DE2924067A1 - Naphtho-lactam derivs. contg. pyrimidine-di:one fragment - useful as dispersion dyes for fibres and plastics - Google Patents

Abstract

Naphtholactam derivs. of formula (I) are new. In (I) R is H or opt. substd. alkyl, cycloalkyl, aralkyl or aryl; R1 is H, Cl, Br, alkyl, alkoxy, NO2 or alkylthio; R2 is H or Cl; R3 is H, Cl, Br, alkyl, alkoxy, NO2, acylamino, alkyl- or arylsulphonamido, alkyl-or arylthio, alkyl- or arylsulphonyl, opt. N-substd. sulphamoyl, alkanoyl, aroyl, alkoxycarbonyl, opt. substd. carbamoyl or CN, and R4 is H, Cl, alkoxy, arylthio, alkylthio, alkoxycarbonyl, opt. substd. carbamoyl or CN, or R3+R4 is thio-o-phenylene or carbonyl -o-phenylene; R5 is H, Cl or alkoxy; X is a gp. of formula X1-X7; where A is H, Me, Et, MeO, EtO, MeSO2, CN, COOMe, COOEt or NO2, and B is H, 1-4C alkyl, beta-(1-4C alkoxy)ethyl or -propyl or gamma-(1-4C alkoxy)propyl. (I) are yellow to violet dispersion dyes for dyeing synthetic (esp. polyester) fibres and for bulk colouration of plastics.

Description

NaDhtholactam derivatives

The invention relates to compounds of the formula I. in which R is hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl, R1 is hydrogen, chlorine, bromine, alkyl, alkoxy, NO2 or aryl mercapto, R2 is hydrogen or chlorine, R3 is hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, acylamino, Alkylsulfonylamino, arylsulfonylamino, alkyl mercapto, aryl mercapto, arylsulfonyl, alkylsulfonyl, optionally N-substituted sulfamide, alkanoyl, aroyl, alkoxycarbonyl, optionally substituted carbamoyl or cyano, R4 hydrogen, chlorine, alkamooxy, aryl mercapto, optionally substituted carbo, alkyloxy-cyano, alkyl mercapto, alkyloxy , R3 and R4 together form a radical of the formula R5 is hydrogen, chlorine or alkoxy and X is a radical of the formula mean, where A is hydrogen, methyl, ethyl, methoxy, ethoxy, ethylsulfonyl, cyano, methoxy carbonyl, ethoxycarbonyl or nitro and B is hydrogen, C1- to C4-alkyl, ß-C1- to C4-alkoxyethyl or -propyl or y-C1- to C4 alkoxypropyl.

R radicals are in particular alkyl having 1 to 8 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, alkoxyalkyl with 3 to 8 carbon atoms, ß-chloroethyl, ß-cyanoethyl, Alkoxycarbonylethyl with 1 to 4 carbon atoms in alkoxy, carbamoylethyl, N-mono- or Ñ, N-disubstituted alkylcarbamoylethyl with 1 to 4 carbon atoms in the alkyl, cyclo- hexyl, Benzyl, phenylethyl or phenyl.

Examples include: propyl, butyl, nexyl, ß-ethylhexyl, B-hydroxyethyl or -propyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxypropyl, Butoxypropyl, amyloxypropyl, methoxycarbonylethyl, ethoxycarbonylethyl or butoxycarbonylethyl and preferably methyl, ethyl or ß-cyanoethyl.

Explanations for R1 to R5: alkyl, alkoxy and aryl mercapto groups for R1 are e.g.

Methyl, ethyl, nethoxy, ethoxy, phenylmercapto or by chlorine, methyl, Methoxy, phenoxy or methoxycarbonyl substituted phenyl mercapto.

