[1]2,850,520 NEW 'VVATER-INSOLUBLE STYRYL DYESTUFF,9 Emest Merian, Bottmin,-en, Bruno J. R. Nicolaus, Basel, and Ofto Senn, Arlesheim, Svfltzerland, assignors to Sandoz A. G., B-nsel, Switzerland, a Swiss firm No Drawing. Application July 12, 1957 Serial No. 671,420 10 CWms priority, application Switzerland Jiily 18, 1956 7 Claims. (Cl. 260-465) The present invention tdlates to new water-insoluble 15 sfyryl dyestuffs which correspond to the formtila Ir 2@850@520 United Steites Pate - nt Office Patented Sept. 2, 1958 2 wh ere;n each of iv and t represents hydro,-en or methyl, y repres-.nts hydrogen, chlor;llc, bromine, methyl or trifluoromethyl, M represents cyano, diffuoromethyl or trifILoromethyl, and v reptesents hy&oge@i ' chlorine or nitro. The process for the production of the new water-insoluble styryl dyestuffs consists in condejasin.@ 1 or 2 moles respecti,7ely of an aldehyde free from water-solubilizing groups and having the formula 20 CH:i:::Cj. A Ra-V-C-V-R2 y 25 Nvherein A represents the eyano radical, or a - carbalkoxy radical, or a benzene-, diphenyl-, naphthalenemonoor -disulfonyl radical which may be substituted by halogen atoms or alkyl groups containin.- less than 6 carbon atoms, or a 1,3,3-trimethylindolium radical combined in the 2 30 position and further substituted if desired, x hydrogen, a methyl, ethyl, methoxy or ethoxy radical, y hydrogen, a methyl, ethyl, metboxy or ethoxy radical or, when A stands for a 1,3,3-trimethylindolium radical, also halogen or the trifluoromethyl radical, R, an alkylene radical with 35 I to 4 carbon atoms, R2 an alk-ylene radical with 2 to 4 carbon atoms, R3 an aliphatic, cycloaliphatic or aromatic radical Nvhich is free from water-solubilizing groups and may be further substituted, one V oxy-en and the other V the imino group, M hydrogen, a low molecular alkyl 40 or alkoxy radical or, when A stands for a 1 ,3,3-trimethylindolium radical, the cyanomethyl, difluoromethyl or trifluoromethyl radical, a carbalkoxy radical, or the Rs-V-CO-V radical in which R3 and V possess the aforenamed meanings, T hydrogen, when A stands for a 45 1,3,3-indolium radical, and the eyano radical, when A has another meaning, and n the iiumber 1 or 2. Especially interesting dyestuffs are those which correspond to the for@aula 60 w 1, x iNH@CO-0-CH-CH, /A r-C t CN 55 wherein each of x, y, i,.? and t represents hydrbgen or methyl, and A represents the eyano radical, a carbalkoxy 60 radical containing less than 8 carbon atoms, a phenylsulfonyl radical which may carry halo-en atoms or alkyl groups with less than 6 carbon atoms, a tetrahydronaphthylsulfonyl or a naphthylsulfonyl radical, or to the x M-Ri N Clio Ra-V-C-V-R2 8 (IV) wherein x, y, R-,, R2, V and M possess the meanings previously recited, with I mol of malonic acid dinitrile or of a -eyanoacetic acid alkyl ester or a benzenesulfonyl or diphenylsulfonyl acetonitrile or a naphthalenemonosulfonyl or naphthalenedisulfonyl acetonitrile, which may be further substiluted by halogen atoms or alkyl grotips havin.- less than 6 carbon atoms, or a 1,3,3-trimethyl-2methyleneindoline which may contain further substituents. Examples of cyanoacetic acid alkyl esters conforming to the presept definition are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.butyl, -2-methoxyethyl, - 2ethoxyethyl, -3-methoxypropyl, -3-ethoxypropyl, -3-methoxybutyl, and -3-ethoxybutyl esters. Suitable compounds containing the acetonitrile radical are phenylsulfonylacetonitrile, ichloro-, dichloro, melhyl-, ethyl-, isopropyl-, tert.butyl- and dimethylphenylsulfonylacetonitrile, naphthyl-, isopropylnaphthyland diphenyldisulfonylacetonit.-ile. Among the 1,3,3-tr imethyl-2-methyleneindolines, the 1,3,3-trimethyl-2-methyleneindoline itself, the 1,3 ,3-trimethyl-2-methylene-5- chloroindoline and the 1,3,3-trimethyl-2-methylene5-nitroindoline merit special mention. The reaction of the aldehyde with the active methylene compound is performed advantageously by causing the aldehyde to act upon the said compound At fairly high temperature in homogeneous solution in an organic solvent aild in presence of a small quantity of a basic substlnce, c. g. ammonia, dimethylamine, diethylamine, piperidine, sodium alcoholate or potassium alcoholate. It is also possible to heat a mixture of the above-mentioned reactants in presence of glacial acetic acid or another organic acid plus a proton acceptor such as ammonia, diethylamine, dimethylamine or piperidine and, if desired, a solvent Ue benzene, toluene, xylene, chloroform or carbontetrachloride, acting as a recycling agent. The water of reaction is continuously drained off so that there is a constant shift in the equilibritim position to the side of the condensation product. Condensation can also be conducted by saturating a honiogencous solution of the two reactants in a suitable solvent with dry hydrogen chloride. This procedur@- gives rise to a hydro.@en chloride addition product, which upon dis,+illing or heating wi@,h tertiary bases such as dimethylani 'line or diethylanfline splits off the hydrogen chlorid@to yield the desired ethylidene compound. Finally, condensation can be carried out by melting formula 6r, together the reactants and a basic catalyst such as amto 0113 1 x H3cNH-CO-0-C)H@CH2 Nt iNI-CHT-0@2 v
