Aryl-mercapto anthraquinone dyestuffs, their preparation and use and dichroic material containing aryl-mercapto anthraquinone dyestuffs

The invention relates to new anthraquinone dyestuffs of the formula ##STR2## their use in dyeing, and dichroic material, preferably in the form of liquid-crystal phases, containing at least one of these anthraquinone dyestuffs.
In formula (I),
R.sub.1 represents alkyl, aralkyl, --CO--X--alkyl, --CO--X--aralkyl, --CO--X--aryl, --O--alkyl, --O--aralkyl, --O--aryl, CN, NO.sub.2, CF.sub.3, halogen or a heterocyclic radical,
R.sub.2 represents H or R.sub.1,
X representing O, S, NH or a direct bond, and
Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 represent hydrogen, NH.sub.2, OH, Hal, NO.sub.2 or an arylmercapto group, and at least one of the substituents Y.sub.1 to Y.sub.4 denotes the arylmercapto group. The alkyl, aralkyl, aryl and heterocyclic radicals mentioned for R.sub.1 and also Y.sub.1 -Y.sub.4 can be substituted.
In particular, Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 represent the following combinations of four:
TABLE 1______________________________________Y.sub.1 Y.sub.2 Y.sub.3 Y.sub.4______________________________________S--Ar S--Ar S--Ar NH.sub.2S--Ar S--Ar NH.sub.2 S--ArS--Ar NH.sub.2 S--Ar S--ArNH.sub.2 S--Ar S--Ar S--ArS--Ar S--Ar S--Ar HS--Ar S--Ar H S--ArS--Ar H S--Ar S--ArH S--Ar S--Ar S--ArS--Ar S--Ar NH.sub.2 NH.sub.2NH.sub.2 NH.sub.2 S--Ar S--ArS--Ar NH.sub.2 NH.sub.2 S--ArNH.sub.2 S--Ar S--Ar NH.sub.2S--Ar NH.sub.2 S--Ar NH.sub.2NH.sub.2 S--Ar NH.sub.2 S--ArS--Ar S--Ar NH.sub.2 OHS--Ar S--Ar OH NH.sub.2NH.sub.2 OH S--Ar S--ArOH NH.sub.2 S--Ar S--ArS--Ar NH.sub.2 S--Ar OHNH.sub.2 S--Ar OH S--ArS--Ar OH S--Ar NH.sub.2OH S--Ar NH.sub.2 S--ArS--Ar S--Ar NH.sub.2 HalS--Ar S--Ar Hal NH.sub.2NH.sub.2 Hal S--Ar S--ArHal NH.sub.2 S--Ar S--ArS--Ar NH.sub.2 S--Ar HalNH.sub.2 S--Ar Hal S--ArS--Ar Hal S--Ar NH.sub.2Hal S--Ar NH.sub.2 S--ArS--Ar S--Ar NH.sub.2 HS--Ar S--Ar H NH.sub.2NH.sub.2 H S--Ar S--ArH NH.sub.2 S--Ar S--ArS--Ar NH.sub.2 S--Ar HNH.sub.2 S--Ar H S--ArS--Ar H S--Ar NH.sub.2H S--Ar NH.sub.2 S--ArS--Ar OH S--Ar OHOH S--Ar OH S--ArS--Ar OH S--Ar HalOH S--Ar Hal S--ArS--Ar Hal S--Ar OHHal S--Ar OH S--ArS--Ar S--Ar OH HS--Ar S--Ar H OHOH H S--Ar S--ArH OH S--Ar S--ArS--Ar OH S--Ar HOH S--Ar H S--ArS--Ar H S--Ar OHH S--Ar OH S--ArS--Ar Hal S--Ar HHal S--Ar H S--ArS--Ar H S--Ar HalH S-- Ar Hal S--ArS--Ar S--Ar H HH H S--Ar S--ArS--Ar H S--Ar HH S--Ar H S--ArS--Ar NH.sub.2 NH.sub.2 NH.sub.2NH.sub.2 S--Ar NH.sub.2 NH.sub.2NH.sub.2 NH.sub.2 S--Ar NH.sub.2NH.sub.2 NH.sub.2 NH.sub.2 S--ArS--Ar NH.sub.2 NH.sub.2 OHNH.sub.2 S--Ar OH NH.sub.2NH.sub.2 OH S--Ar NH.sub.2OH NH.sub.2 NH.sub.2 S--ArS--Ar OH NH.sub.2 NH.sub.2OH S--Ar NH.sub.2 NH.sub.2NH.sub.2 NH.sub.2 S--Ar OHNH.sub.2 NH.sub.2 OH S--ArS--Ar NH.sub.2 OH NH.sub.2NH.sub.2 S--Ar NH.sub.2 OHOH NH.sub.2 S--Ar NH.sub.2NH.sub.2 OH NH.sub.2 S--ArS--Ar NH.sub.2 NO.sub.2 NH.sub.2NH.sub.2 S--Ar NH.sub.2 NO.sub.2NO.sub.2 NH.sub.2 S--Ar NH.sub.2NH.sub.2 NO.sub.2 NH.sub.2 S--ArS--Ar NH.sub.2 NH.sub.2 HNH.sub.2 S--Ar H NH.sub.2NH.sub.2 H S--Ar NH.sub.2H NH.sub.2 NH.sub.2 S--ArS--Ar H NH.sub.2 NH.sub.2H S--Ar NH.sub.2 NH.sub.2NH.sub.2 NH.sub.2 S--Ar HNH.sub.2 NH.sub.2 H S--ArS--Ar NH.sub.2 H NH.sub.2NH.sub.2 S--Ar NH.sub.2 HH NH.sub.2 S--Ar NH.sub.2NH.sub.2 H NH.sub.2 S--ArS--Ar NH.sub.2 H HNH.sub.2 S--Ar H HH H S--Ar NH.sub.2H H NH.sub.2 S--ArS--Ar H NH.sub.2 HH S--Ar H NH.sub.2NH.sub.2 H S--Ar HH NH.sub.2 H S--Ar______________________________________
In Table 1, Ar denotes aryl and Hal denotes halogen.
Possible substituents for the aryl radicals are, in particular, alkyl, such as C.sub.1 -C.sub.7 --alkyl, cycloalkyl, such as C.sub.3 -C.sub.7 --cycloalkyl, aralkyl, such as C.sub.1 -C.sub.4 --alkylaryl, trifluoromethyl, aryl, halogen, such as fluorine, chlorine or bromine, alkoxy, such as C.sub.1 -C.sub.6 --alkoxy, aryloxy, such as phenoxy and naphthyloxy, or --COOT in which T denotes an organic radical.
Examples of suitable aryl radicals are phenyl, biphenyl, naphthyl, indanyl and tetrahydronaphthyl; phenyl is preferred. Preferred substituents in the aryl radicals are C.sub.1 -C.sub.7 --alkyl, in particular methyl and tert.butyl, halogen, in particular Cl and F, phenyl and --COOT.
Alkyl preferably denotes C.sub.1 -C.sub.7 --alkyl and can optionally be substituted by halogen, such as fluorine or chlorine, C.sub.1 -C.sub.4 --alkoxy, hydroxyl, cycloalkyl, in particular cyclopentyl or cyclohexyl, or the cyano group, and/or can optionally be interrupted in the C chain by one or more O and/or S atoms.
Aralkyl denotes especially a C.sub.1 -C.sub.4 --alkylaryl radical in which the aryl radical can optionally be substituted as described above for aryl.
Heterocyclic radicals are especially optionally substituted and/or fused rings carrying 5-ring or 6-ring heterocyclic structures of the oxazole, oxdiazole, thiazole, thiadiazole, imidazole, triazole, oxazoline or dihydro-H-oxazine series.
T preferably represents a C.sub.1 -C.sub.8 --alkyl radical in which the C chain can be interrupted by O and/or S, and which can be substituted by halogen, hydroxyl, C.sub.1 -C.sub.4 --alkoxy, cycloalkyl, in particular cyclopentyl or cyclohexyl, or optionally substituted aryl, in particular optionally substituted phenyl, or T represents optionally substituted aryl, in particular optionally substituted phenyl.
Compounds of the formula (I) which are particularly important within the scope of the present invention are those in which at least one of the substituents Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 represents NH.sub.2 and/or OH, and, additionally, at least one represents --S--aryl, and the remaining substituents, Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4, if any, denote hydrogen.
Dyestuffs of the formula I which are also of particular interest are those in which 1-3 of the substituents Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 represent --NH.sub.2 and/or --OH and, in addition 3-1 of the substituents Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 represent optionally substituted arylmercapto.
Other compounds which are particularly important are those of the formulae ##STR3##
The individual substituents in the formulae II-XIV have the following meanings:
Y.sub.5 denotes --NH.sub.2, --OH or optionally substituted arylmercapto;
Y.sub.2 ', Y.sub.3 ' and Y.sub.4 ' denote optionally substituted arylmercapto;
X.sub.1 denotes --O--, --S-- or ##STR4## R.sub.4 and R.sub.5 denote optionally substituted alkyl which can be interrupted in the C chain by one or more O and/or S atoms, or denotes optionally substituted aryl;
R.sub.3 denotes optionally substituted alkyl which can be interrupted in the C chain by one or more O and/or S atoms, in particular methyl, ##STR5## --OR.sub.4 or --SR.sub.4 ; R.sub.3 ' denotes optionally substituted alkyl which can be interrupted in the C chain by one or more O and/or S atoms, in particular methyl or ##STR6## R.sub.3 " denotes --OR.sub.4 or --SR.sub.4 ; and Y.sub.6 and Y.sub.7 denote --NH.sub.2, --OH or --SR.sub.4, it being necessary for one of the two radicals Y.sub.6 and Y.sub.7 to be --SR.sub.4.
The compounds of the formula (I) are prepared by methods which are in themselves known, such as are described, for example, in Houben-Weyl, Methoden der organischen Chemie ("Methods of Organic Chemistry"), 4th edition, 1979, G. Thieme Verlag, Stuttgart, Volume 7/3c.
The introduction of the arylmercapto radical is effected by reacting an appropriate halogenoanthraquinone or nitroanthraquinone or the corresponding anthraquinonesulphonic acid with an appropriate thiophenol or an organic solvent, for example in an alcohol or in dimethylformamide, dimethyl sulphoxide or N-methylpyrrolidone, or, when reacting an anthraquinonesulphonic acid, also in water, and in the presence of acid-binding agents, such as alkali metal carbonates, hydroxides, oxides or acetates or alkaline earth metal carbonates, hydroxides, oxides or acetates, or in the presence of organic acid-binding agents, such as triethylamine. In this reaction, if the reaction conditions are suitable, nitro groups frequently react preferentially, so that, in the case of some nitrohalogenoanthraquinones, it is possible to carry out the reaction in such a way that only the nitro groups are replaced.
The amino groups are introduced in a known manner, either by reducing a nitro group or by subjecting a corresponding halogenoanthraquinone to tosylamide fusion, followed by scission. In dinitroanthraquinones, such as 1,5-dinitro-4,8-dihydroxyanthraquinone, it is frequently possible to replace or reduce the nitro groups in stages, so that the remaining nitro group is available for further reactions.
In general, the compounds are obtained in a state of purity which is not sufficient for them to be used in liquid-crystal compositions, so that additional purification measures, such as recrystallisation, column chromatography or liquid-liquid partition, are necessary.
The invention also relates to dichroic material, preferably in the form of liquid-crystal phases, containing at least one dyestuff of the formula (I). The liquid-crystal compositions are preferably used in optoelectronic display elements.
The dyestuffs which are used in accordance with the invention possess an excellent fastness to light, a high order parameter and, to a predominant extent, a colour density in liquid-crystal materials which is sufficiently high for industrial use. The properties mentioned are of decisive importance for suitability as dyestuffs in optoelectronic display elements operating on the guest-host principle (German Offenlegungsschrift No. 3,028,593).
Optoelectronic display elements generally consist of two sheets of glass arranged parallel to one another (at a distance of 5-50.mu.). The liquid-crystal material is embedded between electrodes mounted on the inner sides of the glass sheets. The proper functioning of an optoelectronic display depends on the oriented structure of the liquid crystals, which can be modified by the electric field applied.
