COLORED UNSATURATED POLYESTER MATERIAL CONTAINING COPOLYMERIZED METHINE DYES, AND PRODUCTS THEREFROM

Abstract: Colored unsaturated polyesters having copolymerized therein certain methine dyes which condense during polymerization into the polyester chain. The dye moieties are thermally stable at the polymer processing temperatures and are colorfast and nonextractable from the polymer, which makes these colored unsaturated polyesters particularly suitable for crosslinking in the molding of bathroom fixtures (sinks, showers, tubs), boats, certain automotive applications, and the like. The addition of dyes to the polyester in this manner gives less chance of colorant nonuniformity as is the case where the colorant is dispersed in the blend of unsaturated polyester, crosslinking agent, catalyst, etc., prior to casting, molding, and curing operations.

Description: COLORED UNSATURATED POLYESTER MATERIAL CONTAINING COPOLYMERIZED METHINE DYES, ■ AND PRODUCTS THEREFROM 5 This invention relates to colored, unsaturated polyesters which contain certain methine dye moieties chemically linked through copolymerization into the polyester backbone whereby the dye moieties become essentially nonextractable from the polyester. These 10 colored polyesters are thus highly suitable for incorporation into curable polyester materials used in the production of bathroom fixtures (sinks, showers, tubs), boats, automotive parts, and the like wherein resistance to dye extractability is of great 15 consequence. The addition of the methine dye monomers during the polyester preparation also gives greater colorant uniformity than possible, for example, where such colorants are simply blended with the polyester material prior to casting or molding thereof. 20 It is known, of course, that some methine dyes may be used to color polyester fibers using conventional dyeing procedures. It is also known that certain dyes can be melt blended (not copolymerized) with preformed polyesters or dispersed with reactive 25 solvent (curing monomer) into unsaturated polyester material prior to molding and curing, to produce colored product. In other limited cases, certain dyes such as selected anthraquinones are reactable into the polyester chain by copolymerization. 30 Advantages of the present methine moieties over others which might be copolymerized into the polyester include (1) greater thermal stability, for example, than azo dyes which generally are not stable to polymer preparation temperatures, ( 2 ) methine dyes can 35 ' be selected or tailored to absorb light at the proper wavelengths to protect particular contents of a package, (3) certain anthraquinone dyes, for example, which absorb light below 420 nm are generally not stable to UV, (4) the present methine dyes have high extinction coefficients, i.e., less dye is needed to 5 give equivalent color, and (5) generally speaking, methine dyes are much less costly than anthraquinone dyes. In accordance with the present invention, the methine moieties have at least one methine unit defined 10 herein as "the group / C=C conjoined with a conjugated aromatic system." This unit imparts to the moiety and to the polymer the property of ultraviolet or visible light absorption generally within the range of aoout 320 nm to about 650 nm. The moieties preferably have 15 molecular weights of from about 2UU to about 6UU although lower and higher molecular weights are also operable. The moieties are derived from reactants (monomers) having one or more groups which condense during esterification or polycondensation to enter the 20. moiety into the polymer chain. These groups include hydroxyl, carboxyl, carboxylic ester, acid halide, amino and the like. As aforesaid, these methine moieties are thermally stable at polymer processing conditions, for example, including polycondensation 25 temperatures of up to about 3UU°C. Of course, where only one condensable group is present, the methine monomer would act as a chain terminator in known manner. These moieties are useful in total concentrations ranging from about l.U to about 5,UUU, 30 preferably 2.U to about 1,50U parts by weight of moiety per million parts by weight of final polymer (ppm) . The present invention is defined in its broad embodiment as unsaturated polyester material having 35 • copolymerized therein a total of from l.U to aoout 5,U00 ppm, of at least one methine moiety having one BAD ORIGINAL or more methine units, said moiety absorbing in the range of from about 32U nm to about 65U nm, and being nonextractable from said polyester material and stable under the processing conditions therefor. The extractabilities of the present methine moieties can be determined as follows: Extraction Procedure All extractions are done in glass containers with distilled solvents ( water, heptane, etc.) under the time and temperature conditions described below. The sample form is U.5 inch x 2.5 inch molded segments of about lϋ to 2U ml thickness, the thickness, however, not being critical. All samples are washed with cold solvent to remove surface contaminants and are then 2 contacted with 2 ml. of solvent/inch of surface area. After the specified period of ageing in the " solvent, the solvent is transferred to glaas flasks, concentrated, spiked and analyzed. Solvent blanks (controls) are run under the same conditions without polymer. Extraction Conditions 1. water. The samples are added to the solvent at room temperature and heated at 25U°F. (15 psi) for two hours. For half the samples, the solvent is transferred to glass flasks, concentrated, and analyzed; the remaining samples are placed in a 1 U° . oven for 30 days and the solvent then transferred to glass flasks, concentrated, and analyzed. 2. 50% Ethanol/Water (v/v). The samples are added to solvent at room temperature, placed in an oven at 12ϋ° ., concentrated, and analyzed after 24 hours and 30 days. 3. Heptane. The samples are added to solvent at 15U°F. and heated at 150°^. for 2 hours. art of the samples are transferred to glass flasks, concentrated, and analyzed. The remainder of the samples are placed in a 120°F. oven for 30 days and the solvent then transferred to glass flasks, concentrated, and analyzed. Analysis Instrument - Hewlett-Packard 845UA spectrophotometer Cell Path Length - 1 cm Scanning Range - 4UU nm to 650 nm Calibration for Red Methine dye in Anisole - 52U nm absorbance maximum Calibration for Red Methine dye in DMF - 53U nm absorbance maximum The Hewlett-Packard 845UA spectrophotometer is equipped with microprocessor and programming capability with RAM memory and floppy disk storage. The instrument is calibrated at 1UUU ppb, 15UU ppb, and 20UU ppb dye .in anisole and 97U ppb, 146U ppb, and 1940 ppb in the DMF. The calibration data are stored on a floppy disk for recall when needed. The extractability of the present methine moieties from the present cured polyester material is essentially nonexistent. Useful methine reactants or monomers for tne present invention have the general formulas: Table 13 ) (shown in Table 2) (Shown in Table 12) wherein A is selected from the following radicals designated by their exemplary table numbers: ( wherein: R and R 1 are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, and arylthio; n is ϋ, 1, 2; R, and R., are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two of alkyl, -OH, alkoxy, halogen, or hydroxy substituted alkyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, carboxy, cyano, or alkoxycarbonyl; straight or branched lower alkenyl; straight or branched alkyl of 1-8 carbons and sucli alkyl substituted with the following: hydroxy; halogen; cyano; succinimido; hydroxysuccinimido; acyloxysuccinimido; glutarimido; phenylcarbamoyloxy; phthalimido; 4-carboxyphthalimido; phthalimidino; 2-pyrrolidono; cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl; alkylsulfa.