[2]2,850,520 3 monia, dimethylamine, diethylamine, piperidine, ammonium acetate or piperidine acetate in the absence of solvent. The dyestuffs are isolated by one of the-common basic operations, e. g. filtration, evaporation of the solvent, or 5 precipitation from the solvent with a suitable precipitating agent. The new dyestuffs are soluble with fiber-forming polymers m organic solvents. The resulting solutions can be spun by the established methods, both wet and dry. As 10 compaied with the mass coloration of fibers with pigments, the new styryl dyestuffs present an advantage in that they do not cause clogging in the extruder or incrustation of the filters. By virtue of their solubility in_organic solvents the 15 new styryl dyestuffs are also silitdble for the mass pigmentation of offs, lacquer media and synthetic resin@. A certain niimber @of them, notably those- containin.- a sulfonyl group, ha@ie been unexpectedly found to be applicable in the synthetic polymer melt prior to extrusion, 20 a dyeing process employed in the manufacture of the synthetic.polyamide and polyester fibers. In: this connection it is worth noting that almost all of the azo dyestuffs are destroyed under -the temperature conditions obtaining in this process. 25 Many of the_ new styryl dyestuffs, especially those wbich do not contain a sulfonyl group, can be dyed from suspension,- preferably at high temperature and in the presence of agents with dispersin- action. They draw on synthetic polyamide fibers, c. g. nylon and "Perlon" 30 (registered trademark); cehulose ester fibers, e. g. secondary cellulose acetate and cellilose triacetates; polyvinyl fibers; polyacrylonitrile fibers, e. g. "Orlon" (registered trademark); and terephthalic acid ester fibers, e. g. 35 "Terylene," "Dacron@' (registered trademarks). The dyeings are greenish yellow to red in shade. Special mention is due in this connection to the outstandin-, affinity for "Orlon" of those styryl dyestuffs which are - obtainable from an aldehyde of Formula IV and a 1 ,3,3-trimethyl2-methyleneindoline free from water-solubfliz' 40 ing groups but conta'ni'mg further substituents if desired. A number of the dyestuffs also dye wool and silk. Applied to the above-named fibers from suspenston, the dyestuffs give dyeings of very good fastness to water, and gas fumes. The ligbt fastness of the- dyeings on polyamide fibers is good, and on the other fibers very good to outstanding. Dyeings produced in the , spinning solution or the molt,-n mass possess good to very good fast ness to light, -00 water, washing, per@i)iration, cross dyeing, chlorintation in alkaline medium, sublimatio n oxalic acid, d-ry cleaning, gas fumes, rubbing, ironing, peroxide bleaching, heat setting and hydrosumte. In the following examples the parts @ and percentages 55 are by weight. The temperatures are in degrees centigrade and the melting points a re uncorrected. EXAMPLEI 32.6 parts of 1-[N-ethyl-N-(2'-phenylearbamic acid 60 ethyl ester)]-amino-3-methyl-4-benzaldchvde together with 10 parts of cyanoacetic acid methyl ester and I part of piperidine in 30 parts of methyl alcohol are heated to the boi I with r eflux. After some time th-e deep yello@v-colored mass is cooled 65 to O', upon which the new styryl dyestuff crystallizes out in beautiful yellow needles. It is filtered off, washed with cold alcoh6l, and dried. It is readily:soluble in ethyl acetate and acetone and melts at 122'@ It dyes secondary A dyebath is prepared with 0.6 part of the dyestuff Turkey obtained as described above and dispersed wi red oil, 6 parts of a sulfonated fatty alcohol and 3000 parts of water. 100 parts of secondary cerulose acetate are introduced into the bath at room temperature. The temperature is raised to 80' in I hour and this temperature maintained for a further hour. After this time the dyeing process is completed. The fabric is removed, rinsed and dr d. To improve its dispersibilit@.the dyestuff can be ground prior to dyeing with suitable wetting, dispersing or @emulsifying agents, prefer-ably in the presence of inorgani.c salts such as Glauber's salt. It can also be intimately mixed with a dispers'mg agent to give an aqueous paste, which is converted into a dyestuff powder by suitable drying. When an equal quantity of the same aldehyde is condensed in an analogous manner with 8 parts of malonic acid dinitiiie ' a yehow dyestuff is obtained whose melting point is 125'. The above-mentioned 1-[N-ethyl-N-(2'-phenylcarbamic acid ethyl ester)]-amino-3- methyl-4-benzaldehyde is new and is prepared as fohows: 44 parts of N,N-dimethylformamide, 120 parts of phosphorus oxychloride and 29.8 parts of I-IN-ethyl-N-(2'phenylcarbamic acid ethyl ester)]-amin6-3-methylbenzene are heated to 60', and this temperature held for some, time. As soon as the reaction is completed, the reaction mass is poured into a mixture of 300 parts of ice and 300 parts of water with thorough stirring. The@ resultant suspension is adjusted to pH 6.by the addition of a 5% solution of sodium hydroxide.. After some tinie the precipitated product is separated and dried in vacuo. It is a light colored ofl which congeals after some time and melts at 88-89'. E X A M P L E 2 32.6 parts of 1-IN-ethyl-N-(2'-phe@aylcarbamic acid