The oriented structure of the liquid-crystal materials can communicate itself to suitable dyestuffs, so that the latter participate in the structure as "guests".
The dyestuffs according to the invention are used as a solution of a nematic liquid-crystal mixture in guest-host displays of known construction and mode of operation (Heilmeyer et al, Mol. Crystals and Liquid Cryst. 8, 293-309 (1969) and German Offenlegungsschriften Nos. 2,639,675 and 2,568,568). The liquid-crystal material used as the host phase contains at least one dyestuff of the formula (I), and can also contain further dyestuffs. The latter may or may not possess dichroic properties.
The solution consists of about 0.01 to about 30% by weight, preferably about 0.1 to about 10% by weight, of dyestuff (as the guest) and of the host phase, which consists mainly of nematic, liquid-crystal material, and which can contain further additives, for example additives for achieving a cholesteric orientation.
The invention also relates, therefore, to liquid-crystal materials containing anthraquinone dyestuffs of the formula (I). The liquid-crystal material preferably has positive dielectric anisotropy and can be employed in optoelectronic display devices.
Of the various states of order of liquid-crystal materials, the nematic and cholesteric states are preferred, in accordance with the definitions, such as are stated, for example, in R. Steinstrasser and L. Pohl, Angew. Chem. 85, 706 (1973).
In the zero-field state, it is possible to distinguish two orientations of the liquid-crystal material, which depend on the property of the phase boundary and thus on the pretreatment of the glass sheets. The texture is described as homotropic or homogeneous, depending on whether the long axis of the molecules of which the liquid-crystal phase consists are oriented vertically or horizontally in relation to the surface of the sheet. The techniques for producing suitable surfaces are known (Ullmann, 4th Edition (1976), Volume XI, page 657 et seq). The dielectric anisotropy is dependent on the dipole properties of the liquid-crystal compounds. It is positive when the electric field produces a homotropic alignment and negative when this alignment becomes homogeneous. It is preferable to use this dyestuffs according to the invention in liquid-crystal materials having positive dielectric anisotropy. Examples of suitable liquid-crystal materials are mixtures containing mainly 4-cyanobiphenyls. An example is afforded by mixture E 7 of BDH Chemicals Ltd. (U.K.), or those which contain mainly 1-(4-cyanophenyl)-4-alkylcyclohexanes. An example of these is mixture ZLI 1132 of Merck (Darmstadt). Other suitable mixtures are those of the classes of substances mentioned previously with (4-cyanophenyl)-pyrimidines, for example mixture ROTN 30 of F. Hoffmann-La Roche.
Further examples of commercially available and suitable liquid-crystal mixtures which may be mentioned for positive anisotropy of dielectric constant and products based on cyanopyrimidines and cyanoesters, and also mixtures of BCH, PCH and PCH--esters and PCH, BCH, PCH--esters and terphenyl (for example "ROTN 402", "ROTN 103", "Merck 1221 TNC", "Merck 1291 TNC", "Merck 1691", and "Merck 1840").
Additionally, however, it is possible to employ a large number of other components, suitable mixtures generally being those containing the constituent mentioned. Compounds belonging to the following classes of substances are particularly suitable: ##STR7##
Each of the benzene rings present can be substituted by one or more substituents, for example fluorine. In these formulae
R is an alkyl group, a trans-1,4-substituted cyclohexane ring or a 1,4-substituted bicyclo-[2,2,2]octane ring,
X.sub.2 is a 1,4-phenylene, 4,4'-biphenylene or 2,6-naphthylene group,
Z.sub.1 is CN, R', OR' or CO--O--X.sub.2 --Z.sub.2,
Z.sub.2 is CN, R' or OR' and
G and L are --CH.sub.2 CH.sub.2 --, --CH.dbd.CH-- or --C.tbd.C--.
R' has the same meaning as R.
As well as the liquid-crystal compounds and the dyestuff, the liquid-crystal material can contain further customary additives, for example optically active compounds which can convert a nematic phase into a cholesteric phase, or substances for reducing the threshold voltage etc.
The quality of the guest-host interaction can be indicated by the mean deviation of the geometrical axis of the dyestuff molecule from the preferential orientation which is determined by the molecules of the liquid-crystal material. It is possible to define an order parameter S which takes account of the mean deviation and assumes a value of 1.0 in the event of ideal order. In practice, this value is not achieved; the S values are, on the contrary, <1.0. Owing to different techniques of measurement, the values quoted in the literature are not comparable as they stand. The definition of the order parameter and its significance are described by D. L. White and G. N. Taylor, J. Appl. Phys. (5) 1974, 4718-4723, or, for example, in European Laid-Open Application 2,104. The S values of some of the claimed compounds are listed in Tables 2 and 3.
For industrial use, dyestuffs having a high order parameter are particularly valuable. However, they must have a number of other properties. Their photochemical stability must be very good and their colour shade must neither fade nor bleach in the light. In addition, they must have a good stability to chemicals in the liquid-crystal medium, which has a complex composition. Finally, the dyestuff must have a high colour density and must not crystallise even at continuing low temperatures.
It is evident that there are not many substances which fulfill the totality of all the properties in a satisfactory manner. Dichroism of light absorption as a function of the orientation of the host liquid crystals is a necessary requirement for dyestuffs to be usable.
Rendering the dyestuffs adequately soluble while maintaining their dichroic fastness and colour properties presents a particular difficulty. A large number of tests are necessary just for optimising the solubility.
Anthraquinones have already been known in the literature for a fairly long time as dichroic dyestuffs, for example from the following literature references: German Offenlegungsschrift No. 2,363,219, U.S. Pat. No. 3,864,022, U.S. Pat. No. 3,975,285, German Offenlegungsschriften Nos. 2,418,364, 2,815,335, 2,920,730, 3,006,744 and 2,082,196, European Patent No. A1-2,104, European Patent No. A1-49,035 and Japanese Patent Applications Nos. 56/112,967, 56/38,376 and 56/10,583.
All the compounds which are known from the literature prove to be in need of improvement in respect of order parameter, colour density, stability to light and/or colour stimulus specifications.
Depending on their substitution, the dyestuffs according to the invention provide yellow to blue shades of good fastness to light and tinctorial strength.
The dyestuffs which can be employed in accordance with the invention are of particular value for formulating black mixtures for liquid-crystal compositions in combination with anthraquinone and azo dyestuffs. Examples of anthraquinone dyestuffs which are suitable for such combinations are known from European Laid-Open Application No. 26,004, German Offenlegungsschriften Nos. 3,009,940 and 3,009,974, European Laid-Open Application No. 34,832 and German Offenlegungsschriften No. 2,903,095, 3,028,593, 3,036,853 and 3,038,372.
The dyestuffs according to the invention are also particularly suitable for dyeing synthetic polymers, for example fibres or plastics based on polyesters, polyamides, cellulose esters or polycarbonates, by processes which are customary per se.
In the following text, the "Colour Index Hue Indication Chart" (Society of Dyers and Colourists, U.K., and American Association of Textile Chemists and Colorists, U.S.A.) is abbreviated to "CIHIC".

EXAMPLE 1
(a) 95 g of 1-amino-2-methyl-4-bromoanthraquinone and 41 g of anhydrous potassium carbonate are introduced into 500 cc of dimethylformamide, 55 g of 4-tert.-butylthiophenol are added to the mixture, and the latter is heated to 125.degree. to 130.degree. C. in the course of 1 hour and is kept at this temperature until, after approx. 3 hours, the reaction is complete. After cooling to approx. 70.degree. C., the reaction mixture is diluted with 500 cc of methanol and is allowed to cool completely. The dyestuff which has crystallised out is then filtered off with suction, washed with methanol and hot water and dried at 60.degree. C. This gives 66 g (corresponding to 54% of theory) of 1-amino-2-methyl-4-(4-tert.-butylphenylmercapto)-anthraquinone, which is recrystallised from dimethylformamide to remove a blue by-product.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged red which has Indicator Number 10 (CIHIC).
(b) 0.5% of the dyestuff prepared in Example 1a is dissolved in a nematic phase, consisting of a mixture of approx. 24% of trans-4-heptyl-(4-cyanophenyl)-cyclohexane, 37% of trans-4-pentyl-(4-cyanophenyl)-cyclohexane, 26% of trans-4-propyl-(4-cyanophenyl)-cyclohexane and 12% of trans-4-pentyl-(4'-cyanobiphenylyl)-cyclohexane. This gives a liquid-crystal mixture which has a bluish-tinged red colour and in which the dyestuff has an order parameter S of 0.69.
(c) 0.5% of the dyestuff prepared in Example 1a is dissolved in a liquid-crystal phase consisting of 51% of 4'-n-pentyl-4-cyanobiphenyl, 25% of 4'-n-heptyl-4-cyanobiphenyl, 16% of 4'-n-octyl-4-cyanobiphenyl and 8% of 4"-n-pentyl-4-cyanoterphenyl. This gives a liquid-crystal mixture which has a bluish-tinged red colour and in which the dyestuff has an order parameter S of 0.70.
Similar good order parameters are also obtained if other liquid-crystal mixtures are employed, for example those described in pages 12-15.
EXAMPLE 2
(a) 6.8 g of 1-amino-2-(4,5-dihydrooxazol-2-yl)-4-nitroanthraquinone and 2.7 g of anhydrous potassium carbonate are introduced into 50 cc of N-methylpyrrolidone, 3.7 g of 4-tert.-butylthiophenyl are added to the mixture, and the latter is heated to 80.degree. C. in the course of 1 hour and is kept at this temperature until the orange-red starting material has reacted completely. The reaction mixture is then diluted at 70.degree. C. with 50 cc of methanol and is allowed to cool to room temperature. The dyestuff which has crystallised out is filtered off with suction, washed with methanol and hot water and dried at 60.degree. C. This gives 6.9 g (corresponding to 75% of theory) of 1-amino-(2-(4,5-dihydrooxazol-2-yl)-4-(4-tert.-butylphenylmercapto)-anthraquinone, which is recrystallised from 100 cc of dimethylformamide and washed with ethanol.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13 (CIHIC).
(b) In a 0.5% strength, bluish-tinged violet solution of the dyestuff described above in one of the liquid-crystal phases of Examples 1b or 1c, the dyestuff has an order parameter S of 0.75. Similar good order parameters are also obtained if other liquid-crystal mixtures are employed, for example those described on pages 12-15.
(c) The 1-amino-2-(4,5-dihydrooxazol-2-yl)-4-nitroanthraquinone employed in Example 2a can be prepared as follows:
34 g of 1-amino-4-nitroanthraquinone-2-carboxylic acid N-(2-methoxyethyl)-amide, prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and 2-methoxyethylamine, are introduced in 400 cc of 100% strength sulphuric acid, and the solution is warmed at 50.degree. C. until cyclisation is complete. After cooling, the reaction mixture is poured onto 3 kg of ice, and the product is filtered off with suction and washed until neutral. The dry substance weighs 22 g, corresponding to a yield of 70% of theory. It is recrystallised from dimethylformamide.
EXAMPLE 3
(a) 14 g of 1-amino-2-(5,6-dihydro-4H-1,3-oxazin-2-yl)-4-nitroanthraquinone, 5.4 g of potassium carbonate, 100 cc of N-methylpyrrolidone and 5.9 g of 4-chlorothiophenol are reacted as in Example 2. The reaction mixture is worked up as described in that example to give 9.2 g of 1-amino-2-(5,6-dihydro-4H-1,3-oxazin-2-yl)-4-(4-chlorophenylmercapto)-anthraquinone, corresponding to a yield of 51% of theory.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13.
(b) In one of the liquid-crystal phases of Examples 1b or 1c, the dyestuff described above has a blue-violet colour in solution and an order parameter S of 0.73.
(c) The 1-amino-2-(5,6-dihydro-4H-1,3-oxazin-2-yl)-4-nitroanthraquinone employed in Example 2a can be prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid N-(3-methoxypropyl)-amide analogously to the instructions in Example 2c.
