Abstract:
Polyester is dyed through thermofixation in fast shades with azo dyestuffs of the formula ##SPC1## 
     Wherein 
     R 1  is hydrogen, chlorine, bromine, lower alkyl, or lower alkoxy; 
     R 2  is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R 7  CONH-- or R 7  SO 2  NH--; 
     R 3  is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl) or ##EQU1## R 4  is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or ##EQU2## one of R 5  and R 6  is hydrogen or methyl; AND THE OTHER R 5  and R 6  is hydrogen; 
     Each R 7  is independently lower alkyl, chloro(lower alkyl) bromo(lower alkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, lower alkoxyphenyl or cyanophenyl; 
     X is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy(lower alkyl) or lower alkoxy(lower alkoxy); 
     Y is hydrogen, chlorine, or bromine; and 
     Z is methylene or carbonyl.

Description:
This is a division of application Ser. No. 241,810, filed Apr. 6, 1972, now U.S. Pat. No. 3,884,901. 
    
    
     BACKGROUND OF THE INVENTION 
     Azo dyes bearing water solubilizing groups have long been known as dyestuffs for natural polyamide fibers. Typically such azo dyes have contained at least one sulfonic acid group, although a relatively minor amount of the research in azo dyes for natural polyamide fibers has been devoted to sulfonic acid-free azo dyes which contain at least one carboxylic acid group. It is generally recognized in the art that such azo dyes are generally unsuited for the dyeing of synthetic fibers such as polyethylene terephthalate. 
     We have now discovered a novel dyeing process which makes use of the thermofixation process and a specific class of azo dyes which yields excellent dyeings on polyesters, particularly polyethylene terephthalate, with azo dyes containing a free carboxylic acid group. 
     SUMMARY OF THE INVENTION 
     In accordance with the invention there are provided polyester dyeings with compounds of the formula: ##SPC2## 
     Wherein 
     R 1  is hydrogen, chlorine, bromine, lower alkyl, or lower alkoxy; 
     R 2  is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R 7  -CONH-- or R 7  SO 2  NH--; 
     R 3  is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro (lower alkyl), bromo(lower alkyl) or ##STR1## R 4  is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or ##STR2## one of R 5  and R 6  is hydrogen or methyl; and the other R 5  and R 6  is hydrogen; 
     each R 7  is independently lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, lower alkoxyphenyl or cyanophenyl; 
     X is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy(lower alkyl) or lower alkoxy(lower alkoxy); 
     Y is hydrogen, chlorine, or bromine; and 
     Z is methylene or carbonyl. 
     DETAILED DESCRIPTION 
     As the starting material for the preparation of the azo dyestuffs(I) may be mentioned a base of the formula ##SPC3## 
     wherein X, Y and Z are as defined above. The base (II) is converted to a diazotized base of the formula ##SPC4## 
     wherein X, Y and Z are as defined above and An -  is anion. To produce the azo dyestuffs(I), the diazotized base (III) is treated with a coupler of the formula ##SPC5## 
     wherein R 1 , R 2 , R 3  and R 4  are as defined above. 
     A convenient diazotization method involves treating the base (II) in cold water containing enough hydrochloric acid to make the medium strongly acidic and adding thereto an amount of sodium nitrite at least stoichiometrically equivalent to the amount of base, the reaction mass being maintained at or near the temperature of melting ice. A surface active material with emulsifying properties may advantageously be used. The diazotized base is essentially soluble in the acid medium provided the volume is adequate. 
     Another diazotization method involves dissolving sodium nitrite in concentrated sulfuric acid, heating to a temperature of about 60°-70° C, cooling the resulting solution to 0°-10° C and adding thereto the base (II). 
     The azo dyestuffs (I) are made by the reaction of the diazotized base (III) with the coupler (IV) by adding the diazonium salt to a cold aqueous acidic solution of the coupler. A buffering agent, such as sodium acetate may be added to reduce the acidity to a pH of 5 to 7 . The mixture is allowed to react for up to several hours at room temperature and is thereafter filtered and washed acid free. The desired azo dyestuff (I) is thus obtained in the form of a wet cake. 
