2,3,6- AND PREFERABLY ALSO 4-SUBSTITUTED PYRIDINE DERIVATIVES BEARING THE RADICAL OF AMMONIA OR A PRIMARY AMINE IN THE 2- AND 6-POSITIONS. The compounds are eminently suitable as coupling components for the production of azo dyes, the coupling taking place in the 5-position.
|
1. A compound of the formula ##STR211## in which: R1 is hydrogen, alkyl of one to seven carbon atoms or phenyl;
X is cyano or carbamoyl; and each Z, independently of one another, is hydrogen, alkyl of one to eight carbon atoms, hydroxyalkyl of two to eight carbon atoms, cyanoalkyl of two to seven carbon atoms, alkoxyalkyl of two or three carbon atoms in the alkyl and one to eight carbon atoms in the alkoxy, cyclohexoxypropyl, benzyloxypropyl, β-phenyl-ethoxypropyl, phenoxypropyl, tolyloxypropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, hydroxycyclohexyl, β-hydroxyethoxycyclohexyl, norbornyl, hydroxynorbornyl, hydroxymethylnorbornyl, chloromethylnorbornyl, β-hydroxyethylnorbornyl, bicyclooctyl, phenylalkyl or tolylalkyl of one to four carbon atoms in the alkyl, phenyl, phenyl substituted by methyl, methoxy, ethoxy, hydroxy, chloro or β-hydroxyethoxy, allyl, carboxyethyl, carboxypentyl, ω-pyrrolidonylalkyl of two to six carbon atoms in the alkyl, ##STR212## --(CH2)2 O(CH2)2 OH, --(CH2)3 O(CH2)4 OH, --(CH2)3 O(CH2)6 OH, ##STR213## or --(CH2)3 (OC2 H4)n OT, n being 1, 2, 3 or 4, and T being hydrogen, alkyl of one to four carbon atoms, benzyl, phenylethyl, cyclohexyl, phenyl or tolyl.
2. A compound as claimed in
Z2 is hydrogen, an oxygen-containing radical as defined for Z1 or an oxygen-free radical selected from the group consisting of --C2 H5, --C3 H7, --C4 H9, ##STR219## --CH2 C6 H5, --C2 H4 C6 H5, --C3 H7 C6 H5, ##STR220## --C6 H5, --C6 H4 CH3 and --C6 H4 OCH3.
|
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This application is a reissue application of U.S. Pat. No. 3,853,895 issued December 10, 1974, from U.S. Application Ser. No. 328,459, filed January 31, 1973, which in turn is a continuation-in-part of U.S. Application Ser. No. 209,431, filed December 17, 1971 (now abandoned).
This invention relates to compounds of the formula: ##STR1## where R1 is hyrogen, alkyl of one to seven carbon atoms or phenyl, the radicals Z independently of one another mean hydrogen or an unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical and
X is cyano or carbamoyl.
More particularly, the invention relates to compounds of the formula (Ia): ##STR2## IN WHICH R1 is hydrogen, alkyl of one to seven carbon atoms or phenyl,
X is carbamoyl or cyano and the radicals
R independently of one another are unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radicals and one of the radicals R may be hydrogen and at least one of the radicals R contains an oxygen atom.
Examples of alkyl radicals R1 are ethyl, n-propyl, isopropyl, butyl, pentyl, α-ethylpentyl and preferably methyl.
Examples of radicals Z or R are alkyl of one to eight carbon atoms which may be interrupted by oxyten atoms and which may bear hydroxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy as substituents, cycloalkyl and polycycloalkyl which may bear hydroxy, chloro, hydroxyalkyl, chloroalkyl or alkyl as substituents, aralkyl of seven to fifteen carbon atoms, phenyl which may bear chloro, hydroxy, alkoxy, alkyl, hydroxyalkoxy or hyroxyalkyl as substituents, or alkenyl, pyrrolidonylalkyl or carboxyalkyl.
Examples of individual radicals Z or R are:
1. UNSUBSTITUTED OR SUBSTITUTED ALKYL:
Ch3, c2 h5, n-C3 H7, i-C3 H7, n-C4 H9, i-C4 H9, C6 H13, ##STR3## CH2 CH2 OH, (CH2)3 OH, ##STR4## (CH2)4 OH, (CH2)6 OH, ##STR5## (CH2)2 O(CH2)2 OH, (CH2)3 O(CH2)4 OH, (CH2)3 OC2 H4 OH, (CH2)3 OC2 H4 OCH3, (CH2)3 OC2 H4 OC2 H5, (CH2)3 OC2 H4 OCH(CH3)2, (CH2)3 OC2 H4 OC4 H9, (CH2)3 OC2 H4 OCH2 C6 H5, (CH2)3 OC2 H4 OC2 H4 C6 H5, ##STR6## (CH2)3 OC2 H4 OC6 H5, ##STR7## corresponding radicals in which the groupings ##STR8## are present twice, three times or four times, CH2 CH2 OCH3, CH2 CH2 OC2 H5, CH2 C2 OC3 H7, CH2 CH2 OC4 H9, CH2 CH2 OC6 H5, (CH2)3 OCH3, (CH2)3 OC2 H5, (CH2)3 OC3 H7, (CH2)3 OC4 H9, ##STR9## (CH2)3 OCH2 C6 H5, (CH2)3 OC2 H4 C6 H5, (CH2)3 OC6 H5, ##STR10## (CH2)2 CN, (CH2)5 CN, (CH2)6 CN, (CH2)7 ON or (CH2)3 OC8 H17 and C6 H4 CH3 instead of C6 H5
2. unsubstituted or substituted cycloalkyl or polycycloalkyl: ##STR11##
3. aralkyl: ##STR12## and C6 H4 CH3 instead of C6 H5.
4. unsubstituted or substituted phenyl:
C6 h5, c6 h4 ch3, c6 h3 (ch3)2, c6 h4 och3, c6 h4 oc2 h5, c6 h4 oh, c6 h4 och2 ch2 oh or C6 H4 Cl,
5. CH2 CH=CH2, (CH2)2 COOH, (CH2)5 COOH and ##STR13## in which n is 2, 3, 4, or 6.
For the production of compounds of formula (I), compounds of formula (II): ##STR14## in which Y is chloro or a radical of the formula NHR, and
X, r and R1 have the meanings given above may be reacted with an amine of the formula:
reaction conditions which affect the exchange of the chlorine atom(s) include the temperature, the amine component, the molar ratio of the reactants and any diluent or solvent or acid-binding agent used. Amines of low boiling point may of course be reacted under superatmospheric pressure. The reaction with the amine is conveniently carried out at elevated temperature, a temperature of from about 0° to 110° C being adequate for the exchange of the first chlorine atom depending on the basicity of the amine, while temperatures in the range from about 60° to 180° C being advantageous for exchange of the second chlorine atom.