αoyl; vinylsulfonyl; acrylamido; sulfamyl; benzoylsulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycaruonyloxy; alkenylcarbonylamino; groups of the formula wherein Y is -NH-, -ά-alkyl, -0-, -s-, or -CH 0-; -S-R^ SO..CH CH SR, .; wherein R, . is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl; pyridyl; pyrimidinyl; benzoxazolyl; benzimidazolyl; benzothiazolyl; radicals of the formulae -OXR 16 ; -NHXR lg ; -X-R-g; -CONR-^R, 5 ; and -SO^N ,5 5; wherein R,_ is selected from H, aryl, alkyl, and alkyl substituted with halogen, -UH, phenoxy, aryl, -CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; X is -C -, -Cuυ-, or -SO.,-; R, g is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy; and when X is -CO-, R, g also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, aryla ino, aryl, or furyl; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbalkoxy, or halogen; R. and can be a single combined group such as pentamethylene, tetramethylene, ethylene- oxyethylene, ethylene sulfonylethylene, or et y ene-N-et y ene which, with the nitrogen to which it is attached, forms a ring; R-,-, is alkyl, aryl, or cycloalkyl; R 3 is alkylene, arylene, aralkylene, alkyleneoxy, or alkyleneoxyalkylene; Z is a direct single bond, OCO, 0, S, SO, R o 2 =, -oc-alkylene-co-, -OC-arylene-Cυ-, -s-s-, -OCNH-alkylene-NH O, -O NH-arylene-NHCυ-, -υCυ-, arylene, or alkylene; R. - , R Z.X. , and R 0_ are each selected from hydrogen and alkyl; R ? is carboxy, carbalkoxy, or (R) ; R i(J is hydrogen, alkyl, and aryl; R 0 o and R u y are selected from hydrogen and substituted or unsubstituted alkyl, aryl, or cycloalkyl; R,, and R 12 are hydrogen, alkyl, hydroxyl, or acyloxy; R,, is hydrogen, hydroxyl, hydroxyalkoxy, alkoxy, aryloxy, carboxy, carbalkoxy, aralkyloxy, or acylamido; B represents the atoms necessary to complete a five or six membered ring and is selected from P and u are selected from cyano, carbalkoxy, carbaryloxy, carbaralkyloxy, carbamyl, carboxy, N-alkylcarbamyl, N-alkyl-N-arylcarbainyl, N,N-dialkyl- carbamyl, N-arylcarbamyl, N-cyclohexylcarbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, l,3,4-thiadiazol-2-yl, l,3,4-oxadiazol-2-yl, 0 alkyl, SO aryl, and acyl, or and Q may be combined as wherein R1, -/. is defined above and Ri,o_ is CN, CuυH, C0 2 alkyl, carbamyl, or N-alkylcarbamyl; wherein at least one of A, P, and <_> for each dye molecule must be or bear a condensable group selected from carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl) 2 carbamyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy; and wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted where appropriate with hydroxyl, acyloxy, alkyl, cyano, alkoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl. Also in the above definitions, at least one of A, P, and Q for each dye molecule must be or bear a group capable of reacting under polymerization conditions, to incorporate the methine dye into the polymer, including the following: carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-alkylcarbamyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy, wherein the alkyl and/or aryl groups may contain common substituents such as hydroxyl, cyano, acyloxy, carbalkoxy, phenyl, and halogen which do not interfere with the condensation reaction. In all of the above definitions the alkyl or alkylene moieties or portions of the various groups contain from 1-8 carbons, straight or branched chain. - 1U - The unsaturated polyesters useful in this invention include the esterification and polycondensation products of one or more unsaturated dicarboxylic acids or their anhydrides and one or more dihydric or polyhydric alcohols. As the acid component, the α,β-ethylenically unsaturated polycarboxylic acids include those having 2-12 carbon atoms, e.g., maleic, fumaric, substituted fumaric, citraconic, mesaconic, tetraconic, glutaconic, uconic, and the like, as well as mixtures thereof. Honourable polycarboxylic acids, i.e., those which do not contain reactive α,B-ethylenic unsaturation, may also be used if employed in combination with one or more of the aforementioned α / ϋ-ethylenically unsaturated polycarboxylic acids. Where such noncurable polycarboxylic acids are employed, the amount .thereof should not constitute more than -about 80% of the total equivalents of carboxyl groups in the esterification mixture. Preferably, such noncurable polycarboxylic acids will be employed in amounts varying between about 35% and 75% of the above indicated equivalence basis. Among the noncurable polycarboxylic acids that may be used are oxalic, malonic, succinic, glutaric, sebacic, adipic, phthalic, isophthalic, terephthalic, substituted phthalic, such as tetrachlorophthalic, suberic, azelaic, tricarballylic, citric, tartaric, cyclopropanedicarboxylic, cyclohexanedicarboxylic, and the like, as well as mixtures thereof. As the alcohol component, the saturated aliphatic polyhydric alcohols include those preferably containing only two hydroxyl groups. Among such diols are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, butanediol-1,2, butanediol-1,3, butanediol-1,4, pentanediol-1,2, pentanediol-1,4, ρentanediol-1,5, hexanediol-1,6, neopentyl glycol, 2,2,4-trimethyl-l,3-pentanediol and the like, as well as mixtures thereof. However, saturated aliphatic polyhydric alcohols containing more than two hydroxyl groups may also be employed and include glycerol, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, and the like, as well as mixtures thereof. It is usually desirable that such polyols be employed in minor proportions relative to the diol or diols. The components may be reacted in the manner customarily used in preparing ethylenically unsaturated polyester resins, i.e., at elevated temperatures and atmospheric pressure, although pressures slightly above or below atmospheric may be employed if desired. The reaction temperature is not critical but preferably is just below the boiling point of the most volatile component of the reaction mixture which is generally the alcohol component. However, temperatures in excess of the boiling point of the most volatile constituent may be employed it " the reaction vessel has been equipped with a steam-heated reflux condenser which permits water of esterification to escape from the reaction vessel while condensing volatilized reaction components and returning them to the reaction system. In preparing the curable compositions, the unsaturated polyesters are blended with a reactive curing agent, operably in a weight ratio of agent/polyester of 1U/9U to 9U/1U, but preferably from 30/6U to 70/4U. These agents contain one or more CH 2 =C< groups and desirably have boiling points at atmospheric pressure of 6U°C or greater. Such agents include styrene, side-chain substituted styrenes such as the α-methyl styrene, α-ethyl styrene, and the like, ring substituted styrenes, such as alkyl styrenes, e.g., ortho-meta and para-alkyl styrenes, including o-methyl styrene, p-ethyl styrene, meta-propyl styrene, 2,4-diιnethyl styrene, 2,5-diethyl styrene, and the like, halostyrenes, e.g., o-bromostyrene,- p-chlorostyrene, 2,4-dichlorostyrene, and the like. Also included are alkyl esters of acrylic and methacrylic acid, e.g., methyl, ethyl, or butyl acrylate, methyl methacrylate, and the like. Also useful are vinyl acetate, vinyl butyrate, vinyl laurate, acrylonitrile, methacrylonitrile, vinyl chloride, acrylamide, methacrylamide and their derivatives, allyl compounds such as diallyl phthalate, al-lyl acetate, allyl methacrylate, diallyl carbonate, allyl lactate, allyl α-hydroxyisobutyrate, allyl trichlorosilane, allyl acrylate, diallyl malonate, diallyl oxalate, diallyl gluconate, diallyl methyl gluconate, diallyl adipate, diallyl sebacate, diallyl tartronate, diallyl tartrate, diallyl mesaconate, diallyl citraconate, the diallyl ester of muconic acid, diallyl itaconate, diallyl chlorophthalate, diallyl dichlorosilane, the diallyl ester of endomethylenetetrahydrophthalic anhydride, triallyl tricarballylate, triallyltrimesate, triallyl aconitate, triallyl cyanurate, triallyl citrate, triallyl phosphate, trimethallyl phosphate, tetraallyl silane, tetraallyl silicate,- hexallyldisiloxane, and the like. These curing agents may be used singly or in combination with one another. In order to facilitate the curing, it is preferred that a polymerization catalyst be incorporated in the blend at the time of its ' curing. The type and amounts of these catalytic materials are well known in the art, and any material which normally induces polymerization of polyester resinous compositions can be utilized. The optimum reaction conditions are modified to some extent by the choice of the particular catalyst used in the process. A very active catalyst should be used in lower concentrations, and preferably at lower temperatures, than a less reactive material. he preferred catalysts comprise a wide variety of organic superoxides, i.e., organic peroxides ("acidic peroxides") and