     It may be noted that in the particular cases where R 3  and R 4  are together desired to be hydrogen, it is often advantageous to convert the coupler (IV) to the arylaminomethanesulfonic acid salt (V) through the use of formaldehyde and sodium bisulfite in known manner. ##SPC6## 
     Coupling may then be carried out in the usual way. After formation of the monoazo body, hydrolysis of the alkylenesulfo moiety can be brought about by gentle heating in dilute aqueous alkali, forming the azo dyestuff (I) in which R 3  = R 4  = H. (The dyestuff is somewhat soluble in dilute aqueous alkali due to the carboxylic group. Neutralization of the hydrolysis medium facilitates isolation of the azo dyestuff (I) ). The method is especially useful in those cases in which R 1  is hydrogen, alkyl, chlorine or bromine, and often helpful in achieving better yields when R 1  is alkoxyl. 
     The products produced from the coupling reaction, when suitably dispersed, are excellent dyes for polyester fabrics, and are particularly suited for dyeing polyester by thermofixation methods. 
     To prepare the product for application to the polyester substrates the product must be suitably dispersed. This may be done in any of several well-known methods, milling as in a ball-mill with dispersing agents such as lignin sulfonic acid materials, for instance. The resultant aqueous dispersion can be dried, as in a spray-dryer, or preserved and used as a paste. Standardization to any desired lower strength can be done with inert colorless diluents such as inorganic salts for powders, or water for pastes. Other materials such as preservatives, foam-control agents, and wetting agents may be added as desired. 
     Dispersed pastes are made by wet milling the dye in conventional equipment in the presence of a dispersing agent, preferably sodium lignin sulfonate or sodium alkylnaphthalene sulfonate. Various other commercially available dispersing agents, such as sodium salts of carboxylated polyelectrolytes and the naphthalene sulfonates; e.g., the condensation products of sulfonated naphthalene and formaldehyde, such as sodium dinaphthylmethane disulfonate, are conveniently used. The oil disperse paste may be cut or standardized to a standard strength with water. The final color content of the finished paste averages from 10-40 percent by weight (pure color) active dye base. 
     Disperse powders are prepared by wet milling color in the presence of a dispersant, such as those mentioned hereabove, in equipment such as a ball-mill, Werner-Pfleiderer mill or attritor. The dispersed material is oven or spray dried and micropulverized if necessary to provide the dispersed powder. The color is cut or standardized to a standard strength in a blender with a diluent, such as sodium sulfate or dextrin. A wetting agent, such as sodium cetyl sulfate or an alkylphenoxy polyethanol may be added to aid in wetting out the product when it is placed in the dye bath. Disperse powders are usually cut or standardized to 25-60 percent by weight color content (pure color). 
     The dye is preferably applied to the aromatic polyester fiber by thermofixation methods, such as the &#34;Thermosol&#34; process. This process involves padding the cloth with a dilute dye dispersion, followed by drying to remove water (e.g., by preheating with infrared heat) and curing by dry heat fixation using dried hot air or heated contact rolls. Curing or fixation temperatures of 350°-430° F are used for less than 2 minutes, usually for 30 to 90 seconds. Ordinarily, if the padded fabric is entirely polyester, curing is done at 400°-430° F. If the fabric contains cotton or viscose rayon, apart from synthetic fibers, there is little danger of damaging cellulosic portions, but if wool is present, the curing temperature must be kept below 357° F and the time must be reduced to about 30 seconds. 
     For durable press finishing of mixed polyester-cotton blends, after thermofixation the residual unfixed dye is removed from the fabric by scouring and the cleaned fabric is given a durable press cure at 300°-350° F. The new dyes of the invention show an excellent diffusion rate in the polyester fibers at the dyeing temperature and a low diffusion rate at the preferred press curing temperature of 300°-350° F. 
     In order to evaluate the effectiveness of a particular dye for a given type of fiber, the dyed fiber is examined for substantivity of the color, light fastness of the color, and resistance of the color to sublimation. Specific tests for the evaluation of these important properties are described in the examples that follow. 
     The invention is further illustrated by the following examples: 
     EXAMPLE I ##SPC7## 
     