Amines of high basicity react more rapidly than those of low basicity; when exchanging the second chlorine atom it is advantageous to use an excess of amine (more than 10 percent), whereas the first chlorine atom reacts immediately with a molar amount of amine. Examples of suitable diluents or solvents which may be added are alcohols such as methanol, ethanol or isopropanol, glycols and glycol ethers such as methyl glycol, ethyl glycol or butyl glycol, hydrocarbons and halohydrocarbons such as benzene, toluene, ethylene chloride, chloroform, trichloroethylene or chlorobenzene, and also acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or dimethylsulphoxide. The presence of water does not cause any disturbance.
The addition of acid-binding agents is advantageous because then the total amount of amine to be reacted is available for the exchange. Substances which do not themselves react with the chloropyridine derivatives are suitable as acid-binding agents; for example tertiary amines such as triethylamine, tributylamine, triethanolamine, ethyldiisopropylamine, caustic soda solution, sodium carbonate, magnesium oxide or calcium carbonate are suitable. In the case of inexpensive amines, an excess of the amine to be reacted may also serve as acid-binding agent.
Compounds of the formula (Ib); ##STR15## in which R has the meanings given above are of particular industrial significance.
Examples of preferred radicals R containing oxygen are:
Ch2 ch2 oh, ch2 ch2 ch2 oh, ##STR16## (ch2)3 o(ch2)2 oh, (ch2)3 o(ch2)4 oh, (ch2)3 o(ch2)6 oh, (ch2)4 oh, (ch2)6 oh, (ch2)2 o(ch2)2 oh, ##STR17## ch2 ch2 och3, ch2 ch2 oc2 h5, ch2 ch2 oc4 h9, (ch2)3 och3, (ch2)3 oc2 h5, (ch2)3 oc3 h7, (ch2)3 oc4 h9, (ch2)3 oc6 h13, (ch2)3 oc8 h17, ##STR18## (ch2)3 oc2 h4 och3, (ch2)3 oc2 h4 oc4 h9, ##STR19## and (CH2)3 OC2 H4 OC6 H5.
Examples of preferred oxygen-free radicals which are preferably used in combination with an oxygen-containing radical R are besides H:
C2 h5, c3 h7, c4 h9, ##STR20## ch2 c6 h5, c2 h4 c6 h5, c3 h7 c6 h5, ##STR21## c6 h5, c6 h4 ch3, c6 h4 och3.
the new coupling components are outstandingly suitable for the production of azo dyes by reaction with diazotized amines. The dyes which can be obtained in this way are distinguished by excellent fastness properties and by unusual brightness for azo dyes.
The following Examples illustrate the invention. Parts and percentages referred to are by weight unless otherwise stated.
187 parts of 2,6-dichloro-3-cyano-4-methylpyridine is suspended in 500 parts by volume of methanol. 80 parts of 2-hydroxyethylamine is then added at 40° to 45° C followed by 100 parts of triethylamine. The mixture is stirred for five to six hours at 45° to 50° C, about 250 parts by volume of methanol is distilled off and the residue is diluted with 1000 parts by volume of water. After acidification with 50 parts of concentrated hydrochloric acid, the whole is stirred for 1 hour, the deposited precipitate is filtered off, washed with water until neutral and dried. About 210 parts of a colorless powder of the formula: ##STR22## is obtained. The powder contains a minor amount of a product of the formula: ##STR23## The mixture melts at 115° to 120°C
125 parts of this powder is stirred with 300 parts by volume of methoxyethylamine for six hours under reflux.
Excess methoxyethylamine is then extensively distilled off so that the temperature may rise to 130° C and the whole is then diluted with 500 parts of water. The mixture is stirred for one hour at 0° to 10° C and the deposited precipitate is filtered off, washed with water and dried. The main product has the formula: ##STR24## and there is a minor amount of a product having the formula: ##STR25## The product is colorless and melts at 75° to 78°C
A suspension of 50 parts by volume of methanol, 22 parts of norbornylamine, 37 parts of 2,6-dichloro-3-cyano-4-methylpyridine and 25 parts of triethylamine is stirred for six hours at 40° to 50°C Then about 200 parts by volume of ice-water is added, the whole acidified to pH 1, and the precipitated product of the formula ##STR26## (which still contains a small proportion of 2-chloro-3-cyano-4-methyl-6-norbornylaminopyridine isomers) is filtered off, washed with water and dried. About 45 parts of a colorless powder is obtained which melts at 110° to 112°C
45 parts of the moist powder is heated at 130° C to 140° C with 50 parts of the amine of the formula:
the water being allowed to evaporate. After stirring for 5 hours at 130° to 140° C the reaction is completed. The whole is allowed to cool and is acidified with 130 parts by volume of acetic acid. A solution of the coupling component mixture of the formulae: ##STR27## and ##STR28## is obtained, the amount of the product of formula (II) being small.
When the mixture thus obtained is coupled with p-nitroaniline a dye is obtained which dissolves in dimethylformamide to give an orange solution.
A mixture of 300 parts by volume of N-methylpyrrolidone, 150 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 115 parts of p-anisidine and 90 parts of triethylamine is stirred for from six to 7 hours at 70°C It is then poured while stirring onto 1500 parts of ice-water and acidified with hydrochloric acid to pH 1. About 220 parts of a colorless product of the formula: ##STR29## is obtained which is isolated by filtration, washing with water and drying. The powder contains a minor amount of a product of the formula: ##STR30## The mixture melts at 147° to 150°C
50 parts of 2,6-dichloro-3-carbamoyl-4-methylpyridine is stirred with 75 parts of propanolamine-1,3 for 10 hours at 90°C The mixture is precipitated with water and acidified to pH <O. The insoluble residue is filtered off, washed with water and dried. The colourless powder melts at 210° C and probably has the formula (I): ##STR31## The filtrate has caustic soda solution added to it until the pH is from 5 to 6. A crystalline precipitate is thrown down which probably has the formula (II) ##STR32## This is filtered off, washed with water and dried. The product (II) thus obtained also contains traces of the product of the formula (I) and melts at 150° to 160°C
If the reaction mixture is precipitated at pH from 6 to 7, a mixture of the two isomers is obtained which has a melting point of about 143°C
When 2,6-dichloro-3-carbamoyl-4-methylpyridine is treated analogously to the method described in Example 4, mixtures of substituted 2-aminopyridines and 6-aminopyridines are obtained, the amount of 2-amino-3-carbamoyl-4-methyl-6-chloropyridine derivatives being only slightly greater than that of the 6-aminopyridine isomers in question.