hydroperoxides ("alcoholic peroxides"). Mixtures of peroxides and hydroperoxides, including commercially available mixtures such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like, are especially effective as catalysts. Among the useful organic peroxide catalysts are acetyl peroxide, benzoyl peroxide, substituted benzoyl peroxides, halogenated benzoyl peroxides such as p-bromobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide, benzoyl acetyl peroxide, phthalyl peroxide, succinyl peroxide, fatty oil acid peroxides, such as coconut oil peroxide, lauryl peroxide, stearyl peroxide, oleyl peroxide, anisoyl peroxide, toluyl peroxide, and the like. Organic peracids, such as peracetic acid and perbenzoic acid, may also be employed. The useful organic hydroperoxide catalysts include tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, 1-hydroxycyclohexyl hydroperoxide, the terpene oxides, such as ascaridole, 1-ρ-methane hydroperoxide, and the like. Various other types of polymerization catalyst may also be employed, for example, compounds such as aluminum chloride, stannic chloride, boron trifluoride, or the azo-type catalysts such as α,α'-azobisisobutyronitrile. Since the unsaturated polyester may contain a high degree of polymerizable or reactive unsaturation, it is often desirable to blend a polymerization inhibitor therewith to retard internal polymerization of the polyester during any storage period encountered prior to curing. Once the curable composition is contacted with a sufficient amount of a polymerization catalyst, however, the effect of the inhibitor will be overcome. Among the useful inhibitors are phenol, the monoalkyl phenols, such as ortho-, -meta-, and para-cresol as well as mixtures of such isomers, polyalkyl phenols having a plurality of the same or different substituents, e.g., ethyl, propyl, butyl, and higher alkyl radicals attached to their nuclei, catechol, tertiary butyl catechol, hydroquinone, tertiary butyl hydroquinone, resorcinol, eugenol, guaiacol, pyrogallol, benzaldehyde, tannic acid, ascorbic acid, isoascorbic acid, phenylene diamine, sym-di-b-naphthyl-p-phenylene diamine, aniline, and the like. The amount of polymerization inhibitor employed depends on the nature of the unsaturated polyester as well as tiie period of storage stability required. Generally, from about U.UU1% to U.3% by weight, based on the total weight of the curable polyester blend will be sufficient. Inhibitors of this type may be added during preparation of the unsaturated polyester or optionally added later to the curable blend. In addition, other known additives may be employed such as promoters used in conjunction with the catalyst, mold lubricants, fillers and reinforcing materials, other colorants, flow promoters, ultraviolet absorbing agents, and the ' like. The conditions necessary for curing the above ' blends do not depart from the practice ordinarily observed in curing these types of compositions in general. They may=be cured in contact with air or in enclosed molds at temperatures ranging from about 1U°C BAD ORIGINALI to about 16U°C, or even higher as long as they are kept below the point at which the particular curable blend employed begins to decompose. Where it is convenient, it is especially desirable to cure the catalyzed blends by heating to between 9U°C and about 15U°C for a period of about 3 to yu minutes. In general, the methine reactants (monomers) are prepared, for example, by reacting the hydrogenated parent of an aromatic moiety A above, which is electron rich, with a Vilsmeier complex to produce an aldehyde [Bull, societe Chim. de France, No. 1U:1898-99 (October 1962); Angewandte Chemie 72., No. 22, 836-845, November 21, 196U]. For reasons of cost and convenience, phosphorus oxychloride ( ϋCl 3 ) and N,N-dimethylfor amide (DMF) are the preferred reagents. Thus, aromatic amines such as anilines, m-toluidines, 2,5-dimethylanilines, 2,5-dimethoxy- anilines, or the like are converted in high yields into the corresponding aldehydes via the Vilsmeier reaction, which aldehydes are subsequently reacted with an active methylene compound of the formula -Cri 2 -Q in the presence of a base, such as piperidine to produce the methine monomers, as shown in the following reaction sequence Tetrahydroquinolines, benzomorpholines, indoles, thiazoles, and Fischer's base also undergo the Vilsmeier reaction to produce aldehydes, preparation of the methine monomers and intermediate aldehydes via the above route is disclosed in considerable detail in many patents including: U.S. 2,649,471; U.S. 2,850,52U; U.S. 3,247,211; U.S. 3,26U,737 U.S. 3,3 ' 26,96U; U.S. 3,349,uy8; U.S. 3,386,491, U.S. 3,390,168; U.S. 3,453,270; U.S. 3,453,280 U.S. 3,468,619; U.S. 3,504,U1U; U.S. 3,555,U1 U.S. 3,597,434; U.S. 3,652,636; U.S. 3,661,899 U.S. 3,728,374; U.S. 3,787,476; U.S. 3,8_.9,41U U.S. 3,829,461; U.S. 3,846,069; U.S. 3,869,49b U.S. 3,869.498; U.S. 3,879,434; U.S. 3,92U,719; and U.S. 4,U77,962. It is also known that it is not necessary to isolate the intermediate aldehyde before preparing the methine monomers as the Vilsmeier reaction mixture can be reacted directly to produce the desired product (U.S. atents 3,917,604 and 4,088,673). All of these patent teachings are incorporated herein by reference. Since the Vilsmeier complexes also convert hydroxyl groups to halogen, other methods must be employed to prepare methine monomers bearing hydroxyl groups. For example, the monomers can be prepared according to the scheme (HϋC 2 H 4 ) 2 -. ).-CH= -. S 3H comprising reacting N,N-di-b-hydroxyethylaniline with formaldehyde and m-nitrobenzenesulfonic acid in the presence of concentrated HC1 and iron filings to produce the intermediate 4'-(di-b-hydroxyethyl- amino)-benzalaniline-m-sulfonic acid, which can be reacted with active methylenes to produce the monomers (U.S. ' 2,583,551) . Another method for producing methine monomers containing dicyanovinyl groups is described in U.S. 4,UU6,178 wherein aromatic amines are reacted with l-halogeno-2,2-dic.yanoethylene to produce corresponding methine compounds as follows: Intermediate aldehyde compounds containing groups such as acyloxy or alkoxycarbonyl can be hydrolyzed to prepare methine monomers containing hydroxyl or carboxy groups, respectively, which are capable of being reacted into the condensation polymer. The following examples will illustrate the common reaction of an aromatic aldehyde with an active methylene to produce a typical methine monomer. Example 1 4-(N,N-Dimethylamino)cinnamaldehyde (1.75 g, 0.01 ), metiiyl cyanoacetate (U.99 g, U.U1 m) , methanol (20 mL), and piperidine (3 drops) are mixed and heated together at reflux for 3U minutes. After being allowed to cool, the reaction mixture is filtered. The orange dye (2.5 g) is washed with methanol and air-dried and has the following structure. ϊhis yellow dye absorbs light at λ maχ 464 nm with a molar extinction coefficient of 38,0UU. EXAMPLE 2 Ethyl 2-cyano-3-(4-hydroxyphenyl)ρroρenoate shown below is prepared by the reaction of 4-hydroxybenzaldehyde with ethyl cyanoacetate in the presence of a base catalyst in toluene. This pale yellow dye absorbs UV light at λ τ i π nu,x v 350 nm with a molar extinction coefficient of 27,000. EXAMPLE 3 Ethyl [ [4-(dimethylamino)ρhenyl]methylene]- propenedioate shown below is prepared by the reaction of 4-(dimethylamino)benzaldehyde with diethyl malonate in the presence of a base catalyst in toluene. This pale yellow dye absorbs UV light at \ ^ „ 373 nm with a molar extinction coefficient of 33,U0U. The following tables further exemplify the useful methine reactants. TABLE 1 Example No. (R)n Ri 2 P t Q 4 H CH 2 CH 2 0H CH 2 CH 2 OH CN, CN 5 H . CH 2 CH 2 OH CH 2 CH 2 OH CN, S0 2 CH 3 6 3-CH 3 CH 2 CH 2 OH CH 2 CH 2 OH CN, CONHC 6 H 5 7 3-CH 3 CH 2 CH 2 OH CH 2 CH 2 OH CN, S0 2 CH 3 LO 8 H CH 2 CH 2 OH CH 2 CH 2 0H CN, cυc 6 H 5 I 9 H CH 2 CH 2 OH CH 2 CH 2 OH CN, 1 11 1 10 3-CH3 CH 2 CH(OH)CH 3 C 2 H 5 CN, C0 2 CH 3 11 2,5-di-OCH 3 CH 2 CH(OH)CH 2 OH C 2 H 5 CN, C0NH 2 12 2-OCH 3 , 5-CH 3 C 2 H 5 C 2 H 5 CN ' , CO 2 C 2 H 5 13 2-OCH 3 , 5-C1 C 2 H 5 C 2 H 5 CN, C0 2 C 6 H5 14 2-SCH 3 C 2 H 5 C 2 H 5 CN, C0 2 C 6 Hi 1 15 2-OC 6 H 5 C 2 H 5 C 2 H. CN, CONHC 2 H_,OH 0 16 H C 2 H„0CCH 3 C 2 H 5 CN, CO2CH3 17 H C 2 H-,OCCH 3 C2H..OCCH3 CN, CN 18 3-CH 3 C 2 H_,0CCH 3 C 2 H OCCH 3 CN, C0 2 CH 3 19 3-CH 3 2 , H π . O ' C .CCH- C2H1.OCCH3 CO2C2H5, CO2C2H5 20 H 2" H...0C CH 2 H"u >♦OC CH; __ r_.i> " CN C 6 H 5 21 H C.li.c C. >HH....OOCC<CH3 -oc-ό—-c- • 22 H C 2 H_,OCCH 3 C 2 H 5 _ 0 g- - r > c ' Hs O 1 0 C0 2 CH 3 , C 6 H 5 23 H CH 3 CH 3 -OC-C ' C^ 24 H C 6 H 5 CH 2 CH 2 OCCH 3 CN, C0 2 CH 3 25 3-CH 3 C 6 H 5 CH 2 CH2OΪCH3 CN, COOH 26 3-0C 2 H,,0CCH : • p-CHaCeH,, CH 2 CH 2 OCCH 3 CN, C0 2 CH 2 CH 2 CH 2 CH 3 27 3-CHs m-ClC 6 Hι. CH 2 CH2OH CN, C0 2 CH 3 28 H CH 2 C 6 H 5 CH 2 C 6 H 5 CN, C0 2 CH 3 29 3-CHs CH2C6H5 CH2- \ _ / •-C02CH3 CN, CN 30 3-CH 3 CH 2 - » .