U.S. patent number RE29,640 [Application Number 05/711,863] was granted by the patent office on 1978-05-23 for certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Johannes Dehnert, Gunther Lamm.
United States Patent |
RE29,640 |
Lamm , et al. |
May 23, 1978 |
**Please see images for:
( Certificate of Correction ) ** |
Certain substituted 2,6-diamino-4-methyl-nicotinitriles the
corresponding nicotinamides and derivatives thereof
Abstract
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.
Inventors: |
Lamm; Gunther (Ludwigshafen,
DT), Dehnert; Johannes (Ludwigshafen, DT) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DT)
|
Family
ID: |
27585152 |
Appl.
No.: |
05/711,863 |
Filed: |
August 5, 1976 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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209431 |
Dec 17, 1971 |
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Reissue of: |
328459 |
Jan 31, 1973 |
03853895 |
Dec 10, 1974 |
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Foreign Application Priority Data
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Dec 19, 1970 [DT] |
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2062717 |
Nov 15, 1971 [DT] |
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2156545 |
Mar 10, 1972 [DT] |
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2211663 |
Apr 6, 1972 [DT] |
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2216570 |
Jun 2, 1972 [DT] |
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2226933 |
Oct 21, 1972 [DT] |
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2251702 |
Oct 21, 1972 [DT] |
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2251719 |
Dec 1, 1972 [DT] |
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2258823 |
Dec 2, 1972 [DT] |
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2259103 |
Dec 6, 1972 [DT] |
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2259684 |
Dec 13, 1972 [DT] |
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2260827 |
Dec 27, 1972 [DT] |
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2263458 |
Dec 16, 1972 [JA] |
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47-125836 |
Dec 13, 1972 [UK] |
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57442/72 |
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Current U.S.
Class: |
546/289; 534/653;
534/770; 534/773; 546/278.4; 546/285; 546/308 |
Current CPC
Class: |
C07D
213/74 (20130101); C07D 213/77 (20130101); C07D
213/82 (20130101); C07D 213/85 (20130101); C09B
29/3639 (20130101); C09B 31/153 (20130101); C09B
62/82 (20130101) |
Current International
Class: |
C07D
213/74 (20060101); C07D 213/85 (20060101); C07D
213/82 (20060101); C07D 213/00 (20060101); C07D
213/77 (20060101); C09B 29/00 (20060101); C09B
29/42 (20060101); C09B 31/153 (20060101); C09B
62/82 (20060101); C09B 62/44 (20060101); C09B
31/00 (20060101); C07D 213/57 () |
Field of
Search: |
;260/294.9,295.5A,295.5B,295.5T |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Karrer, Organic Chemistry, 4th Englsh Edition, p. 928, Elsevier
Pub. Co., (NY), 1950. .
Chemical and Engineering News, p. 18, Apr. 3, 1972..
|
Primary Examiner: Rotman; Alan L.
Attorney, Agent or Firm: Keil, Thompson & Shurtleff
Parent Case Text
.Iadd.
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). .Iaddend.