The physical properties given in Table 1 relate to mixtures.
| TABLE 1 |
| ______________________________________ |
| ##STR33## |
| Melting |
| point, |
| Number R1 °C |
| ______________________________________ |
| ##STR34## 115-199 |
| 6 (CH2)3 OC2 H5 |
| 120 |
| 7 C4 H9 (n) |
| 121-122 |
| 8 C6 H13 (n) |
| 89-90 |
| 9 |
| ##STR35## 140-145 |
| 10 |
| ##STR36## 180-190 |
| 11 (CH2)3 OCH3 |
| 105 |
| 12 C3 H7 (n) |
| 124 |
| 13 CH2 CH2 OH |
| 130 |
| 14 (CH2 CH2 O)2 H |
| 110 |
| 15 CH3 >150 |
| 16 C2 H5 143 |
| 17 |
| ##STR37## 190 |
| ______________________________________ |
When 2,6-dichloro-3-cyano-4-methylpyridine is treated by a method analogous to those described in Examples 1 to 3, there are obtained (by exchange of one chlorine atom) mixtures of 2-amino-3-cyano-4-methyl-6-chloropyridine and 2-chloro-3-cyano-4-methyl-6-aminopyridine derivatives, the proportion of the 2-chloro-3-cyano-4-methyl-6-amino isomers being clearly less.
| TABLE 2 |
| ______________________________________ |
| ##STR38## |
| Melting |
| point, |
| Number R1 °C |
| ______________________________________ |
| 18 (CH2)5 COONa |
| 85 - 91 |
| 19 (CH2)5CH3 |
| 40 - 47 |
| 20 (CH2 CH2 O)2 H |
| 79 - 83 |
| 21 (CH2)2 OCH3 |
| 90 - 100 |
| 22 C4 H9 (n) 50 - 60 |
| 23 C3 H7 (i) 95 - 105 |
| 24 (CH2)3 OCH3 |
| 75 - 85 |
| 25 |
| ##STR39## 1 |
| 26 (CH2)3 OH 110 - 114 |
| 27 (CH2)2 OH 125 |
| 28 |
| ##STR40## 145 - 154 |
| 29 |
| ##STR41## 147 - 149 |
| 30 H 225 - 230 |
| 31 |
| ##STR42## 165 - 175 |
| 32 |
| ##STR43## 103 - 105 |
| 33 |
| ##STR44## Tar |
| 34 |
| ##STR45## 103 |
| 35 |
| ##STR46## 90 - 92 |
| 36 (CH2)3 OCH2 C6 H5 |
| 2 |
| 37 |
| ##STR47## 105 - 110 |
| 38 |
| ##STR48## 170 - 185 |
| 39 |
| ##STR49## 147 |
| 40 |
| ##STR50## 120 - 128 |
| 41 |
| ##STR51## 170 |
| 42 |
| ##STR52## 107 - 110 |
| 43 |
| ##STR53## 3 |
| 44 |
| ##STR54## 185 |
| 45 CH2 CH2 COOH |
| 170 |
| 46 C14 H29 62 |
| 47 |
| ##STR55## 130 - 140 |
| 48 |
| ##STR56## 160 |
| 49 CH3 140 |
| 50 |
| ##STR57## 80 |
| 51 (CH2)3 O(CH2)2 OH |
| 75 - 80 |
| 52 (CH2)3 OC3 H7 (i) |
| Oil |
| 53 CH2 CH2C6 H5 |
| 118 - 123 |
| 54 (CH2)3 OC2 H4 OC6 H5 |
| Oil |
| 55 |
| ##STR58## 172 |
| 56 |
| ##STR59## Oil |
| 57 |
| ##STR60## 115 |
| ______________________________________ |
| 1 Greasy product. |
| 2 Tar becoming solid on prolonged standing. |
| 3 Viscous oil. |
When the products set out in Tables 1 and 2 are treated with aliphatic or aromatic amines at temperatures above 100° or 80° C respectively, the corresponding coupling products are obtained.
In the case of pyridine derivatives which contain a carbamoyl group the reaction has to be carried out however at the lowest possible temperature because otherwise hyrolysis and/or decarboxylation of the --CONH2 group may take place.