^ ^>.--CC00 22 CCHH 33 CCHH 22 -- »» ^( / — C0 2 CH 3 CN, COC(CH 3 ) 3 31 3-CH 3 CH 2 -»^ ^.--QC.\l CCHH 22 CCHH 22 0OCC(CH3 CN, C0 2 CH 3 • = • 32 3-CH3 CH 2 --^ ^.-0CH 3 CH2CH2OCC6H5 CN, C0 2 CH 2 CH 2 0CH 3 33 3-CH 3 CH 2 CH 2 OCC 6 H 5 C 2 H 5 CN, C0 2 CH 3 34 3-CH3 CH 2 CH 2 OCNHC 6 H 5 C 2 H 5 CN, C0 2 CH 3 35 H CeHs CeHs CN, CO2CH3 36 3-CHs CH 2 CH 2 CN C 2 H 5 CN, CO2CH3 NJ \ . 37 H CH 2 CH 2 C0 2 CH 3 CH 2 CH 2 C0 2 CH 3 Λ 1 ! 38 H CH 2 CH 2 C0 2 H CH 2 CH 2 C0 2 H CN, CN 39 H CH 2 CH 2 C 6 H 5 CH 2 CH 2 OH CN, 40 H CH 2 CH 2 C1 CH 2 CH 2 CN CN, C0 2 CH 3 41 H CH 2 -« /«-C00H CH 2 - « ^ /— C00H CN, CN • __ • • _= • 43 H -CH 2 CH 2 S0 2 CH 2 CH 2 - CN, C0 2 CH 3 , 44 H -CH 2 CH 2 N(S0 2 CH 3 )CH 2 CH 2 - CN, C0 2 CH 3 45 3-CH 3 -CH 2 CH 2 -OCH 2 CH 2 - CN, C0 2 CH 3 46 H -CH 2 CH 2 CH CH 2 CH2 _ CN, C0 2 CH 3 47 3-CH 3 C 2,H" s CN, C0 2 CH 3 48 3-CH 3 C 2 H 5 -CH 2 CH 2 N, A M 1 CN, Cϋ 2 CH 3 COOH 49 3-CH 3 C 2 H 5 -CH 2 CH 2 (C 6 H 5 ) 0 2 CH 3 CN, C0 2 CH 3 K3 50 3-CH 3 C 2 H 5 -CH 2 CH 2 OC 6 H 5 CN, C0 2 CH 3 C COO--ςCHH 2 ; 51 3-CH3 C 2 H 5 CH 2 C H 2 N I CN, C0 2 CH 3 CO-CH; 52 H CH 2 CH 2 OC 2 H s CH 2 CH 2 OC 2 Hs CN, C0 2 CH 3 53 3-CHs CH 2 CH 3 CH 2 CH 2 OCH 2 CH 2 OC 2 H5 CN, C0 2 CH 3 54 3-CH3 CH 2 CH 3 55 3-CH 3 CH 2 CH 3 56 3-CH 3 CH; CH 2 CH 57" 3-CH 3 CH 2 C 6 H 5 CN, C0 2 CH 3 58 H CH 2 C 6 Hj i C 2 H S CN, C0 2 CH 3 59 3-CH3 C 2 H 5 CH 2 CH 2 CH 2 SO 2 CH 3 CN, C0 2 CH 3 60 3-CH 3 C 2 H 5 CH 2 CH 2 O OC 2 H 3 CN, CO 2 CH3 61 3-CH 3 -CH 2 CH=CH 2 -CH 2 CH=CH 2 CN, CO2CH3 62 3-CH3 -C2H5 ■ CH 2 CH 63 3-CHs -C 2 H 5 -CH 2 CH CN, C0 2 CH(CH 3 )z 64 3-CH 3 -C2H5 65 3-CH3 -C 2 H S 66 3-CH 3 -C 2 H 5 -CH CH S0 2 CH—CH 2 C0 2 CH 3 , CN 67 3-CH 3 -C 2 H 5 -CH2CH2 O2CH2CH2SC6H5 C0 2 CH 3 , CN 68 3-CH 3 // ' -C 2 H 5 ■ CH 2 CH 2 S- » ζ /*"" C1 C0 2 CH 3 , CN 69 3-CH3 -C 2 H 5 — CH 2 CH 2 SC _, H 9 n C0 2 CH 3 , CN 70 3-CH3 -C 2 H 5 • CH 2 CH 2 N(C 2 H.,CN)S0 2 CH 3 C0 2 CH 3 , CN 71 3-CH3 -C 2 H 5 -CH 2 CH2CONH2 C0 2 CH 3 , CN 72 3-CH3 -C 2 H 5 • CH 2 CH 2 CON(C 2 H 5 ) 2 C0 2 CH 3 , CN 73 3-CH 3 -C 2 H 5 -CH 2 CH(OCOCH 3 )CH 2 OCOCH 3 CN, CN 74 3-CH 3 -C 2 H 5 -CH 2 CH 2 OCC 6 H 5 CN, CN 75 3-CH3 -C 2 H 5 ■ CH 2 CH 2 jO( CCβHn CN, CN t 4_. 76 3-CHs -C 2 H 5 -CH 2 CH 2 S0 2 N(C 2 Hs ) 2 CN, CO2CH3 77 3-CH3 -C 2 H 5 -CH 2 CH 2 S0 2 N(CH 3 )C 6 H 5 CN, CO2CH3 78 3-CH3 -C 2 H 5 CN, CO2CH3 -N- 79 3-CH 3 -C 2 H 5 -CH 2 CH 2 -S -I C 2 H.,OH 80 3-CH3 ■ C 2 H 5 • CH 2 CH 2 S -_ 81 3-CH 3 -C, 2 Hπ 5 -CH 2 CH 2 S0 2 - » ^ z' -01 N C0 2 CH 3 82 3-CH 3 -C 2 H 5 —CH 2 CH 2 CN, C0 2 CH 3 83 3-CH 3 -C 2 H 5 CN, Cϋ 2 CH 3 84 3-CH 3 -C 2 H 5 -CH(CH 3 )CH 2 C0 2 CH 3 CN, C0 2 CH 3 85 3-CH3 -C 2 H 5 -CH(CH 3 )CH 2 C0 2 C 2 H 5 86 3-CH 3 -C 2 H 5 -CH 2 CH 2 0CH 2 CH 2 0H CN, -C / C-CβH; 87 3-CH 3 -C 2 H 5 -CH 2 CH 2 OCCH 2 C 6 H 5 CN, CONH-*^ S ^ 88 3-CH3 -C 2 H S -CH 2 CH 2 0CCH 2 0C 6 Hs CN, CO2CH3 89 3-CH3 -C 2 H 5 -CH 2 CH(C 6 iHI 5 )OCCH 3 C 6 H 5 , CN 90 3-CH3 -C 2 H 5 -CH 2 CH(OCOCH 3 )CH 2 C1 C0 2 CH 3 , CN 91 3-CH3 -C 2 H 5 -CH 2 CH 2 0CH 2 C1 CO2CH3 , CN 2 X o o o X o o X o =0 o X J X o I o I X o I ro CN < ι TABLE 2 Example 93 H C 2 H 5 -CH 2 CH 2 - -S0 2 - CN, C0 2 CH 3 94 3-CH 3 C 2 H 5 — CH 2 CH 2 — -S0 2 - CN, C0 2 CH 3 95 3-CH3 C 2 H 5 -CH2CH2- -0- • CN, C0 2 CH 3 1 96 3-CH 3 C 2 H 5 -CH 2 CH 2 0- -CH 2 CH 2 - CN, C0 2 CH 3 to -J 97 3-CH 3 C 2,H π 5 -CH 2 CH 2 - -080- CN, C0 2 CH 3 1 98 3-CH3 C 2 H 5 -CH2- CN, C0 2 CH 3 \ / 99 3-CH3 C 2 H 5 — CH CH 2 — -S-S- CN, C0 2 CH 3 100 3-CH3 C 2 H 5 -CH 2 CH 2 - -0CCH 2 CH 2 C0- CN, C0 2 CH 3 - 101 3-CH3 C 2 H 5 -CH 2 CH2- -θϊ(CH 2 CO- CN, C0 2 CH 3 102 3-CH 3 C 2 H 5 — CH 2 CH 2 ~ -NHC(CH 2 ) 6 CNH- CN, C0 2 CH 3 103 3-CH; C 22 Hns CH 2 CH 2 - 104 3-CH; » C 2 Hs CH 2 CH 2 - -o.-. - .-.o- CN, C0 2 CH 3 « = • 105 H C 2,"H. CH 2 CH 2 - CN, C0 2 CH 3 106 H CH 2 CH 2 CN CH 2 CH 2 — -0U0- CN, C0 2 CH 3 0 107 H CH 2 CH 2 CN CH 2 CH 2 - -OC- CN, CO2CH3 0 0 00 108 H CH 2 CH 2 CN CH 2 CH 2 - -OC(CH 2 KCO- CN, CN 1 109 H CH 2 CH 2 CN CH 2 CH 2 OCH 2 CH 2 - -o_- " >-.o- CN, CN 110 H CH 2 CH 2 CN CH 2 CH 2 ~ -o.- - .-_o- CN, SO 2 CH 3 • -= • 111 H CH 2 CH 2 CN CH2CH2- -__- - -__- CN, S0 2 C 6 Hs • = • 113 2,5-diOCH 3 C 2 H 5 —CH 2 CH 2 - 114 3-C1 C 2 2H"5 -CH 2 CH 2 - • -s- CN, C0 2 C 6 H 5 115 2-OCH 3 , 5-C1 C H 5 -CH2CH2- -OCCH 2 CH 2 CH 2 CO- CN, Cu 2 C 2 H_,CN 116 3-CH 3 C 6 6H" 5 -CH2CH2- X.CH.C. CN, C0 2 CH 3 117 3-CH3 C 6 6H"! ! -CH 2 CH(CH 3 )- -OCCH 2 CH 2 CH 2 CO- CN, C0 2 CH 3 1 118 3-CH3 CH 2 CH 2 CgH 5 -CH 2 - CN, C0 2 CH 3 \ _ / t LΩ 119 3-CH3 CH 2 CH 2 OC 2 H 5 —CH 2 CH 2 CH2— .o_-.C - 1 CN, C0 2 CH 3 120 3-CHs CH 2 CH 2 OC 6 H 5 -CH 2 CH 2 CH 2 CH 2 - \ _ / CN, CO2CH3 121 3-CHs CH 2 CH -CH2CH2- 122 3-CH3 CH2CH2CH2CH3 -CH 2 CH 2 - 123 3-CH 3 CH 2 CH 2 OH -CH 2 CH 2 - 124 3-CH 3 CH 2 CH 2 C0 2 CH 3 —CH 2 CH 2 — -so 2 - CN, CN 125 3-CH 3 CH 2 CH 2 C1 -CH 2 CH 2 - -0C(CH 2 ] ι,CO- CN, CO2CH3 126 3-CH 3 C 2 H 5 -CH 2 CH 2 - single bond -rø i Hs 127 3-CH3 C 2 H 5 -CH 2 CH 2 - -OC(CH 2 ) .CO- -1- ens 128 3-CH3 C 2 H Ϊ —CH 2 CH — -OC(CH2 UCO- Cu 2 C 2 H 5 , C0 2 C 2 H 5 129 3-CH 3 C 2 H 5 -CH 2 CH 2 - -OC(CH 2 >Jθ- C0 2 C 2 H 5 , S0 2 CH 3 130 3-CH 3 C 2 H 5 —CH 2 CH 2 _ -OC(CH 2 )H?0- CN, C 6 H 5 OX 131 3-CH 3 CH(CH 3 )CH 2 C0 2 CH 3 -CH 2 CH 2 - -0C(CH 2 ϊjo- CN, CONH 2 o 132 3-CH 3 C 2 H 5 — CH 2 CH 2 — -θH(CH 2 )Jϋ- COC 6 H 5 , COC 6 H 5 133 3-CH 3 C 2 H 5 -CH 2 CH 2 - -OC(CH 2 )Jo C0 2 C 6 H 5 , C0 2 C 6 H 5 134 3-CH 3 C 2 H 5 — CH 2 CH 2 _ -OC(CH 2 Ϊ H ?0 CN, CONHC 2 H.,OH 135 3-CH 3 C 2 H 5 -CH 2 CH2- -θϋ(CH 2 )J CN, 136 3-CH 3 C 2 Hs — CH 2 CH 2 — -OC(CH 2 )io CN, CONHCeHx 1 137 3-CH3 C2H5 — CH 2 CH 2 — -θi.(CH 2 )io CONH 2 , CONH 2 TABLE 3 Example No. ( R )n R 4 , R5 £6 ? t Q 138 H C 2 H 5 CH 3 , CH 3 CH 3 CN, CO 2 CH 3 139 H CH 2 CH 2 OH CH 3 , CH 3 CH 3 CN, SO 2 CH 3 140 H CH 2 CH 2 OH CH 3 , CH 3 CH 3 C0 2 ( H 3 , CU 2 CH 3 141 H CH 2 CH 2 OH CH 3 , CH 3 CH 3 CN, S0 2 C 6 H5 142 7-CH 3 CH 2 CH 2 OH CH 3 , CH 3 CH 3 CN, C0 2 C 2 H 5 143 7-CH3 C 2 H_,OCCH 3 CH 3 , CH 3 CH 3 - CN, CN 145 7-CH3 C 2 H_,CN CH 3 , CH 3 CH 3 CN, C0 2 CH 3 0 COOH C 6 H. 149 7- -CH 3 C 2 Hι,0H CH 3 , CH 3 CH 3 ■ oc-c •■ '-'- C- 150 7- -CH 3 - C 2 H_,OH CH 3 , CH 3 CH 3 CN, CONHC 2 Hι,OH 151 7- -CH 3 C 2 H OH CH 3 , CH 3 CH 3 COC(CH 3 )z, CN 152 H C 2 H_,OH CH 3 , CH 3 CH 3 CN, Cϋ 2 CH 3 153 H C H_,OCC 2 H 5 CH 3 , CH 3 CH; CN, C0 2 C 2 H 5 154 H C 2 H_,OCC 6 H 5 CH 3 , CH 3 CH; CN, C0NH 2 155 H C 2 H_,OCOC 2 H 5 CH 3 , CH 3 CH 3 CN, C0 2 C 6 H 5 156 H CH 2 C 6 H 5 CH 3 , CH 3 CH 3 CN, C0 2 CH 3 157 H 158 H CH 2 CeH 11 CH 3 , CH 3 CH 3 CN, C0 2 C 2 Hι,CN 159 7-CH 3 C.H 9 _ n H, CH 3 H CN, C0 2 CH 3 160 7-CH3 CH 2 CH 2 OCH 2 CH 2 OH H, CH 3 H CN, CN O 161 7-CH 3 CH2CH2OCCH3 H, CH 3 H CN, S0 2 CH 3 162 7-CH 3 CH 2 CH 2 N(C 6 H5 )S0 2 CH 3 H, CH 3 H CN, C0 2 CH 3 en en en en en en en tn X X X X X X X X X X X X X o u o O CJ O X X O o X X X X X X X X // \ // " 1 II — . • • • //\ X X X \ _ / ^ / X X o o o o 1 II 1 1 \ 1 X o X — » • • o o o n X X X X o X — * o ^ / X CO o o / CJ o o o 2 — « X • \ / 3KJ OKJ CKJ OKJ OKJ o o o X 1 o X z cn o o o o u o o o o co o o *_ ^ - ^ X X X X X X X X X X X X X X o o o o o o o o o o o o o * —* 179 7-Br CH 2 CH 2 S0 2 -»^ / —Cl CH 3 , CH 3 CH 3 C0 2 C 2 H s , C0 2 C 2 H 5 x cι 180 7-C1 CH 2 -«^ »-C00H CH 3 , CH 3 CH 3 COCeHs, SU •=• 181 7-OCH 3 CH 2 CH(0CCH 3 )CH 2 O CH3 CH 3 , CH 3 CH3 CN, CN 182 7-CH3 CH 2 CH(OH)CH OH CH 3 , H H CN, CN 183 7-CH 3 CH 2 CH(OH)CH 2 OH CH 3 , H H J-T- _! H! 184 7-CH 3 CH 2 CH=CH 2 CH 3 , H H CN, C0 2 CH 3 185 7-CH 3 186 7-CH 3 CH3, H H CN, C0 2 CH 3 TABLE 4 Example No. ( R )rN Hi ϋ4 > « 187 H C 2 H„OH H CN, CN 188 H C 2 Hi,OH H CN, S0 2 CH 3 189 H C 2 H_,OH H CN, S0 2 C 6 H 5 190 H H CN, CONHCeHs 191 H C 2 Hι,OH H CN, CONHC 2 H.,OH n 192 H CH 2 CH 2 OCCH 3 H CN, CN * 193 H CH 2 CH 2 θ cH 3 H CN, S0 2 CH 3 194 6- CHj CH 2 CH 2 OCCH 3 H CN, CO2CH3 195 6- CH 3 CH 2 CH 2 OC-C 6 H Is 3-CH 3 CN, CO2CH3 196 6- CH 3 CH 2 CH 2 OCCHj 3-CH 3 -o.-.