For R3 the same radicals as for R1 are to be mentioned, as well as naphthyl mercapto, Benzthiazolyl-2-mercapto, Acylaminophenylmercapto, Diacyliminophenylmercapto, Acetylamino, Propionylamino, benzoylamino, benzoylamino substituted by chlorine, methyl or methoxy, Methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino, tolylsulfonylamino, Methyl mercapto, ethyl mercapto, ß-hydroxyethyl mercapto, ß-hydroxypropyl mercapto, Butyl mercapto, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, tolylsulfonyl, chlorophenylsulfonyl, Acetyl, chloroacetyl, propionyl, butyryl, benzoyl, through methyl, methoxy, chlorine or Bromine-substituted benzoyl, sulfamoyl, N-methyl-, N-ethyl-, N-butyl-, N-phenyl-, N-chlorophenyl-, N-methylphenyl-, N-methoxyphenyl-, N-trifluoromethylphenyl-, N-methyl-N-phenyl-, N, N-dimethyl-, N, N-diethyl-, N, N-dipropyl- or N, N-dibutylsulfamoyl, pyrrolidinosulfonyl, Piperidinosulfonyl or morpholinosulfonyl.

In addition, there are the residues of the formulas NHCONH2, NHCONHCH3 or NHCONHC6H5 into consideration.

R4 radicals are, in addition to hydrogen and chlorine, the alkoxy and alkoxy groups mentioned for R1 Aryl mercapto residues.

Alkoxycarbonyl radicals R3 and R4 are, for. B. methoxycarbonyl, ethoxycarbonyl, n- and iso-propoxycarbonyl, butoxycarbonyl, 2-ethylhexoxycarbonyl, ß-hydroxyethoxycarbonyl, B-alkoxyethoxycarbonyl or B-dimethylaminoethoxycarbonyl.

Examples of substituted carbamoyl radicals are: methylaminocarbonyl, Ethyl, propyl, iso-propyl, butyl, iso-butyl and 2-ethylhexylaminocarbonyl, ß-Hydroxyäthylaminocarbonyl, ß-Methoxyäthylaminocarbonyl, y-Hydroxy-, y-Methoxy-, y-ethoxy, y-butoxypropylaminocarbonyl, dimethyl, diethyl, dibutylaminocarbonyl, Pyrrolidinocarbonyl, piperidinocarbonyl and morpholinocarbonyl.

Alkoxy radicals R5 are z. B. methoxy or ethoxy.

B radicals are in addition to hydrogen z. B. n- or i-butyl, n- or i-propyl, ß-butoxy or propoxyethyl or y-butoxy or propoxypropyl and especially methyl, Ethyl, ß-methoxy or ß-ethoxyethyl or propyl or γ-methoxy or γ-ethoxypropyl.

Preferred for A are hydrogen, methyl, methoxy or ethoxy and for B hydrogen or methyl.

To prepare the compounds of the formula I, compounds of the formulas II can be used 8th RN = CS-alkyl RR2) ½R5 4 RR where X is oxygen or sulfur and AO is an anion and alkyl has 1 to 4 carbon atoms, with compounds of the formula III implement, R to R5 and X have the meanings given.

For X1 = O the presence of a condensing agent is necessary, this is not necessary for the other compounds II.

Suitable condensing agents are phosphorus halides such as phosphorus pentachloride, Phosphorus trichloride or phosphorus oxytribromide and especially phosphorus oxytrichloride.

The reaction can be carried out in an inert solvent, such as glycol and polyglycol diet, butyrolactone, toluene, Chlorobenzene, dichlorobenzene, Carry out nitrobenzene or dioxane or in an excess of the condensing agent.

When converting the naphtholactam derivatives without a condensing agent the solvents already mentioned are also suitable; B. pyridine, Glacial acetic acid, dimethylformamide or N-methylpyrrolidone should be mentioned.

Details of the reaction procedure and conditions can be found in the examples which contain information about parts and percentages, unless otherwise noted, refer to weight.

Compounds of the formula Ia are of particular importance in B1 hydrogen, halogen, aroyl or aryl mercapto and X is a radical of the formula mean.

The compounds of the formula I are yellow to purple and are suitable as disperse dyes for synthetic fibers, especially polyester as well for coloring plastics in bulk. As plastics are z. B. polystyrene, Polycarbonate, polyurethanes, polyamides or polyolefins called. Draw the colors are distinguished by their brilliance and good fastness properties.