| TABLE 3 |
| __________________________________________________________________________ |
| ##STR61## |
| Number |
| R1 R2 Melting point, ° |
| __________________________________________________________________________ |
| C. |
| 58 CH2 CH2 OH |
| CH3 125 - 130. |
| 59 CH2 CH2 OH |
| (CH2)3 OH 47 - 50. |
| 60 CH2 CH2 OH |
| (CH2)3 OCH3 |
| 104 - 105. |
| 61 CH2 CH2 OH |
| CH2 CH2 OH 156. |
| 62 (CH2)3 OH |
| CH3 215 (hydrochloride). |
| 63 |
| ##STR62## (CH2)3 OH 220 - 223. |
| 64 (CH2)3 O(CH2)4 OH |
| H Viscous oil. |
| 65 (CH2)3 O(CH2)4 OH |
| (CH2)3 OH " |
| 66 (CH2)3 O(CH2)4 OH |
| (CH2)3 OCH3 |
| " |
| 67 (CH2)3 O(CH2)4 OH |
| (CH2)2 OCH3 |
| " |
| 68 (CH2)3 O(CH2)6 OH |
| (CH2)2 OCH3 |
| " |
| 69 (CH2)3 O(CH2)6 OH |
| (CH2)3 OH " |
| 70 (CH2)3 O(CH2)6 OH |
| (CH2)2 OH " |
| 71 (CH2)3 O(CH2)6 OH |
| (CH2)3 OH " |
| 72 CH2 CH2 OCH3 |
| CH2 CH2 OCH3 |
| 75 - 76. |
| 73 CH2 CH2 OCH3 |
| CH2 CH2 OH 108 - 111. |
| 74 CH2 CH2 OCH3 |
| C6 H13 (n) Oil which has green |
| fluorescence. |
| 75 CH2 CH2 OCH3 |
| H 108. |
| 76 (CH2)3OCH3 |
| H 95 - 98. |
| 77 (CH2)3 OH |
| (CH2)3 OH 84 - 87. |
| 78 |
| ##STR63## H 215 - 220. |
| 79 " CH2 CH2 OH 137. |
| 80 " CH2 CH2 OCH2 CH2 OH |
| 125 - 130. |
| 81 |
| ##STR64## (CH2)3 OH 170. |
| 82 " (CH2 CH2 O)2 H |
| 175 - 180. |
| 83 |
| ##STR65## (CH2)3 OH 169 - 170. |
| 84 |
| ##STR66## CH2 CH2 OH 155 - 158. |
| 85 C6 H5 CH2 CH2 CH2 OH |
| 150 (hydrochloride). |
| 86 |
| ##STR67## CH2 CH2 OH 173. |
| 87 |
| ##STR68## CH2 CH2 OH 136 - 140. |
| 88 " CH2 CH2 OCH3 |
| 134 - 138. |
| 89 |
| ##STR69## CH2 CH2 OH 90 - 95 esterified with |
| acetic acid. |
| 90 " CH2 CH2 OCH3 |
| 105. |
| 91 CH2 CH2C6 H5 |
| CH2 CH2 OCH3 |
| 60. |
| 92 CH2 CH2C6 H5 |
| CH2 CH2 OH 167 - 170. |
| 93 C4 H9 (n) |
| CH2 CH2 OH Oil having green |
| fluorescence. |
| 94 C4 H9 (n) |
| CH2 CH2 OCH2 CH2 OH |
| " |
| 95 C2 H5 CH2 CH2 OCH2 CH2 OH |
| " |
| 96 CH2 CH2 OC2 H5 |
| CH2 CH2 OCH2 CH2 OH |
| " |
| 97 (CH2)5 CH3 |
| CH2 CH2 OCH2 CH2 OH |
| " |
| 98 (CH2)3OCH2 CH(CH3)2 |
| CH2 CH2 OCH2 CH2 OH |
| " |
| 99 H (CH2)3O(CH2)4 OH |
| Viscous oil |
| 100 H (CH2)3O(CH2)6 OH |
| " |
| 101 H (CH2)3O(CH2)2 OH |
| " |
| 102 H (CH2)3OCH2C6 H5 |
| " |
| 103 H (CH2)3OCH2 CH2 OC6 |
| H5 " |
| 104 H (CH2)3OCH2 CH2C6 H5 |
| " |
| 105 H (CH2)3O CH2 CH2OCH3 |
| " |
| 106 H |
| ##STR70## " |
| 107 H (CH2)3OCH2 CH2 OC4 |
| H9 " |
| 108 H |
| ##STR71## " |
| 109 H |
| ##STR72## " |
| 110 H |
| ##STR73## " |
| 111 H (CH2)3 O(CH2 CH2 O)2 |
| CH3 " |
| 112 H |
| ##STR74## " |
| 113 |
| ##STR75## H " |
| 114 H (CH2)3 O(CH2)2 OH |
| " |
| 115 H (CH2)3 O(CH2)4 OH |
| " |
| 116 H (CH2)3 O(CH2)6 OH |
| " |
| 117 H (CH2)6 OH " |
| 118 H (CH2)3OC2 H4OC3 H7 |
| " |
| Shade on coupling with |
| ##STR76## |
| __________________________________________________________________________ |
| 119 (CH2)3 OC6 H5 |
| CH2 CH2 OH Orange. |
| 120 (CH2)3 OC6 H5 |
| CH2 CH2 CH2 OH |
| " |
| 121 (CH2)3 OC6 H5 |
| CH2 CH2 OCH2 CH2 OH |
| " |
| 122 (CH2)3 OCH2 C6 H5 |
| CH2 CH2 OCH2 CH2 OH |
| " |
| 123 (CH2)3 OCH2 C6 H5 |
| (CH2)3 OH " |
| 124 (CH2)3 OCH2 C6 H5 |
| CH2 CH2 OH " |
| 125 |
| ##STR77## CH2 CH2 OH " |
| 126 |
| ##STR78## (CH2)3 OH " |
| 127 (CH2)3 OCH2 CH2 C6 H5 |
| CH2 CH2 OH " |
| 128 (CH2)3 OCH2 CH2 C6 H5 |
| (CH2)3 OH " |
| 129 (CH2)3 OCH2 CH2 OC6 H5 |
| (CH2)3 OH " |
| 130 (CH2)3 OCH2 CH2 OC6 H5 |
| CH2 CH2 OH " |
| 131 (CH2)3 OCH2 CH2 OC6 H5 |
| CH2 CH2 OCH3 |
| " |
| 132 (CH2)3 OCH2 CH2 OC6 H5 |
| CH2 CH2 CH2 OCH3 |
| " |
| 133 |
| ##STR79## CH2 CH2 OH " |
| 134 " (CH2)3 OH " |
| 135 " (CH2 CH2 O)2 H |
| " |
| 136 |
| ##STR80## CH2 CH2 OH " |
| 137 |
| ##STR81## (CH2)3 OH " |
| 138 |
| ##STR82## CH2 CH2 OH " |
| 139 " (CH2)3 OH " |
| 140 " (CH2 CH2 O)2 H |
| " |
| Melting point, ° |
| __________________________________________________________________________ |