- - ' ' Hi X o to \ l o o en — _ rt \ l X X X X X X X X X X o X f o o o •=• o o o o o o 8 1 z 1 / \ 3 fl o z o o z • • o o o o o o o-o O-O o o o o o _ ^ υ o o o υ o I 1 OKJ o=o / * _ * . ^ ^ ^ . •» o o 2 2 z z z C3-0 C-KD z 2 z z 2 z 1 1 o o o o o 1 1 o o o o X X X X X X X X X X X X X X o o o o o o o I o 1 1 o I o 1 1 o 1 o I 1 o 1 o 1 1 ro 00 ro 00 ro oo ro ro oo ro ro ro ro ro X X X X c X o X o o o o o o o X X X X 1 o o 1 o X X X I 1 o 1 o o 1 ID U3 SΩ LΩ LΩ SΩ <£> SΩ SΩ r » 03 ON o CN ro -J" in <£> t— CO σ*ι o ON ON CM o σ o o o o O o o o !-. CN CN CN CN CN CN CN CN CN CN CN ^ ^ ^ ^ ^ ^ ^ ^ ^ * . 2 2 z 3 3 z 2 z 2 z z z o o o o o o o o o o o o o X X X X X X X X „ X X X X X o o o 1 o o o O 1 o o o o 1 o ro ro ro oo ro ro ro oo ro oo ro ro ro X X X X x x x x x x x X X o o 1 o o o o o o o o o I I I I I I I I o 1 LΩ SΩ SΩ VO vO i_3 O l_D lO l_3 VD LΩ U3 CN • // • // \ \ / \ •—_• / . •=_• m \ \ X X X 2-X en o o o / / z=o 2KJ o o o 1 1 o o o ^ • * •-. %» z 2 2 z z O o O o o X X X X o o 1 o X 1 o ro OO OO ro ro X X o X J o o X 1 o X o LΩ LΩ SΩ CN CN CN CN CN TABLE 5 229 H CH 3 CH 3 CN, C0 2 CH 3 230 H CH 3 C 6 Hs CN, C0 2 CH 3 231 H H C 6 H 5 CN, C0 2 C 2 H s X so 232 H CH 2 CH 2 OCCH 3 C 6 Hs CN, S0 2 CH 3 233 H CH 2 CH 2 OCCH 3 C 6 H 5 CN, S0 2 CeH 5 234 H CH 2 CH 2 OCCH 3 C 6 Hs CN, CN 235 H CH 2 CH 2 OCCH 3 C 6 H 5 236 H C CHH 2 22 vCC- πHH 2 22 uOOCC-vCC-πHH 3 3 C -5 6 1H15 S C _..N»,, CuOiNiuHtC-b 6 uH 5 . 237 H CH 2 CH 2 OH C 6 Hs 238 H CH 2 CH 2 OH C 6 H 5 CN, CONH 2 240 H CH 2 CH 2 OH C 6 H 5 CN, C0 2 C 6 H S 241 H CH 2 CH 2 OH CeHs CN, CONH 2 242 H CH 3 CeHs - .-ϊ3_ _ϊ Hs 244 CH 3 '-Br CN, Cϋ 2 CH 3 \ o 245 H CH 3 0 2 C 2 HHOH \ •-CH3 CN, C = • 246 5-CH 3 CH 3 CH 3 CN, C0 2 CH 3 247 5-C1 CH 3 CH 3 CN, C0 2 CH 3 248 5-OCH 3 CH 3 CH 3 CN, C0 2 CH 3 249 H CH 2 C 6 H 5 C 6 Hs CN, C0 2 CH 3 250 H CH 2 - , CN \ / •-C0 2 CH 3 CeHs CN 251 CH. \ '-COOH CeHs CN, CN 252 H CH 2 CH 2 CN CβH5 CN, C0 2 CH 3 253 H CH 2 CH 2 CONH 2 CeHs CN, C0 2 CH 2 CH 2 CN 254 H CH 2 CH 2 CH 2 NHCC 6 H 5 C 6 H 5 CN, C0 2 CH 3 255 H CH 2 CH 2 CH 2 NHS0 2 C 6 H5 C 6 H S CN, C0 2 CH 3 256 H CH 2 CH 2 CH 2 N(CH 3 )S0 2 CH 3 C 6 H 5 CN, C0 2 CH 3 257 H CH 2 CH 2 CH 2 N(C 2 H ll OH)Sθ 2 CH 3 C 6 H 5 CN, C0 2 CH 3 258 H CH 3 H CN, C0 2 CH 3 260 H CH 3 H CN, COOH 261 H CH 3 C 6 H 5 CN, C0 2 CH 2 C 6 H 5 262 H CH 3 C 6 H 4 -p-COOH CN, C0 2 CH 2 C 6 Hιi 263 H _,H 9 _ n C 6 H_,-p-C0 2 CH 3 CN, C0 2 CH 3 X X X o o o o o o o o ^ * . z z 2 o o o X O O o r— oo ON SO l_5 so CN CN CN ύ 3_ «! \ / X X X X X X Z X X / o o o o o O o o o o O // \ so CO / ω /^/ j ca \ < o X EH II o X X X X X X / \ ON o o o o o o «! X X X X X X o o o o o o X X X X X X X X X X X X o o o o o o o o o o o o « Si x x x x x x x x x x X X o o o o o o o o o o o o cυ ex • r-i CN oo - tn U3 r— 00 ON o ε o r* r-~ r- P- r- r~ r~ r- r^ r~ oo O <- z CN CN CN CN CN CN CN CN CN OM CN CN X M O // ^ // ^ X \ •— _ • / \ • ~» / en o c \ \ X X X X X X o 2HE o o o o o J / / z=o z=o 3 z o o o o o 2 O 1 1 O o o o o o o O o * - %» %_. 3 z 2 2 2 2 2 z 2 2 z o o O O O o o o O o 1 1 X X X X x X X to O O O o υ O O o X X X o o o X X X rt o o o X X X X X X X X X X o o o o - o o o o o o o CN CO- -r in LΩ r- co ON O •—I CN 03 00 00 00 CO 00 00 co ON ON ON CN CN CN CN CN CN CN CN CN CN X x o o o o I I I o //\ \//\ //\ // I II I \ / • • • N / X,/ \ • X X X X X X X X en 1 o o o o o o o o / ZK o o o o o o o o o o o I CO en CO o o o o o o o o 2 2 2 2 2 z 2 2 2 2 z O o O o o o o o o o o o o I X I // \ \ \ // co i en i en \ / / / I en X X X X X X s / to to ^ / / o o O o O O O X X X X O o o o X c X X X X o υ o o o en X X X X X X X X X X X o o o o o o o o o o o o ro -* in SΩ f" » O ON o CNJ ro O ON N ON ON ON ON O 33 o σ o CN CN CN CN CN CN CN 00 OO oo ro ro 1 1 X O O X o o tn i i i - o. 3 .-{ / \ • /- • /« X Cύ X X X X X X X o -* in _3 r~ oo ON ro ro ro ro ro ro ro ro ro oo X X o o X o o o X X X X X X X o=o OKJ CKJ o o o o o o o o o o o Ή CN CO • "3 1 in 1 1 r- CO N CN CN CN CN CN CN CN ΓNI CN CN oo ro 00 ro ro oo 00 oo ro oo ^ * . ^ ^ ^ «• ^ %> * . Z 2 2 z z z Z 2 z z z 2 o O O o o o o o o o o O X o X OKJ X o o o //\ // \ X X • \ • \ X o o X i en i co o o o • / • / O O ^ / x / X X X X X X • • X o 2 o o o 1 1 o XCKJ X X CKJ 0=0 CKJ OKJ OKJ 0=0 OKJ OKJ o o o o o o o o o o o o X X -J 1 ro x o o o I //\ \ / 2 o X o OKJ o CN oo TABLE 8 Example No. ϋ7 * * 343 H CN, C0 2 CH 3 344 H C0 2 CH 2 CH 3 , C0 2 CH 2 CH 3 345 H C0 2 CH 3 , S0 2 CH 3 346 H C0 2 CH 3 , S0 2 C 6 H 5 tn 347 H CN, C0NHC 2 H.,0H 348 H CN, C0 2 CH 2 CH 2 OH 349 H CN, C0 2 CH 2 CH 2 OC 2 H 5 35U H CN, C0 2 CH 2 CH 2 C1 351 H CN, CO2CH2CH2C6H5 352 H CN, C0 2 CH 2 CH 2 OC 6 H 5 353 H CN, C0 2 CeHs 354 H CN, C0 2 C 6 Hn 355 H CN, Cϋ 2 CH 2 C 6 Hιι 356 H CN, C0 2 CH 2 C 6 H 5 357 5-CH 3 CN, C0 2 CH 2 CH(CH 3 ) 2 i t to UI U ) to o to t tJto toto to t X X z m o o o ^-» X X X X X X o o o o o o -— * * X X X X X X X o o o o o o o X X X X X X o o o o o o o o o o o o o o o o o o o o 1 o o 1 o o o o 1 o o 1 1 o o o o 1 in in in in in in in in m in in in in ro rr in Ω r- CO ON o CN oo rr in r~ r- P- r~ r- r- r- CO 00 00 X 00 CO ro ro ro ro 00 oo ro ro 00 ro oo 00 o X X 2 o O X o o o o X X o o o X X X X o o o o X o X X X o X X X X X X O X X X X o o o o o o O o o X o o o ^ o 2 o o o o o o o o o o o o o X o o o o o o o o o o o o o o o o 2 2 2 Z Z Z Z 2 Z 2 2 2 2 0 2 o o o o υ o o O O O O O O O O CN OS I o o o φ ex • SΩ r~ CO ON o CN ro rr in ø r— CO ON o ε o CO CO CO CO ON ON ON ON ON ON ON ON ON ON σ CO 2 m 00 ro ro 00 00 oo oo ro 00 00 OO 00 rr __ X X X X X X o o o o o o | l l l I I X ro ro ro oo oo oo CN ro rr m SΩ r- CO ON a CD o o o o o o X o rr r rr rr rT rr rT rr rr rr N— \ 412 3-CH 3 CH CH 2 ,θO8CcCH 3 CH 2 CH 2 ,θO8C<CH 3 CN, -C ϋ 1 ' V ^ 413 3-CH 3 CH 2 CH(0H)CH 2 0H C 2 H S CN, CN 414 3-CHs CH 2 CH(OH)CH 2 OH C 2 H 5 CN, S0 2 CH 3 415 3-CH 3 CH 2 CH(O )CCCCHH 33 ))CCHH 22 OOCCCH 3 C 2 H 5 CN, S0 2 C 6 H 5 416 3-CH 3 CH 2 CH(OH)CH 3 C 2 H 5 CN, S0 2 C 6 Hn 417 3-CHs CH 2 CH 2 OCOC 2 2H" S CH 2 CH 2 OCOC 2 2HH5 CN, CN 418 3-CH3 CH 2 CH 2 OCC 6 6H"" 5 2 πs CN, CN 419 3-CHs Cl / 420 3—CH 3 CH 2 CH OCC 2oH" 5 CH 2 CH 2 OCC 2 H 5 CN, S0 , 22 -- « /-~C<l 421 3-CH 3 CH 2 CH 2 422 3-CH 3 CH 2 CH 2 423 3-CHs CH 2 CH 2 X o o o o X o X o X o I 00 CN rr z o z 2 2 2 z z z z z z 2 2 o o o o o O o o o o o o o o « X X φ • in LΩ r- CO ON o CN ro rr m SΩ _~ oo ε o CN CN CN CN CN ro m ro ro oo ro m oo ro CO 2 ■ <r rr rr rr -r rr rr T rr rr rr rr rr rr X __ 439 H 4-OCH 2 Hι,OH CN, CN 440 H 4-OCH 2 H_,OH CN, Cϋ 2 CH 3 441 H 4-OCH 2 HH.„OθCCCCH 3 CN, Cϋ 2 CH 3 442 H 4-0--^ X» -COOH -o.-c^ Hs ϋ COOH C 6 H 5 443 H 4-OCH 2 --^ ^.-C0 2 CH 3 -OC-C— C^ tn I II ^ *_ 446 4-OCH 2 --^ X» -C0 2 CH 3 CN, S 2 - « ζ ^'-OCHs 447 4-0CH 2 - « ^ ^ — C0 2 CH 3 CN, SO2CH3 448 4-OCH 2 --^ ^--C0 2 CH 3 CN, S0 2 CeHs 449 H 4-OCH 2 - » ^ ^•-C0 2 CH 3 CN, S0 2 CH 2 CH 2 OH x O X X o o o o X X X X X X X X X X X X X X •— » o J o o o ^ o o o X o o o o J 2 2 o o o o o o o o X o o o z o o o o o o o o o o o o o o o o o o o o o o o * . %- * _ * . .. * » O 2 2 2 2 2 2 2 O 2 2 z 2 2 2 z z z o o o o o o o O o o o o o o o o o o o CN 00 rr in SΩ r- 00 ON σ --. CN oo rr in vO r- in in in in in in in m in in O SΩ vo VO vo VO O SΩ rr rr rr rr rr -r rr rr rT rr rr rr rT rr rr rr rT rr X 2 o o X X O o o o X o X o X o X X X X o X o o o o o o X X o o X X o X X X X X CO o o X o o o o o o o 2 ^ o o o o o o o o o X z o y o o o o o o o o o X o CO o o 2 2 2 2 z z z z z o o z z o o o o o o o o o o o o X X x x x x x x x x x X X o o o o o o o o o o o o o VO X X X X X X X X X X X X X o o o o o o o o o o o o o n x x x x x x x x x x X o 1 α X X X X X X X X X X o o o o o o - o o o o o X X o o .X ^ X X X X X X X X X X X X ^ o o o X X X X X X X X X / \ // \ I II ^ / N / X • OKJ X 1 X X X X X X X X o X 2 o o o o o- o o o o 2 =0 OKJ OKJ OKJ o=o OKJ OKJ 0=0 OKJ OKJ X o o o o o o o o o o o o X X X X X X X X X X X X o o o o o o o o o o o o X X X X X X X X X X X X o o o o o o o o o o o o X o o SΩ r- X CN 00 rr m vo t— X ON o r-l CN CO 00 00 CO CO CO 00 00 CO ON ON ON rT rr rr rr rT rr rr rr rr rr T rr ^ * » %» ^ ^ •- ^ » * ^ z z z z z z z z z z o o o o O " o o o o o X X X X X X X X X X o o o o o o o o o o X X X X X X X X X X X X X X X o X X X X X X X m O J o o o o o o X o o o o o o o o o o 1 1 1 1 1 1 o \ / • • • • • ■ • z y\ // \ //\ \ y\ y\ // \ X • • . . * . • • • • • • o X 1 II I II 1 11 1 II 1 II 1 II 1 II OKJ o • • • • • • • • • • • • • • o N / NX / Nx / Nx / N / NX / NX / X • • • • • • • X o 1 1 1 1 1 1 1 o X X X X X X X X X to X o o o o o o o o o o z 2 z z z z o o o o o o X X X X X X o o o o o o X X X X X X X X X X X X X X X X o o o o o o =0 0=0 OKJ o=o OKJ OKJ o o o o o o X X X X X X o o o o o o X X X X X X o o o o o o t X X X O X X X o X •_:• o o o 2 2 / \ 2 O o o • • 2 o o o o o o Nx // o o CO CO ^ ^ * » * . / *"" •» *» * . 