Claims
We claim:
1. A compound of the formula ##STR211## in which: R.sup.1 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,
.beta.-phenyl-ethoxypropyl, phenoxypropyl, tolyloxypropyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
hydroxycyclohexyl, .beta.-hydroxyethoxycyclohexyl, norbornyl,
hydroxynorbornyl, hydroxymethylnorbornyl, chloromethylnorbornyl,
.beta.-hydroxyethylnorbornyl, bicyclooctyl, phenylalkyl or
tolylalkyl of one to four carbon atoms in the alkyl, phenyl, phenyl
substituted by methyl, methoxy, ethoxy, hydroxy, chloro or
.beta.-hydroxyethoxy, allyl, carboxyethyl, carboxypentyl,
.omega.-pyrrolidonylalkyl of two to six carbon atoms in the alkyl,
##STR212## --(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH,
--(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH, --(CH.sub.2).sub.3
O(CH.sub.2).sub.6 OH, ##STR213## or --(CH.sub.2).sub.3 (OC.sub.2
H.sub.4).sub.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 claim 1 of the formula ##STR214## in
which: Z.sup.1 is an oxygen-containing radical selected from the
group consisting of --CH.sub.2 CH.sub.2 OH, --CH.sub.2 CH.sub.2
Ch.sub. 2 OH, ##STR215## --(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH,
--(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH, --(CH.sub.2).sub.3
O(CH.sub.2).sub.6 OH, --(CH.sub.2).sub.4 OH, --(CH.sub.2).sub.6 OH,
--(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH, ##STR216## --CH.sub.2
CH.sub.2 OCH.sub.3, --CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5,
--CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, --(CH.sub.2).sub.3 OCH.sub.3,
--(CH.sub.2).sub.3 OC.sub.2 H.sub.5, --(CH.sub.2).sub.3 OC.sub.4
H.sub.9, --(CH.sub.2).sub.3 OC.sub.3 H.sub.7, --(CH.sub.2).sub.3
OC.sub.6 H.sub.13, --(CH.sub.2).sub.3 OC.sub.8 H.sub.17, ##STR217##
--(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.3, --(CH.sub.2).sub.3
OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, ##STR218## and
--(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 ; and
Z.sup.2 is hydrogen, an oxygen-containing radical as defined for
Z.sup.1 or an oxygen-free radical selected from the group
consisting of
--C.sub.2 H.sub.5, --C.sub.3 H.sub.7, --C.sub.4 H.sub.9, ##STR219##
--CH.sub.2 C.sub.6 H.sub.5, --C.sub.2 H.sub.4 C.sub.6 H.sub.5,
--C.sub.3 H.sub.7 C.sub.6 H.sub.5, ##STR220## --C.sub.6 H.sub.5,
--C.sub.6 H.sub.4 CH.sub.3 and --C.sub.6 H.sub.4 OCH.sub.3.
3. the compound of the formula ##STR221##
4. The compound of the formula ##STR222##
5. The compound of the formula ##STR223##
6. The compound of the formula ##STR224##
Description
This invention relates to compounds of the formula: ##STR1## where
R.sup.1 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 R.sup.1 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 R.sup.1 are ethyl, n-propyl, isopropyl,
butyl, pentyl, .alpha.-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:
Ch.sub.3, c.sub.2 h.sub.5, n-C.sub.3 H.sub.7, i-C.sub.3 H.sub.7,
n-C.sub.4 H.sub.9, i-C.sub.4 H.sub.9, C.sub.6 H.sub.13, ##STR3##
CH.sub.2 CH.sub.2 OH, (CH.sub.2).sub.3 OH, ##STR4##
(CH.sub.2).sub.4 OH, (CH.sub.2).sub.6 OH, ##STR5## (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH,
(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OH, (CH.sub.2).sub.3 OC.sub.2
H.sub.4 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2
H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH(CH.sub.3).sub.2,
(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9,
(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.2 C.sub.6 H.sub.5,
(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 C.sub.6 H.sub.5,
##STR6## (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5,
##STR7## corresponding radicals in which the groupings ##STR8## are
present twice, three times or four times, CH.sub.2 CH.sub.2
OCH.sub.3, CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, CH.sub.2 C.sub.2
OC.sub.3 H.sub.7, CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, CH.sub.2
CH.sub.2 OC.sub.6 H.sub.5, (CH.sub.2).sub.3 OCH.sub.3,
(CH.sub.2).sub.3 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 OC.sub.3
H.sub.7, (CH.sub.2).sub.3 OC.sub.4 H.sub.9, ##STR9##
(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5, (CH.sub.2).sub.3
OC.sub.2 H.sub.4 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.6
H.sub.5, ##STR10## (CH.sub.2).sub.2 CN, (CH.sub.2).sub.5 CN,
(CH.sub.2).sub.6 CN, (CH.sub.2).sub.7 ON or (CH.sub.2).sub.3
OC.sub.8 H.sub.17 and C.sub.6 H.sub.4 CH.sub.3 instead of C.sub.6
H.sub.5
2. unsubstituted or substituted cycloalkyl or polycycloalkyl:
##STR11##
3. aralkyl: ##STR12## and C.sub.6 H.sub.4 CH.sub.3 instead of
C.sub.6 H.sub.5.