| C. |
| 141 |
| ##STR83## |
| ##STR84## Viscous oil. |
| 142 |
| ##STR85## (CH2)3 OH " |
| 143 |
| ##STR86## (CH2 CH2 O)2 H |
| " |
| 144 |
| ##STR87## (CH2)2 OCH3 |
| " |
| 145 |
| ##STR88## (CH2)3 OCH3 |
| " |
| 146 |
| ##STR89## |
| ##STR90## " |
| 147 (CH2)6 OH |
| ##STR91## " |
| 148 |
| ##STR92## |
| ##STR93## " |
| 149 (CH2 CH2 O)2 H |
| ##STR94## " |
| 150 |
| ##STR95## |
| ##STR96## " |
| 151 (CH2)3 O(CH2)2 OH |
| (CH2)3 O(CH2)2 OH |
| " |
| 152 (CH2)3 O(CH2)4 OH |
| (CH2)3 O(CH2)4 OH |
| " |
| 153 (CH2)3 O(CH2)6 OH |
| (CH 2)3 O(CH2)6 OH |
| " |
| 154 |
| ##STR97## CH2 CH2 OH " |
| 155 |
| ##STR98## (CH2)3 OH " |
| 156 |
| ##STR99## |
| ##STR100## " |
| 157 |
| ##STR101## (CH2 CH2 O)2 H |
| " |
| 158 |
| ##STR102## (CH2)3 O(CH2)2 OH |
| " |
| 159 |
| ##STR103## (CH2)3 O(CH2)4 OH |
| " |
| 160 |
| ##STR104## (CH2)3 O(CH2)6 OH |
| " |
| 161 (CH2)3 OH |
| (CH2)3 OH 84° bis 87° |
| C. |
| 162 (CH2 CH2 O)2 H |
| (CH2 CH2 O)2 H |
| Viscous oil. |
| 163 |
| ##STR105## (CH2)2 OCH3 |
| " |
| 164 |
| ##STR106## (CH2)3 OCH3 |
| " |
| 165 |
| ##STR107## (CH2)3OC3 H7 |
| " |
| 166 (CH2 CH2 O)2 H |
| ##STR108## " |
| 167 (CH2)2 OH |
| ##STR109## " |
| 168 (CH2)3 OH |
| ##STR110## " |
| 169 |
| ##STR111## |
| ##STR112## " |
| 170 |
| ##STR113## |
| ##STR114## " |
| 171 |
| ##STR115## |
| ##STR116## " |
| 172 (CH2)3 OH |
| (CH2)3 O(CH2)2 OH |
| " |
| 173 (CH2)3 OH |
| (CH2)3 O(CH2)4 OH |
| " |
| 174 (CH2)3 OH |
| (CH2)3 O(CH2)6 OH |
| " |
| 175 (CH2 CH2 OH |
| (CH2)3 O(CH2)6 OH |
| " |
| 176 (CH2 CH2 OH |
| (CH2)3 O(CH2)4 OH |
| " |
| 177 CH2 CH2 OH |
| (CH2)3 O(CH2)2 OH |
| " |
| 178 CH2 CH2 OCH3 |
| (CH2)3 O(CH2)2 OH |
| " |
| 179 CH2 CH2 OCH3 |
| (CH2)2 O(CH2)2 OH |
| " |
| 180 (CH2)3 OCH3 |
| (CH2)2 O(CH2)2 OH |
| " |
| 181 (CH2)3 OC3 H7 |
| (CH2)2 O(CH2)2 OH |
| " |
| 182 (CH2)2 OCH3 |
| (CH2)3 O(CH2)4 OH |
| " |
| 183 (CH2)3 OCH3 |
| (CH2)3 O(CH2)4 OH |
| " |
| 184 (CH2)3 OCH3 |
| (CH2)3 O(CH2)2 OH |
| " |
| __________________________________________________________________________ |
| Shade on coupling with |
| ##STR117## |
| __________________________________________________________________________ |
| 185 CH2 CH2 OCH2 CH2 OH |
| CH3 Orange. |
| 186 CH2 CH2 OCH2 CH 2 OH |
| C2 H5 " |
| 187 CH2 CH2 OCH2 CH2 OH |
| C3 H7 " |
| 188 CH2 CH2 OCH2 CH2 OH |
| C4 H9 " |
| 189 CH2 CH2 OCH2 CH2 OH |
| C5 H11 " |
| 190 CH2 CH2 OCH2 CH2 OH |
| C6 H13 " |
| 191 CH2 CH2 OCH2 CH2 OH |
| ##STR118## " |
| 192 CH2 CH2 OCH2 CH2 OH |
| CH2 CH2 OH " |
| 193 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 OH " |
| 194 CH2 CH2 OCH2 CH2 OH |
| ##STR119## " |
| 195 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 O(CH2)2 OH |
| " |
| 196 CH2 CH2 OCH2 CH2 OH |
| ##STR120## " |
| 197 CH2 CH2 OCH2 CH2 OH |
| ##STR121## " |
| 198 CH2 CH2 OCH2 CH2 OH |
| (CH2)2 OCH3 |
| " |
| 199 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 OCH3 |
| " |
| 200 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 OC2 H5 |
| " |
| 201 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 OC3 H7 (n) |
| " |
| 202 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 OC3 H7 (i) |
| " |
| 203 CH2 CH2 OCH2 CH2 OH |
| (CH2)3 OCH2 CH(CH3)2 |
| " |
| 204 CH2 CH2 OCH2 CH2 OH |
| ##STR122## " |
| __________________________________________________________________________ |
| Melting point, ° |
| __________________________________________________________________________ |
| C. |
| 205 CH2 CH2 OCH3 |
| ##STR123## 116-117. |
| 206 CH2CH2 OH |
| ##STR124## 188-189. |
| 207 CH2CH2 OH |
| H >150. |
| 208 (CH2)3COOH |
| ##STR125## 185-188. |
| 209 (CH2)3O(CH2)2 OH |
| C2 H5 Viscous oil. |
| 210 (CH2)3O(CH2)2 OH |
| C3 H7 (n) " |
| 211 (CH2)3O(CH2)2 OH |
| C4 H9 (n) " |
| 212 (CH2)3O(CH2)2 OH |
| C5 H11 (n) " |
| 213 (CH2)3O(CH2)2 OH |
| C6 H13 (n) " |
| 214 (CH2)3O(CH2)2 OH |