EXAMPLE 4
(a) 4.1 g of 4-methylthiophenol are added to a suspension of 11.6 g of phenyl 1-amino-4-nitroanthraquinone-2-carboxylate, prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and phenol, and 4.2 g of potassium carbonate (anhydrous) in 50 cc of N-methylpyrrolidone, and the mixture is stirred at 80.degree. C. until the starting material has reacted completely. The reaction mixture is diluted at 40.degree. C. with 20 cc of water. After cooling to room temperature, the crystals which have separated out are filtered off with suction, washed with a mixture of N-methylpyrrolidone and water and then with hot water and dried at 60.degree. C. This gives 7.2 g (corresponding to 53% of theory) of phenyl 1-amino-4-(4-methylphenylmercapto)-anthraquinone-2-carboxylate, which can be purified by recrystallisation from dimethylformamide.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13 (CIHIC).
(b) A 0.5% strength solution of the dyestuff described above in one of the liquid-crystal phases of Examples 1b or 1c has a bluish-tinged violet colour. The order parameter S of the dyestuff is found to be 0.75 or 0.74.
Similar good order parameters are also obtained in other liquid-crystal mixtures, for example those described on pages 12-15.
EXAMPLE 5
(a) 11.6 g of phenyl 1-amino-4-nitroanthraquinone-2-carboxylate (see Example 3a), 4.2 g of potassium carbonate (anhydrous) and 4.8 g of 4-chlorothiophenol are introduced into 50 cc of N-methylpyrrolidone, and the mixture is heated at 80.degree. C. until the starting material has reacted completely. The mixture is then diluted at 70.degree. C. with 50 cc of methanol and is allowed to cool. The crystals which have separated out are filtered off with suction, washed with methanol and hot water and dried. This gives 8.3 g, corresponding to 65% of theory, of methyl 1-amino-4-(4-chlorophenylmercapto)-anthraquinone-2-carboxylate, which has been formed by reacting the phenyl ester with the methanol used for the precipitation. The dyestuff can be purified by recrystallisation from dimethylformamide.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13 (CIHIC).
(b) In one of the liquid-crystal phases of Examples 1b or 1c, the dyestuff described above has a bluish-tinged violet colour in solution and an order parameter S of 0.74.
EXAMPLE 6
(a) 7.7 g of pentyl 1-amino-4-nitroanthraquinone-2-carboxylate, prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and n-pentanol, 2.7 g of anhydrous potassium carbonate and 2.7 g of 4-methylthiophenol are introduced into 50 cc of N-methylpyrrolidone, and the mixture is heated to 125.degree.-130.degree. C. in the course of 1 hour and is stirred at this temperature until, after about 1.5 hours, complete reaction has been achieved. The reaction mixture is allowed to cool and is diluted at 40.degree. C. with 20 cc of water. When the mixture has cooled completely, the dyestuff which has been precipitated is filtered off with suction and washed with a mixture of N-methylpyrrolidone and water and then with hot water. After drying at 60.degree. C., 6.7 g of n-pentyl 1-amino-4-(4-methylphenylmercapto)-anthraquinone-2-carboxylate are obtained, corresponding to a yield of 72% of theory. The dyestuff can be purified by recrystallisation from dimethylformamide.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13 (CIHIC).
(b) When dissolved in one of the liquid-crystal phases of Examples 1b or 1c, the dyestuff described above has an order parameter S of 0.74. The solution has a blue-violet colour.
EXAMPLE 7
(a) If the 4-methylthiophenol in Example 5 is replaced by 4.9 g of n-pentyl 3-mercaptobenzoate, prepared analogously to the instructions of P. F. Wiley (J. Org. Chem. 16, (1951), 812) for the methyl and ethyl esters, the procedure otherwise being as described in that example, 6.1 g of n-pentyl 1-amino-4-(3-pentoxycarbonylphenylmercapto)-anthraquinone-2-carboxylate, corresponding to a yield of 54% of theory, are obtained after a reaction time of 3 hours at 125.degree.-130.degree. C. and appropriate working up.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13 (CIHIC).
(b) The dyestuff described above imparts a blue-violet colour to a liquid-crystal phase such as was used in Examples 1b or 1c, and, in these phases, has an order parameter S of 0.74.
(c) n-Pentyl 1-amino-4-(4-methoxycarbonylphenylmercapto)-anthraquinone-2-carboxylate, which is readily soluble in the liquid-crystal phases of Examples 1b or 1c, giving a blue-violet colour, and has an order parameter S of 0.74 in these phases, is obtained entirely analogously to the procedure described in (a) from methyl 4-mercaptobenzoate, which is also described by P. F. Wiley (J. Org. Chem. 16 (1951), 813), but which can also be synthesized from the 4-mercaptobenzoic acid prepared by S. Smiles and D. C. Harrison (J. Chem. Soc. (London) 121 (1922), 2024) (in this connection see also the communication from D. Bramley and N. H. Chamberlain in J. Chem. Soc. (London) 1942, 376).
EXAMPLE 8
(a) 7.8 g of n-propyl 1-amino-4-bromoanthraquinone-2-carboxylate, 2.7 g of anhydrous potassium carbonate and 3.7 g of 4-tert.-butylthiophenol are introduced into 50 cc of N-methylpyrrolidone, and the mixture is heated to 125.degree.-130.degree. C. in the course of 1 hour. The reaction mixture is stirred at this temperature until the starting material has reacted, and is then diluted at 40.degree. C. with 20 cc of water. When the mixture has cooled completely, it is filtered with suction and the product is washed with a mixture of N-methylpyrrolidone and water and then with hot water, and dried at 60.degree. C. This gives 5.5 g of n-propyl 1-amino-4-(4-tert.-butylphenylmercapto)-anthraquinone-2-carboxylate, corresponding to a yield of 57% of theory.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicator Numbers 12 and 13 (CIHIC).
(b) The dyestuff described above imparts a blue-violet colour to a liquid-crystal phase such as was used in Examples 1b or 1c, and has an order parameter S of 0.71 in these phases. Similar good order parameters are also obtained in other liquid-crystal mixtures, for example those described on pages 12-15.
EXAMPLE 9
(a) If the 4-methylthiophenol in Example 4 is replaced by 6.2 g of 4-phenylthiophenol, prepared from 4-biphenylsulphonic acid, which is known from the literature, by converting the latter into the sulphonyl chloride and reducing this by the method of A. W. Wagner (Chem. Ber. 99, (1966), 375) using red phosphorus and iodine in glacial acetic acid, the procedure otherwise being as described above, after appropriate working up, 9.5 g of phenyl 1-amino-4-(4-biphenylmercapto)-anthraquinone-2-carboxylate (60% of theory) are obtained; this can be purified by recrystallisation from dimethylformamide.
The colour shade of the dyestuff when adsorbed onto silica gel is a bluish-tinged violet which is between Indicators Numbers 12 and 13 (CIHIC).
(b) In one of the liquid-crystal phases of Examples 1b or 1c, the dyestuff described above has a blue-violet colour in solution and an order parameter S of 0.78.
EXAMPLE 10
(a) 4.5 g of phenyl 1-amino-4,5,8-trichloroanthraquinone-2-carboxylate and 2 g of anhydrous potassium carbonate are introduced into 100 cc of dimethylformamide, 4 g of 4-methylthiophenol are added, and the mixture is then heated to 80.degree. C. under a gentle stream of nitrogen and is kept at this temperature until the reaction is complete. The reaction mixture is then diluted at 40.degree. C. with 40 cc of water, is allowed to cool completely and is filtered with suction, and the product is washed with a mixture of dimethylformamide and water and then with water. After drying at 60.degree. C., 4.8 g of phenyl 1-amino-4,5,8-tri-(4-methylphenylmercapto)-anthraquinone-2-carboxylate are obtained, corresponding to a yield of 67% of theory.
The colour shade of the dyestuff when adsorbed onto silica gel is a reddish-tinged blue which is between Indicator Numbers 13 and 14 (CIHIC).
(b) The dyestuff described above imparts a blue colour to a liquid-crystal phase such as was used in Examples 1b or 1c, and has an order parameter S of 0.81 in this phase.
(c) The phenyl 1-amino-4,5,8-trichloroanthraquinone-2-carboxylate employed in Example 10a had been prepared as follows:
A mixture of 60 g of phenol and 4 g of anhydrous potassium carbonate is subjected to incipient vacuum distillation, in the course of which approx. 20 g of phenol and water are removed by distillation. 15.6 g of 1-amino-4,5,8-trichloroanthraquinone-2-carboxylic acid chloride, prepared from 1-amino-4,5,8-trichloroanthraquinone-2-carboxylic acid, described in German Auslegeschrift No. 1,154,490, Example 15, and excess thionyl chloride, are introduced to the cold melt, and the mixture is then heated at 60.degree. C. for 30 minutes. It is then diluted at about 40.degree. C. with 20 cc of water, is allowed to cool completely and is filtered with suction, and the product is washed with water and dried. This gives 12.2 g of the product, corresponding to a yield of 68% of theory.
(d) Pentyl 1-amino-4,5,8-tri-(4-methylphenylmercapto)-anthraquinone-2-carboxylate, which is also soluble in the liquid-crystal phases used in Example 1b or 1c, producing a reddish-tinged blue colour, and which has an order parameter of 0.79 therein, is obtained, entirely analogously to the procedure described under (a), from the analogous pentyl ester, prepared in accordance with
(c) from pentanol and 1-amino-4,5,8-trichloroanthraquinon-2-carboxylic acid chloride.
EXAMPLE 11
(a) 7.9 g of 1-amino-4-nitroanthraquinone-2-carboxylic acid N-(n-hexyl)-amide and 2.7 g of anhydrous potassium carbonate are introduced into 50 cc of N-methylpyrrolidone, 2.7 g of 4-methylthiophenol are added, and the mixture is heated at 80.degree. C. until the reaction is complete. The mixture is then diluted at 70.degree. C. with 50 cc of methanol, is allowed to cool and is filtered with suction, and the product is washed with methanol and water. This gives 6.0 g of 1-amino-4-(4-methylphenylmercapto)-anthraquinone-2-carboxylic acid N-(n-hexyl)-amide, corresponding to a yield of 63% of theory.
The colour shade of the dyestuff when adsorbed onto silica gel is a violet which is between Indicator Numbers 11 and 12 (CIHIC).
(b) The dyestuff described above imparts a violet colour to a liquid-crystal phase such as was used in Examples 1b or 1c, and has an order parameter S of 0.75 in this phase.
(c) The 1-amino-4-nitroanthraquinone-2-carboxylic acid N-(n-hexyl)-amide employed in Example 11a can be prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid by reacting the latter with excess thionyl chloride, distilling off the thionyl chloride and reacting the distillation residue with n-hexylamine.
EXAMPLE 12
1,4-Dichloroanthraquinone-6-carboxylic acid, which is described in Houben-Weyl, Methoden der organischen Chemie ["Methods of Organic Chemistry"], 4th Edition, 1979, G. Thieme Verlag, Stuttgart, Volume 7/3C, page 261, can also be converted, entirely analogously to the process described in Example 10, via its acid chloride into the corresponding n-pentyl ester or phenyl ester or a carboxamide, for example N-(n-hexyl)-carboxamide. The two chlorine atoms are then replaced by arylmercapto radicals in the manner described. This gives red compounds having the following order parameters:
(a) n-Pentyl 1,4-di-(4-chlorophenylmercapto)-anthraquinone-6-carboxylate, S=0.76
(b) Phenyl 1,4-diphenylmercaptoanthraquinone-6-carboxylate, S=0.75
(c) 1,4-Di-(4-methylphenylmercapto)-anthraquinone-6-carboxylic acid N-(n-hexyl)-amide, S=0.78
(d) 1,4-Di-(4-methylphenylmercapto)-anthraquinone-6-carboxylic acid anilide, S=0.79.
Further examples are listed in Table 2 which follows. The table relates to dyestuffs of the formula ##STR8##
In this formula, Q indicates the .beta.-substituents; X in the table designates the position in which Q is attached to the anthraquinone ring, that is to say the 2-, 3-, 6- or 7-position.