ethyl ester)]-amino-3- methyl-4-benzaldehyde ate carefuhy -melted with 20 parts of 2-1(4'- methyl)7.phehylsulfonyll@ acetonitrile and I part of piperidine, aiid t@e -melt stirred for some time at 100'. As soon as the reaction is completed the reaction mass is allowed to cool and then pulverized. The new styryl cellulose acetate and cerulose tria!cetate, terephthalic 70 - 18 parts of 1,3,3-trimethyi-2- methyleneindoline and:43 acid ester fibers, polyamide and polyacrylonitrile fibers tart of 1- INN-di-(2'-phenylearbamic acid ethyl ester) I in brilliant greenish yellow shades of excellent fastiiess am-mo-3-methyl-4-benzaldehyde and 50 part,s -of glacial, to viater and sea water. The dye'mgs also possess high acetic acid are heated with reflux. The solution soon Wrns fastness to light, sublimation, gas fumes, washing, pe@, dark ied in color. After some time the mass is disspiration, ironing, and heat setting. 70 charged into ic(-, wate.r with constant stiffing,@ and then alcohol, its melting point then being 145'. Its ac etonesolubility is higher than 100 grams per liter.- App@ed in cellulose acetate and tr,iacetate spinning solutions, the dyestuff yields br!]Hant greenish yellow shades which possess very good fastness properties. 100 parts of cellulose acetate are mixed for a short time with 300 parts of a solvent (93 percent aceto I ne plus 7 percent methanol), and the mixture left overnight to sweu. 0.5 p a r t o f t h e d y e s t u f f o b t a i n e d a c c o r d i n g t o t h i s e x - , ample is,dissolve d in 60 arts of the solvent by si le p M P shaking, the solution being added to the cellulose acetate spinmng solution. The mixture is stirred in an open nlmng vessel until 60 parts of the solvent have evaporated. The dyed mass is pumped into the spinning pot and spun in the normal way. The dyed filament is greenish yellow in shade -and exhibits excelleiit fastness to light, washing, cross dyeing, chlorine in alkaline medium, oxalic acid, peroxide, bleaching, gas fumes, rubbing and hydroSulfite. EXAMPLE 3 washing, perspiration, sublimalion, ironing, heat setting 4D dyestuff thus formed can be re I -crystallized from methyl
[3]precipitated with commbn salt. A good yield of the produced by one of the processes described in the above, hydrochloride of the base is obtained. The dried styryl an d correspond to the general formula dyestuff dissolves well in acetone and melts at 90'. It Bi02H4 is applied to cellulose acetate and triacetate spinning CH@ CH A solutions to give very brileant red shades. On "Orlon" 5 " c:@>- it is dyed from aqueous suspension in brileant red shades. B2 I @N The dyestuff has very good fastness properties on these y (V) fibers. The meanings of BI, B2, A, y and n are given in the colWhen the 43 parts of 1-[N,N-di-2'-phenylcarbaniic umns so headed. A further column contains the melting acid ethyl ester) I -amin(@-3-methyl-4-benzaldehyde in Ex- 10 points of the dystaffs, and in the final column the shade ample 3 is replaced by 32.6 parts of 1-[N-ethyl-N-(2'- produ ced in solution-dyed cellulose acetate is noted. Table I Ex. Bi B2 A y 'A M. P., Sbade in cellulose No. degrees acetate 4 ----- Etbylearbamic acid Ethyl -------------- -- Cyano ---------------------- Motbyl --- 1 122 Greenisb yeH6w. radical. ----- ----- do --------------- ----- do ---------------- Carboxyhaethyl ------------- --- do -------1155 Do. ----- Phenylearbainic acid Phenylearbamic acid 41- mothylphenyl sulfonyl ---- --- do -------1165 Do. radical. etbyl radical. 7----- ----- do ---------------- Methyl -------------- Oyano ----------- ----------- Hydrogen- 1 142 Do. 8----- ----- do ---------------- Ethyl ---------------- ---- do --------- --------------- --- do -------1136 Do. 9----- ----- do ---------------- Methyl -------------- Carboxymethyl ------------- --- do -------1116 Do. 10 ---- ----- do ---------------- ----- do ---------------- 41- methylphenylsulfonyl ---- --- do -------1122 Do. 11 ---- ----- do ---------------- Ethyl ---------------- Phenylsalfoiiyl --- ----------- Alethyl ---1 142 Do. 12 ---- ---- do ---------------- ----- do ---------------- 5,6,7,8- tetrahydroiiaphthyl-2- ---do -------1 146 Do. sulfoiayl. 13 ---- ----- do@ --------------- ----- do ---------------- 3,4- dichlorophenylsulfonvl --- Methoxy--1 157 Do. 14 ---- ----- do ---------------- ----- do ---------------- Cyano ---------- ------------ --- do -------1153 Do. 15 ---- ----- do ---------------- ----- do ---------------- 41 methylphenylsulfonyl ---- --- do -------1107 Do. 16 ---- ----- do ---------------- ----- do ---------------- Carboxymethyl ------------- --- do ------1188 Do. 17 ---- ----- do - ------------ -----d---------------- Naphthyl-2- silfonyl --------- Methyl ---1 134 Do. ll::- ---do:---:::: --------- ---- doo ---------------- 4-chlorophenyl-lsulfonyl ---- --- do -------1126 Do. 19 _:I:: .. d. _ --------- ----- do ---------------- 1, 11-diphenyl-4,41- disulfolayl- ---do ------- 2 150 Do. 20 ---- Carbo 4c acid ethyl ----- do ------- --------- CyaiLo ---------------------- --- do ------- 1 123 Do. .t,@@@de 21 ---- do ---------------- ----- do ---------------- Carboxymethyl -- ----------- --- do -------1119 Do. phenylcarbamic acid ethyl ester)]-amfno-3-methyl-4- Table ? contains fi-irther water-insoluble