4. unsubstituted or substituted phenyl:
C.sub.6 h.sub.5, c.sub.6 h.sub.4 ch.sub.3, c.sub.6 h.sub.3
(ch.sub.3).sub.2, c.sub.6 h.sub.4 och.sub.3, c.sub.6 h.sub.4
oc.sub.2 h.sub.5, c.sub.6 h.sub.4 oh, c.sub.6 h.sub.4 och.sub.2
ch.sub.2 oh or C.sub.6 H.sub.4 Cl,
5. CH.sub.2 CH=CH.sub.2, (CH.sub.2).sub.2 COOH, (CH.sub.2).sub.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 R.sup.1 have the meanings given above may be reacted with
an amine of the formula:
R--NH.sub.2.
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.degree. to 110.degree. 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.degree. to
180.degree. 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:
Ch.sub.2 ch.sub.2 oh, ch.sub.2 ch.sub.2 ch.sub.2 oh, ##STR16##
(ch.sub.2).sub.3 o(ch.sub.2).sub.2 oh, (ch.sub.2).sub.3
o(ch.sub.2).sub.4 oh, (ch.sub.2).sub.3 o(ch.sub.2).sub.6 oh,
(ch.sub.2).sub.4 oh, (ch.sub.2).sub.6 oh, (ch.sub.2).sub.2
o(ch.sub.2).sub.2 oh, ##STR17## ch.sub.2 ch.sub.2 och.sub.3,
ch.sub.2 ch.sub.2 oc.sub.2 h.sub.5, ch.sub.2 ch.sub.2 oc.sub.4
h.sub.9, (ch.sub.2).sub.3 och.sub.3, (ch.sub.2).sub.3 oc.sub.2
h.sub.5, (ch.sub.2).sub.3 oc.sub.3 h.sub.7, (ch.sub.2).sub.3
oc.sub.4 h.sub.9, (ch.sub.2).sub.3 oc.sub.6 h.sub.13,
(ch.sub.2).sub.3 oc.sub.8 h.sub.17, ##STR18## (ch.sub.2).sub.3
oc.sub.2 h.sub.4 och.sub.3, (ch.sub.2).sub.3 oc.sub.2 h.sub.4
oc.sub.4 h.sub.9, ##STR19## and (CH.sub.2).sub.3 OC.sub.2 H.sub.4
OC.sub.6 H.sub.5.
Examples of preferred oxygen-free radicals which are preferably
used in combination with an oxygen-containing radical R are besides
H:
C.sub.2 h.sub.5, c.sub.3 h.sub.7, c.sub.4 h.sub.9, ##STR20##
ch.sub.2 c.sub.6 h.sub.5, c.sub.2 h.sub.4 c.sub.6 h.sub.5, c.sub.3
h.sub.7 c.sub.6 h.sub.5, ##STR21## c.sub.6 h.sub.5, c.sub.6 h.sub.4
ch.sub.3, c.sub.6 h.sub.4 och.sub.3.
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.
EXAMPLE 1
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.degree. to 45.degree. C followed by 100 parts of
triethylamine. The mixture is stirred for five to six hours at
45.degree. to 50.degree. 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.degree.
to 120.degree. 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.degree. C and the whole is then
diluted with 500 parts of water. The mixture is stirred for one
hour at 0.degree. to 10.degree. 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.degree. to 78.degree. C.
EXAMPLE 2
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.degree. to 50.degree. 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.degree. to
112.degree. C.
45 parts of the moist powder is heated at 130.degree. C to
140.degree. C with 50 parts of the amine of the formula:
H.sub.2 N--CH.sub.2 --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --OH
the water being allowed to evaporate. After stirring for 5 hours at
130.degree. to 140.degree. 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.
EXAMPLE 3
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.degree. 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.degree. to 150.degree. C.
EXAMPLE 4
50 parts of 2,6-dichloro-3-carbamoyl-4-methylpyridine is stirred
with 75 parts of propanolamine-1,3 for 10 hours at 90.degree. 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.degree. 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.degree. to 160.degree. 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.degree. 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 R.sup.1 .degree. C.
