Patent Publication Number: US-4579939-A

Title: Azo dyes from substituted 2-aminothiophenes and acyclic active methylene couplers

Description:
This invention relates to yellow dyes derived from substituted 2-aminothiophene and acrylic active methylene coupling components. They are of particulr interest as colorants for polyester fibers by dyeing and printing methods. 
     The present dyes have the general formula ##STR3## wherein: X is alkyl, allyloxy, alkoxy, aryl, aryloxy, amino, alkylamino, arylamino, cyclohexoxy, cycloalkylamino, N,N-dialkylamino, or N-alkyl-N-arylamino; Y is hydrogen, alkyl, or aryl; Z is alkyl, aryl, alkylsulfonyl, cyano or COX where X is defined above; R is cyano, carbamyl, alkanoyl, aroyl, alkoxycarbonyl, alkylcarbamyl, arylcarbamyl, cycloalkylcarbamyl, dialkylcarbamyl, benzimidazolylcarbamyl, naphthylcarbamyl, pyridylcarbamyl, or benzothiazolylcarbamyl; R 1  is selected from the above R groups and ##STR4## wherein R 2  represents the atoms necessary to complete an azole radial selected from benzothiazole, benzimidazole, benzoxazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, and pyrazole; wherein the hydrocarbon moieties of each of the above radicals or groups may be substituted with up to three of --OH, alkoxy, hydroxyalkoxy, alkanoyloxy, alkylcarbamyl, dialkylcarbamyl, arylcarbamyl, --NO 2 , hydroxyalkyl, alkanoylamino, alkanoyl, alkoxycarbonyl, --CF 3 , aryloxy, halogen, alkoxyalkoxy, aryl, --CN, alkenyl, phthalimido, succinimido, furyl, cyclohexyl, or cycloalkyl substituted with hydroxyalkyl; and wherein the alkyl groups or moieties within the above definitions of X, Y, Z, R and R 1  contain from 1-12, preferably 1-8, and most preferably 1-6 carbons and are straight or branched chain. 
     The dyes of this invention impart bright greenishyellow shades to polyesters by dyeing and printing methods and are particularly valuable for mixing with blue colorants to produce bright green colors. The new dyes may also serve as water-insoluble pigments and are suitable for coloring lacquers, natural or synthetic resins, and for printing textile fibrous materials or paper. Several of the dyes show outstanding stability to high pH conditions. The colorants containing higher alkyl groups have good solubility in organic solvents and are suitable, for example, for coloring hydrocarbons, such as fuel oil. The dyes, in general, exhibit improved properties such as fastness to light, sublimation, chlorine, heat, ozone, oxides of nitrogen, gas, perspiration, crock, and wash, and exhibit good build, pH stability, bloom resistance, dye bath exhaustion, depth of shade, leveling, strike rate, migration, and the like over dyes such as are disclosed in Br. Pat. No. 1,394,365. 
     In general, the present dyes are prepared by diazotizing substituted 2-aminothiophenes II ##STR5## and coupling with active methylenes III under basic conditions. Reactants II are prepared as disclosed for example in [Z. Chem., Volume 2, page 305 (1962); Chem. Ber., Volume 98, page 3571 (1965), and Volume 99, page 2712 (1966), and Chem. Heterocyclic Compounds, Volume 2, page 285 (1966); and Volume 3, page 178 (1967)]. Dyes where the COX group is an aniline substituent are best prepared by treating the corresponding carbomethoxy derivative with an aliphatic amine or ammonia to effect an ester-amide interchange reaction such as ##STR6## 
     Typical useful coupling components include the following: 2,4-pentanedione (acetylacetone); 1-phenyl-1,3-butanedione (benzoylacetone); 1,3-diphenyl-1,3-propanedione (dibenzoylmethane); acetoacetanilide; acetoacet-o-anisidide; acetoacet-m-xylidide; acetoacet-o-chloroanilide; α-cyanoacetanilide; malononitrile; ethyl cyanoacetate; α-benzoylacetanilide; methylpivaloylacetate; 2-cyanomethylbenzimidazole; and 2-cyanomethylbenzoxazole. 
     The following examples will illustrate the invention: 
    
    
     EXAMPLES 1-10 
     Diazotization and Coupling 
     Sodium nitrite (7.2 g) was added portionwise to concd. H 2  SO 4  (50 ml) with stirring, allowing the temperature to rise. The solution was cooled and 100 ml of 2:5 acid (2 parts propionic acid:5 parts acetic acid--by volume) was added at less than 20° C., followed by cooling to about 0° C. 2-Amino-3,5-dicarbethoxy-4-methylthiophene, 25.7 g., 0.10 m (gm. mole) was added at 0°-5° C. and then another 100 ml of 2:5 acid was added at &lt;5° C. and stirring continued for 1.5 hr. 