Example. 1 169 parts of naphtholactam and 162 parts of 4H-pyrido-1,2a] -pyrimidine-2,4-dione are introduced into 1200 parts by volume of chlorobenzene and the mixture is stirred at 100.degree. 225 parts of phosphorus oxy-trichloride are added dropwise over the course of one hour, and the mixture is stirred at 100 ° C. for a further 4 hours. Now some water is added and the chlorobenzene is distilled off with steam. The yellow-brown color salt solution is filtered and excess ammonia solution is added, whereupon the colorant precipitates. After filtering off with suction, washing with water and drying, 292 parts of the dye of the formula are obtained The same dye is obtained by heating a) equivalent amounts of thionaphtholactam and 4H-pyrido-1,2a] pyrimidine-2,4-dione in N-methylpyrrolidone to 170 ° C. until the evolution of hydrogen sulfide has ceased, or b) equivalents Reacts amounts of naphtholactamimidechloride hydrochloride and 4H-pyrido-C1,2a2-pyrimidine-2,4-dione in boiling pyridine.

Example 2 31.3 parts of the dye obtained according to Example 1 become 16 parts of dimethyl sulfate are added in 150 parts of nitrobenzene at 100 ° C. and 1 Hour stirred. After working up, 35.2 parts of a water-soluble dye are obtained. the polyacrylonitrile fabric dyes vivid golden yellow tones.

Example 3 277 parts of 4-phenylmercaptonaphtholactam and 168 parts of 2-hydroxy-4-oxo-4H-pyrimido- [3, 2a] -thiazole are introduced into 1500 parts by volume of dichlorobenzene and 190 parts of phosphorus oxy-trichloride are added at 100.degree. The mixture is stirred for a further 6 hours at 100-105 ° C. and 500 parts by volume of ethanol are then added dropwise. After cooling, the crystal slurry is suctioned off, washed with ethanol, digested with dilute ammonia solution, suctioned off again and washed with water. After drying, 339 parts of the dye of the formula are obtained in the form of dark red crystals. With the dye, dyeings and prints in brilliant scarlet shades with excellent fastness properties, in particular light and heat-setting fastness, are obtained on polyester fabric. When incorporated into thermoplastics, the dye gives fluorescent reddish colorations with good lightfastness.

EXAMPLE 4 276 parts of N-ethyl-4-bromonaphtholactam and 218 parts of 2-hydroxy-4-oxo-4H-pyrimido-2a-benzothiazole are added to 1000 parts by volume of ethylene glycol dimethyl ether and 200 parts of phosphorus oxy-trichloride are added at 80 ° C. over the course of 2 hours. The mixture is refluxed for 12 hours, then allowed - without heating - to run in 500 parts by volume of methanol. After cooling, it is filtered off with suction and, as described in Example 3, worked up. 406 parts of the dye of the formula are obtained in the form of a red-brown crystal powder. With the dye, in thermoplastics, for example in polystyrene or polycarbonate, brilliant red tones of very good lightfastness are obtained.

Dyes with equally good properties are obtained if the 2-hydroxy-4-oxo-4H-pyrimido-C, 2a3-benzothiazole is replaced by equivalent amounts of the substituted derivatives replaced.

Example 5 248 parts of 4-bromonaphtholactam and 170 parts of 2-hydroxy-4-oxo-4H-pyramido- [3,2a] -thiazole are introduced into 750 parts by volume of dehydrated nitrobenzene and the mixture is stirred at 80.degree. 220 parts of phosphorus oxy-trichloride are run in over the course of 10 minutes and the mixture is stirred at 85 ° C. for a further 4 hours. The heating is now switched off and 200 parts by volume of methanol are added dropwise. It is kept at a gentle boil for 30 minutes, filtered off with suction while warm and washed with methanol. After drying, 336 parts of the compound are obtained in the form of scarlet crystals with a bromine content of 19.5% (calculated 20.1 5 '). When printed on polyester, the dye provides brilliant yellow-orange nuances with excellent lightfastness.

Example 6 In 140 parts by volume of N-methylpyrrolidone, 39.8 parts of the dye obtained according to Example 5, 17 parts of 2-mercaptobenzothiazole and 15 parts entered anhydrous potassium carbonate and stirred at 155 ° C. for 20 hours.

During the cooling process, 25 parts of acetic acid are added, the dye crystallizing out. After filtering off with suction, washing with methanol and hot water and drying, 47.2 parts of the compound are obtained in the form of a red crystal powder. With the dye, brilliant orange prints with excellent fastness properties are obtained on polyester fabric. A coloristically very similar dye is obtained if 11.5 parts of 2-mercaptopyridine are used instead of 2-mercaptobenzothiazole and the procedure described above is used.