styryl dyebenzaldehyde or by 31 parts of 1-IN-ethyl-N-(2'-phenyl35 stuffs which corresporid to the fonnula carbamic acid ethyl ester)]-amino-4-benzaldehyde or by w I x 44 parts of 1-[N,N-di-(2'-phenylcarbamic acid ethyl Ra--NH@000-CHCH2 A -amino-4-benzaldehyde respectively, three styryl ester) I NCH=C dyestuffs are obtained with the melting points 44', 60' / <t> and 101'. These products have siniilar dyeing properties A( AT-CH2-- CH2 I CN y (VI) to those described in the first paragraph of this example. They are characterized by the symbols R3, w, M, Y, x In the following Table I descriptive data of further and A in columns (I) to (VI) and by the sliade provaluable styryl dyestuffs are presented. They can be duced in solution@dyed cellulose acetate in column (Vli). T able 2 Ex. (I) (11) (Ili) (IV ) (V) (VI) (VII) ,NO. R3 w M y x A Shade in eeuulose acetate 22 ---- Phen7l ---------------- -Methyl--- Hydrogen- Methyl--- _Hydrogen- Oyano -------------------- Greenish yellow. 23 ---- ----- do ----------------- -- do ---- @-- Methyl --- --- do ------- --(io ------- ---- do ---------------------- Do. 24 ---- ----- do ----------------- --- do ------- Ethyl ----- --- do ------- --- do ------- ----- do --------------------- Do. 25 ---- ----- do ----------------- --- do ------- --- do ------- --- do --- ---- Methyl --- ----- do --------------------- Do. 26 ---- ----- do ----------------- --- do ------- Methyl --- --- do ------ - Methoxy -- ----- do --------------------- Do. 27 ---- ----- do ----------------- --- do ------- Hydrogen- Methoxy-- ---do ------- ----- do --------------------- Do. 28 ---- ----- do ----------------- Hydrogen- Methyl--- _@deotb _@l --- Hydrogen - ----- do ----------- ---------- Do. 29 ---- ----- do ----------------- --- do - ------ --- do ------- ---- Methyl --- ----- do --------------------- Do. 30 ---- ----- do ----------------- --- do ------- --- do ------- --- do - ------ Methoxy -- ----- do --------------------- Do. 31 ---- ----- do ----------------- --- do ------- Ethyl ----- --- do ------- --- do ------- ----- do --------------------- Do. 32 ---- ----- do ----------------- --- do ------- --- do ------- Methoxy-- ---do ------- ----- do --------------------- Do. 33 ---- ----- do ----------------- --- do ------- @vlethoxy-- Ethyl ---- - Hydrogen - ----- do --------------------- Do. 34 ---- ----- do ----------------- --- do ------- Ethoxy--- Ethoxy--- ---do ------- ----- do --------------------- Do. 35 ---- Ethyl ------ I----------- --- do ------- HydrogenMethyl --- --- do ------- ---- do ----- ---------------- Do. 36 ---- Butyl ----------------- --do ------- --- do ------- --- do -- ----- --- do ------- ----- do ------- -------- Do. 37---- Cyclohexyl ------------ --- do ------- --- do ------- --- do ------ --- do ------- ----- do -------------------- Do. 38 ---- 41-methylpheiayl ------- --- do - ------ --- do ------- --- do ------- --- do ------- ----- do ----------- ---------- Do. 3i) ---- 31-methylphenyl ------- --- do - ------ --- do ------- --- do ------- --- do ------- ----- do ----------- ---------- DD. 40 ---- 31,41-dimethylphenyl-- ---do ------- --- do ------- --- do ------- --- do ------- ----- do --------------------- Do. 41---- Pheiayl ---------------- Methyl --- --- ------- --- do ------ - --- do ------- Carbomethoxy ------------ Do. 42 ---- ----- do ----------------- --- do ------- --- do ------- --- do - ------ --- do ------- Carbethoxy --------------- Do. 43 ---- ---- do ----------------- --- do ------- --- do ------- --- do - ------ --- do ------- Carbopropoxy ------------- Do. 44 ---- ----- do ----------------- --- do ------- --- do ------- --- do - ------ --- do ------- Carboisopropoxy ---------- Do. 45 ---- ----- do ----------------- --- do ------- --- do ------- --- do - ------ --- do ------- Carbobutoxy -------------- Do. 46 ---- ----- do ----------------- Hydrogen- ---do ------- --- do ---- --- --- do ------- Carbethoxy --------------- Do. 47 ---- ----- do ----------------- --- do ------- --- do ------- --- do - ------ --- do ------- Carbopropoxy ------------- Do. 48 ---- ----- do ----------------- --- do ------- @--do ------- --- do - ------ --- do ------- Carboisopropoxy ---------- Do. 49 ---- ----- do ----------------- --- do ------- --- do ------- Hydrogen Ethyl ----- C@yano -------------------- Do. 60 ---- ----- do ----------------- --- do ------- --- do ------- --- do - ------ Ethoxy --- ----- do --------------------- Do. 51 ---- ----- do ----------------- Methyl --- Ethyl ----- --- do ------- Hydrogen- Carbomethoxy-@ ---------- Do, 52 ---- ----- do ----------------- --- do ------- TTydrogen- ---do ---- --- Ethyl ----- 41-isopropylphenylsulfo- Do. 3 1 Y I . 53 ---- ----- do ----------------- --- do ------- --- do--- do Ethoxy --- 41-chlorophenylsulfonyl---- Do. 54 ---- ----- do ----------------- Hydrogen-@-do-@-:::: :::do::::::: Hydrogen- Carbo-isoamyioxy --------- Do. 55 ---- --- @-do ----------------- --do ------- -@-do ------- --- do - ------ --- do Carbo-amyloxy ----- ---- Do. 56 ---- ----- df> ----------------- --- do ------- --- do -------- --- do - ------ @-do::::::: ICarbo - (31 -me@@oxy) - bu -Do. I t o x y . 57 ---- ----- do ----------------- --- do ------- --- do....... do ------- --- do ------- ICarbb- (31-ethoxy) -butoxy- Do.