     Each of the following couplers 1-10 (0.01 m of each): 
     Example 1-2,4-Pentanedione; 
     Example 2-1,3-Diphenyl-1,3-propanedione; 
     Example 3-Malononitrile; 
     Example 4-Acetoacetanilide; 
     Example 5-Acetoacet-o-anisidide; 
     Example 6-Acetoacet-o-chloroanilide; 
     Example 7-Acetoacet-m-xylidide; 
     Example 8-Acetoacet-p-phenetidide; 
     Example 9-α-Benzoylacetanilide; and 
     Example 10-Methyl pivaloylacetate; 
     was dissolved in approximately 400 ml of ice-water mixture to which 12 ml of 50% NaOH solution had been added. A 0.01 m aliquot of the above diazonium salt solution was added rapidly to each coupler solution. If the coupling mixture became thick, additional ice-water mixture was added. After allowing to couple for about 15 minutes, the yellow dyes were collected by filtration, washed with water, and dried in air. The dyes produced bright yellow shades on polyester fibers and had moderate to excellent lightfastness and good pH stability. 
     EXAMPLE 11 
     A 0.01 m portion of 2-amino-3,5-dicarbomethoxy-4-methylthiophene, was diazotized and coupled with 0.01 m of acetoacetanilide as described above to yield 4.0 g. of the dye ##STR7## 
     EXAMPLE 12 
     The dye from Example 11 (0.01 m), 2-aminoethanol (15 ml), and N,N-dimethyl formamide (15 ml) were stirred and heated together at 30°-35° C. for 15 min. The reaction mixture was drowned into 300 ml of ice-water mixture and treated with 15 ml of concd. HCl. The yellow dye was collected by filtration, washed with water, and dried in air. Ester-amide interchange occurred mostly at the 3-carbomethoxy group to give the dye. ##STR8## 
     Prolonged heating at higher temperature gave additional reaction at the 5-carbomethoxy group to give the bis-amide dye. ##STR9## 
     The following examples in Table I further illustrate the invention. The preferred dyes are those where: X is alkoxy or alkylamino; Y is H or alkyl; Z is carboalkoxy, acyl, cyano, or aryl; R is alkanoyl or aroyl; and R 1  is alkanoyl or arylcarbamyl. 
     
         TABLE I
  ##STR10##
  Ex.      No. X Y Z R R.sub.1
        13 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2
  H.sub.5
 ##STR11##
  COCH.sub.3  14 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5
  ##STR12##
  COCH.sub.3  15 OCH.sub.2 CHCH.sub.2 CH.sub.3 C.sub.2
  H.sub.5
 ##STR13##
  COOCH.sub.2 NHCH.sub.2  16 NHC.sub.2 H.sub. 5 CH.sub.3 CO.sub.2 C.sub.2
 H.sub.5 CONHC.sub.4 H.sub.9n COCH.sub.3 17 OC.sub.2 H.sub.5 H CO.sub.2
 C.sub.2 H.sub.5 CON(C.sub.2 H.sub.5).sub.2 COCH.sub.2 Cl  18 Ph CH.sub.3
 COCH.sub.2
  OOCCH.sub.3
 ##STR14##
  CONHCH.sub.3  19 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5
  ##STR15##
  COCH.sub.3  20 OC.sub.2 H.sub.5 H CO.sub.2
  Ph
 ##STR16##
  CONHPh  21 NHPh CH.sub.3 CO.sub.2 C.sub.2
  H.sub.5
 ##STR17##
   CONHPh  22 OC.sub.2
  H.sub.5 CH.sub.3 Ph
 ##STR18##
  CONHPh  23 OC.sub.6 H.sub.11 Ph CO.sub.2 C.sub.2
  H.sub.5
 ##STR19##
  COCH.sub.3
  24 NHCH.sub.3 CH.sub.3 COCH.sub.3
 ##STR20##
  CONHPh  25 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2