Example 7 In 500 parts by volume of ethylene glycol monoethyl ether are 79.7 Parts of the dye obtained according to Example 5 and 35 parts of 60% sodium sulfide entered and refluxed for 8 hours. 750 parts of water are used to and filtered. The filtrate is conc with 30 parts by volume. Hydrochloric acid added and the precipitated solid is filtered off with suction and washed with water.

The moist press cake is with 350 parts of N-methylpyrrolidone, 350 Parts of water and 60 parts of 50 pointer sodium hydroxide solution were brought into solution and the solution 35 parts of dimethyl sulfate are added at room temperature.

The mixture is stirred for a further 2 hours at 50 ° C., diluted with 500 parts by volume of water and filtered off with suction. After drying, 64 parts of the compound are obtained which results in bright red mass colorations in polystyrene.

Example 8 214 parts of 4-nitronaphtholactam and 220 parts of 2-hydroxy-4-oxo-4H-pyrimido- [3.2a] -benzthiazole are introduced into 600 parts by volume of butyrolactone and 200 parts of phosphorus oxy-trichloride are added at 80.degree. The mixture is stirred for 6 hours at 950 ° C., and after the heating has been switched off, 750 parts by volume of methanol and 200 parts by volume of aqueous ammonia solution are added. After suctioning off, washing and drying, 328 parts of a compound of the constitution are obtained When incorporated into thermoplastics, the dye gives brilliant orange colorations of high lightfastness and thermal stability.

Example 9 A slurry of 41.4 parts of that of Example 8 The dye obtained in 150 parts by volume of butyrolactone is stirred at 100 ° C. and with a solution of 95.5 parts of tin (II) chloride dihydrate in 122 parts by volume of conc. Hydrochloric acid added. The mixture is stirred for 4 hours at 100 ° C., 2GO parts by volume of water are added, lets it cool down and sucks off. After washing with dilute hydrochloric acid, the press cake becomes digested in dilute ammonia solution and sucked off again. After the Drying 32.6 parts of an amino compound in 200 parts by volume of N-methylpyrrolidone 14 parts of acetyl chloride are added at 60 ° C. The color of Blue-violet to red. After two hours at 60 ° C., the mixture is diluted with 100 parts by volume Methanol and sucks off.

After drying, 33 parts of the dye are obtained which, when incorporated into thermoplastics, provides orange colorations with good fastness properties.