[4]2,850,520 7 In Table 3 water-insoluble styryl dyestuffs are enumer, In Table -4 are listed water-insoluble styryl dyestuffs aied which correspond to the formula of the formula w w H-COO-@H-CH S02-D -Rr-O@C 0--:- HN-@H-CH2 2 H= A M-CH2-CH2 ON MCH2--CH2 O N y (vil) 10 'Ihey are characterized by the symbols w, y, M and D They are characterized b th6 symbols R3, w, M, y, x y in cblumns (I) to (IV) and by the shade produced in and A in columns (1) to (VI) and by the shade produced solution-dyed cellulose acetate in column (V). in solution-dyed cellulose acetate in column (VH). Table 3--- ---- -- - (V) (I) (]El) (]:II) (IV) Sbade in No. w y m - - D cellulose --- --- acetate 68--- TTydr6gen- Methyl --- Methyl --- Phenyl--@ ----------------------- - Greenish yeuow. 59--- ---do ------- --- ------- --- do ------- 4-methylphenyl ---- ------- ---- Do. 60--- ---do ------- --- do ------- --- do ------- 31,41-dimetbylphenyl ------- ------ - Do. 61 --- --- do ------- --- do ------- --- do -------- 41-ethylphenyl ------------------ -Do. 62--- ---do ------- --- do ------- --- do ------- 4'-isopropylphenyl ----- - -------- - Do' 63 --- --- do ------- --- do ------- --- do ------- 41-tort@butylphenyl -------------- - Do. 64--- ---do ------- --- do ------- --- do ------- 41-eblorophenyl ------------------ -Do. 65--- ---do ------- --- do ------- --- do ------- Naphthyl-2 ---------------------- - Do. 66 --- --- do ------- --- do ------- --- do ------- 51,61,71,81-tetrabydronapbtbyl-2-- -Do. 67 etb --- --- do ------- --- do ------- Phenyl -------------------------- -Do. 0_@l -methylphenyl ------------- 68--- ---- --- ------- --- do ------- 4' --- Do. 69--- ---do ------- --- do ------- Ethyl-@ --- Phenyl ------ --, ---------------- -Do. 70--- ---do ------- --- do ------- --- do ------- 41-metbylphenyl ------- ---------- Do. 7f--- ---do ------- --- do ------- ---- do ------- 4'-cblorophenyl ------- ------------ Do. 72 --- Hydrogen- ---do ------- --- do ------- Phenyl -------------------------- Do. 73 --- --- do ------- --- do ------- --- do ------- 41-iiaethylphenyl ---------------- Do. 74 --- e@@l --- ---I------- Hydrogp.- Phonyl -------------------------- Do. 75--- -!@d ---- --- do ------- --- do ------- 41-raethylpbenyl ---------------- Do. 76--- Hydrogen- ---do ------- --- do ------- 31,41-dimetbylphenyl ------------ Do. 77--- ---do ------- --- do ------- --- do ------- 41-tert. butylphenyl ------------- Do. 78 --- --- do ------- HydrogeiL --- do ------- Phenyl -------------------------- Do. 79 --- --- do ------- --- do ------- --- do ------- 41-methylphenyl ---------------- Do. 80--- Metbyl --- --- do ------- --- do ------- Phonyl -------------------------- Do. 81--- ---do ------- --- do ------- --- do ------- 41-methylphenyl ---------------- Do. 82 --- --- do ------- --- do ----- Methyl --- Pbenyl -------------------------- D6. 83--- ---do ------- --- do ----- :: --- do ------- 41-iaethylphenyl ---------------- Do. 84 --- Hydrogen- ---do ------- --- do ------- ----- do- ----- Do. ----------- 7---------- 85 --- --- do ------- --- do ------- --- do ------- Phenyl -------------------------- Do. 86 ---do ------- --- do ------- Ethyl ----- ----- do ----------------------- --- Do. 87--- ---do ------- - -do ------- Methyl --- 5',6',7',8'-tetrahydronaphthyl-21- Do. 88 --- --- do ------- --- do ------- 'thyl-::::l 4'-methylphenyl ---------------- Do. 89--- Methyl --- --- do ------- --- d.__ ----- do --------------------------- Do. 90--- ---do ------- --- do ------- --- do ------- I Pbenyl -------------------------- Do. 91--- Hydrogen- Methyl --- Hydrogen1',I"-diphehyl-e ---------------- Do. ------- Table4 (III)-- --(rv) (V) (VI) (VIII) EX. --- --- No. Shade in R y A ------ -Wcellulose a c e t a t e 92 ---- Phenyl ----------- -IIy4rogen- Hydrogen- Methyl --- Hydrogen- Oyano ------ -------------------------- Greenish y e l l o w . 