  H.sub.5
 ##STR21##
  COCH.sub.3
  26
 ##STR22##
  CH.sub.3 CO.sub.2 C.sub.2
  H.sub.5
 ##STR23##
  COCH.sub.2 OC.sub.2 H.sub.5  27 OC.sub.2 H.sub.5 CH.sub.3 COC.sub.2
 H.sub.5 COCH.sub.3
  ##STR24##
   28 NHC.sub.6 H.sub.11 Ph CO.sub.2 C.sub.2 H.sub.5 COC.sub.2 H.sub.5
  ##STR25##
   29 OC.sub.2 H.sub.5 H SO.sub.2
  CH.sub.3 OPhp-Cl
 ##STR26##
   30 OC.sub.2
  H.sub.5 H Ph CN
 ##STR27##
   31 OC.sub.2 H.sub.5 C.sub.2 H.sub.4
  OH COPh CN
 ##STR28##
   32 OC.sub.2 H.sub.5 Php-OH COCH.sub.2
  Ph CN
 ##STR29##
   33 OC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 CO.sub.2 C.sub.2
 H.sub.5 CONHC.sub.6 H.sub.5 CONH.sub.2 34 OC.sub.2 H.sub.5 CH.sub.2
 CH.sub.2 OC.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 CONHC.sub.6
  H.sub.4p-Br COC(CH.sub.3).sub.2  35 OC.sub.2 H.sub.5 CH.sub.3 CN
  ##STR30##
  COCH.sub.2 C.sub.6 H.sub.11  36 OC.sub.2 H.sub.5 CH.sub.2 CH.sub.2
 OC.sub.2 H.sub.2 OC.sub.2
  H.sub.5 CO.sub.2
 ##STR31##
  COCH.sub.2 Ph  37 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5
  ##STR32##
  COCH.sub.2 CH.sub.2 OH  38 OC.sub.2
  H.sub.5 CH.sub.3 CN
 ##STR33##
  COCH.sub.3  39 OCH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 OH CO.sub.2
 C.sub.4 H.sub.9n COCH.sub.2 CH.sub.2 OH COCH.sub.3 40 NHC.sub.2 H.sub.4
 OH CH.sub.3 CO.sub.2 C.sub.4 H.sub.9n COCH.sub.2 OC.sub.2 H.sub.5
 COCH.sub.3 41 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2
 H.sub.5 COCH.sub.2 OCH.sub.2 CH.sub.2 OH COC.sub.6 H.sub.5 42 OCH.sub.3
 Php-NHCOCH.sub.3 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2
 H.sub.5 COC.sub.6 H.sub.4p-OOCCH.sub.3 COC.sub.6
  H.sub.4p-Cl 43 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.6 H.sub.5 COCH.sub.3
 COCH.sub.3   44 OCH.sub.3 CH.sub.2 NHCOCH.sub.3 CO.sub.2 CH.sub.2
 C.sub.6
  H.sub.5
 ##STR34##
  COCH.sub.2 CH.sub.2 CN  45 OCH.sub.3 Php-Cl CO.sub.2 CH.sub.2 CH.sub.2
 OC.sub.6
  H.sub.5
 ##STR35##
  COCH.sub.3  46 OCH.sub.3 CH.sub.2 Cl CO.sub.2 CH.sub.2 CH.sub.2 OH
  ##STR36##
  COCH.sub.2 OOCH.sub.3  47 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.2 CH.sub.2
 CN
  ##STR37##
  COCH.sub.3  48 OCH.sub.3 CH.sub.2 Br CO.sub.2 CH.sub.2 CH.sub.2 Cl
  ##STR38##
  COCH.sub.3  49 OCH.sub.3 CH.sub.2 CH.sub.2 CF.sub.3 C.sub.6 H.sub.5
  ##STR39##
  COOCH.sub.2 NHCH.sub.3  50 NH.sub.2 CH.sub.2 Ph C.sub.6 H.sub.5
 CONHC.sub.4 H.sub.9n COCH.sub.3 51 NHC.sub.3 H.sub.6 OCH.sub.3 H C.sub.6
 H.sub.4p-OCH.sub.3 CON(C.sub.2 H.sub.5).sub.2 COCH.sub.2 Cl
  52 NHC.sub.2 H.sub.4 OH CH.sub.2 C.sub.6 H.sub.11 C.sub.6
  H.sub.4p-CH.sub.3
  ##STR40##
  CONHCH.sub.3  53 OCH.sub.3 CH.sub.2 CH.sub.2 CN C.sub.2 H.sub.5
  ##STR41##
  COCH.sub.3  54 NHC.sub.2 H.sub.4 OH H C.sub.2
  H.sub.5
 ##STR42##
  CONHPh  55 OC.sub.2
  H.sub.5 H
 ##STR43##
  ##STR44##
  CONHPh  56 OCH.sub.3 CH.sub.2
  COOCH.sub.3
 ##STR45##
  ##STR46##
  CONHPh
  57 OCH.sub.3 CH.sub.3 COCH.sub.3
 ##STR47##
  COCH.sub.3  58 OCH.sub.3 C.sub.6 H.sub.5 CO.sub.2 C.sub.2 H.sub.5
  ##STR48##
  CONHPh
  59 OCH.sub. 3 CH.sub.3 CN
 ##STR49##
  COCH.sub.3  60 NHC.sub.2 H.sub.4
  OH CH.sub.3 CN