______________________________________ ##STR34## 115-199 6
(CH.sub.2).sub.3 OC.sub.2 H.sub.5 120 7 C.sub.4 H.sub.9 (n) 121-122
8 C.sub.6 H.sub.13 (n) 89-90 9 ##STR35## 140-145 10 ##STR36##
180-190 11 (CH.sub.2).sub.3 OCH.sub.3 105 12 C.sub.3 H.sub.7 (n)
124 13 CH.sub.2 CH.sub.2 OH 130 14 (CH.sub.2 CH.sub.2 O).sub.2 H
110 15 CH.sub.3 >150 16 C.sub.2 H.sub.5 143 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 R.sup.1 .degree. C.
______________________________________ 18 (CH.sub.2).sub.5 COONa 85
- 91 19 (CH.sub.2).sub.5CH.sub.3 40 - 47 20 (CH.sub.2 CH.sub.2
O).sub.2 H 79 - 83 21 (CH.sub.2).sub.2 OCH.sub.3 90 - 100 22
C.sub.4 H.sub.9 (n) 50 - 60 23 C.sub.3 H.sub.7 (i) 95 - 105 24
(CH.sub.2).sub.3 OCH.sub.3 75 - 85 25 ##STR39## .sup.1 26
(CH.sub.2).sub.3 OH 110 - 114 27 (CH.sub.2).sub.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 (CH.sub.2).sub.3 OCH.sub.2
C.sub.6 H.sub.5 .sup.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## .sup.3 44 ##STR54## 185 45
CH.sub.2 CH.sub.2 COOH 170 46 C.sub.14 H.sub.29 62 47 ##STR55## 130
- 140 48 ##STR56## 160 49 CH.sub.3 140 50 ##STR57## 80 51
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH 75 - 80 52 (CH.sub.2).sub.3
OC.sub.3 H.sub.7 (i) Oil 53 CH.sub.2 CH.sub.2C.sub.6 H.sub.5 118 -
123 54 (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 Oil 55
##STR58## 172 56 ##STR59## Oil 57 ##STR60## 115
______________________________________ .sup.1 Greasy product.
.sup.2 Tar becoming solid on prolonged standing. .sup.3 Viscous
oil.
When the products set out in Tables 1 and 2 are treated with
aliphatic or aromatic amines at temperatures above 100.degree. or
80.degree. 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 --CONH.sub.2 group may take place.
TABLE 3
__________________________________________________________________________
##STR61## Number R.sup.1 R.sup.2 Melting point, .degree.
__________________________________________________________________________
C. 58 CH.sub.2 CH.sub.2 OH CH.sub.3 125 - 130. 59 CH.sub.2 CH.sub.2
OH (CH.sub.2).sub.3 OH 47 - 50. 60 CH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3 104 - 105. 61 CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH 156. 62 (CH.sub.2).sub.3 OH CH.sub.3 215
(hydrochloride). 63 ##STR62## (CH.sub.2).sub.3 OH 220 - 223. 64
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH H Viscous oil. 65
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH (CH.sub.2).sub.3 OH " 66
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH (CH.sub.2).sub.3 OCH.sub.3 "
67 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH (CH.sub.2).sub.2 OCH.sub.3
" 68 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH (CH.sub.2).sub.2
OCH.sub.3 " 69 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.3 OH " 70 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.2 OH " 71 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.3 OH " 72 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2
CH.sub.2 OCH.sub.3 75 - 76. 73 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2
CH.sub.2 OH 108 - 111. 74 CH.sub.2 CH.sub.2 OCH.sub.3 C.sub.6
H.sub.13 (n) Oil which has green fluorescence. 75 CH.sub.2 CH.sub.2
OCH.sub.3 H 108. 76 (CH.sub.2).sub.3OCH.sub.3 H 95 - 98. 77
(CH.sub.2).sub.3 OH (CH.sub.2).sub.3 OH 84 - 87. 78 ##STR63## H 215
- 220. 79 " CH.sub.2 CH.sub.2 OH 137. 80 " CH.sub.2 CH.sub.2
OCH.sub.2 CH.sub.2 OH 125 - 130. 81 ##STR64## (CH.sub.2).sub.3 OH
170. 82 " (CH.sub.2 CH.sub.2 O).sub.2 H 175 - 180. 83 ##STR65##
(CH.sub.2).sub.3 OH 169 - 170. 84 ##STR66## CH.sub.2 CH.sub.2 OH
155 - 158. 85 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OH 150
(hydrochloride). 86 ##STR67## CH.sub.2 CH.sub.2 OH 173. 87
##STR68## CH.sub.2 CH.sub.2 OH 136 - 140. 88 " CH.sub.2 CH.sub.2
OCH.sub.3 134 - 138. 89 ##STR69## CH.sub.2 CH.sub.2 OH 90 - 95
esterified with acetic acid. 90 " CH.sub.2 CH.sub.2 OCH.sub.3 105.