93 ---- ----- dQ--@ -------- ----- do---- Methyl--- ----do ---- ----- do ---- --- -- do --------------------------------- Do. gi ----- ----- do ------------ ----- do---- -Ethyl ----- ---- do ---- ----- do ---- ----- do --------------------------------- Do. 95 ---- ----- do ----------- -- @-@do ---- Eydr-ogen- --I@lethoxy -- ----- do---- --- -do --------------------------------- Do. 96 ---- ----- do ----------- ----- do ---- ----- do---- ]@lethyl --- Metboxy -- ---- - do --------------------------------- Do@ 97 ---- ----- do ------------ Methyl --- ----- do---- ---do ---- ----- do---- ----- do --------------------------------- Do. 98 ---- ----- d6 ----------- ----do ---- ----- do ---- ----- do ---- Methyl --- ----- do --------------------------------- Do. 99 ---- ----- do ----------- -HydrogenEthyl ----- ----do---- HydrogenCarbomethoxy ------------------------- Do. 100 --- ----- do ----------- ---- do ---- -- --do ---- ----- do ---- ----- do---- Carbethoxy ------------- Do. 101 --- ----- do ----------- ----- do ---- ----- dp---- ----do ---- ----- do ---- Carbopropoxy -- ------------------------ Do. 102 --- ----- do ----------- ----- dQ ----- ----- do ---- ----- dQ ---- ----- do ---- Carbo-isopropo,@i ---------------------- Do. 103 --- ----- do ----------- ----- dQ ---- Hydrogen- ----do ---- ----- do ---- PheiiylsulfQny@ ------------------------- Do. 104 --- ----- dQ ----------- ----- dQ---- ----do---- ----do ---- ----- do ---- 41- methylphenylsulfonyl --------------- Do. 105 --- ----- do ----------- ----- do-. -- ----- do---- ----do---- -----do---- 31,4@- dimethylphenylsalfonyl ----------- Do. 106 --- ----- do ----------- ----- ----do ---- ----- do ---- 4'fethyJpbenylsalfonyl ----------------- Do. 107---- ------do ----------- ----- do ---- ----- do----- -----do ---- ----- do ---- 4-1- isopropylpheiaylsalfonyl ------------- Do. 108 --- ----- do.. --- ----- ----do ---- ----- do---- ---do---- ----do ---- 4'rtert-butylp,henylsulfonyl ------------- Do. 109 --- ----- do-@ --------- ----- do ---- ----- (10-@--- ---do ----- ----- (lo---- 41-chl , prophen ylsulfony l ----- ----------- Do. 110 --- ----- do ----------- ----- do ---- ----- do--,- ----do ---- ----- do---- Napbthyl-21- sulfonyl ------------------- Do. ill --- ----- do ----------- ,----- do ---- ----- do ---- ----- do ---- ----- do---- 5',6',71,8'-tetrahydroiaaphthyl-21 -sal- Do. fonyl. 112--- _Al@ethyl ---------- ----- do ---- ----- -----do ---- 41- me.thylphenylsulfonyl. -------------- Do. 113 Etliyl ----- ----- do ---- ----- do---- - ---do ---- ----- do ---- --- -- do -------------------------------- Do: - ----- do ---- ----- do---- -- --d-o ---- ----- do ---- --- -- do- . ------------------------ Do 115- Ethox yetbyl ----- ----- do..--- ----- do ---- ----- do ---- ----- doI Do ------- ------- ------- --- - --- ----
[5]The water-insoluble stml dyestuffs of Table 5 correspond to the formula 2,850,520 columns (1) to (IV) and by the shade produced in solution-dyed cerulose acetate in column (V). CH3 <=>-NH-coo-CHr-C,H2 IE[go\N CH=CH--@l \\ M-CES-Cl@ @Rs and are characterized by the symbols M, y, x and Ml in columns (I) to (IV) and by the shade produced in Table 6 solution-dyed cellulose acetate in column Table 5 20 (1) (ri) (M) (M (V) Shad6in (I) (]:I) (In) (IV) (V) No. w m x A cellulose acetate Ex. She@de in No. m v x Ml cellulose aceta te 135-- Hydrogen- Hydrogen- Hydrogen- 1,11-di phbnylyl. Greenish 25 4 41 yellow. 136-- Methyl --- --- do ------- --- do ------ @ ----'do Do. 116 ------ Hydrogen- Hydrogen- Methyl --- HydrogenRed. 137-- ---do ------- Methyl --- --- do ------- ----- do: ----------- Do. 117 ------ --- do ------- Methyl --- --- do ------- --- do ------- Bluish red. 138-- ---do ------- Ethyl -- --- --- do ------- ----- do ----------- Do. 118 ------ --- do ------- MethoxT-- ---do ------- --- do ---- --- Do. 139-- TTydrogen- ---do ------- --- do ------- ----- do ----------- Do. 119 ------ --- do ------ Methyl--- Methoxy-- ---do ------- Do. 140-- ---do ------- Methyl --- --- do ------- ----- do ----------- Do. 120 ------ --- do ------ Methoxy-- ---do------ ---do ------ Do. 141-- ---do ------- Hydrogen- ---do ------- Naphthylene- Do. t 1.5. 