         __________________________________________________________________________A. Diazo    There is charged to a 3000 ml. beaker300.0 ml.    water60.0 g.  hydrochloric acid (32%)55.1 g.  4&#39;-chloro-3&#39;-amino-o-benzoylbenzoic acid (0.2 mole) and 5.0 g.  &#34;Tween 20&#34; (a commercially available surface active material).    The mixture is heated to 80° C, allowed to stir and cool    to    30° C and iced to 0° C. At 0-5° C there is    added to the mixture,    during a period of 15 minutes, a solution of15.0 g.  sodium nitrite dissolved in 50.0 ml.    cold water.    The diazotization mixture is stirred 2 hours at 0-5° C,    then the    excess nitrous acid is destroyed with sulfamic acid and the    diazo clarified and kept at 0-5° C.B. Coupler    A 4000 ml. beaker is charged with400.0 ml.    water at 60° C25.0 g.  N,N-dimethylaniline (0.206 mole) and30.0 g.  hydrochloric acid (32%).    The mixture is stirred to complete solution and iced to    0° C.C. Coupling    The diazo solution is added to the coupler solution at    0≅5° C.    The mixture is stirred sixteen hours, during which time the    temperature is allowed to rise to that of the room. The solids    are then isolated by filtration and the filter cake is washed    acid free and dried.    Yield: 77.0 g.; 95.5% (0.2 mole = 81.5 g.)D. Dispersion    A laboratory ball-mill is charged with60.0 g.  dry color (A, above)58.0 g.  &#34;Lignosol FTA&#34; (a commercially available ligninsulfonic acid    dispersing agent) and282.0 ml.    cold water.    The mixture is ball-milled for 12 hours. A paste of 15% color    content was obtained.    Dispersion: adequate, as shown by filter tests.E. Evaluation:    When applied to polyethylene terephthalate by the recognized    method (carrier, pressure, thermofixation) golden yellow hues    of excellent light fastness and sublimation fastness are    obtained.    The dye is especially suitable for thermofixation__________________________________________________________________________    dyeing. 
    
     EXAMPLE II ##SPC8## 
     
         __________________________________________________________________________A. Diazo    There is charged to a 3000 ml. beaker300.0 ml.    water60.0 g.  hydrochloric acid (32%)55.1 g.  4&#39;-chloro-3&#39;-amino-o-benzoic acid (0.2 mole) and 5.0 g.  &#34;Tween 20&#34;.    The mixture is heated to 80° C, allowed to stir and cool    to    30° C and iced to 0° C. At 0-5° C there is    added to the mixture,    during a period of 15 minutes, a solution of15.0 g.  sodium nitrite dissolved in50.0 ml. cold water.    The diazotization mixture is stirred 2 hours at 0-5° C,    then    the excess nitrous acid is destroyed with sulfamic acid and the    diazo clarified and kept at 0°5° C.B. Coupler    A 4000 ml. beaker is charged with200.0 g. ice,200.0 ml.    water,67.6 g.  2,2&#39;(3-acetamidophenylimino)diethanol diacetate (0.21 mole),40.0 g.  hydrochloric acid (32%) and50.0 g.  acetic acid.    The mixture is stirred to solution and iced to 0° C.C. Coupling    Coupling is carried out in the way described in Example I,    Part C.    Yield: 111.0 g. 91% (0.2 mole = 121.6 g.)D. Dispersion    A laboratory ball-mill is charged with60.0 g.  monoazo material, (part C, above)58.0 g.  &#34;Lignosol FTA&#34; and282.0 ml.    cold water.    The mixture is milled for 12 hours. A disperse paste containing    15% of dye base is obtained. The dispersion is satisfactory    as shown by filter tests.E. Evaluation:    Dyeings of clear red hues are obtained by treating polyethylene    terephthalate fabric in known manners with the dispersion from    D above. The dye dispersion is especially well suited for    thermofix dyeing. Resistance to sublimation is outstandingly    good.__________________________________________________________________________ 
    
     EXAMPLE III ##SPC9## 
     
         __________________________________________________________________________A. Diazo    There is charged to a 3000 ml. beaker350.0 ml.    water60.0 g.  hydrochloric acid (32%)54.2 g.  4&#39;-methoxy-3&#39;-amino-o-benzoylbenzoic acid (0.2 mole) and4.0 g.   &#34;Tween 20&#34;.    The mixture is heated to 70° C, allowed to stir and cool    to    30° C and iced to 0° C. At 0-5° C there is    added to the mixture,    during a period of 15 minutes, a solution of15.0 g.  sodium nitrite dissolved in50.0 ml. cold water.    The diazotization mixture is stirred 3 hours at 0- 5° C.    Then    the excess nitrous acid is destroyed with sulfamic acid and the    diazo clarified and kept at 0-5° C.B. Coupler    A 4000 ml. beaker is charged with400.0 ml.    water at 60° C25.0 g.  N,N-dimethylaniline (0.206 mole) and30.0 g.  32% hydrochloric acid.    The mixture is stirred to complete solution and iced to    0° C.__________________________________________________________________________ 
    