91 CH.sub.2 CH.sub.2C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 60.
92 CH.sub.2 CH.sub.2C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH 167 - 170.
93 C.sub.4 H.sub.9 (n) CH.sub.2 CH.sub.2 OH Oil having green
fluorescence. 94 C.sub.4 H.sub.9 (n) CH.sub.2 CH.sub.2 OCH.sub.2
CH.sub.2 OH " 95 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.2
CH.sub.2 OH " 96 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 OH " 97 (CH.sub.2).sub.5 CH.sub.3
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH " 98
(CH.sub.2).sub.3OCH.sub.2 CH(CH.sub.3).sub.2 CH.sub.2 CH.sub.2
OCH.sub.2 CH.sub.2 OH " 99 H (CH.sub.2).sub.3O(CH.sub.2).sub.4 OH
Viscous oil 100 H (CH.sub.2).sub.3O(CH.sub.2).sub.6 OH " 101 H
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH " 102 H
(CH.sub.2).sub.3OCH.sub.2C.sub.6 H.sub.5 " 103 H
(CH.sub.2).sub.3OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " 104 H
(CH.sub.2).sub.3OCH.sub.2 CH.sub.2C.sub.6 H.sub.5 " 105 H
(CH.sub.2).sub.3O CH.sub.2 CH.sub.2OCH.sub.3 " 106 H ##STR70## "
107 H (CH.sub.2).sub.3OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 " 108 H
##STR71## " 109 H ##STR72## " 110 H ##STR73## " 111 H
(CH.sub.2).sub.3 O(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.3 " 112 H
##STR74## " 113 ##STR75## H " 114 H (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OH " 115 H (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
" 116 H (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH " 117 H
(CH.sub.2).sub.6 OH " 118 H (CH.sub.2).sub.3OC.sub.2
H.sub.4OC.sub.3 H.sub.7 " Shade on coupling with ##STR76##
__________________________________________________________________________
119 (CH.sub.2).sub.3 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH Orange.
120 (CH.sub.2).sub.3 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OH
" 121 (CH.sub.2).sub.3 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.2
CH.sub.2 OH " 122 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH " 123 (CH.sub.2).sub.3
OCH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 OH " 124
(CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH "
125 ##STR77## CH.sub.2 CH.sub.2 OH " 126 ##STR78## (CH.sub.2).sub.3
OH " 127 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH " 128 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2
C.sub.6 H.sub.5 (CH.sub.2).sub.3 OH " 129 (CH.sub.2).sub.3
OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 OH " 130
(CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 CH.sub.2
CH.sub.2 OH " 131 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6
H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 " 132 (CH.sub.2).sub.3
OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2
OCH.sub.3 " 133 ##STR79## CH.sub.2 CH.sub.2 OH " 134 "
(CH.sub.2).sub.3 OH " 135 " (CH.sub.2 CH.sub.2 O).sub.2 H " 136
##STR80## CH.sub.2 CH.sub.2 OH " 137 ##STR81## (CH.sub.2).sub.3 OH
" 138 ##STR82## CH.sub.2 CH.sub.2 OH " 139 " (CH.sub.2).sub.3 OH "
140 " (CH.sub.2 CH.sub.2 O).sub.2 H " Melting point, .degree.