121 ------ --- do ------- Chloro ---- Hydrogen---do ------- Soaxle 30 142-- Methyl --- --- do ------- --- do ------- ----- do ----------- Do. 122 ------ --- do ------- Bromo ---- --- do ------- --- do ------- Do. 123 ------ --- do ------- Trifluoro- ---do ------- --- do ------- Do. 143-- ---do ------- --- d( ------- Methyl --- ----- do ----------- Do. methyl. 144-- ---do ------- --- do ------- Methoxy -- ----- do ----------- Do. 124 ------ Methoxy-- Methyl --- --- do ------- --- do ------- Red. 145-- Hydrogen- ---do ------- --- do ------- Naphthylene- Do. 125 ------ Ethoxy------do ------- --- do ------- --- do ------- Do. 2.6. 126 ------ Cyano --- do ------- --- do ------- --- do ------- Do. do do ------- Methyl --- ----- do ----------- Do. 14 127 ------ -DifiLioro- ---do ------- --- do ------- --- do ------- ScaTlet. 14!7'-: :- :d":::::::l :::do ------- Methomy -- ----- do ------------ Do. 3Itethyl. 35 14,- t' do ------- --- do ------- ----- do ----------- Do. 128 ------ Trifluoro- ---do ------- --- do ------- --- do ------- Do. 149-: @de.--Yl--:: :::do ------- Hydrogen - ----- do ----------- Do. ethyl. 150-- Hydrogen- ---do ------- --- do ------ do ----------- Do. ------- --- do ------- Do. 129 ------ C Ia:rab o --- do ------- --- do ,:aethoxy. 130 Phenyl- ---do ------- --- do ------- --- do ------- Red. carbamid. EXAMPLE 151 1 I_H rogen- ---do ------- - ::dlo:::::::l Iloro --- Do. 40 __@d ...... d.__.: 132 Trydrogen- --- Do. 133 ------ I --- do ------- --- do ------- --- do------ Nitro----- Do. 200 parts of ceflulose triacetate, 5 parts of the dyestuff 134 ------ 1---do ------- Methyl--- ---do ------- --- do ------- Do. obtained according to Example 10 which has the formula <::>NH-CO-0-CHrCH2 so -<@:>c H '\N- >-CH=C 0ji, CN The water-insoluble styryl dyestuffs of Table 6 have 927 parts of methylene chloride and 49 parts of ethanol the formula are compounded to a homogeneous paste. This is pumped w 60 int o the spinning pot in the norinal way and sprn. The I x filament is dyed a bright greenish yellow which possesses <=>-NH-COO-OH-CH2 so A \ NCH=C / ex cellent fastness properties. CN EXAMPLE 152 (X) A solution composed of 400 parts of polyethyle ne, 4 and are characterized by the symbols w, M, x and A in parts of the dyestuff of the formula CHS Co-o-CH2-- CH2 s o \ N OH=o / -<=> CIE[E-O -< 5- \ CN
[6]2,85-0,520- whicli@@is. obtained according to Exanfl5li, I 1,:and 600:partsof xylene is extruded,thrqugh , orifices of 0.5,m@m.-dianieter into mixtures of butyl aicohol and butylphthalate. The precipitated greenish yerow filament is washed in petroleum ether and dried in warm air. EXAMPLE 153 1 part of the dyestuff of the -formula <D@-NII-CO-O-C]E[3--C -U' so \N e@Er--C CN obtained according to Example 12 and 150 parts of poly vinyl chloride are7 dissolved in 849 parts of cyclohdxanone at 80'. The hot solution is then spun into a precipitation- @ath of 500 parts of cyclohexanone and 9500 parts of 2-ethylhexanone at 30'. The greenish yelloW-Mament is reeled, dried under tension, and orientated EXAMPLE 154. 2 piiu of the dyestuff of the formula CH3 II-;-00-0-0]Err-clr2 so cHt-OH2 CNobtained according to Example 13, 280 parts of postchlorinated polyvinyl chloride and 10 parts @ of diethyl sulfide are dissolved in 708 parts of acetone at 40'. The mass is pumped into the sbinning pot -and spun in the normal way. The filament is precipitated by water, orientated and dried at 40 to 70'., It is dyed in a greenish yellow shade. EXAMPLE 155 A mixture of 1 part of the dyestuff of the formula <:D>-N-H-CO-0-0-Ht- . c so N Cll =o CH:- C@, ON obtained according to Example 15 and 199 parts of a copolymer compqsed of 60.1% of vinyl chloride and 39.9% of acrylonitrite are mixed with 800 parts of Eicetone for 4 hours at 50'. A homogeneous yello w solution is: obtained, which is filtered and spun into filainent, using water as precipitating agent. 