The order parameter in the nematic phases of Examples 1b or 1c is indicated in columns S.sub.1, S.sub.2, S.sub.3 and S.sub.4. The data are determined in a 0.5% strength solution at a layer thickness of 23 .mu.m, and are evaluated in accordance with the known procedure (for example British Patent Specification No. 2,071,685). The order parameters indicated in the table have the following meanings
in column S.sub.1, they relate to dyestuffs in which Ar denotes phenyl;
in column S.sub.2, they relate to dyestuffs in which Ar denotes 4-chlorophenyl;
in column S.sub.3 they relate to dyestuffs in which Ar denotes 4-methylphenyl; and
in column S.sub.4, they relate to dyestuffs in which Ar denotes 4-tert.-butylphenyl.
Under the heading Q, C.sub.6 H.sub.5 represents phenyl, C.sub.6 H.sub.4 represents phenylene, C.sub.3 H.sub.7 represents n-propyl, C.sub.4 H.sub.9 represents n-butyl and C.sub.5 H.sub.11 represents n-pentyl.
The numbers marked with dashes and placed in brackets denote the position, on the phenoxy radical, of the following substituent.
TABLE 2__________________________________________________________________________Y' Y" Y"' X Q S.sub.1 S.sub.2 S.sub.3 S.sub.4__________________________________________________________________________1 SAr SAr SAr (2) CH.sub.3 0.73 0.722 SAr SAr SAr (2) CH.sub.2 CH(CH.sub.3).sub.2 0.68 0.79 0.78 0.743 SAr SAr SAr (2) 2-Oxazolinyl 0.68 0.79 0.78 0.744 SAr SAr SAr (2) CONHC.sub.6 H.sub.5 0.69 0.79 0.78 0.745 SAr SAr SAr (2) COOCH.sub.3 0.66 0.77 0.76 0.726 SAr SAr SAr (2) COOC.sub.3 H.sub.7 0.75 0.747 SAr SAr SAr (2) COOC.sub.5 H.sub.11 0.76 0.75 0.718 SAr SAr SAr (2) COOC.sub.6 H.sub.5 0.71 0.81 0.80 0.769 SAr SAr SAr (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.72 0.81 0.81 0.7710 SAr SAr SAr (2) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.72 0.82 0.81 0.7711 SAr SAr SAr (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.71 0.81 0.80 0.7612 SAr SAr SAr (2) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.73 0.82 0.82 0.7813 SAr SAr SAr (2) OCH.sub.3 0.7214 SAr SAr SAr (2) OC.sub.4 H.sub.9 0.75 0.74 0.6915 SAr SAr SAr (2) OCH.sub.2 C.sub.6 H.sub.5 0.75 0.74 0.6916 SAr SAr SAr (2) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.65 0.76 0.76 0.7117 SAr SAr SAr (2) OC.sub.6 H.sub.5 0.69 0.79 0.79 0.7518 SAr SAr SAr (2) OC.sub.6 H.sub.4 (2')Cl 0.70 0.80 0.79 0.7519 SAr SAr SAr (2) OC.sub.6 H.sub.4 (3')Cl 0.71 0.80 0.80 0.7620 SAr SAr SAr (2) OC.sub.6 H.sub.4 (3')F 0.70 0.80 0.79 0.7521 SAr SAr SAr (2) OC.sub.6 H.sub.4 (4')CH.sub.3 0.70 0.80 0.79 0.7522 SAr SAr SAr (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.71 0.81 0.80 0.7623 SAr SAr SAr (2) OC.sub.6 H.sub.4 (4')SCH.sub.3 0.69 0.79 0.79 0.7524 SAr SAr SAr (2) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.69 0.79 0.79 0.7525 SAr SAr SAr (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.69 0.79 0.78 0.7426 SAr SAr SAr (2) OC.sub.6 H.sub.4 (4')Cl 0.69 0.79 0.78 0.7427 SAr SAr SAr (2) O2-Naphthyl 0.80 0.80 0.7628 SAr SAr SAr (2) CN 0.62 0.74 0.6829 SAr SAr SAr (2) Br 0.74 0.6830 SAr SAr SAr (2) Cl 0.7331 SAr SAr NH.sub.2 (7) CH.sub.3 0.69 0.77 0.76 0.7332 SAr SAr NH.sub.2 (7) 2-Oxazolinyl 0.81 0.81 0.7833 SAr SAr NH.sub.2 (7) CONHC.sub.6 H.sub.5 0.75 0.82 0.8134 SAr SAr NH.sub.2 (7) COOC.sub.5 H.sub.11 0.79 0.7635 SAr SAr NH.sub.2 (7) COOC.sub.6 H.sub.5 0.77 0.82 0.8136 SAr SAr NH.sub.2 (7) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.78 0.82 0.82 0.8137 SAr SAr NH.sub.2 (7) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.77 0.82 0.82 0.8038 SAr SAr NH.sub.2 (7) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79 0.83 0.82 0.8239 SAr SAr NH.sub.2 (7) OC.sub.4 H.sub.9 0.71 0.78 0.7540 SAr SAr NH.sub.2 (7) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.80 0.79 0.7641 SAr SAr NH.sub.2 (7) OC.sub.6 H.sub.5 0.76 0.82 0.82 0.7942 SAr SAr NH.sub.2 (7) OC.sub.6 H.sub.4 (4')OCH.sub.3 0.77 0.82 0.82 0.8043 SAr SAr NH.sub.2 (7) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.82 0.8244 SAr SAr NH.sub.2 (7) OC.sub.6 H.sub.4 (4') COOC.sub.5 H.sub.11 0.82 0.81 0.7945 S Ar SAr NH.sub.2 (7) CN 0.77 0.7746 SAr SAr NH.sub.2 (2) CH.sub.2 CH(CH.sub.3).sub.2 0.8247 SAr SAr NH.sub.2 (2) CONHC.sub.6 H.sub.4 (4')CH.sub.3 0.75 0.82 0.8148 SAr SAr NH.sub.2 (2) COOC.sub.5 H.sub.11 0.79 0.79 0.7649 SAr SAr NH.sub.2 (2) COOC.sub.6 H.sub.5 0.77 0.82 0.8150 SAr SAr NH.sub.2 (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.8251 SAr SAr NH.sub.2 (2) OC.sub.6 H.sub.5 0.76 0.82 0.8252 SAr SAr NH.sub.2 (2) OC.sub.6 H.sub.4 (3')F 0.82 0.82 0.8053 SAr SAr NH.sub.2 (2) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.76 0.8254 SAr SAr NH.sub.2 (2) O2-Naphthyl 0.82 0.82 0.8055 SAr SAr NH.sub.2 (2) CN 0.77 0.7456 SAr SAr NH.sub.2 (2) Cl 0.7757 SAr SAr NH.sub.2 (3) CH.sub.3 0.77 0.7658 SAr SAr NH.sub.2 (3) 2-Oxazolinyl 0.8159 SAr SAr NH.sub.2 (3) CONHC.sub.6 H.sub.5 0.75 0.82 0.81 0.7960 SAr SAr NH.sub.2 (3) COOC.sub.5 H.sub.11 0.72 0.79 0.79 0.7661 SAr SAr NH.sub.2 (3) COOC.sub.6 H.sub.5 0.77 0.82 0.8162 SAr SAr NH.sub.2 (3) OCH.sub.3 0.69 0.77 0.7663 SAr SAr NH.sub.2 (3) OC.sub.6 H.sub.5 0.76 0.82 0.7964 SAr SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.81 0.7965 SAr SAr NH.sub.2 (3) CN 0.7766 SAr SAr H (2) CF.sub.3 0.69 0.78 0.7767 SAr SAr H (2) 2-Oxazolinyl 0.74 0.81 0.8068 SAr SAr H (2) CONHC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.74 0.81 0.81 0.7869 SAr SAr H (2) COOC.sub.5 H.sub.11 0.78 0.7870 SAr SAr H (2) COOC.sub.6 H.sub.5 0.76 0.82 0.82 0.8071 SAr SAr H (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.77 0.82 0.82 0.8072 SAr SAr H (2) COOC.sub.6 H.sub.4 (4')Cl 0.82 0.82 0.8073 SAr SAr H (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.82 0.8074 SAr SAr H (2) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.78 0.82 0.82 0.8175 SAr SAr H (2) OC.sub.4 H.sub.9 0.77 0.7476 SAr SAr H (2) OC.sub.6 H.sub.5 0.75 0.81 0.81 0.7877 SAr SAr H (2) OC.sub.6 H.sub.4 (2')Cl 0.8278 SAr SAr H (2) OC.sub.6 H.sub.4 (3')CH.sub.3 0.8179 SAr SAr H (2) OC.sub.6 H.sub.4 (3')F 0.82 0.81 0.7980 SAr SAr H (2) OC.sub.6 H.sub.4 (4')CH.sub.3 0.82 0.81 0.7981 SAr SAr H (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.76 0.82 0.8282 SAr SAr H (2) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.75 0.8183 SAr SAr H (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.81 0.7884 SAr SAr H (2) O 2-Naphthyl 0.76 0.82 0.7985 SAr SAr H (2) CN 0.76 0.76 0.7386 SAr SAr H (2) Cl 0.7587 SAr SAr H (3) CH.sub.2 CH(CH.sub.3).sub.2 0.81 0.7888 SAr SAr H (3) COOC.sub.5 H.sub.11 0.71 0.78 0.7589 SAr SAr H (3) COOC.sub.6 H.sub.5 0.76 0.82 0.8290 SAr SAr H (3) COOC.sub.6 H.sub.4 (4')Cl 0.76 0.82 0.8091 SAr SAr H (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.82 0.8092 SAr SAr H (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.78 0.82 0.8193 SAr SAr H (3) OCH.sub.3 0.76 0.7594 SAr SAr H (3) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.79 0.78 0.7595 SAr SAr H (3) OC.sub.6 H.sub.5 0.75 0.8196 SAr SAr H (3) OC.sub.6 H.sub.4 (2')Cl 0.8297 SAr SAr H (3) OC.sub.6 H.sub.4 (3')F 0.75 0.82 0.8198 SAr SAr H (3) OC.sub.6 H.sub.4 (4')CH.sub.3 0.82 0.81 0.7999 SAr SAr H (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.76 0.82 0.82100 SAr SAr H (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.74 0.81 0.78101 SAr SAr H (3) OC.sub.6 H.sub.4 (4')Cl 0.81 0.81 0.78102 SAr SAr H (3) CN 0.76103 SAr SAr H (3) Br 0.76 0.76 0.73104 SAr SAr H (6) 2-Oxazolinyl 0.81 0.80 0.77105 SAr SAr H (6) CONHC.sub.6 H.sub.4 (3')F 0.81 0.81 0.78106 SAr SAr H (6) COOC.sub.5 H.sub.11 0.78 0.75107 SAr SAr H (6) COOC.sub.6 H.sub.5 0.76 0.82 0.82 0.80108 SAr SAr H (6) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.77 0.82 0.80109 SAr SAr H (6) COOC.sub. 6 H.sub.4 (3')COOC.sub.5 H.sub.11 0.76 0.82 0.82110 SAr SAr H (6) CN 0.76111 SAr NH.sub.2 NH.sub.2 (2) CH.sub.3 0.76112 SAr NH.sub.2 NH.sub.2 (2) 2-Oxazolinyl 0.81 0.81 0.79113 SAr NH.sub.2 NH.sub.2 (2) CONHC.sub.6 H.sub.5 0.77 0.82 0.80114 SAr NH.sub.2 NH.sub.2 (2) COOC.sub.5 H.sub.11 0.79 0.78 0.76115 SAr NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.5 0.79 0.82 0.81116 SAr NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79 0.82 0.82117 SAr NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79 0.82 0.82118 SAr NH.sub.2 NH.sub.2 (2) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.79 0.79 0.77119 SAr NH.sub.2 NH.sub.2 (2) OC.sub.6 H.sub.5 0.82 0.81 0.80120 SAr NH.sub.2 NH.sub.2 (2) OC.sub.6 H.sub.4 (3')F 0.82 0.80121 SAr NH.sub.2 NH.sub.2 (2) OC.sub.6 H.sub.4 (4')CH.sub.3 0.78 0.82122 SAr NH.sub.2 NH.sub.2 (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.77 0.82 0.81123 SAr NH.sub.2 NH.sub.2 (2) CN 0.77 0.75124 SAr NH.sub.2 NH.sub.2 (6) CH.sub.3 0.71 0.76 0.76 0.74125 