2 2 2 2 o=o o=o z z z z O o o o 1 1 o o o o α x X X o o o o , o o X • 1 1 X • • X X X X X o //\ o y\ //^ o o o o o o ^ -* OKJ o=o OKJ OKJ OKJ OKJ X 1 II X 1 II 1 o o o o o o o o • • o • • • NX / Nx / Nx / X X X X X X X X • X • • o o o o o o o o 1 o 1 1 X X X X X X X X X X X X X X o o o o o o o o o o o o o o X X X X X X X o o 1 1 ro ro oo CO N o r-t CN O rr in o 03 ON o r-t e-L CN CN CN CN CN CN CN CN CN CN ro ro in in in in m m in m in in in m in m x o I 2 o • o // \ X X 1 II o o • • N / <>> X X • X X X X X X X X X X o o 1 o o o o o o o o o 2 O o O 2 o o o o o o o o o o o o O O CO o o o o o o o o o ^ ^ ^ * » ^ . * . •» ^ 2 2 2 2 2 2 z z z z z z z 2 O O o o o o o o o o o o rt X X o X o 1 o 1 o X o 1 I oo CN ro X X co o o X o I CN ro rr in VO r~ X ON o i-l CN ro rr in oo ro 00 oo oo oo oo oo rr rr rr rr rr rr in m in in in U0 in in in in in in in in X o X m o X X -_r <o 1 o X co o-o x X X X jj X o o o o o x 1 o X o S z o o o o o i o o o o o o o-o o o > * » o=o ^ 2 2 z z o z z o o o 1 o o X X X X X X X o o o o o o o X X X o o o X 2 2 z z o o o o O o o o o o o z z 2 2 2 2 o o o O O O X X X o o o O o 2 2 o 2 2 o o o o o X 1 X o II 1 X X o o 1 X II • o X y\ / o • • 1 II • • • //\ Nx / • X \ It 1 1 rt rt <o o 1 X rt co 1 • • z • X X X x o=o • o X X X N / y\ rt ζj o o o //\/ o o o • •— X 1 / -* • . \l // 1 1 II o-»— • X • — • X t II — • rt X • • • • \ X Nx/ Z-O /Nχ/\ Z-O O • / / • • / X o 1 ___;• •=■ CO 1 CO 1 • _=• " o=o O / \ / \ > 2 • / \ • • • • \ /\/ • • o X X NX // Nx // • • NX // X o •— • * — • . — » — ' 1 1 vo r ^ X ON σ CN o VO vo VO r~ in in in m m in in //\ . • 1 II • • N / X X • o o 1 z o z o o o o o CO en X • • • J y\ y\ y\ . . . • O 1 II 1 II 1 II o • • • ■ • • 1 Nx/ Nx / Nx/ • » • • // \ X 1 1 • • o Z z 1 II • • X — -*. -— • x / o • 1 X X •— • 1 • X o o \ y\ o-z z-x 1 X X / o 1 II • o o •__• • • y\ o o / \ Nx/ • • CKJ OKJ ■ • • 1 11 Nx // 1 • • X X o N / o o 1 X • — ' — ' TABLE 14 6 5 , Example No. <K ) n ϋl ________ 578 H C 2 H.,0H CN, CN 579 H C 2 Hι,0H CN, S0 2 CH 3 580 H C 2 H_,0H CN, S0 2 C 6 H 5 ^ 581 H C 2 Hι,0H CN, CONHCeHs to 582 H- C 2 Hι,0H CN, C0NHC 2 Hι.0H 583 H CH 2 CH 2 OCCH 3 CN, CN 584 H CH 2 CH 2 OCCH 3 CN, S0 2 CH 3 585 4,8-di-CH 3 CH 2 CH 2 OCCH 3 CN, C0 2 CH 3 586 8-CH3 CH 2 CH 2 OC-C 6 H CN, C0 2 CH 3 587 8-CH3 CH 2 CH 2 0CCH 3 -o.-.^ ClHs 588 8-CH3 CH 2 CH(OH)CH 3 -o.-K- CeHi X X X o o X o o o o o o o o X o m X o o o o ' X X o 1 1 1 >-— o o • • • Ό o o y\ // \ y\ X o X X X X X 1 • • • . o 1 o z o • 1 II 1 II 1 II OKJ • OKJ <- o o o //\ • • • • • • o //\ z o o o en N / NX / / X 1 II • • • X 1 tl X X X X X O' • • 1 1 1 o • • o o o o o NN / X Nx/ X • X X X X • X X X X X o 1 o o o o o t o o o o o X o 1 X X o 1 X X 1 -H o o X o 1 1 o X o X X •H •-. •-. 1 1 X Ό Ό X. ro r-l r-t X X o 1 1 1 X X o o X ON 1 o 1 o o -r ^ » * o 1 o 1 CN rr X X X rr 00 vo X X ON o CN ro rr in vo r~ X ON o ■—I ra ON ON ON Cf ON ON ON ON ON 3 o in in in in in in in in in in in O VO o \ •^-# // x -— » \ / X •=_» X X X X X o X X X X \ X o o o o o • — " o o o o > o o / o o o O o z o o o o o o z=o o o o o o o o o o o o o 1 • * ^ • * %» * • ** ^ ^ 2 2 z z z z z z z z z z 2 O o o o o o o o o o o o o X o tn 1 X •— • • •— • // N // \ — • // ^ '-. o • • / / x X X \ / 1 II \ / X o o X •zz • • • \ / •=• N o II o X o \ NX / .=. / N X X — ' o en • / \ o=o en X o o z X X / 1 CKJ o=o \ / — • 2 o o 2KJ \ / \ / X o o X o o OKJ o=o 1 o \ / 3 o o en o en o o o CO en Z CM II X CM X X X X X X X X X X X X o o o o o o o o o o o o o <« CM X X X X X X X X X X X X X o o o o o o o o o o o o O I 1 1 1 1 1 1 1 1 1 X o X 1 rt X rt o rt o X X X X X X X X X X X 1 o 1 o o 1 o X 1 o 1 o o o 1 o j o o o rr X X X X X X X ON ON ON rr rr CN ro rr in VO r~ X ON CN ro rr o α o o o o o o vo VO VO VO VO vo VO vo vo vo vo vo * . * * ^ %. z z z z z o o o o o X • — • o // x 1 X X • z X X z en— — \ / o o 1 1 1 1 z=« OKJ OKJ o=o o=o 0=0 o=o 1 o o \ / \ / CO z 2 1 X X o o X X X o o o X X o o X X X 1 1 o CJ o X o o X 1 o X X o o ^ -Ό ■ a X X X 1 1 o o o X ON 1 1 1 rr rT CN rr o X m o X X X to CM co oi X O o X X X o o X X o o o z z Q. 3Z o o o o z o o o O CO en o o o CO o o z z z z z 2 2 2 2 o o o o o o O o o X X o 1 o 1 X CO X X X X X X X X X o X X X o o o X o o o o o >— o o o o o o o o o o o o o z o o o o o o o o o o o o o o o o o o o • * ^ ^ • * z 2 2 z 2 2 z 2 z z 2 2 z 2 o o o o o o o o o o o o o o X o m 1 X • — • * •— • // Nx //\ •—» • // — . o • • // ^ • • X X \ _ / 1 II • • \ / X o o X • • \ / o II o X \ Nx/ •___:• / \3 _r X X ' — ' o m CO • / \ CKJ CO X o o z — • X X / 1 CKJ oo z ZKJ \ / X o o X o o ι-1 o o 1 o \/ z o o CO o CO o o o CO CO CO z II — X X X X X X X X X X X X . X X o o o o o o o o o o o o o o X X X X X X X X X X X X X o o o o o o o o o o o o o o 1 1 1 1 1 1 1 1 r-l CN 00 rr m VO r~ X as X r-. CN 00 rT rr rr rr rr rr rr rT rT rr in in m in in VO VO VO VO VO o o vo VO O SΩ vo VO O o > ** ^ * . * . z z z 2 2 2 2 o o o o o o o TABLE 16 Example No. K1 *ιo P> Q 662 CO 663 l2- ^•-COOH 3,5-di-C6H5 , CN, S0 2 CH 3 \ • 664 \ -OC.H H OH 5-CHs CN, S0 2 C 6 Hs • / • 665 -C 2 H OH 3-CH 3 CN, CONHCeHs = .-' 666 \ - 3-CeHs CN, C0NHC2H«,0H • = •> C00H 667 CH 2 - / - ' ,.- _r , ni".u 3-CeHs CN, CN 668 CH 2 - « ^ -C0 2 CH 3 3,5-di-C 6 H_,-p-CH 3 CN, SU 2 CH 3 669 * \•-C0 2 CH 3 3,5-di-C 6 H -p-Cl CN, CO 2 CH 3 \ •=•/ 670 C K 6H"5 3,5-di-C 6 H H -p-COOH CN, C0 2 CH 3 671 C 2 H OH 3,5-di-di-C 6 Hi,-p-OCH 3 672 C 2 H.,0H 3,5-di-CH 3 _ 0 g_g_2J c "'" 673 CH 2 CH 2 0CCH 3 3-C 6 H 5 CN, CN 674 CH 2 CH 2 OCCH 3 3-C 6 H 5 CN, C0 2 CH 3 675 CH 2 CH 2 0CCH 3 3-C 6 H.,-p-CH 3 CN, S0 2 CH 3 CD 676 CH 2 CH 2 OCC 6 H 5 3,5-di-CH 3 CN, C0 2 C 2 H 5 677 CH 2 CH 2; Ol CCH 3 3,5-di-CH 3 -_-ε< c "" 678 CH 2 CH(OH)CH 3 3,5-di-CH 3 679 CH 2 CH OCH 2 CH2 OCCH 3,5-di-CH 3 680 CH 2 Cg H s 3,5-di-CH 3 CN, C0 2 CH 3 X X X X X X X X O o • ~ * o o o o o o X / \ O z O o z • • o O o o o o o o o o o NX _ // o o o o o o o • . * . ^ / \ ^ *-. * » ^ _ z z z z CKJ o=o 2 z z z z 2 z o o o o 1 1 o o o o o o o r-t CN ro rT m VO r » X ON σ CN X X X X X X X X X ON ON ON VO vo vo vo vo vo VO VO VO vo vo VO 693 CH 2 CH 2 S0 2 -.^ / »-CH 3 3-C 6 H,,-p-CH 3 CN, C0 2 CH 3 694 CH 2 CH 3,5-di-CH 3 CN, CO2CH3 695 -CH 2 C 1 3,5-di-CH 3 CN, C0 2 CH 3 696 -CH 2 CH=CH 2 3,5-di-CH 3 CN, CO 2 CH 3 697 -CH 2 CH 2 0C 2 H_,0H 3,5-di-CH 3 CN, CN 698 -CH 2 CH 2 S0 2 CH=CH2 3,5-di-C 6 H 5 CN, C0 2 CH 3 00 _ 699 -CH 2 CH(OH)CH 2 OH 5-CH3 CN, C0C(CH 3 )2 700 -CHjCgHj 1 3-CH3 CN, C0 2 CH 3 701 -CH 2 CH 2 S0 2 N(CH 3 ) 2 3-CeHs CN, C0 2 CH 3 702 -CH 2 CH 2 CON(CH 3 )C 6 H 5 3-CeHs CN, C0 2 CH 3 703 -CH 2 C :HH 2 ,Oι CCH.CI 3,5-di-C 6 H l| -p-CH 3 CN, C0 2 CH 3 ^ * » «- • * 2 2 2 2 2 O o O o o X o X o o 1 o ex o 1 1 ex X 1 υ X 1 ro X o o X • - — • // 1 X X X X 2 o eo o , / o o I I I I — • OKJ 0=0 o=o o=o OKJ K. 1 o o V V co 1 X X o o X X X o o o X X o o X x X 1 1 o o o o o \/ o \ co I X o o / 33 fi o o CN 2 O 2 V II SI o \ o / Z II O o -CJ I 8-o o o-o I o-o I I I OKJ 0=0 OKJ 2 o o o O o ° I. I I I X o X o o o 1 o • o //\ I . . X I II z rH o • * o o Nx/ X X c X • X X o 1 o 1 o o o o. NX / X X X X X X X X o o o o o o o X o o o O COOH C 6 H 5 ./ 729 3,4-di-CH 3 -OC-C 730 H C 6 H 5 C0 2 C 2 Hs, Sϋ 2 CH 3 731 3,5-di-CeHs H CN, CU 2 CH 3 732 H C 6 H„-p-OCH 3 CN, Cϋ 2 CH 3 733 5-OCH 3 , 3-CH 3 , 4-C 6 H s H CN, C0 2 CH 3 734 4-OCH 3 , 5-CH 3 CH 3 CN, C0 2 CH 3 735 CH 2 CH(OH)CH 3 -o.- --C- C6 H i N / eHs 00 co 736 H CH 2 CH(OH)C 6 H 5 -0--.