| ##STR126## " |
| 215 (CH2)3O(CH2)2 OH |
| ##STR127## " |
| 216 (CH2)3O(CH2)2 OH |
| ##STR128## " |
| 217 (CH2)3O(CH2)2 OH |
| ##STR129## " |
| 218 (CH2)3O(CH2)2 OH |
| ##STR130## " |
| 219 |
| ##STR131## CH2 CH2 OH " |
| 220 " (CH2)3 OH " |
| 221 " (CH2)2 O(CH2)2 OH |
| " |
| 222 |
| ##STR132## (CH2)2 O(CH2)2 OH |
| " |
| 223 " (CH2 O(CH2)2 OH |
| " |
| 224 |
| ##STR133## (CH2)2 O(CH2)2 OH |
| " |
| 225 " (CH2)3 O(CH2)2 OH |
| " |
| 226 |
| ##STR134## (CH2)3 O(CH2)2 OH |
| " |
| 227 " (CH2)2 O(CH2)2 OH |
| " |
| 228 |
| ##STR135## CH2 CH2 OH " |
| 229 " (CH2)2 OH " |
| 230 " (CH2)2 O(CH2)2 OH |
| " |
| 231 |
| ##STR136## (CH2)2 O(CH2)2 OH |
| " |
| 232 " (CH2)3 O(CH2)2 OH |
| " |
| 233 |
| ##STR137## (CH2)3 O(CH2)2 OH |
| " |
| 234 |
| ##STR138## (CH2)2 O(CH2)2 OH |
| " |
| 235 " (CH2)2 O(CH2)2 OH |
| " |
| 236 |
| ##STR139## (CH2)2 O(CH2 )2 OH |
| " |
| 237 |
| ##STR140## CH2 CH2 OH " |
| 238 CH2 CHCH2 |
| (CH2)2 O(CH2)2 OH |
| " |
| 239 CH2 CHCH2 |
| (CH2)3 O(CH2)2 OH |
| " |
| __________________________________________________________________________ |
| Shade on coupling with |
| ##STR141## |
| __________________________________________________________________________ |
| 240 |
| ##STR142## C2 H5 Orange. |
| 241 " C3 H7 (n) " |
| 242 " C4 H9 (n) " |
| 243 " C6 H13 (n) " |
| 244 " (CH2)3 OH " |
| 245 " (CH2)2 O(CH2)2 OH |
| " |
| 246 " (CH2)3 O(CH2)2 OH |
| " |
| 247 " (CH2)3 O(CH 2)4 OH |
| " |
| 248 |
| ##STR143## C2 H5 " |
| 249 " C3 H7 (n) " |
| 250 " C4 H9 (n) " |
| 251 " C6 H13 (n) " |
| 252 " (CH2)2 OH " |
| 253 " (CH2)3 OH " |
| 254 " (CH2)2 O(CH2)2 OH |
| " |
| 255 " (CH2)3 O(CH2)2 OH |
| " |
| 256 " (CH2)3 O(CH2)4 OH |
| " |
| 257 |
| ##STR144## C2 H5 " |
| 258 " C3 H7 " |
| 259 " C4 H9 " |
| 260 " CH2 CH2 OH " |
| 261 " (CH2)3 OH " |
| 262 " (CH2)2 O(CH2 )3 OH |
| " |
| 263 " (CH2)2 OCH3 |
| " |
| 264 " (CH2)3 O(CH2)2 OH |
| " |
| 265 " (CH2)3 O(CH2)4 OH |
| " |
| 266 |
| ##STR145## C2 H5 " |
| 267 " C3 H7 (n) " |
| 268 " C4 H9 (n) " |
| 269 " C6 H13 (n) " |
| 270 H |
| ##STR146## Golden yellow. |
| 271 |
| ##STR147## CH2 CH2 OH Orange. |
| 272 " (CH2)3 OH " |
| 273 " (CH2)3 O(CH2)2 OH |
| " |
| 274 " (CH2)3 O(CH2)2 OH |
| " |
| 275 " (CH2)3 O(CH2)4 OH |
| " |
| 276 " (CH2)2 OCH4 |
| " |
| 277 " (CH2)3 OCH3 |
| " |
| 278 |
| ##STR148## (CH2)3 OCH3 |
| Orange. |
| 279 " (CH2)2 OCH3 |
| " |
| 280 |
| ##STR149## (CH2)2 OCH3 |
| " |
| 281 " (CH2)3 OCH3 |
| " |
| __________________________________________________________________________ |
| TABLE 4 |
| __________________________________________________________________________ |
| ##STR150## |
| Shade coupling with |
| Number |
| R1 |
| R2 R3 |
| ##STR151## |
| __________________________________________________________________________ |
| 282 CH2 CH2 C6 H5 |
| CH2 CH2 OH |
| H Orange. |
| 283 CH2 CH2 C6 H5 |
| CH2 CH2 OH |
| C2 H3 |
| " |
| 284 CH2 CH2 C6 H5 |
| (CH2)3 OH |
| C2 H5 |
| " |
| 285 CH2 CH2 C6 H5 |
| (CH2)2 O(CH2)2 OH |
| H " |
| 286 CH2 CH2 C5 H5 |
| (CH2)2 O(CH2)2 OH |
| C2 H5 |
| " |
| 287 CH2 CH2 C6 H5 |
| CH2 CH2 OH |
| C3 H7 (n) |
| " |
| 288 |
| ##STR152## |
| CH2 CH2 OH |
| H 41 |
| 289 |
| ##STR153## |
| CH2 CH2 OH |
| C3 H7 (n) |
| " |
| 290 |
| ##STR154## |
| (CH2)3 OH |
| C3 H7 (n) |
| " |
| 291 |
| ##STR155## |
| (CH2)3 OH |
| H " |
| 292 |
| ##STR156## |
| (CH2)3 OH |
| C2 H5 |
| " |
| 293 CH2 CH2 OH |
| CH2 CH2 OH |
| ##STR157## |
| " |
| 294 CH2 CH2 OH |
| CH2 CH2 OH |
| C5 H11 (n) |
| " |
| 295 CH2 CH2 OCH3 |
| (CH2 CH2 O)2 H |
| C6 H5 |
| " |
| 296 (CH2)3 OCH3 |
| (CH2 CH2 O)2 H |
| C6 H5 |
| " |
| 297 H |
| ##STR158## |
| H Golden yellow. |
| 298 H |
| ##STR159## |
| C3 H7 (n) |
| " |
| 299 H (CH2)3 O(CH2)4 OH |
| H " |
| 300 H (CH2)3 O(CH2)2 OH |
| H " |
| __________________________________________________________________________ |