     C. Coupling 
     The coupling of the materials from Part A and Part B is carried out in the manner described in Example I, Part C. Yield: 71.-g. 88% (0.2 mole = 80.6 g.) 
     D. Dispersion 
     A 15% color content disperse paste is made in the manner described in Example I, Part D. 
     E. Evaluation 
     Dyeings on polyethylene terephthalate fabric produced by the disperse paste, Part D above, in established ways show clear scarlet dyeings of good properties, especially in resistance to sublimation. 
     EXAMPLE IV ##SPC10## 
     A. Diazc 
     A diazonium solution is prepared exactly in the manner of Example I, Part A. 
     B. Coupler 
     A coupler solution is prepared exactly in the way described in Example I, Part B, except that 30.6 g. N,N-diethylaniline (M.W. 149; 0.205 mole) is used instead of N,N-dimethylaniline. 
     C. Coupling 
     The diazonium salt and the coupler are combined exactly in the way described in Example I, Part C, and the product isolated and treated similarly. The dry weight of the monoazo body produced is 84.5 g, or 97% of the theoretical yield of 87.0 g. 
     D. Dispersion 
     A 15% disperse paste is prepared in the way described in Example I, Part D. 
     E. Evaluation 
     Dyeings of the disperse paste (Part D, above) on polyethylene terephthalate fabric show a clear yellowish orange hue. Properties are very like those of the product of Example I, being excellent in fastness to light and to sublimation. The dye gives excellent color yield when dyed by the thermofixation method. 
     EXAMPLES V-LVII 
     By substituting an equimolar amount of the base (II) for the 3&#39;-amino-4&#39;-chloro-o-benzoylbenzoic acid and an equimolar amount of coupler (IV) for the N,N-dimethylaniline of Example I, otherwise following the procedure of Example I, azo dyestuffs (I) which dye polyethylene terephthalate via thermofixation in the shade indicated are obtained. 
     