'The Mame@i is- orient@ted and heat-set in boiling water. It is dyed a greenish yellow shade with good fastne@s ]@rbperties. EXAMPLE 156 165 parts of polyacrylonitrffe and I part of the dyestuff obtained according to Example 17 and having the formula CHS <=>-NH=co-o-c -HI--CAI o C. CE4-.;-C@, CN 12 are@dis oliied-k-834-parts-,6f dimethylformamide at 1606. The mass is spun into filament by- the@ ex'trusion- m- ethod commonly used for viscose rayon, water be'mg used as precipitating agent. The filament is subsequentlv orientated in a water bath at 90'. It is dyed in a bright yenow shade which shows good fastness properties. F-XAMPLE 157 20 1 part of the d@i!@tu# the.fo.rmula CHO .<=>-NH-00-0-CH2-0 -Hi@ ON Cll=@"--SO2 25 OHS IEE@CO-0-CHt-0 -H, ON <=>-N \x CH=@ ol and 179 parts of polyacrylonitrile are dissolved in 820 partsofdini6.thyfforn@imideatloo.l. Theresultantbi@i6 is pumped -through the - spinnerette @ into a - precipitatin@bath 6f gly&ol -at 140'-. The Mam-ejit is reeled, - orienta-t@e- -d45 w-a--Slied w-ith water tb remov-e- the- -r-et-a-ined glycol, and finally dried. Greenish yellow dyeings with good fastness properties are obtained. Hi EXAMPLE 158 60 25 parts of the dyestuff of the formula CITJ <=>-NII-CO-0 CHr-C]Er2 - CN \N CH=o -C]13-CH2 CN 65 which-is obtained as specified in Example 1 are mixed with 5000 parts of Rilsan and the mixture melted in a nittogen atmosphere dt230"-by th6 n6rmal 'method., -The thick liquid mass is spun into greenish yellow filaments with good fastness properties.
[7]!2,850,520 13 14 EXAMPLE 159 25 parts of the dyestuff of the formula CH3 <:::>-NH-00-0-@HCH2 OHB 902- CHS N 011=C CH3- CH2 ON are mixed Nvith 5000 parts of iiylon (nylon 66) and the EXAMPLE 162 mixture melted by the normal method in a nitrogen atmosphere at about 285'. Upon spinning, the thick liquid 0.5 part of the dyestuff of the formula C H 3 + H-00-0-CH2-- CHs H3C mass yields greenish yellow fhaments with good fastnessproperties. The filament can be orientated and/or crimped and heat-set to render it shrinkproof. EXAMPLE 160 25 25 parts of the dyestuff of the formula CH3 I CHS so <::>-NTH-CO-0-CH-CH2 C NT '@NT CH=C CH3--CH2 c N are mixed with 5000 parts of the condensate of - tereph- 35 thalic acid and glycol or the dimethyl ester of this acid and glycol. The mixture is melted in the normal way in a nitrogen atmosphere at about 280', givin- a thick liquid mass which is spun into greenish yellovi filaments which 40 exhibit good fastness properties. EXAMPLE 161 1 part of the dyestuff CH3 45 <=>NH-CO-0-CH2-C\H2N ON CH=C CHs-OH2--CHr-OH2 ON 50 is mixed with 300 parts of polyethyleile and spun by the normal extrusion method. Bright geenish yellow filaments or bristles are obtained. Polystyrene can be solution-dyed with this dyestuff on similar lines. \ N-<::>-CH=CH- Anion NC-CH2-C@s @Hs is added to 100 parts of cellulose acetate and the mixture spun accordin-, to the procedure given in Example 2. Bright red filaments of very good fastness are obtained. When the cyanoethyl group in this dyestuff is replaced by the trifluoroethyl group, the resultant dyestuff yields a rather more yellowish shade in cellulose acetate fibers, though the standard of fastness is the sam.-. When in place of theunsubstituted aniline derivative the derivative which contains a methyl group in the m-position to the tertiary amino group is employed, the dyestuffs so obtained are a slightly morepronounced bluish red, both in substance, in solution, and in the fiber. Similar properties are possessed by the correspondin.- N-difluoroethylamino dyestuffs and the dyestuffs which in place of the phenylcarbamic acid ethyl radical carry the phenylcarbamic acid isopropyl radical. The latter-named dyestuffs are also wefl suited for the mass dyeing of ceflulose acetate fibers in red shades. Formulae of representative dyestuffs of the foregoing examples are: EXAMPLE 1 <=>-NH-CO-0-CH2-CH2 CH3 COO-CHS C113-CH2 CN and its variant of paragraph 3 <=>- NH-CO-O-CHTC\H2N CHs CN CH=o / CHS-C@@ CN EXAMPLE 2 <=>NH-CO-0-CHr-C\H2 C IE[a s 0 -<=)-OHS / N-<=@-CH=C CHs-CH2 0 N EXAMPLE 3 CH3 CH3 H3CI C17 N-<=>CH=CH-C) H-CO-0-CHr-CH2 \\N EXAMPLE 11 CHB NHCO-0-CH2- CH2 so /N-C @-CEE--o ORZ-CH2 ON
[8]2)850,520 15 EXAMPLE 12 OHS H-00-0-CH2- C,H2 so N C H=o C114- CH2 C N EXAMPLE 22 c-usco-0--@@iil-CTT2 -- C N 10 CN Having thus d.isclosed the invention what is