SAr NH.sub.2 NH.sub.2 (6) CH.sub.2 CH(CH.sub.3).sub.2 0.61 0.81 0.79126 SAr NH.sub.2 NH.sub.2 (6) 2-Oxazolinyl 0.77 0.81 0.81 0.79127 SAr NH.sub.2 NH.sub.2 (6) CONHC.sub.6 H.sub.5 0.77 0.82 0.80128 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.3 H.sub.7 0.73 0.78 0.75129 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.5 H.sub.11 0.74 0.79 0.78 0.76130 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.5 0.79 0.82131 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79 0.82 0.82132 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.80 0.82 0.82 0.82133 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.82 0.82 0.82134 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79 0.82 0.82135 SAr NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.81 0.82 0.82 0.82136 SAr NH.sub.2 NH.sub.2 (6) OC.sub.4 H.sub.9 0.73 0.78 0.77 0.75137 SAr NH.sub.2 NH.sub.2 (6) OCH.sub.2 C.sub.6 H.sub.5 0.73 0.78 0.77 0.75138 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.5 0.78 0.82 0.80139 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (2')OC.sub.2 H.sub.5 0.82 0.82 0.80140 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (2')Cl 0.82 0.82 0.80141 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (3')CH.sub.3 0.78 0.82 0.82 0.80142 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (3')Cl 0.79 0.82 0.82 0.81143 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (3')F 0.78 0.82 0.82 0.80144 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')CH.sub.3 0.78 0.82145 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79 0.82146 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.82 0.82 0.80147 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.81 0.80148 SAr NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')Cl 0.82 0.81 0.80149 SAr NH.sub.2 NH.sub.2 (6) O2-Naphthyl 0.82 0.81150 SAr NH.sub.2 NH.sub.2 (6) CN 0.72 0.77 0.77151 SAr NH.sub.2 NH.sub.2 (6) Br 0.72 0.77 0.77152 NH.sub.2 SAr NH.sub.2 (2) CH.sub.2 CH(CH.sub.3).sub.2 0.82153 NH.sub.2 SAr NH.sub.2 (2) CONHC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.82154 NH.sub.2 SAr NH.sub.2 (2) COOC.sub.5 H.sub.11 0.81 0.80 0.79155 NH.sub.2 SAr NH.sub.2 (2) COOC.sub.6 H.sub. 5 0.81 0.83 0.82156 NH.sub.2 SAr NH.sub.2 (2) COOC.sub.6 H.sub.4 (3')F 0.81 0.83 0.82157 NH.sub.2 SAr NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.82 0.83 0.83158 NH.sub.2 SAr NH.sub.2 (2) OCH.sub.2 C.sub.6 H.sub.5 0.75 0.80 0.80 0.78159 NH.sub.2 SAr NH.sub.2 (2) OC.sub.6 H.sub.5 0.80 0.82 0.82 0.82160 NH.sub.2 SAr NH.sub.2 (2) OC.sub.6 H.sub.4 (3')F 0.82161 NH.sub.2 SAr NH.sub.2 (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.83 0.82162 NH.sub.2 SAr NH.sub.2 (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.80 0.82163 NH.sub.2 SAr NH.sub.2 (2) CN 0.79164 NH.sub.2 SAr NH.sub.2 (3) CH.sub.3 0.79 0.78165 NH.sub.2 SAr NH.sub.2 (3) 2-Oxazolinyl 0.82 0.82 0.81166 NH.sub.2 SAr NH.sub.2 (3) CONHC.sub.6 H.sub.5 0.80 0.82 0.82 0.82167 NH.sub.2 SAr NH.sub.2 (3) COOCH.sub.3 0.82168 NH.sub.2 S Ar NH.sub.2 (3) COOC.sub.5 H.sub.11 0.81 0.80 0.79169 NH.sub.2 SAr NH.sub.2 (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.81 0.83 0.82170 NH.sub.2 SAr NH.sub.2 (3) COOC.sub.6 H.sub.4 (4')Cl 0.81 0.83 0.82171 NH.sub.2 SAr NH.sub.2 (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.81 0.82 0.82172 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.5 0.82 0.82 0.82173 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (2')OC.sub.2 H.sub.5 0.80 0.82174 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (2')Cl 0.80 0.82 0.82175 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.82 0.82176 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (3')Cl 0.81 0.82177 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (3')F 0.80 0.82 0.82178 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')CH.sub.3 0.80 0.82 0.82179 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')OCH.sub.3 0.81 0.82180 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.83 0.82181 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.80 0.82 0.82 0.82182 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82183 NH.sub.2 SAr NH.sub.2 (3) OC.sub.6 H.sub.4 (4')Cl 0.80 0.82 0.82 0.82184 NH.sub.2 SAr NH.sub.2 (3) CN 0.75 0.79 0.79185 NH.sub.2 SAr NH.sub.2 (3) Br 0.75 0.79 0.79186 SAr NH.sub.2 OH (6) CH.sub.3 0.74 0.73 0.71187 SAr NH.sub.2 OH (6) COOC.sub.5 H.sub.11 0.76188 SAr NH.sub.2 OH (6) COOC.sub.6 H.sub.5 0.77 0.81 0.81 0.79189 SAr NH.sub.2 OH (6) COOC.sub.6 H.sub.4 (4')Cl 0.77 0.81 0.81 0.79190 SAr NH.sub.2 OH (6) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.77 0.81 0.81 0.79191 SAr NH.sub.2 OH (6) OC.sub.4 H.sub.9 0.75 0.73192 SAr NH.sub.2 OH (6) OC.sub.6 H.sub.5 0.75 0.79193 SAr NH.sub.2 OH (6) OC.sub.6 H.sub.4 (3')F 0.80 0.78194 SAr NH.sub.2 OH (6) OC.sub.6 H.sub.4 (4')CH.sub.3 0.80 0.78195 SAr NH.sub.2 OH (6) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79196 SAr NH.sub.2 OH (6) CN 0.74 0.74197 SAr NH.sub.2 OH (2) CH.sub.3 0.68 0.74198 SAr NH.sub.2 OH (3) 2-Oxazolinyl 0.79199 SAr NH.sub.2 OH (3) CONHC.sub.6 H.sub.5 0.75 0.79 0.79 0.77200 SAr NH.sub.2 OH (7) COOC.sub.5 H.sub.11 0.76 0.76 0.74201 SAr NH.sub.2 OH (2) COOC.sub.6 H.sub.5 0.77 0.81 0.81 0.79202 SAr NH.sub.2 OH (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.77 0.81 0.81203 SAr NH.sub.2 OH (7) COOC.sub.6 H.sub.4 (4')Cl 0.81 0.81 0.79204 SAr NH.sub.2 OH (2) COOC.sub.6 H.sub.4 (4')COOC.sub. 5 H.sub.11 0.81 0.79205 SAr NH.sub.2 OH (7) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79 0.82206 SAr NH.sub.2 OH (3) OC.sub.4 H.sub.9 0.75 0.75 0.73207 SAr NH.sub.2 OH (7) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.72 0.76 0.74208 SAr NH.sub.2 OH (2) OC.sub.6 H.sub.5 0.75 0.79 0.77209 SAr NH.sub.2 OH (3) OC.sub.6 H.sub.4 (3')CH.sub.3 0.75 0.80 0.79210 SAr NH.sub.2 OH (2) OC.sub.6 H.sub.4 (3')F 0.80 0.80 0.78211 SAr NH.sub.2 OH (7) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.81212 SAr NH.sub.2 OH (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79213 SAr NH.sub.2 OH (2) CN 0.74 0.72214 NH.sub.2 SAr OH (3) CH.sub.3 0.76 0.76 0.74215 NH.sub.2 SAr OH (3) 2-Oxazolinyl 0.81 0.81216 NH.sub.2 SAr OH (3) CONHC.sub.6 H.sub.5 0.77 0.81217 NH.sub.2 SAr OH (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.81218 NH.sub.2 SAr OH (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82219 NH.sub.2 SAr OH (3) OC.sub.6 H.sub.4 (3')COOC.sub.5 H.sub.11 0.81 0.81 0.79220 NH.sub.2 SAr OH (3) CN 0.77221 NH.sub.2 SAr OH (3) Br 0.76222 NH.sub.2 SAr OH (7) CH.sub.2 CH(CH.sub.3).sub.2 0.81223 NH.sub.2 SAr OH (7) CONHC.sub.6 H.sub.5 0.81224 NH.sub.2 SAr OH (7) COOC.sub.5 H.sub.11 0.79 0.78225 NH.sub.2 SAr OH (7) COOC.sub.6 H.sub.5 0.82 0.82226 NH.sub.2 SAr OH (7) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.81 0.82 0.82 0.82227 NH.sub.2 SAr OH (7) OC.sub.4 H.sub.9 0.78 0.77 0.75228 NH.sub.2 SAr OH (7) OC.sub.6 H.sub.5 0.77 0.82 0.80229 NH.sub.2 SAr OH (7) OC.sub.6 H.sub.4 (3')F 0.78 0.82 0.80230 NH.sub.2 S Ar OH (7) OC.sub.6 H.sub.4 (4')SCH.sub.3 0.82 0.81231 NH.sub.2 SAr OH (7) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.81 0.81 0.79232 NH.sub.2 SAr OH (7) CN 0.77 0.76 0.74233 NH.sub.2 SAr Cl (3) CH.sub.3 0.75234 NH.sub.2 SAr Cl (3) COOC.sub.5 H.sub.11 0.78 0.77235 NH.sub.2 SAr Cl (3) COOC.sub.6 H.sub.5 0.78 0.82 0.82 0.80236 NH.sub.2 SAr Cl (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.82237 NH.sub.2 SAr Cl (3) OC.sub.6 H.sub.5 0.77 0.81 0.81238 NH.sub.2 SAr Cl (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82239 NH.sub.2 SAr Cl (3) CN 0.71 0.76240 SAr NH.sub.2 H (6) CH.sub.3 0.75 0.75 0.73241 SAr NH.sub.2 H (6) 2-Oxazolinyl 0.76 0.80 0.80 0.78242 SAr NH.sub.2 H (6) CONHC.sub.6 H.sub.5 0.76 0.81 0.80 0.79243 SAr NH.sub.2 H (6) COOCH.sub.3 0.79244 SAr NH.sub.2 H (6) COOC.sub.3 H.sub.7 0.77 0.76245 SAr NH.sub.2 H (6) COOC.sub.5 H.sub.11 0.73 0.78 0.77246 SAr NH.sub.2 H (6) COOC.sub.6 H.sub.5 0.82 0.82 0.80247 SAr NH.sub.2 H (6) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79 0.82 0.81248 SAr NH.sub.2 H (6) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.82 0.81249 SAr NH.sub.2 H (6) COOC.sub.6 H.sub.4 (4')Cl 0.78 0.82 0.82250 SAr NH.sub.2 H (6) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.82 0.80251 SAr NH.sub.2 H (6) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.80 0.82 0.82252 SAr NH.sub.2 H (6) CN 0.76 0.76253 SAr NH.sub.2 H (6) Br 0.76254 SAr NH.sub.2 H (2) CH.sub.3 0.75 0.75 0.73255 SAr NH.sub.2 H (2) 2-Oxazolinyl 0.80 0.80256 SAr NH.sub.2 H (2) CONHC.sub.6 H.sub.5 0.76 0.81257 SAr NH.sub.2 H (2) COOC.sub.5 H.sub.11 0.78 0.75258 SAr NH.sub.2 H (2) COOC.sub.6 H.sub.5 0.82 0.80259 SAr NH.sub.2 H (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79 0.82 0.81260 SAr NH.sub.2 