         __________________________________________________________________________                                                    Hue on                                                    Polyethy-                                                    lene TereEX.  X     Y  Z   R.sub.1                 R.sub.2    R.sub.3       R.sub.4   phthalate__________________________________________________________________________V    Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    OrangeVI   Cl    H  CO  H   H          C.sub.2 H.sub.5                                          CH.sub.2 CH.sub.2 CN                                                    OrangeVII  Cl    H  CH.sub.2             H   H          CH.sub.3      CH.sub.3  Reddish                                                    yellowVIII OCH.sub.3      H  CH.sub.2             H   H          CH.sub.2 CH.sub.2 CN                                          CH.sub.2 CH.sub.2 CN                                                    scarletIX   Br    H  CO  H   H          CH.sub.2 CH.sub.2 CN                                          H         orangeX    Cl    H  CO  H   NHCOCH.sub.3                            C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                    scarletXI   Cl    H  CO  CH.sub.3                 H          CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    orangeXII  H     H  CO  OCH.sub.3                 CH.sub.3   CH.sub.2 CH.sub. 2 OH                                          CH.sub.2 CH.sub.2 OH                                                    reddish                                                    orangeXIII H     H  CO  OCH.sub.3                 OCH.sub.3  CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    dull                                                    redXIV  Cl    H  CO  OC.sub.2 H.sub.5                 NHCOCH.sub.3                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        bordeauxXV   Cl    H  CO  OCH.sub.3                 NHCOCH.sub.3                            CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.                                          CH.sub.2 CH.sub.2 OCOC.sub.                                          2 H.sub.5 bordeauxXVI  Cl    H  CH.sub.2             OC.sub.2 H.sub.5                 NHCOCH.sub.3                            CH.sub.2 CH.sub.2 CN                                          C.sub.2 H.sub.5                                                    rubineXVII Cl    H  CO  OC.sub.2 H.sub.5                 NHCOCH.sub.3                            CH.sub.2 CH.sub.2 OCOCH.sub.2 Cl                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .2 Cl     bordeauxXVIIICH.sub.3      H  CO  H   H          CH.sub.3      CH.sub.3  orangeXIX  C.sub.2 H.sub.5      H  CO  H                  ##STR3##  CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        dull redXX   Cl    H  CO  OCH.sub. 3                 CH.sub.3   CH.sub.2 CH.sub.2 Br                                          CH.sub.2 CH.sub.2 CN                                                    redXXI  H     H  CO  OCH.sub.3                 OCH.sub.3  H             H         yellowish                                                    redXXII Cl    H  CO  H                  ##STR4##  CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    redXXIIICl    H  CO  OCH.sub.3                 H          H             H         yellowish                                                    orangeXXIV Cl    H  CO  H   Cl         C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                    orangeXXV  Cl    H  CO  OCH.sub.3                 NHSO.sub.2 CH.sub.3                             ##STR5##     CH.sub.2 CH.sub.2 OCOC.sub.                                          2 H.sub.5 plumXXVI Cl    H  CO  H   Br         CH.sub.3      CH.sub.3  reddish                                                    orangeXXVIIBr    H  CO  OC.sub.2 H.sub.5                 OC.sub.2 H.sub.5                            CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    bluish                                                    redXXVIIICl    H  CO  H                  ##STR6##                             ##STR7##     CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        redXXIX H     H  CO  H   H          CH.sub.2 CH.sub.2 CN.sub.2 CH.sub.3                                          CH.sub.2 CH.sub.2 CN                                                    reddish                                                    yellowXXX  Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OCH.sub.3                                          CH.sub.2 CH.sub.2 OCH.sub.3                                          .         orangeXXXI Cl    H  CO  H   H          CH.sub.2 CH.sub.2 Cl                                          CH.sub.2 CH.sub.2 CN                                                    orangeXXXIICl    H  CO  H                  ##STR8##  CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 COCH.sub.                                          3         redXXXIIICl    H  CO  H   H          CH.sub.3 CH.sub.2 OCOC.sub.3 H.sub.7                                          CH.sub.3  orangeXXXIVCl    H  CO  H   H          CH.sub.2 CH.sub.2 OCOCH.sub.2 CN                                          C.sub.2 H.sub.5                                                    orangeXXXV Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OCOCH.sub.2 Br                                          CH.sub.2 CH.sub.3                                                    orangeXXXVIH     Cl CO  H   CH.sub.3   CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 CN                                                    yellowish                                                    scarletXXXVIICl    Cl CO  H   H          CH.sub.3      CH.sub.3  orangeXXXVIIIOCH.sub.3      H  CO  Br  H          CH.sub.2 CH.sub.2 CN                                          H         reddish                                                    scarletXXXIXH     Br CH.sub.2             OCH.sub.3                  ##STR9##  CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        dull violetXL   CH.sub.3      H  CO  OCH.sub.3                  ##STR10## CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        dull violetXLI  H     Br CO  H   H          C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                    orangeXLII OCH.sub.2--      H  CO  Cl  H          CH.sub.2 CH.sub.2 CN                                          CH.sub.3  scarletCH.sub.2 OHXLIIICH.sub.3      H  CO  OC.sub.2 H.sub.5                  ##STR11## CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7                                          CH.sub.2 CH.sub.2 OCOC.sub.                                          3 H.sub.7 bordeauxXLIV H     H  CH.sub.2             OC.sub.2 H.sub.5                 NHCOCH.sub.2 CN                             ##STR12##    CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        bordeauxXLV  OCH.sub.2 CH.sub.2--      H  CH.sub.2             OCH.sub.3                 OCH.sub.3  CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    plumOCH.sub.3XLVI H     H  CO  H   NHCOCH.sub.2 Cl                            CH.sub.2 CH.sub.2 OH                                          CH.sub.2 CH.sub.2 OH                                                    redXLVII(CH.sub.3).sub.2 CH      H  CO  H   H                             ##STR13##    CH.sub.3  orangeXLVIIIOCH.sub.3      Br CH.sub.2             H   NHCOCH.sub.2 Br                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        bluish                                                    redXLIX OCH.sub.3      H  CO  CH.sub.3                 H          CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        redL    OCH.sub.3      H  CO  H                  ##STR14## CH.sub.2 CH.sub.2 OCOCH.sub.3                                          CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        bluish redLI   Cl    H  CO  OCH.sub.3                  ##STR15##                             ##STR16##    CH.sub.2 CH.sub.2 OCOCH.sub                                          .3        bordeauxLII  Cl    H  CO  OCH.sub.3                 CH.sub.3                             ##STR17##    C.sub.2 H.sub.5                                                    redLIII Cl    H  CO  H   H          C.sub.2 H.sub.5                                           ##STR18##                                                    orangeLIV  Cl    H  CO  H   H          CH.sub.3                                           ##STR19##                                                    orangeLV   Cl    H  CO  H   H          C.sub.2 H.sub.5                                           ##STR20##                                                    orangeLVI  H     H  CO  H   CH.sub.3   C.sub.4 H.sub.9                                           ##STR21##                                                    scarletLVII Cl    H  CO  H   H          CH.sub.2 CH.sub.2 CN                                           ##STR22##                                                    orange__________________________________________________________________________