| TABLE 5 |
| __________________________________________________________________________ |
| ##STR160## |
| Shade after coupling with |
| Number |
| R1 R2 |
| ##STR161## |
| __________________________________________________________________________ |
| 301 CH2 CH2 CH2 OCH3 |
| (CH2)3 OH |
| Red. |
| 302 CH2 CH2C6 H5 |
| CH2 CH2 OH |
| Red. |
| 303 CH2 CH2C6 H5 |
| (CH2)3 OH |
| Red. |
| 304 |
| ##STR162## (CH2)3 OH |
| Red. |
| 305 |
| ##STR163## (CH2)2 OH |
| Red. |
| 306 (CH2)3 OCH2 C6 H5 |
| (CH2)2 OH |
| Red. |
| 307 (CH2)3 OCH2 C6 H5 |
| (CH2)3 OH |
| Red. |
| 308 (CH2)3 OCH2 CH2 OC6 H5 |
| (CH2)3 OH |
| Red. |
| 309 (CH2)3 OCH2 CH2 OC6 H5 |
| (CH2)2 OH |
| Red. |
| 310 (CH2)2 O(CH2)2 OH |
| (CH2)2 OCH3 |
| Red. |
| 311 (CH2)2 O(CH2)2 OH |
| (CH2)3 OCH3 |
| Red. |
| 312 (CH2)2 OCH3 |
| (CH2)2 O(CH2)2 OH |
| Red. |
| 313 (CH2)3 OCH3 |
| (CH2)2 O(CH2)2 OH |
| Red. |
| 314 H (CH2)2 O(CH2)2 OH |
| Yellowish red. |
| 315 H (CH2)3 O(CH2)2 OH |
| " |
| 316 H (CH2)3 O(CH2)4 OH |
| " |
| 317 CH2CH2 OH |
| CH2 CH2C6 H5 |
| Red. |
| 318 (CH2)3 OH |
| CH2 CH2C6 H5 |
| Red. |
| 319 (CH2)3 OCH3 |
| CH2 CH2C6 H5 |
| Red. |
| 320 CH2CH2C6 H5 |
| (CH2)3 OCH3 |
| Red. |
| 321 |
| ##STR164## CH2 CH2 OH |
| Red. |
| 322 |
| ##STR165## (CH2)3 OH |
| Red. |
| 323 |
| ##STR166## (CH2)2 O(CH2)2 OH |
| Red. |
| 324 |
| ##STR167## CH2CH2 OH |
| Red. |
| 325 " (CH2)3 OH |
| Red. |
| 326 " (CH2)2 O(CH2)2 OH |
| Red. |
| 327 " (CH2)3O(CH2)2 OH |
| Red. |
| 328 C4 H9 (n) |
| (CH2)3O(CH2)2 OH |
| Red. |
| 329 C4 H9 (n) |
| (CH2)2 O(CH2 )2 OH |
| Red. |
| 330 (CH2)2 O(CH2)2 OH |
| C4 H9 (n) |
| Red. |
| 331 (CH2)2 O(CH2)2 OH |
| ##STR168## Red. |
| 332 |
| ##STR169## (CH2)2 O(CH2)2 OH |
| Red. |
| 333 |
| ##STR170## (CH2)3 OH |
| Red. |
| 334 |
| ##STR171## (CH2)3 OH |
| Red. |
| 335 H (CH2)2 OH |
| Red. |
| 336 |
| ##STR172## (CH2)2 OH |
| Bluish red. |
| 337 " (CH2)3 OH |
| " |
| 338 " (CH2)2 O(CH2)2 OH |
| " |
| 339 |
| ##STR173## (CH2)2 O(CH2)2 OH |
| " |
| 340 (CH2)2 OH |
| (CH2)2 OH |
| Red. |
| 341 (CH2)3 OH |
| (CH 2)3 OH |
| Red. |
| 342 (CH2)3 O(CH2)4 OH |
| (CH2)3 OH |
| Red. |
| 343 (CH2)3 O(CH2)2 OH |
| (CH2)2 OCH3 |
| Red. |
| 344 (CH2)3 O(CH2)2 OH |
| (CH2)3 OCH3 |
| Red. |
| 345 (CH2)3 O(CH2)2 OH |
| (CH2)3 OCH3 |
| Red. |
| 346 H (CH2)2 O(CH2)2 OH |
| Yellowish red. |
| 347 |
| ##STR174## CH2CH2OH |
| Red. |
| 348 " (CH2)3 OH |
| Red. |
| 349 " (CH2)2 O(CH2)2 OH |
| Red. |
| 350 |
| ##STR175## (CH2)2 O(CH2)2 OH |
| Red. |
| 351 " (CH2)2 OH |
| Red. |
| 352 " (CH2)3 OH |
| Red. |
| 353 |
| ##STR176## (CH2)3 OH |
| Red. |
| 354 |
| ##STR177## (CH2)2 OH |
| Red. |
| 355 |
| ##STR178## (CH2)2O(CH2)2 OH |
| Red. |
| 356 |
| ##STR179## CH2CH2OH |
| Red. |
| __________________________________________________________________________ |
The Examples described in the above Tables are prepared by always first introducing the radical R1.
25 parts of the coupling component of the formula: ##STR180## is stirred with 75 parts of 90 percent sulphuric acid for six to eight hours at 80° to 100°C The reaction mixture is then precipitated on 500 parts of ice, adjusted to pH 4 to 6 by adding caustic soda solution and extracted with ethyl acetate. After the extractant has been evaporated about 20 parts of the coupling component of the formula: ##STR181## is obtained as a dark oil. A red dye is obtained therefrom after coupling with diazotized p-nitroaniline
30 parts of 2,6-diamino-3-cyano-4-methylpyridine is stirred with 200 parts by volume of concentrated sulphuric acid for ten hours at 50°C The whole is then allowed to cool, 250 parts of ice is added and it is left overnight. The deposited precipitate is filtered off and washed witht acetone. After drying, 36 parts of a colourless powder of the formula: ##STR182## is obtained which melts at 250° C with decomposition.