__________________________________________________________________________
C. 141 ##STR83## ##STR84## Viscous oil. 142 ##STR85##
(CH.sub.2).sub.3 OH " 143 ##STR86## (CH.sub.2 CH.sub.2 O).sub.2 H "
144 ##STR87## (CH.sub.2).sub.2 OCH.sub.3 " 145 ##STR88##
(CH.sub.2).sub.3 OCH.sub.3 " 146 ##STR89## ##STR90## " 147
(CH.sub.2).sub.6 OH ##STR91## " 148 ##STR92## ##STR93## " 149
(CH.sub.2 CH.sub.2 O).sub.2 H ##STR94## " 150 ##STR95## ##STR96## "
151 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OH " 152 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 153 (CH.sub.2).sub.3
O(CH.sub.2).sub.6 OH (CH.sub. 2).sub.3 O(CH.sub.2).sub.6 OH " 154
##STR97## CH.sub.2 CH.sub.2 OH " 155 ##STR98## (CH.sub.2).sub.3 OH
" 156 ##STR99## ##STR100## " 157 ##STR101## (CH.sub.2 CH.sub.2
O).sub.2 H " 158 ##STR102## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH "
159 ##STR103## (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 160
##STR104## (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH " 161
(CH.sub.2).sub.3 OH (CH.sub.2).sub.3 OH 84.degree. bis 87.degree.
C.
162 (CH.sub.2 CH.sub.2 O).sub.2 H (CH.sub.2 CH.sub.2 O).sub.2 H
Viscous oil. 163 ##STR105## (CH.sub.2).sub.2 OCH.sub.3 " 164
##STR106## (CH.sub.2).sub.3 OCH.sub.3 " 165 ##STR107##
(CH.sub.2).sub.3OC.sub.3 H.sub.7 " 166 (CH.sub.2 CH.sub.2 O).sub.2
H ##STR108## " 167 (CH.sub.2).sub.2 OH ##STR109## " 168
(CH.sub.2).sub.3 OH ##STR110## " 169 ##STR111## ##STR112## " 170
##STR113## ##STR114## " 171 ##STR115## ##STR116## " 172
(CH.sub.2).sub.3 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 173
(CH.sub.2).sub.3 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 174
(CH.sub.2).sub.3 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH " 175
(CH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH " 176
(CH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 177
CH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 178
CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH "
179 CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2).sub.2 O(CH.sub.2).sub.2
OH " 180 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH " 181 (CH.sub.2).sub.3 OC.sub.3 H.sub.7
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 182 (CH.sub.2).sub.2
OCH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 183
(CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH "
184 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).sub.2
OH "
__________________________________________________________________________
Shade on coupling with ##STR117##
__________________________________________________________________________
185 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH CH.sub.3 Orange. 186
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub. 2 OH C.sub.2 H.sub.5 " 187
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH C.sub.3 H.sub.7 " 188
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH C.sub.4 H.sub.9 " 189
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH C.sub.5 H.sub.11 " 190
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH C.sub.6 H.sub.13 " 191
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH ##STR118## " 192 CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 OH CH.sub.2 CH.sub.2 OH " 193 CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OH " 194 CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 OH ##STR119## " 195 CH.sub.2 CH.sub.2
OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 196
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH ##STR120## " 197 CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 OH ##STR121## " 198 CH.sub.2 CH.sub.2
OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.2 OCH.sub.3 " 199 CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OCH.sub.3 " 200
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OC.sub.2
H.sub.5 " 201 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OC.sub.3 H.sub.7 (n) " 202 CH.sub.2 CH.sub.2
OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i) " 203
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH (CH.sub.2).sub.3 OCH.sub.2
CH(CH.sub.3).sub.2 " 204 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
##STR122## "
__________________________________________________________________________
Melting point, .degree.
__________________________________________________________________________
C. 205 CH.sub.2 CH.sub.2 OCH.sub.3 ##STR123## 116-117. 206
CH.sub.2CH.sub.2 OH ##STR124## 188-189. 207 CH.sub.2CH.sub.2 OH H
>150. 208 (CH.sub.2).sub.3COOH ##STR125## 185-188. 209
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH C.sub.2 H.sub.5 Viscous oil.