The table lists other dyes that were obtained by following the procedure of the examples described above: aq 4 sz ho n ^ on H tffi tlx Q [@ O II III oo H 0 OK 0HCN k O ci 0 cl k M 0 HO cci; iy) {i0i red-orange cl 03B II C2H5O) ¼? \ I0 oran. 31 z3 = @ VVU VX H 1 1 LC) 7; 1 dz = -cl-c6H4-s H 04 4 2 HO i HQQ> J p 'X oo eQ III 1 d M NH 0 NHO n X bO k 012H4CN N-CHCN Iio II red I II 2H5 u purple ~ ffi¼I) iH. (eH3) = golden yellow above II III 1 color a XZ oa, pkh; UE 6n5 HO I6IS P1 Ifls6H5 yellow-brown c2114c00cH3 0 m N red orange \OH S r NHO II 1N yellow-orange I r = V H 0 04 A = H II III 1 shade cl bO a> E ri o cl ZIsiH HOsJ'cls½Ü? ioH) red c, <a #> X (d O rl r10 fic FP Pk X o HH x S ru oi OH OH Zi ' Zi- iP 1 9 t D ß O 1S H Ow HO H HH HC) ¢ Z s COo HH i H i WoS II III 1 shade clc3ö;) INH. OCM? INHNS orange NIHO 1 NH NO C4H9OOOIHo II o4H9oooyÜi0 II OH3210113 1I OH3 OH3 red-orange II III 1 shade ho zo n aa XH o rl d> C, k M PO = I a tc ri X HoÄIxN OH3NHCO; XN red-orange o) \ SI NH F3C o2s') 1 II F3Oo2s¼yINoHNi II U II (»i½i # Ls scarlet U Io u 0 Z crj m : = H 0 4 II III 1 shade 0 bO õ wc o 110 4X% II red tufted p OPPE: as oooo <O Cu 2 M b rc r O2N025 H0O00OH 0 N½) i} yIO00OH yellow 3 2 3 u 1i0f0ti O1y # if) N0ji yellow OH B. woo U m n U HHH æ æ z NOZ HH SU> 4 B II III 1 shade o 4 + r ¼Ü; oI) iooIe bo ppi + r koo <O o> O kk Cu bD RXX 1 II N% IONeii orange n red HO Haf ° g Xt L- (gF cH30) L 8% $ N; Red 11 W0 WX t HO III 1 shade cl 1 HO N '' Cl NH 0 yellow Ciio \ IO W [öi Ah 4X C'H3 ua = E pp cr ko m R. zo o 9 .CH3 Cl% OIiHo II Ci 01HO 0 8> Z ' Uu H uu H 4 d 0 F H x UQ II II 1 shade aa oo + raf: pp E4 rl Q) X ho bß Asz yellow - rs Ro Zzo 3: 0 6 o ° 9mO HO'N¼ '% Äjki :) »yellow : no U HH 4 4 O o W o HW °> II III 1 shade bO bO 0113 oo E 4 moot geibstichig pn # no p 0311600113 011N-C03H60C113 Ii to t = ( Cl Cl 04119 Xm 9 Zq ÄÖ3) $ ')' 0Ns geiborange tn U H Om z WHERE ffig ° fm II III 1 shade CH3 \ NH , C11 NOC% IO 011 \ N11 O 0113/2 92115 -02H5 t = ( .a W II ox 8 N s5: k: HC) m II OHffi% i0.8i yellow ll R. HH X H j II III. 1 shade bß bO Q -ì M C21150 s N yellow s 110 ox to o ci I rl kc, ia pp ca mp 1 k C Yri m + r id oo OP) r10 X o bO mh bO no Crc kbO cn kM Pk 1 = ( 0 n NS 06115802I) 1NH0 O6H5so2IWINHON rotstiohig yellow 0 whether to \ ZN % N110 (around o 65 red to him cq = xD WO HC) C) VC) e rXa2 H O <Z ss Hi O S0 9 H m Xn% HQC) II III shade Z H a 3 E Ol # O rc 9 o? Pa pp Ev SQQ = yellow Cit kM II 011300 ÄÜoff0 yellow MI) H yellow % ICl 110 N 3 0113 I% IOH3 0 N NH e ~ Ta NSl yellow rc E n R. H <s ffl = 4 ii H f O 9 ta Zg H tJ CD II III 1 shade 4th n D o # aa, OO 124 o cm H01N002115% $ jLI0O2H5 red M. 2 U 0 cU O H XUE C \ l O C) O OC) AQ z < HH C <z O = tt H i Om N HOO

Claims (1)

Claims 7 1. Naphtholactam derivatives of the general formula in which R is hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl, R1 is hydrogen, chlorine, bromine, alkyl, alkoxy, NO2 or aryl mercapto, R2 is hydrogen or chlorine, R3 is hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, acylamino, Alkylsulfonylamino, arylsulfonylamino, alkyl mercapto, aryl mercapto, arylsulfonyl, alkylsulfonyl, optionally N-substituted sulfamide, alkanoyl, aroyl, alkoxycarbonyl, optionally substituted carbamoyl or cyano, R4 hydrogen, chlorine, alkoxy, aryl mercapto, optionally substituted cyanogen, or alkoxy carbonyl, alkylmercapto, alkoxycarbonyl and R4 together is a radical of the formula R5 is hydrogen, chlorine or alkoxy and X is a radical of the formula mean, where A is hydrogen, methyl, ethyl, methoxy, ethoxy, methylsulfonyl, cyano, methoxycarbonyl, ethoxycarbonyl or nitro and B is hydrogen, C1- to C4-alkyl, B-C1- to C4-alkoxyethyl or propyl or y-C1- to C4 alkoxypropyl. Compounds according to claim 1 of the formula in which B¹ is hydrogen, halogen, aroyl or aryl mercapto and X1 is a radical of the formula mean. 5. Use of the compounds according to Claim 1 for dyeing polyesters or of plastics in bulk.