H (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.82 0.82 0.81261 SAr NH.sub.2 H (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82 0.82262 SAr NH.sub.3 H (2) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82263 SAr NH.sub.2 H (2) OC.sub.6 H.sub.5 0.77 0.81 0.81 0.79264 SAr NH.sub.2 H (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.76 0.81 0.79265 SAr NH.sub.2 H (2) CN 0.76 0.76266 SAr NH.sub.2 H (3) CH.sub.2 CH(CH.sub.3).sub.2 0.80267 SAr NH.sub.2 H (3) 2-Oxazolinyl 0.76 0.80 0.78268 SAr NH.sub.2 H (3) CONHC.sub.6 H.sub.5 0.81 0.79269 SAr NH.sub.2 H (3) COOC.sub.5 H.sub.11 0.78270 SAr NH.sub.2 H (3) COOC.sub. 6 H.sub.5 0.82 0.80271 SAr NH.sub.2 H (3) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.79 0.82 0.82 0.81272 SAr NH.sub.2 H (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82273 SAr NH.sub.2 H (3) OC.sub.4 H.sub.9 0.72 0.77274 SAr NH.sub.2 H (3) OC.sub.6 H.sub.5 0.77 0.81 0.81 0.79275 SAr NH.sub.2 H (3) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.81 0.79276 SAr NH.sub.2 H (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.81 0.80277 SAr NH.sub.2 H (3) O2-Naphthyl 0.82278 SAr NH.sub.2 H (3) CN 0.76 0.76 0.74279 NH.sub.2 H SAr (3) CH.sub.3 0.72280 NH.sub.2 H SAr (3) 2-Oxazolinyl 0.77 0.77 0.75281 NH.sub.2 H SAr (3) CONHC.sub.6 H.sub.5 0.78 0.78 0.76282 NH.sub.2 H SAr (3) COOCH.sub.3 0.76 0.75283 NH.sub.2 H SAr (3) COOC.sub.5 H.sub.11 0.75 0.74 0.72284 NH.sub.2 H SAr (3) COOC.sub.6 H.sub.5 0.80 0.78285 NH.sub.2 H SAr (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.75 0.80 0.80286 NH.sub.2 H SAr (3) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.80 0.78287 NH.sub.2 H SAr (3) COOC.sub.6 H.sub.4 (4')Cl 0.80 0.79288 NH.sub.2 H SAr (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.75 0.77289 NH.sub.2 H SAr (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.81 0.79290 NH.sub.2 H SAr (3) OCH.sub.2 C.sub.6 H.sub.5 0.74291 NH.sub.2 H SAr (3) OC.sub.6 H.sub.5 0.78 0.78 0.76292 NH.sub.2 H SAr (3) OC.sub.6 H.sub.4 (2')Cl 0.79 0.78293 NH.sub.2 H SAr (3) OC.sub.6 H.sub.4 (3')CH.sub.3 0.74 0.78 0.76294 NH.sub.2 H SAr (3) OC.sub.6 H.sub.4 (3')F 0.74 0.79 0.78295 NH.sub.2 H SAr (3) OC.sub.6 H.sub.4 (4')CH.sub.3 0.74 0.79 0.76296 NH.sub.2 H SAr (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79297 NH.sub.2 H SAr (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.78 0.76298 NH.sub.2 H SAr (3) CN 0.73 0.70299 NH.sub.2 H SAr (3) Cl 0.72300 NH.sub.2 H SAr (2) 2-Oxazolinyl 0.77 0.77 0.75301 NH.sub.2 H SAr (2) CONHC.sub.6 H.sub.5 0.78302 NH.sub.2 H SAr (2) COOC.sub.5 H.sub.11 0.75303 NH.sub.2 H SAr (2) COOC.sub.6 H.sub.5 0.80 0.79 0.78304 NH.sub.2 H SAr (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.80305 NH.sub.2 H SAr (2) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.75306 NH.sub.2 H SAr (2) OC.sub.6 H.sub.5 0.73 0.78 0.78 0.76307 NH.sub.2 H SAr (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.80 0.79308 NH.sub.2 H SAr (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.78 0.78309 NH.sub.2 H SAr (2) CN 0.73 0.72310 NH.sub.2 H SAr (7) CH.sub.3 0.66 0.72 0.71 0.69311 NH.sub.2 H SAr (7) 2-Oxazolinyl 0.77 0.77 0.75312 NH.sub.2 H SAr (7) CONHC.sub.6 H.sub.4 (4')CH.sub.3 0.73 0.78 0.78 0.76313 NH.sub.2 H SAr (7) COOCH.sub.3 0.76 0.73314 NH.sub.2 H SAr (7) COOC.sub.5 H.sub.11 0.75 0.74315 NH.sub.2 H SAr (7) COOC.sub.6 H.sub.5 0.75 0.80 0.79 0.78316 NH.sub.2 H SAr (7) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.75 0.80 0.78317 NH.sub.2 H SAr (7) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.76 0.80 0.78318 NH.sub.2 H SAr (7) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.80 0.79319 NH.sub.2 H SAr (7) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.81 0.79320 NH.sub.2 H SAr (7) CN 0.73 0.72 0.70321 NH.sub.2 SAr H (3) CH.sub.3 0.73 0.78 0.77322 NH.sub.2 SAr H (3) CH.sub.2 CH(CH.sub.3).sub.2 0.82 0.82323 NH.sub.2 SAr H (3) 2-Oxazolinyl 0.82 0.82 0.80324 NH.sub.2 SAr H (3) CONHC.sub.6 H.sub.5 0.79 0.82 0.81325 NH.sub.2 SAr H (3) COOC.sub.3 H.sub.7 0.79 0.79326 NH.sub.2 SAr H (3) COOC.sub.5 H.sub.11 0.75 0.80 0.80327 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.5 0.80 0.82 0.82328 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.82329 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.81 0.83 0.82 0.82330 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.83331 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.4 (4')Cl 0.82 0.82332 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.80 0.82 0.82 0.82333 NH.sub.2 SAr H (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.83334 NH.sub.2 SAr H (3) OC.sub. 4 H.sub.9 0.79 0.77335 NH.sub.2 SAr H (3) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.76 0.80336 NH.sub.2 SAr H (3) OC.sub.6 H.sub.5 0.79 0.82 0.82 0.81337 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (2')Cl 0.82338 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.82339 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (3')F 0.79 0.82 0.81340 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (4')CH.sub.3 0.79 0.82 0.82341 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82 0.82 0.82342 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.82 0.81343 NH.sub.2 SAr H (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79 0.82 0.82 0.81344 NH.sub.2 SAr H (3) O2-Naphthyl 0.82 0.82345 NH.sub.2 SAr H (3) NO.sub.2 0.78346 NH.sub.2 SAr H (3) Br 0.78347 NH.sub.2 SAR H (2) CH.sub.3 0.78348 NH.sub.2 SAr H (2) 2-Oxazolinyl 0.82 0.80349 NH.sub.2 SAr H (2) CONHC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79 0.82350 NH.sub.2 SAr H (2) COOC.sub.5 H.sub.11 0.80 0.80 0.78351 NH.sub.2 SAr H (2) COOC.sub.6 H.sub.5 0.80 0.82 0.82352 NH.sub.2 SAr H (2) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.80 0.80 0.78353 NH.sub.2 SAr H (2) OC.sub.6 H.sub.5 0.79 0.82 0.81354 NH.sub.2 SAr H (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.82355 NH.sub.2 SAr H (2) CN 0.78356 NH.sub.2 SAr H (6) CH.sub.3 0.78 0.75357 NH.sub.2 SAr H (6) 2-Oxazolinyl 0.82 0.82358 NH.sub.2 SAr H (6) CONHC.sub.6 H.sub.4 (3')Cl 0.82 0.82359 NH.sub.2 SAr H (6) COOC.sub.5 H.sub.11 0.75 0.80 0.80360 NH.sub.2 SAr H (6) COOC.sub.6 H.sub.5 0.82 0.82 0.82361 NH.sub.2 SAr H (6) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.80 0.82 0.82362 NH.sub.2 SAr H (6) CN 0.78363 NH.sub.2 SAr H (6) Cl 0.73364 OH SAr OH (3) CH.sub.3 0.73 0.73365 OH SAr OH (3) CH.sub.2 CH(CH.sub.3).sub.2 0.74 0.79 0.77366 OH SAr OH (3) 2-Oxazolinyl 0.74 0.78367 OH SAr OH (3) CONHC.sub.6 H.sub.5 0.79368 OH SAr OH (3) COOC.sub.5 H.sub.11 0.76 0.76369 OH SAr OH (3) COOC.sub.6 H.sub.5 0.77 0.81 0.79370 OH SAr OH (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.77 0.81371 OH SAr OH (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82 0.82372 OH SAr OH (3) OCH.sub.2 C.sub.6 H.sub.5 0.75373 OH SAr OH (3) OC.sub.6 H.sub.5 0.75 0.79 0.79 0.77374 OH SAr OH (3) OC.sub.6 H.sub.4 (3')Cl 0.78375 OH SAr OH (3) OC.sub.6 H(4')C.sub.6 H.sub.5 0.81 0.79376 OH SAr OH (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79 0.79 0.77377 OH SAr OH (3) CN 0.74378 OH SAr OH (3) Cl 0.71379 OH SAr H (3) CH.sub.3 0.70 0.75 0.72380 OH SAr H (3) COOC.sub.5 H.sub.11 0.73 0.78381 OH SAr H (3) COOC.sub.6 H.sub.5 0.82 0.82382 OH SAr H (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82383 OH SAr H (3) OC.sub.6 H.sub.5 0.76 0.81 0.80 0.79384 OH SAr H (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.80385 OH SAr H (3) CN 0.76 0.75386 OH SAr H (2) CH.sub.2 CH(CH.sub.3).sub.2 0.80387 OH SAr H (2) 2-Oxazolinyl 0.80 0.80388 OH SAr H (2) COOC.sub.3 H.sub.7 0.76 0.74389 OH SAr H (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub. 0.78 0.82 0.82390 OH SAr H (2) OC.sub.4 H.sub.9 0.77 0.76391 OH SAr H (2) OC.sub.6 H.sub.4 (3')F 0.81 0.81392 OH SAr H (2) O2-Naphthyl 0.82393 OH SAr H (2) CN 0.75394 OH SAr H (6) CH.sub.3 0.75395 OH SAr H (6) 2-Oxazolinyl 0.80 0.80 0.78396 OH SAr H (6) CONHC.sub.6 H.sub.4 (3')F 0.76 0.81 0.79397 OH SAr H (6) COOCH.sub.3 0.79 0.78398 OH SAr H (6) COOC.sub.6 H.sub.4 (3')F 0.82 0.82 0.80399 OH SAr H (6) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.80 0.82400 Cl SAr H (2) CH.sub.3 0.74 0.74401 Cl SAr H (6) COOC.sub.6 H.sub.5 0.81 0.80402 SAr H H (2) CH.sub.3 0.74 0.74 0.71403 SAr H H (2) CH.sub.2 CH(CH.sub.3).sub.2 0.75 0.80 0.79404 SAr H H (2) 2-Oxazolinyl 0.75 0.79 0.79405 S Ar H H (2) CONHC.sub.6 H.sub.5 0.75 0.80 0.78406 SAr H H (2) COOC.sub.3 H.sub.7 0.76 0.75 0.73407 SAr H H (2) COOC.sub.5 H.sub.11 0.77 0.76408 SAr H H (2) COOC.sub.6 H.sub.5 0.82 0.81 0.80409 SAr H H (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.81 0.80410 SAr H H (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.82 0.82 0.80411 SAr H H (2) COOC.sub.6 H.sub.4 (4')Cl 0.77 