The free base of the formula: ##STR183## is obtained from the salt by a conventional method.
| TABLE 6 |
| __________________________________________________________________________ |
| ##STR184## |
| Melting |
| Number |
| R1 R2 point, °C |
| __________________________________________________________________________ |
| 359 C6 H5 |
| C6 H5 |
| 128-130 |
| 360 |
| ##STR185## |
| ##STR186## 178 |
| 361 CH3 CH3 140-150 |
| 362 CH(CH2)2 |
| CH(CH3)2 |
| 118-120 |
| 363 C3 H7 (n) |
| C3 H7 (n) |
| 122-123 |
| 364 CH2CHCH2 |
| CH2CHCH2 |
| 77 |
| 365 C4 H9 (n) |
| C4 H9 (n) |
| 97 |
| 366 C6 H13 (n) |
| C6 H13 (n) |
| Oil |
| 367 |
| ##STR187## |
| ##STR188## 193 |
| 368 H H 225 |
| 369 |
| ##STR189## |
| ##STR190## 175 |
| 370 CH2 C6 H5 |
| CH2C6 H5 |
| 170 |
| 371 CH2CH2C6 H5 |
| CH2CH2C6 H5 |
| 110 |
| 372 C2 H5 |
| C2 H5 |
| 1 205 |
| 373 C6 H5 |
| C4 H9 (n) |
| 115 |
| 374 C6 H5 |
| H (2) |
| 375 C4 H9 (n) |
| H 100 |
| 376 C2 H5 |
| C6 H5 |
| 218-220 |
| 377 CH2 CH2 C6 H5 |
| H 100 |
| 378 |
| ##STR191## |
| ##STR192## Ca.60 |
| 379 H CH2CH2C6 H5 |
| Ca.100,1 188 |
| 380 C8 H17 (n) |
| H Oil |
| 381 C14 H29 |
| H Ca.90-105 |
| 382 H |
| ##STR193## Tar |
| 383 |
| ##STR194## H Tar |
| 384 CH2CH2CN |
| CH2CH2CN |
| 170-176 |
| 385 CH2CH2CN |
| CH2CH2C6 H5 |
| Ca.120 |
| 386 H (CH2)5 CN |
| 142 |
| __________________________________________________________________________ |
| 1 Hydrochloride. |
| 2 Tarry: becomes solid after prolonged standing. |
| Table 7 |
| ______________________________________ |
| ##STR195## |
| Shade when |
| coupled with |
| Ex. X R1 R2 |
| ##STR196## |
| ______________________________________ |
| 387 CH3 |
| H CH2 CH2 OH |
| Yellowish red. |
| 388 CH3 |
| H (CH2)3 OH |
| " |
| 389 CH3 |
| H |
| ##STR197## " |
| 390 CH3 |
| H CH2 CH2 C6 H5 |
| " |
| 391 C3 H7 |
| C6 H5 |
| CH2 CH2 OH |
| Bluish red. |
| 392 C3 H7 |
| C6 H5 |
| (CH2)3 OH |
| " |
| 393 C3 H7 |
| C6 H5 |
| (CH2)2 O(CH2)2 OH |
| " |
| 394 C3 H7 |
| ##STR198## |
| (CH2)2 O(CH2)2 OH |
| " |
| 395 C3 H7 |
| " CH2 CH2 OH |
| " |
| 396 C3 H7 |
| " (CH2)3 OH |
| " |
| 397 H C6 H5 |
| (CH2)3 OH |
| " |
| ______________________________________ |
190 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 750 parts of isopropanol and approx. 300 parts of ammonia are stirred in an autoclave for 15 hours at 180°C The mixture is allowed to cool, excess ammonia is evaporated and 450 parts by volume of isopropanol is distilled off. The residue is mixed with approx. 600 parts of water, the pH is adjusted to approx. 0 with concentrated hyrochloric acid and the solution filtered. Then 50 percent caustic soda solution is added until the pH of the mixture is approx. 9, the mixture allowed to cool to 0°-10° C and then filtered, and the residue is washed with water and dried. 130 to 145 parts of a colorless powder of the formula ##STR199## is obtained which melts at 225°C
300 parts of 2,6-dichloro-3-cyano-4-methylpyridine is mixed with about 500 parts by volume of liquid ammonia and treated in an autoclave for 2 hours at approx. 80°C Excess ammonia is allowed to evaporate, the residue is diluted with approx. 2500 parts by volume of water, and the pH is adjusted to 0 to 1 with hydrochloric acid. The insoluble residue is filtered off, washed with water and dried. Approx. 260 parts of a colorless powder of the formula ##STR200## which contains a minor amount of the isomeric 2-chloro-3-cyano-4-methyl-6-aminopyridine and melts at 210° C is obtained.
168 parts of this powder is mixed with about 170 parts of β-hydroxyethylamine and 170 parts by volume of isopropanol. The mixture is heated for 7 to 10 hours under reflux, the solvent is distilled off, the residue is diluted with about 400 parts of water, and the pH is adjusted to 1 to 2. A deep-colored solution of about 192 parts of the coupling component of the formula ##STR201## is obtained, a minor portion of which consists of 2-amino-4-methyl-5-cyano-6-β-hydroxyethylaminopyridine.
A greenish yellow dye may be obtained by coupling with diazotized 2-aminobenzonitrile.
| TABLE 8 |
| __________________________________________________________________________ |
| ##STR202## |
| Shade when coupled with |
| No. |
| R1 R2 X |
| ##STR203## |
| __________________________________________________________________________ |
| 400 |
| H CH3 CN Golden yellow. |
| 401 |
| H C2 H5 |
| CN " |
| 402 |
| H C3 H7 |
| CN " |
| 403 |
| H C2 H4 OCH3 |
| CN " |
| 404 |
| H C2 H4 OCH3 |
| CONH2 |
| Yellowish red. |
| 405 |
| H C3 H6 OCH3 |
| CONH2 |
| " |
| 406 |
| H C3 H6 OCH3 |
| CN Golden Yellow. |
| 407 |
| H C4 H9 (n) |
| CN Yellow orange. |
| 408 |
| H C4 H9 (n) |
| CONH2 |
| Yellowish red. |
| 409 |
| H CH2 CHCH2 |
| CN Golden yellow. |
| 410 |
| H |
| ##STR204## |
| CONH2 |
| Yellowish red. |
| 411 |
| H |
| ##STR205## |
| CN Orange. |
| 412 |
| H |
| ##STR206## |
| CONH2 |
| Red. |
| 413 |
| ##STR207## |
| CH2 CH2 OH |
| CONH2 |
| Red. |
| 414 |
| ##STR208## |
| (CH2)3 OH |
| CONH2 |
| Red. |
| 415 |
| CH2 CH2 OH |
| ##STR209## |
| CONH2 |
| Red. |
| 416 |
| ##STR210## |
| CH2 CH2 OH |
| CONH2 |
| Red. (M.P. 150-153°C) |
| __________________________________________________________________________ |
Lamm, Gunther, Dehnert, Johannes
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| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Aug 05 1976 | BASF Aktiengesellschaft | (assignment on the face of the patent) | / |
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