210 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH C.sub.3 H.sub.7 (n) " 211
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH C.sub.4 H.sub.9 (n) " 212
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH C.sub.5 H.sub.11 (n) " 213
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH C.sub.6 H.sub.13 (n) " 214
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH ##STR126## " 215
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH ##STR127## " 216
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH ##STR128## " 217
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH ##STR129## " 218
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH ##STR130## " 219 ##STR131##
CH.sub.2 CH.sub.2 OH " 220 " (CH.sub.2).sub.3 OH " 221 "
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 222 ##STR132##
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 223 " (CH.sub.2
O(CH.sub.2).sub.2 OH " 224 ##STR133## (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH " 225 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
" 226 ##STR134## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 227 "
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 228 ##STR135## CH.sub.2
CH.sub.2 OH " 229 " (CH.sub.2).sub.2 OH " 230 " (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH " 231 ##STR136## (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH " 232 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
" 233 ##STR137## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 234
##STR138## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 235 "
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 236 ##STR139##
(CH.sub.2).sub.2 O(CH.sub.2 ).sub.2 OH " 237 ##STR140## CH.sub.2
CH.sub.2 OH " 238 CH.sub.2 CHCH.sub.2 (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH " 239 CH.sub.2 CHCH.sub.2 (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OH "
__________________________________________________________________________
Shade on coupling with ##STR141##
__________________________________________________________________________
240 ##STR142## C.sub.2 H.sub.5 Orange. 241 " C.sub.3 H.sub.7 (n) "
242 " C.sub.4 H.sub.9 (n) " 243 " C.sub.6 H.sub.13 (n) " 244 "
(CH.sub.2).sub.3 OH " 245 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH "
246 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 247 "
(CH.sub.2).sub.3 O(CH.sub. 2).sub.4 OH " 248 ##STR143## C.sub.2
H.sub.5 " 249 " C.sub.3 H.sub.7 (n) " 250 " C.sub.4 H.sub.9 (n) "
251 " C.sub.6 H.sub.13 (n) " 252 " (CH.sub.2).sub.2 OH " 253 "
(CH.sub.2).sub.3 OH " 254 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH "
255 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 256 "
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 257 ##STR144## C.sub.2
H.sub.5 " 258 " C.sub.3 H.sub.7 " 259 " C.sub.4 H.sub.9 " 260 "
CH.sub.2 CH.sub.2 OH " 261 " (CH.sub.2).sub.3 OH " 262 "
(CH.sub.2).sub.2 O(CH.sub.2 ).sub.3 OH " 263 " (CH.sub.2).sub.2
OCH.sub.3 " 264 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 265 "
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 266 ##STR145## C.sub.2
H.sub.5 " 267 " C.sub.3 H.sub.7 (n) " 268 " C.sub.4 H.sub.9 (n) "
269 " C.sub.6 H.sub.13 (n) " 270 H ##STR146## Golden yellow. 271
##STR147## CH.sub.2 CH.sub.2 OH Orange. 272 " (CH.sub.2).sub.3 OH
"
273 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 274 "
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 275 " (CH.sub.2).sub.3
O(CH.sub.2).sub.4 OH " 276 " (CH.sub.2).sub.2 OCH.sub.4 " 277 "
(CH.sub.2).sub.3 OCH.sub.3 " 278 ##STR148## (CH.sub.2).sub.3
OCH.sub.3 Orange. 279 " (CH.sub.2).sub.2 OCH.sub.3 " 280 ##STR149##
(CH.sub.2).sub.2 OCH.sub.3 " 281 " (CH.sub.2).sub.3 OCH.sub.3 "
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
##STR150## Shade coupling with Number R.sup.1 R.sup.2 R.sup.3
##STR151##
__________________________________________________________________________
282 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH H