-I \ 737 H CH2CH2CH2NHCOCH3 CN, CO2CH3 738 H CH 2 CH 2 OH CN, S0 2 CH 3 739 H CH 2 CH 2 OH CN, S0 2 C 6 H 5 740 H CH 2 CH 2 OH CN, COC(CH 3 ) 3 74 1 H CβH 11 CN, C0 2 CH 2 C 6 H 5 742 CH 2 CH 2 OC -<CH 3 CN , C0C 6 H 5 X X X X X o o o o o OKJ OKJ OKJ OKJ 0=0 o o o o o X X X X X o o o o o X X X X X X o o o o o o 756 C 6 H,,-p-Cl CN, CONHC 2 H„OH 757 2,4-di-C 6 H 5 C fi H 11 CN, CONH-*^ X« -C0 2 CH 3 758 2-CHs H CN, S0 2 -» ^•-C0 2 CH 3 759 2,5-di-C 6 H 5 H CN, C0 2 CH 2 CH 2 CH 2 0CH 3 760 2,4,5-tri-C 6 H 5 H CN, C0 2 C 6 Hιι 761 2-C1, 5-C 6 H 5 CH 3 CN, C0 2 CH 2 CH 2 0H 762 2,5-di-CH j CfiH j ! CN, S0 2 CH 2 CH 2 CH 2 θH 763 2-C 6 H 5 C 6 H 5 CN , C0 2 C 6 H 5 I o 764 2,5-di-CH 3 CH 2 CH 2 OH 765 2,5-di-CH 3 CH 2 CH 2 OH 766 2,5-di-CH 3 CH 2 CH 2 OH 767 2,5-di-CH 3 CH 2 CH 2 o?CC(H 3 C N , 768 2,5-di-CH 3 CHi 22 vC_πH 22 υOCv-CH 3 CN, S0 2 CH 3 769 2,5-di-CH 3 CH 2 CH 2 O CH 3 CN, COC(CH 3 ) 3 770 2,5-di-CH 3 CH 2 CH 2 OCCH 3 CN, COC 6 H 5 771 2,5-di-CH 3 CH 2 CH 2 OCCH 3 0 CN C 6 H: 5 772 2,5-di-CH 3 CH 2 CH(OCCH 3 )CH 3 -OC-C= 773 2,5-di-CH 3 CH 2 CH 2 0- « •-C0 2 CH 3 CN, CN / LΩ ro 774 2,5-di-CH 3 CH 2 CH 2 C1 CN, CO 2 CH 3 775 2,5-di-CH 3 CH 2 CH 2 -»^ ^--COOH - ^ 776 2,5-di-CH 3 C fi H. -CN, 777 2,5-di-CH 3 CH 2 CH 2 C0 2 CH 3 CN, x o o o I X o o X 2 o- o X X o o X X o o CN CN X ON r- r- X X o X CX o o r * . \ / o X o o X X a. o X o o 1 i o ^ o 0 _ o o o X o o 1 * . o CKJ * . z o o z z o 1 o o o x \ en / X x o o O o O x o X X . o X X o o O o X OKJ 1 o o X • X y\ X X 1 1 II o • ' — • •— • • • 1 1 // Nx Z' N // x ro Q NX/ en eo • • • • • X o » 1 1 \ / \ / \ / z=» 2=» • : O 1 1 __Z« • zz» •__z* o=o. 'z= • - I \ 1 \ 1 \ 1 \ 1 \ 1 \ 1 \ en en CO o 2-X eo en / / / / / / / X X X o o o O O o I // N • \ / \ / o z=o I z o x o Nx/ _• I \ CO / o X o X The preparation of the unsaturated polyesters of this invention is according to well known techniques in the art as described, for example, in U.S. Patents: 3,642,672; 3,549,586; 4,299,927;- and 5 4,355,136 incorporated herein by reference. It is preferred that these polyesters have an acid number of from about 10 to about 28, an inherent viscosity of from about 0.05 to about 0.25, and a number average molecular weight of from about llϋϋ to about 3800. 10 Typical colored polyester material prepared in accordance with this invention are as follows: EXAMPLE 8ul - reparation of Unsaturated polyester Material from Neopentyl lilycol, Isophthalic Acid, and Maleic Anhydride 15 Copolymerized With Methine Colorant and Cured With Styrene The reaction apparatus " comprising a one-litre flask is fitted with a stirrer, thermometer, nitroyen inlet tube, and heated Vigreux column. he top of the 20 igreux column is also fitted with a Dean-Stark trap and cold water condenser. The flask is charg.ed with 251.6 g of neopentyl glycol (2.415 mol), 191.U g of isophthalic acid (1.15 m), U.0951 g (200 ppm) of the reac.tive methine compound and 0.55 g of dibutyltin oxide. The flask is then heated to reflux and held at this temperature until the theoretical amount of distillate is collected from this esterification stage. The reaction system is 30 cooled to 145°C and 112.8 g of maleic anhydride (1.15 m) and 0.055 g of toluhydroquinone are added. The esterification and polycondensation reactions are . cl continued for one hour at 175°C, then for one hour at 185°C, and then at 195°C until an acid number of 18.1 for the unsaturated polyester is obtained. The inherent viscosity of this polyester is U.133, the number average molecular weight is 2640 and the color is bright red-orange, ufficient of this polyester material is blended or dissolved in styrene monomer to give 40 wt. % monomer and the system then blended with 1 wt % benzoyl peroxide. One-eighth inch thick sheet castings are prepared by decanting the blend between glass plates separated by 1/8-inch thick spacers and sealed around three sides with a 1/8-inch thick gasket. The blend is cured by heating for two hours at 70°C,.then for one hour at lϋϋ ' °C, then for two hours at 125°C, and then' for one hour at 15U°C. After cooling, the cured polyester sheet is removed and cut into bars. The flexural strength of the.bars is 18.46 3 x 10 psi. EXAMPLE 802 - Preparation of Unsaturated polyester Material from Propylene Glycol, Isophthalic Acid, and Maleic Anhydride Copolymerized With Methine Colorant and Cured ith styrene The following components are charged into the equipment described in Example 801: 192.5 g propylene glycol (2.53 mol); 191.0 g isophthalic acid (1.15 mol); 0.50 g dibutyltin oxide; and 0.0869 g. ( C CCtiHH 3 l-,CCOOC 2 ,HH 4 „ )) 2 „NN--- / These components are reacted as described in Example 8U1 until the theoretical amount of distillate is collected. The reaction is cooled to 145°C and 112.8 g maleic anhydride (1.15 mol) and 0.05 g of toluhydroquinone are added. The reaction is continued for one hour at 175°C, then for one hour at 185°C, and then at 195°C until an acid number of 14.1 for the unsaturated polyester is obtained. The inherent viscosity of this polyester is 0.11, the number average molecular weight is 1912, and the color is yellow. A curable blend of this unsaturated polyester and sheet casting and bars thereof were prepared as in Example 801. The bars had a flexural strength of 18.60 x lϋ 3 psi. The above inherent viscosities, acid numbers, number average molecular weights, and flexural strengths were determined as follows: Acid number by ASTM D-1639-70; Number Average Molecular Weight by ASTM D-08.03 (Gel Permeation Chromatography) ; Flexural Strength by ASTM D-79U-81; Inherent Viscosity according to ' ASTM D2857-70 procedure in a Wagner Viscometer of Lab Glass Inc. of Vineland, N.J. having a 1/2 ml. capillary bulb, using a polymer concentration of U.5% by weight in 6U/4U by weight, phenol/tetrachloroethane solvent. The procedure comprises heating the polymer/solvent system at 120°C. for 15 minutes to enhance dissolution of the polymer, cooliny the solution to 25°C. and measuring the time of flow at 25°C. The I.V. is calculated from the equation 25°C. In t s (n) 0.50% C where: (η) = Inherent viscosity at 25°C. at a polymer concentration of 0.5 g./100 ml. of solvent; In = Natural logarithm; t s = Sample flow time; t 0 = Solvent-blank flow time; and - 1U 1 - C = Concentration of polymer in grams per 100 ml. of solvent = 0.50. This invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims: CLAIMS 1. A composition comprising unsaturated polyester material having copolymerized therein a total of from 1.0 to about 5,000 ppm of at least one methine moiety having one or more methine units, said moiety absorbing in the range of from about 32U nm to about 650 nm, and being nonextractable from said polyester material and stable under the processing conditions therefor. 2. The composition of claim 1 wherein the polyester has an I.V. of about U.05 to about 0.25, an acid number of from about 10 to about 28, and a number average molecular weight of from about 1100 to about 3800. 3. The composition of claim 1 wherein the polyester acid component is comprised of 40-60 mole % isophthalic acid and conversely 60-40 mole % of either or a mixture of maleic and fumaric acid, and the alcohol component is comprised of propylene glycol, neopentyl glycol, or mixtures thereof. 4. The composition of claim 3 wherein the polyester acid component is comprised of isophthalic acid and maleic acid, and the alcohol is neopentyl glycol or neopentyl glycol mixed with less than about 75 mole % propylene glycol. 5. The composition of any of claims 1-4 wherein each methine moiety is derived from a reactive compound of the formula wherein each A is selected from the following radicals wherein: R and R' are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, and arylthio; n is 0, 1, 2; R, and R 2 are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two of alkyl, -OH, alkoxy, halogen, or hydroxy substituted alkyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, carboxy, cyano, or alkoxycarbonyl; straight or branched lower alkenyl; straight or branched alkyl of 1-8 carbons and such alkyl substituted with the following: hydroxy; halogen; cyano; succinimido; hydroxysuccinimido; acyloxysuccinimido; glutarimido; phenylcarbamoyloxy; phthalimido; 4-carboxyρhthalimido; phthalimidino; 2-pyrrolidono; cyclohexyl; phenyl;. phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; sulfamyl.; benzoyl- sulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxy¬ carbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula wherein Y is -NH-, -..-alkyl, -0-, -S-, or -CH 0-; -^-R^ '" S0 2 CH 2 CH SR 14 ; wherein -, . is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl; pyridyl; pyrimidinyl; benzoxazolyl; benzimidazolyl; benzothiazolyl; radicals of the formulae -OX 16 ; -NHXR,,; -X-R,g; -CON , 5 R 15 ; and , -SO 2.,NRl,ι C ιRI,D c ; wherein Rl,b c is selected from H, aryl, alkyl, and alkyl substituted with halogen, -uri, phenoxy, aryl, -CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; X is -Cυ-, -Cuυ-, or -S0 ~; 16 is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alxanoyloxy, and alkoxy; and when x is -Cυ-, _. 