensation agent; and wherein, if in the meanings of the symbols in the formula (1) a hydroxyl group occurs, this is present as an acyloxy group in the starting compounds of the formula (2) or (3), and subsequent to the condensation reaction is converted by hydrolysis into the hydroxyl group.

12. Process according to Claim 11, in which is used as starting material a naphtholactam wherein R,, R4 and R, represent optionally substituted low-molecular alkyl radicals, and R4 and R, together with the nitrogen atom, optionally with the inclusion of a further hetero atom, can form a ring.

13. Process according to Claim 11, in which process is used as starting material a naphtholactam wherein R represents ClCl-alkyl or benzyl.

14. Process according to Claim 11, in which process is used as starting material a naphtholactam wherein R represents ethyl or methyl.

15. Process according to Claim 11, in which process is used as starting material a naphtholactam wherein R, represents a C1-C.1-alkyl radical optionally substituted with low-molecular alkoxy.

16. Process according to Claim 11, in which process is used as starting material an amine of the formula (3) wherein Rl represents a low-molecular hydroxyalkyl group, and R2 represents a low-molecular alkyl radical optionally substituted with hydroxy, C1-C4-alkoxy, chlorine or cyano.

17. Process according to Claim 11, in which process a naphtholactam of the formula

wherein Z, R and R3 have the same meanings as in Claim 11, is reacted with an aniline of the formula

wherein R1 and R2 have the meanings given in Claim 11.

18. Process according to Claim 17, in which process is used as starting material a naphtholactam of the formula (4) wherein Z represents a bromine atom.

19. Process according to Claim 11, in which process a naphtholactam of the formula

wherein R represents CH3 or C2H:,, and Y represents COOCH,, COOC,H,, CN or COOCH2CH2OCH3, is reacted with an aniline of the formula

wherein R2 represents C2H:., C2H,OH or CH2CH(OH)C2H

20. Process according to Claim 19, in which process a naphtholactam of the formula (6), wherein R represents C2H: and Y represents COOC2Hs, is reacted with an amine of the formula (7) wherein R2 represents C2H.1OH.

21. Process according to claim 11, substantially as herein described.

22. Naphtholactam dyes according to claim 1 when prepared by a process according to any of claims 11-21.

23. Any cationic naphtholactam dye claimed in claim 1 and identified in Example 1 or 2 or in Table I as any of Nos. 1-182, 185-193, 196-210 or in Table II (Nos. 1-64).

24. Any cationic naphtholactam dye claimed in claim 1 and identified in Table I by any of the numbers 183-184; 194-195 and 211.

25. Use of the dyes according to any of claims 1-10, 22, 23 and 24 for dyeing or printing materials made from fully synthetic fibres.

26. Dyeing or printing process according to claim 25 in which polyacrylonitrile material is dyed.

27. Fully-synthetic fibre material dyed or printed according to claim 25 or 26.