0.81 0.81412 SAr H H (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.81 0.81413 SAr H H (2) OC.sub.4 H.sub.9 0.71 0.76 0.73414 SAr H H (2) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.72 0.77415 SAr H H (2) OC.sub.6 H.sub.5 0.76 0.80416 SAr H H (2) OC.sub.6 H.sub.5 (2')Cl 0.81 0.80 0.79417 SAr H H (2) OC.sub.6 H.sub.4 (3')CH.sub.3 0.76 0.80 0.80418 SAr H H (2) OC.sub.6 H.sub.4 (3')F 0.81 0.80 0.79419 SAr H H (2) OC.sub.6 H.sub.4 (4')OCH.sub.3 0.77 0.81 0.81 0.79420 SAr H H (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.82 0.81 0.80421 SAr H H (2) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.76 0.80 0.78422 SAr H H (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.75 0.80 0.78423 SAr H H (2) O2-Naphthyl 0.81 0.81 0.79424 SAr H H (2) CN 0.70 0.75 0.75 0.72425 SAr H H (2) Cl 0.74426 H H SAr (2) CH.sub.3 0.63 0.60427 H H SAr (2) CH.sub.2 CH(CH.sub.3).sub.2 0.70 0.70428 H H SAr (2) 2-Oxazolinyl 0.70429 H H SAr (2) CONHC.sub.6 H.sub.5 0.65 0.71 0.70430 H H SAr (2) COOC.sub.3 H.sub.7 0.65 0.64431 H H SAr (2) COOC.sub.6 H.sub.5 0.73 0.73 0.70432 H H SAr (2) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.69 0.74 0.71433 H H SAr (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.73 0.72434 H H SAr (2) CN 0.64435 H SAr H (2) CH.sub.3 0.77 0.76 0.74436 H SAr H (2) CH.sub.2 CH(CH.sub.3).sub.2 0.77 0.82 0.80437 H SAr H (2) 2-Oxazolinyl 0.81 0.81 0.79438 H SAr H (2) CONHC.sub.6 H.sub.5 0.82 0.82439 H SAr H (2) COOC.sub.3 H.sub.7 0.78 0.78440 H SAr H (2) COOC.sub.5 H.sub.11 0.74 0.79441 H SAr H (2) COOC.sub.6 H.sub.5 0.82 0.82442 H SAr H (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.82 0.82 0.82443 H SAr H (2) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.80 0.82 0.82444 H SAr H (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79 0.82 0.81445 H SAr H (2) CN 0.77 0.77 0.75446 H SAr H (2) Cl 0.77447 NH.sub.2 NH.sub.2 NH.sub.2 (2) CH.sub.3 0.72448 NH.sub.2 NH.sub.2 NH.sub.2 (3) 2-Oxazolinyl 0.78 0.78 0.77449 NH.sub.2 NH.sub.2 NH.sub.2 (3) CONHC.sub.6 H.sub.5 0.79 0.78450 NH.sub.2 NH.sub.2 NH.sub.2 (7) COOC.sub.3 H.sub.7 0.74 0.74 0.73451 NH.sub.2 NH.sub.2 NH.sub.2 (6) COOC.sub.5 H.sub.11 0.73 0.75 0.74452 NH.sub.2 NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.5 0.78 0.80453 NH.sub.2 NH.sub.2 NH.sub.2 (7) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.80 0.79454 NH.sub.2 NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.80455 NH.sub.2 NH.sub.2 NH.sub.2 (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.82 0.82 0.81456 NH.sub.2 NH.sub.2 NH.sub.2 (3) OC.sub.6 H.sub.5 0.79 0.79 0.78457 NH.sub.2 NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (3')F 0.79 0.78458 NH.sub.2 NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')CH.sub.3 0.79 0.79 0.78459 NH.sub.2 NH.sub.2 H (2) CH.sub.3 0.71 0.71 0.70460 NH.sub.2 NH.sub.2 H (2) COOC.sub.5 H.sub.11 0.74 0.73461 NH.sub.2 NH.sub.2 H (2) COOC.sub.6 H.sub.5 0.77 0.79 0.79462 NH.sub.2 NH.sub.2 H (2) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.81 0.80463 NH.sub.2 NH.sub.2 H (2) OC.sub.6 H.sub.5 0.75 0.78 0.78 0.77464 NH.sub.2 NH.sub.2 H (2) OC.sub.6 H.sub.4 (3')CH.sub.3 0.78 0.77465 NH.sub.2 NH.sub.2 H (3) CH.sub.3 0.71 0.71 0.70466 NH.sub.2 NH.sub.2 H (3) CH.sub.2 CH(CH.sub.3).sub.2 0.77467 NH.sub.2 NH.sub.2 H (3) 2-Oxazolinyl 0.77 0.76468 NH.sub.2 NH.sub.2 H (3) CONHC.sub.6 H.sub.5 0.75 0.78 0.77 0.76469 NH.sub.2 NH.sub.2 H (3) COOCH.sub.3 0.75470 NH.sub.2 NH.sub.2 H (3) COOC.sub.5 H.sub.11 0.74 0.74 0.73471 NH.sub.2 NH.sub.2 H (3) COOC.sub.6 H.sub.5 0.77 0.79 0.79472 NH.sub.2 NH.sub.2 H (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.80 0.79 0.79473 NH.sub.2 NH.sub.2 H (3) COOC.sub.6 H.sub.4 (4')Cl 0.79 0.78474 NH.sub.2 NH.sub.2 H (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.77 0.79475 NH.sub.2 NH.sub.2 H (3) OCH.sub.2 C.sub.6 H.sub.5 0.73 0.72476 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.5 0.75 0.78 0.78 0.77477 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.4 (2')OC.sub.2 H.sub.5 0.76 0.78 0.77478 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.4 (3')CH.sub.3 0.78 0.78 0.77479 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.4 (3')F 0.76 0.78 0.78480 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.4 (4')CH.sub.3 0.76 0.78 0.78481 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.79 0.79482 NH.sub.2 NH.sub.2 H (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.75 0.77 0.76483 NH.sub.2 NH.sub.2 H (3) O2-Naphthyl 0.79484 NH.sub.2 NH.sub.2 H (3) CN 0.72485 NH.sub.2 NH.sub.2 H (3) Cl 0.71486 NH.sub.2 NH.sub.2 H (6) CH.sub.3 0.71487 NH.sub.2 NH.sub.2 H (6) CONHC.sub.6 H.sub.5 0.75 0.78488 NH.sub.2 NH.sub.2 H (6) COOCH.sub.3 0.73 0.75 0.75489 NH.sub.2 NH.sub.2 H (6) COOC.sub.6 H.sub.5 0.77 0.79 0.79 0.78490 NH.sub.2 NH.sub.2 H (6) COOC.sub.6 H.sub.4 (4')Cl 0.79491 NH.sub.2 NH.sub.2 H (6) OC.sub.6 H.sub.5 0.78492 NH.sub.2 NH.sub.2 H (6) CN 0.72493 H NH.sub.2 NH.sub.2 (2) CH.sub.3 0.71 0.71494 H NH.sub.2 NH.sub.2 (2) 2-Oxazolinyl 0.77495 H NH.sub.2 NH.sub.2 (2) CONHC.sub.6 H.sub.5 0.78 0.77496 H NH.sub.2 NH.sub.2 (2) COOC.sub.3 H.sub.7 0.70 0.73 0.73497 H NH.sub.2 NH.sub.2 (2) COOC.sub.5 H.sub.11 0.74 0.73498 H NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.5 0.77 0.79 0.79 0.78499 H NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79500 H NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.80501 H NH.sub.2 NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79502 H NH.sub.2 NH.sub.2 (6) CH.sub.2 CH(CH.sub.3).sub.2 0.77 0.76503 H NH.sub.2 NH.sub.2 (6) 2-Oxazolinyl 0.77 0.77504 H NH.sub.2 NH.sub.2 (6) CONHC.sub.6 H.sub.5 0.75 0.77 0.76505 H NH.sub.2 NH.sub.2 (6) COOC.sub.3 H.sub.7 0.73 0.73506 H NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.5 0.77 0.79 0.79 0.78507 H NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.78 0.80 0.79508 H NH.sub.2 NH.sub.2 (6) COOC.sub.6 H.sub.4 (4')Cl 0.77 0.79 0.78509 H NH.sub.2 NH.sub.2 (6) OC.sub.4 H.sub.9 0.73510 H NH.sub.2 NH.sub.2 (6) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.75 0.75 0.74511 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.5 0.75 0.78 0.78 0.77512 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (2')OC.sub.2 H.sub.5 0.78 0.77513 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (3')CH.sub.3 0.76 0.77514 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (3')F 0.76 0.78515 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')CH.sub.3 0.76 0.78 0.77516 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')OCH.sub.3 0.79 0.78517 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')SCH.sub.3 0.78518 H NH.sub.2 NH.sub.2 (6) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.75 0.78 0.76519 H NH.sub.2 NH.sub.2 (6) CN 0.72520 H NH.sub.2 NH.sub.2 (6) Br 0.72521 H NH.sub.2 NH.sub.2 (7) CH.sub.3 0.71 0.70522 H NH.sub.2 NH.sub.2 (7) 2-Oxazolinyl 0.75 0.77 0.76523 H NH.sub.2 NH.sub.2 (7) CONHC.sub.6 H.sub.5 0.75 0.77 0.76524 H NH.sub.2 NH.sub.2 (7) COOC.sub.5 H.sub.11 0.71 0.74 0.73525 H NH.sub.2 NH.sub.2 (7) COOC.sub.6 H.sub.5 0.79 0.78526 H NH.sub.2 NH.sub.2 (7) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.77 0.79 0.79527 H NH.sub.2 NH.sub.2 (7) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.78 0.80528 H NH.sub.2 NH.sub.2 (7) OCH.sub.2 C.sub.6 H.sub.5 0.73529 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.5 0.75 0.78 0.78 0.77530 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (2')Cl 0.76 0.78 0.77531 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (3')F 0.76 0.78 0.77532 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')CH.sub.3 0.78 0.77533 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')OCH.sub.3 0.76 0.79 0.78534 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.79535 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')SCH.sub.3 0.78 0.78 0.77536 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.76 0.78 0.78 0.77537 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.78 0.77 0.76538 H NH.sub.2 NH.sub.2 (7) OC.sub.6 H.sub.4 (4')Cl 0.78 0.77539 H NH.sub.2 NH.sub.2 (7) O2-Naphthyl 0.79540 H NH.sub.2 NH.sub.2 (7) CN 0.72 0.72541 H NH.sub.2 NH.sub.2 (7) Cl 0.71 0.71542 NH.sub.2 H NH.sub.2 (2) CH.sub.3 0.71 0.70543 NH.sub.2 H NH.sub.2 (2) 2-Oxazolinyl 0.77 0.76544 NH.sub.2 H NH.sub.2 (2) CONHC.sub.6 H.sub.5 0.78 0.77 0.76545 NH.sub.2 H NH.sub.2 (2) COOC.sub.5 H.sub.11 0.74 0.74 0.73546 NH.sub.2 H NH.sub.2 (2) COOC.sub.6 H.sub.5 0.79 0.78547 NH.sub.2 H NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.79548 NH.sub.2 H NH.sub.2 (2) OCH.sub.3 0.71 0.70549 NH.sub.2 H NH.sub.2 (2) OC.sub.6 H.sub.5 0.78 0.78 0.77550 NH.sub.2 H NH.sub.2 (2) OC.sub.6 H.sub.4 (4')Cl 0.78 0.77551 NH.sub.2 H NH.sub.2 (3) CH.sub.3 0.68 0.70552 NH.sub.2 H NH.sub.2 (3) 2-Oxazolinyl 0.75 0.77553 NH.sub.2 H NH.sub.2 (3) COOCH.sub.3 0.75554 NH.sub.2 H NH.sub.2 (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.80 0.79555 NH.sub.2 H NH.sub.2 (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.81 0.81 0.80556 NH.sub.2 H NH.sub.2 (3) OCH.sub.3 0.71 0.71557 NH.sub.2 H NH.sub.2 (3) OCH.sub.2 C.sub.6 H.sub.5 0.73 0.73 0.72558 NH.sub.2 H NH.sub.2 (3) OC.sub.6 H.sub.5 0.75 0.78 0.78 0.77559 NH.sub.2 H NH.sub.2 (3) OC.sub.6 H.sub.4 (2')OC.sub.2 H.sub.5 0.76 0.78 0.77560 NH.sub.2 H NH.sub.2 (3) OC.sub.6 H.sub.4 (3')F 0.76 0.78 0.78 0.77561 NH.sub.2 H NH.sub.2 (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.77 0.79 0.79 0.78562 NH.sub.2 H NH.sub.2 (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.75 0.78 0.77 0.76563 NH.sub.2 H NH.sub.2 (3) CN 0.72564 NH.sub.2 H NH.sub.2 (7) CH.sub.3 0.71 0.71565 NH.sub.2 H NH.sub.2 (7) 2-Oxazolinyl 0.77 0.77566 NH.sub.2 H NH.sub.2 (7) CONHC.sub.6 H.sub.5 0.78 0.77567 NH.sub.2 H NH.sub.2 (7) COOC.sub.5 H.sub.11 0.74 0.74568 NH.sub.2 H NH.sub.2 (7) COOC.sub.6 H.sub.5 0.79 0.79569 NH.sub.2 H NH.sub.2 (7) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.77 0.80 0.79 0.79570 NH.sub.2 H NH.sub.2 (7) CN 0.72571 NH.sub.2 H NH.sub.2 (7) Cl 0.71572 NH.sub.2 H H (3) CH.sub.3 0.67 0.70573 NH.sub.2 H H (3) CH.sub.2 CH(CH.sub.3).sub.2 0.74 0.76 0.75574 NH.sub.2 H H (3) 2-Oxazolinyl 0.74 0.76 0.76575 NH.sub.2 H H (3) CONHC.sub.6 H.sub.5 0.74 0.76 0.75576 NH.sub.2 H H (3) COOCH.sub.3 0.74 0.73577 NH.sub.2 H H (3) COOC.sub.3 H.sub.7 0.69 0.71578 NH.sub.2 H H (3) COOC.sub. 5 H.sub.11 0.70 0.73 0.72579 NH.sub.2 H H (3) COOC.sub.6 H.sub.5 0.76 0.79 0.77580 NH.sub.2 H H (3) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79 0.79 0.78581 NH.sub.2 H H (3) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.77 0.79 0.79582 NH.sub.2 H H (3) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.77 0.79 0.79583 NH.sub.2 H H (3) COOC.sub.6 H.sub.4 (4')Cl 0.76 0.78 0.78584 NH.sub.2 H H (3) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.78 0.78585 NH.sub.2 H H (3) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.80 0.80 0.79586 NH.sub.2 H H (3) OCH.sub.3 0.70587 NH.sub.2 H H (3) OC.sub.4 H.sub.9 0.72 0.72 0.71588 NH.sub.2 H H (3) OCH.sub.2 C.sub.6 H.sub.5 0.72 0.72 0.71589 NH.sub.2 H H (3) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.74 0.74 0.72590 NH.sub.2 H H (3) OC.sub.6 H.sub.5 0.74 0.77 0.77 0.76591 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (2')OC.sub.2 H.sub.5 0.77 0.76592 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (2')Cl 0.75 0.77 0.76593 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (3')CH.sub.3 0.75 0.77 0.77 0.76594 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (3')Cl 0.76 0.78 0.78 0.77595 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (3')F 0.75 0.77 0.77 0.76596 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')CH.sub.3 0.75 0.77 0.76597 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')OCH.sub.3 0.75 0.78 0.77598 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79 0.78 0.77599 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')SCH.sub.3 0.77600 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')COOC.sub.2 H.sub.5 0.77 0.76601 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.74 0.77 0.76 0.75602 NH.sub.2 H H (3) OC.sub.6 H.sub.4 (4')Cl 0.74 0.77 0.76603 NH.sub.2 H H (3) O 2-Naphthyl 0.78 0.77604 NH.sub.2 H H (3) CN 0.68 0.71 0.71605 NH.sub.2 H H (3) CF.sub.3 0.73 0.74606 NH.sub.2 H H (2) CH.sub.3 0.70607 NH.sub.2 H H (2) 2-Oxazolinyl 0.74 0.76 0.76608 NH.sub.2 H H (2) CONHC.sub.6 H.sub.5 0.74 0.77 0.76609 NH.sub.2 H H (2) COOC.sub.6 H.sub.5 0.76 0.79 0.77610 NH.sub.2 H H (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.79611 NH.sub.2 H H (2) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.79 0.79 0.78612 NH.sub.2 H H (2) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.78 0.80613 NH.sub.2 H H (2) O(CH.sub.2).sub.2 C.sub.6 H.sub.5 0.74 0.74 0.72614 NH.sub.2 H H (2) OC.sub.6 H.sub.5 0.77 0.77 0.76615 NH.sub.2 H H (2) OC.sub.6 H.sub.4 (3')CH.sub.3 0.77 0.77 0.76616 NH.sub.2 H H (2) OC.sub.6 H.sub.4 (3')F 0.75 0.77617 NH.sub.2 H H (2) OC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.79 0.77618 NH.sub.2 H H (2) OC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.74 0.77 0.76 0.75619 NH.sub.2 H H (2) CN 0.71620 H H NH.sub.2 (7) CH.sub.3 0.63621 H H NH.sub.2 (7) CH.sub.2 CH(CH.sub.3).sub.2 0.70622 H H NH.sub.2 (7) 2-Oxazolinyl 0.69623 H H NH.sub.2 (7) COOC.sub.3 H.sub.7 0.61 0.64624 H H NH.sub.2 (7) COOC.sub.5 H.sub.11 0.66625 H H NH.sub.2 (7) COOC.sub.6 H.sub.5 0.70 0.73 0.72626 H H NH.sub.2 (7) COOC.sub.6 H.sub.4 (4')CH.sub.3 0.71 0.73 0.72627 H H NH.sub.2 (7) OC.sub.4 H.sub.9 0.65628 H H NH.sub.2 (7) CN 0.64629 H H NH.sub.2 (2) CH.sub.2 CH(CH.sub.3).sub.2 0.67 0.70630 H H NH.sub.2 (2) 2-Oxazolinyl 0.67 0.70631 H H NH.sub.2 (2) CONHC.sub.6 H.sub.5 0.70632 H H NH.sub.2 (2) COOC.sub.6 H.sub.5 0.70 0.73 0.72 0.71633 H H NH.sub.2 (2) COOC.sub.6 H.sub.4 (3')CH.sub.3 0.70 0.73 0.73 0.71634 H H NH.sub.2 (2) COOC.sub.6 H.sub.4 (4')COOC.sub.5 H.sub.11 0.72 0.72 0.71635 H H NH.sub.2 (2) CN 0.64636 H NH.sub.2 H (6) CH.sub.3 0.67 0.70637 H NH.sub.2 H (6) CH.sub.2 CH(CH.sub.3).sub.2 0.76 0.76638 H NH.sub.2 H (6) 2-Oxazolinyl 0.76 0.76639 H NH.sub.2 H (6) COOC.sub.6 H.sub.5 0.76 0.79 0.78 0.77640 H NH.sub.2 H (6) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.78 0.80 0.79641 H NH.sub.2 H (6) CN 0.71 0.71642 H NH.sub.2 H (6) Cl 0.70 0.70643 H NH.sub.2 H (2) CH.sub.3 0.70 0.70644 H NH.sub.2 H (2) CH.sub.2 CH(CH.sub.3).sub.2 0.76645 H NH.sub.2 H (2) COOC.sub.5 H.sub.11 0.73 0.73646 H NH.sub.2 H (2) COOC.sub.6 H.sub.5 0.76 0.79 0.78 0.77647 H NH.sub.2 H (2) COOC.sub.6 H.sub.4 (4')OCH.sub.3 0.79 0.79648 H NH.sub.2 H (2) COOC.sub.6 H.sub.4 (4')C.sub.6 H.sub.5 0.78 0.80649 H NH.sub.2 H (2) OCH.sub.3 0.70650 H NH.sub.2 H (2) CN 0.71651 NH.sub.2 H H (3) CONHCH.sub.3 0.69 0.75 0.76 0.73652 NH.sub.2 H H (3) CONHC.sub.4 H.sub.9 0.70 0.76 0.77 0.74653 NH.sub.2 H H (3) CONHC.sub.5 H.sub.11 0.71 0.76 0.77 0.75654 NH.sub.2 H H (3) COSC.sub.6 H.sub.5 0.74655 NH.sub.2 H H (3) COSC.sub.6 H.sub.4 (4')CH.sub.3 0.76656 NH.sub.2 H H (3) COSC.sub.6 H.sub.4 (4')Cl 0.77657 NH.sub.2 H H (3) COSC.sub.6 H.sub.4 (4')C(CH.sub.3).sub.3 0.75658 SAr H H (2) CONHC.sub.5 H.sub.11 0.73 0.78 0.77 0.76659 SAr H H (2) COSC.sub.6 H.sub.4 (4')CH.sub.3 0.77660 SAr H H (2) CH.sub.2 C.sub.6 H.sub.5 0.74 0.75 0.76 0.73661 NH.sub.2 H H (3) CH.sub.2 C.sub. 6 H.sub.5 0.73 0.73662 NH.sub.2 H H (3) CH.sub.2 C.sub.6 H.sub.4 (4')CH.sub.3 0.74 0.75663 NH.sub.3 H H (3) ##STR9## 0.73 0.75 0.74664 NH.sub.3 H H (3) ##STR10## 0.72 0.75 0.73665 SAR H H (2) ##STR11## 0.73 0.77 0.75666 NH.sub.3 SAr SAr (3) ##STR12## 0.74 0.80 0.77__________________________________________________________________________
Table 3 below relates to dyestuffs of the formula ##STR13## X.sub.1 indicates the position of the substituent Q.sub.1 and X.sub.2 indicates the position of the substituent Q.sub.2.
In other respects the information given for Table 2 applies.
TABLE 3__________________________________________________________________________Y' Y" Y"' X.sub.1 Q.sub.1 X.sub.2 Q.sub.2 S.sub.1 S.sub.2 S.sub.3 S.sub.4__________________________________________________________________________667 H SAr H (2) COOC.sub.6 H.sub.5 (6) COOC.sub.6 H.sub.5 0.78 0.80 0.81 0.79668 H SAr H (2) COOC.sub.5 H.sub.11 (6) COOC.sub.5 H.sub.11 0.76 0.81 0.80 0.78669 H H SAr (2) COOC.sub.6 H.sub.4 (3')F (7) COOC.sub.6 H.sub.3')F 0.69 0.75 0.74 0.73670 H H SAr (2) COOC.sub.5 H.sub.11 (7) COOC.sub.5 H.sub.11 0.67 0.73 0.72 0.70671 NH.sub.2 SAr NH.sub.2 (3) COOC.sub.6 H.sub.5 (7) COOC.sub.6 H.sub.5 0.78 0.80 0.81 0.79672 NH.sub.2 SAr NH.sub.2 (3) COOC.sub.5 H.sub.11 (7) COOC.sub.5 H.sub.11 0.75 0.79673 NH.sub.2 NH.sub.2 SAr (3) COOC.sub.6 H.sub.5 (6) COOC.sub.6 H.sub.5 0.77 0.79 0.76674 NH.sub.2 NH.sub.2 SAr (3) COOC.sub.5 H.sub.11 (6) COOC.sub.5 H.sub.11 0.75 0.77 0.78__________________________________________________________________________

Number	Name	Date
3018154	Downey et al.	Jan 1962
3164436	Altermatt	Jan 1965
3337553	Altermatt	Aug 1967
3894060	Hederich et al.	Jul 1975
3929843	Botros	Dec 1975
3975285	Ohnishi et al.	Aug 1976
4008222	Machatzke	Feb 1977
4232949	Huffman	Nov 1980
4232950	Benham	Nov 1980
4294581	Mensch et al.	Oct 1981
4455253	Thompson	Jun 1984
4496221	Harrison et al.	Jan 1985
4506957	Harrison et al.	Mar 1985

Number	Date	Country
74523	Mar 1983	EPX
2094822	Sep 1982	GBX
2093475	Sep 1982	GBX
2118203	Oct 1983	GBX

Aryl-mercapto anthraquinone dyestuffs, their preparation and use and dichroic material containing aryl-mercapto anthraquinone dyestuffs

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