1. r o also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl; al oxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbalkoxy, or halogen; R, and R can be a single combined group such as pentamethylene, tetramethylene, ethyleneoxy- ethylene, ethylene sulfonylethylene, or XR 17 ethylene-N-ethylene which, with the nitrogen to which it is attached, forms a ring; R 17 is alkyl, aryl, or cycloalkyl; R 3 is alkylene, arylene, aralkylene, alkyleneoxy, or alkyleneoxyalkylene; Z is a direct single bond, OCϋ, 0, S, Sθ2. R 17 S0 2 N=/ " ϋC ~ alk Y lene ~<-0-, -OC-arylene-CO-, -S-S-, -OCNH-alkylene-NHCO, -oGNri-arylene-.riCo-, -OCϋ-, arylene, or alkylene; R, , R 5 , and Rg are each selected from hydrogen and alkyl; . R_ is carboxy, carbalkoxy, or (R) n ; R, is hydrogen, alkyl, and aryl; Ro u and Ry.. are each selected from hydrogen and substituted or unsubstituted alkyl, aryl, or cycloalkyl; R, , and R- 2 are each selected- from hydrogen, alkyl, hydroxyl, or acyloxy; R 13 is hydrogen, hydroxyl, hydroxyalkoxy, alkoxy, aryloxy, carboxy, carbalkoxy, aralkyloxy, or acylamido; B represents the atoms necessary to complete a five or six membered ring and is selected from each P and . are selected- from cyano, carbalkoxy, carbaryloxy, carbaralkyloxy, carbamyl, carboxy, N-alkylcarbainyl, N-alkyl-N-arylcarbamyl, N,N-dialkylcarbamyl, N-arylcarbamyl, N-cyclohexyl¬ carbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 1,3,4-thiadiazol-2-yl, l,3,4-oxadiazol-2-yl, Sϋ 2 alkyl, SU 2 aryl, and acyl, or and u may be combined as wherein R, 7 is def-ined above and R- 8 is CN, COUH, CO_ alkyl, carbamyl, or N-alkylcarbainyl; wherein at least one of A, P, and g for each dye molecule must be or bear a condensable group selected from carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl) 2 carbaιnyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy; and wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted where appropriate with hydroxyl, acyloxy, alkyl, cyano, alicoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl. 6. The composition of claim 5 wherein the reactive compound has the formula I. 7. The composition of claim 6 wherein A has the formula 8. The composition of claim 7 wherein: R is H, alkyl, halogen or alkoxy; and R, and 2 are each selected from H, alkyl, cycloalkyl, cycloalkyl substituted with one or more of alkyl, OH, CN, alkoxy, carbalkoxy or alkanoyloxy, and alkyl substituted with one or more of OH, CN, alkanoyloxy, carbalkoxy, aryl, substituted aryl, alkoxy, alkoxyalkoxy, haloyen, succinimido or carbamyl. . The composition of claim 5 wherein A has the formula 10. The composition of claim 9 wherein: R is H, alkyl, halogen or alkoxy; R, is selected from H, alkyl, cycloalkyl, cycloalkyl substituted with one or more of alkyl, OH, CN, alkoxy, carbalkoxy or alkanoyloxy, and alkyl substituted with one or more of OH, CN, alkanoyloxy, carbalkoxy, aryl, substituted aryl, alkoxy, alkoxy¬ alkoxy, halogen, succinimido or carbamyl; and R., ^ and R g are each H or alkyl. 11. The composition of claim 5 wherein A has the formula 12. The composition of claim 11 wherein R and R' are each selected from H, alkyl, halogen and alkoxy; and is H, alkyl, cycloalkyl, cycloalkyl substituted with one or more of alkyl, OH, CN, alkoxy, carbalkoxy or alkanoyloxy, and alkyl substituted with one or more of OH, CN, alkanoyloxy, carbalkoxy, aryl, substituted aryl, alkoxy, alkoxyalkoxy, halogen, succinimido or carbamyl. 13. The composition of claim 5 wherein the reactive compound has the formula 14. The composition of claim 13 wherein each R is H, alkyl, halogen or alkoxy; each R, is H, alkyl, cycloalkyl, cycloalkyl substituted with one or more of alkyl, OH, CN, alkoxy, carbalkoxy or alkanoyloxy, and alkyl substituted with one or more of OH, CN, alkanoyloxy, carbalkoxy, aryl, substituted aryl, alkoxy, alkoxyalkoxy, halogen, succinimido or carbamyl; and - 11U - Z is a direct bond, 0, S, •OCϋ-, -OC-, -OC-alkylene-CO-, 15. The composition of any of claims 1-4 wherein the condensable group is one or more of carooxy, carbalkoxy or hydroxy. 16. The composition of any of claims 1-4 wherein the reactive compound is 17. The composition of any of claims 1-4 wherein the reactive compound is 18. The composition of any of claims 1-4 wherein the reactive compound is - Il l - 19. The composition of any of claims 1-4 wherein the reactive compound is 20. The composition of any of claims 1-4 wherein the reactive compound is 21. The composition of any of claims 1-4 wherein the reactive compound is 22. The composition of any of claims 1-4 blended with a curing agent and wherein each methine moiety is derived from a reactive compound of the formula wherein each A is selected from the following radicals wherein: R and R' are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, and arylthio; n is 0, 1, 2; R, and R are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two of alkyl, -OH, alkoxy, halogen, or hydroxy substituted alkyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, carboxy, cyano, or alkoxycarbonyl; straight or branched lower alkenyl; straight or branched alkyl of 1-8 carbons and such alkyl substituted with the following: hydroxy; halogen;, cyano; succinimido; hydroxysuccinimido; acyloxysuccini ido; glutarimido; phenylcarbamoylox ; phthalimido; 4-carboxyphthalimido; phthalimidino; 2-ρyrrolidono; cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; sulfa yl; benzoyl- sulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxy¬ carbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula wherein Y is -NH-, -ώ-alkyl, -0-, -S-, or -CH υ-; _i >-^ 14 ; S0 2 CH CH 2 S 14 ; wherein R.. is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy. alkanoylamino, ' cyano, or alkoxycarbonyl; pyridyl; pyrimidinyl; benzoxazolyl; benzimidazolyl; benzothiazolyl; radicals of the formulae -OXR1.6,; -NHXR1, c 6; -X-R1,6,; -CUNR1,5 C R1,5_ ; and -SO y N ,5R15; wherein R,,- is selected from H, aryl, alkyl, and alkyl substituted with haloyen, -uri, phenoxy, aryl, -CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; X is -CO-, -COO-, or -SO._..-; Ri, c o is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy; and when X is -CO-, R, g also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbalkoxy, or halogen; R. and R.. can be a single combined group such as pentamethylene, tetramethylene, ethyleneoxy- ethylene, ethylene sulfonylethylene, or which, with the nitrogen to which it is attached, forms a ring; R, ? is alkyl, aryl, or cycloalkyl; R_ is alkylene, arylene, aralkylene, alkyleneoxy, or alkyleneoxyalκylene; z is a direct single bond, υcυ, 0, s, sυ^. 17 S0 2 =, -OC-alkylene-CO-, -OC-arylene-Cu-, -S-S-, -OCNri-alkylene-NHCO, -OCNH-arylene-NHCO-, -OCO-, arylene, or alkylene; R . R 5 / and R g are each selected from hydrogen and alkyl; R_ is carboxy, carbalkoxy, or (R) ; R,,. is hydrogen, alkyl, and aryl; Ro u and R_y are each selected from hydrogen and substituted or unsubstituted alkyl, aryl, or cycloalkyl; R,- and R- 2 are each selected from hydrogen, alkyl, hydroxyl, or acyloxy; R, 3 is hydrogen, hydroxyl, hydroxyalkoxy, alkoxy, aryloxy, carboxy, carbalkoxy, aralkyloxy, or acylamido; B represents the atoms necessary to complete a five or six membered ring and is selected from 1 * _|P 7 / each p and <j are selected from cyano, carbalkoxy, carbaryloxy, carbaralkyloxy, carbamyl, carboxy, N-alkylcarbamyl, N-alkyl-N-arylcarbamyl, N,N-dialkylcarbamyl, N-arylcarbamyl, N-cyclohexyl¬ carbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 1,3,4-thiadiazol-2-yl, l,3,4-oxadiazol-2-yl, SO alkyl, SO aryl, and acyl, or P and _ may be combined as wherein R, 7 is defined above and , a is CN, COOH, CU alkyl, carbamyl, or N-alkylcarbamyl; wherein at least one of A, P, and y for each dye molecule must be or bear a condensable group selected from carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl) carbamyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy; and wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted where appropriate with hydroxyl, acyloxy, alkyl, cyano, alkoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl. 23. The cured composition of claim 22. 24. Formed articles of the cured composition of claim 23.

Inventors: HILBERT SAMUEL DAVID, PRUETT WAYNE PAYTON, WANG RICHARD HSU-SHIEN, WEAVER MAX ALLEN, HILBERT, SAMUEL, DAVID, PRUETT, WAYNE, PAYTON, WANG, RICHARD, HSU-SHIEN, WEAVER, MAX, ALLEN
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1986
Main classification: C08G63
IPC codes: C08G63, C08L67, C09B23, C09B69