 ##STR50##
  COCH.sub.2 OC.sub.2 H.sub.5
  61 OCH.sub.3 CH.sub.3
 ##STR51##
  COCH.sub.3
  ##STR52##
   62 OC(CH.sub.3).sub.3 CH.sub.3 COC.sub.2 H.sub.5 COC.sub.2 H.sub.5
  ##STR53##
   63 C.sub.6 H.sub.5 CH.sub.3 COC.sub.2
  H.sub.5 OPhp-Cl
 ##STR54##
   64 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 COC.sub.2
  H.sub.5 CN
 ##STR55##
   65 N(CH.sub.3)C.sub.6 H.sub.5 CH.sub.3 COC.sub.2
  H.sub.5 CN
 ##STR56##
   66 OC.sub.4
  H.sub.9n CH.sub.3
 ##STR57##
  CN
  ##STR58##
  67 OCH(CH.sub.3).sub.2 CH.sub.3
 ##STR59##
  CONHC.sub.6 H.sub.5 CONH.sub.2  68 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.6
 H.sub.13n CONHC.sub.6 H.sub.4p-Br COC(CH.sub.3 ).sub.2  69 OC.sub.4
 H.sub.9n CH.sub.3 CO.sub.2 C.sub.8
  H.sub.17n
 ##STR60##
  COCH.sub.2 C.sub.6 H.sub.11  70 OC.sub.6 H.sub.13n Php-OCH.sub.3
 CO.sub.2 CH.sub.2 CH.sub.2
  CH(CH.sub.3).sub.2
 ##STR61##
  COCH.sub.2 Ph  71 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 CH.sub.2
  CH(C.sub.2 H.sub.5)C.sub.4
  H.sub.9n
 ##STR62##
  COCH.sub.2 CH.sub.2 OH  72 OCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4
 H.sub.9n CH.sub.3 CO.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9n
  ##STR63##
  COCH.sub.3  73 OCH(CH.sub.3)C.sub.2 H.sub.5 CH.sub.3 CO.sub.2 CH.sub.2
 CH(CH.sub.3)C.sub.3 H.sub.7n COCH.sub.2 CH.sub.2 OH COCH.sub.3 74
 OC.sub.10 H.sub.21n Php-CN CO.sub.2 C.sub.10 H.sub.21n COCH.sub.2
 OC.sub.2 H.sub.5 COCH.sub.3 75 NHCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4
 H.sub.9n CH.sub.3 CO.sub.2 CH.sub.2 CHCH.sub.2 COCH.sub.2 OCH.sub.2
 CH.sub.2 OH COC.sub.6 H.sub.5 76 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9n
 CH.sub.3 CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9n COC.sub.6
  H.sub.4p-OOCCH.sub.3 COC.sub.6 H.sub.4p-Cl  77 OC.sub.2 H.sub.5
 CH.sub.3
  ##STR64##
  COCH.sub.3 COCH.sub.3  78 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.12
  H.sub.25n
  ##STR65##
  COCH.sub.2 CH.sub.2 CN  79 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 CH.sub.2
 CHCH.sub.2
  ##STR66##
  COCH.sub.3
  80
 ##STR67##
  CH.sub.3 CO.sub.2 C.sub.2
  H.sub.5
 ##STR68##
  COCH.sub.2 OOCH.sub.3
  81 OCH.sub.3 CH.sub.3
 ##STR69##
  ##STR70##
  COCH.sub.3
  82 OCH.sub.3 CH.sub.3
 ##STR71##
  ##STR72##
  COCH.sub.3  83 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.2 CH.sub.2
  NHCOCH.sub.3
  ##STR73##
  COOCH.sub.2 NHCH.sub.3
  84 OCH.sub.3 CH.sub.3
 ##STR74##
  CONHC.sub.4 H.sub.9n COCH.sub.3
  85 OCH.sub.3 CH.sub.3
 ##STR75##
  CON(C.sub.2 H.sub.5).sub.2 COCH.sub.2 Cl  86 OCH.sub.3 CH.sub.3
 CO.sub.2 CH.sub.2 CH.sub.2
  Br
 ##STR76##
  CONHCH.sub.3  87 OCH.sub.3 H SO.sub.2
  CH.sub.3
 ##STR77##
  COCH.sub.3  88 OCH.sub.3 H SO.sub.2
  CH.sub.3
 ##STR78##
  CONHPh  89 NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH CH.sub.3 CO.sub.2
 C.sub.2
  H.sub.5
 ##STR79##
  CONHPh
  90 OCH.sub.3 CH.sub.3 CONH.sub.2
 ##STR80##
  CONHPh
 
    
     The invention has been described in detail with particular reference to preferred embodiment thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.