Orange. 283 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH
C.sub.2 H.sub.3 " 284 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH C.sub.2 H.sub.5 " 285 CH.sub.2 CH.sub.2 C.sub.6
H.sub.5 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH H " 286 CH.sub.2
CH.sub.2 C.sub.5 H.sub.5 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
C.sub.2 H.sub.5 " 287 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2
CH.sub.2 OH C.sub.3 H.sub.7 (n) " 288 ##STR152## CH.sub.2 CH.sub.2
OH H 41 289 ##STR153## CH.sub.2 CH.sub.2 OH C.sub.3 H.sub.7 (n) "
290 ##STR154## (CH.sub.2).sub.3 OH C.sub.3 H.sub.7 (n) " 291
##STR155## (CH.sub.2).sub.3 OH H " 292 ##STR156## (CH.sub.2).sub.3
OH C.sub.2 H.sub.5 " 293 CH.sub.2 CH.sub.2 OH CH.sub.2 CH.sub.2 OH
##STR157## " 294 CH.sub.2 CH.sub.2 OH CH.sub.2 CH.sub.2 OH C.sub.5
H.sub.11 (n) " 295 CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2 CH.sub.2
O).sub.2 H C.sub.6 H.sub.5 " 296 (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2 CH.sub.2 O).sub.2 H C.sub.6 H.sub.5 " 297 H ##STR158## H
Golden yellow. 298 H ##STR159## C.sub.3 H.sub.7 (n) " 299 H
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH H " 300 H (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OH H "
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
##STR160## Shade after coupling with Number R.sup.1 R.sup.2
##STR161##
__________________________________________________________________________
301 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2).sub.3 OH Red.
302 CH.sub.2 CH.sub.2C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH Red. 303
CH.sub.2 CH.sub.2C.sub.6 H.sub.5 (CH.sub.2).sub.3 OH Red. 304
##STR162## (CH.sub.2).sub.3 OH Red. 305 ##STR163## (CH.sub.2).sub.2
OH Red. 306 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.2 OH Red. 307 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6
H.sub.5 (CH.sub.2).sub.3 OH Red. 308 (CH.sub.2).sub.3 OCH.sub.2
CH.sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 OH Red. 309
(CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
(CH.sub.2).sub.2 OH Red. 310 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.2 OCH.sub.3 Red. 311 (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH (CH.sub.2).sub.3 OCH.sub.3 Red. 312
(CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red. 313 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH Red. 314 H (CH.sub.2).sub.2 O(CH.sub.2).sub.2
OH Yellowish red. 315 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH " 316
H (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 317 CH.sub.2CH.sub.2 OH
CH.sub.2 CH.sub.2C.sub.6 H.sub.5 Red. 318 (CH.sub.2).sub.3 OH
CH.sub.2 CH.sub.2C.sub.6 H.sub.5 Red. 319 (CH.sub.2).sub.3
OCH.sub.3 CH.sub.2 CH.sub.2C.sub.6 H.sub.5 Red. 320
CH.sub.2CH.sub.2C.sub.6 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Red. 321
##STR164## CH.sub.2 CH.sub.2 OH Red. 322 ##STR165##
(CH.sub.2).sub.3 OH Red. 323 ##STR166## (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH Red. 324 ##STR167## CH.sub.2CH.sub.2 OH Red.
325 " (CH.sub.2).sub.3 OH Red. 326 " (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH Red. 327 " (CH.sub.2).sub.3O(CH.sub.2).sub.2
OH Red. 328 C.sub.4 H.sub.9 (n) (CH.sub.2).sub.3O(CH.sub.2).sub.2
OH Red. 329 C.sub.4 H.sub.9 (n) (CH.sub.2).sub.2 O(CH.sub.2 ).sub.2
OH Red. 330 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH C.sub.4 H.sub.9
(n) Red. 331 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH ##STR168## Red.
332 ##STR169## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH Red. 333
##STR170## (CH.sub.2).sub.3 OH Red. 334 ##STR171## (CH.sub.2).sub.3
OH Red. 335 H (CH.sub.2).sub.2 OH Red. 336 ##STR172##
(CH.sub.2).sub.2 OH Bluish red. 337 " (CH.sub.2).sub.3 OH " 338 "
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 339 ##STR173##
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 340 (CH.sub.2).sub.2 OH
(CH.sub.2).sub.2 OH Red. 341 (CH.sub.2).sub.3 OH (CH.sub. 2).sub.3
OH Red. 342 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH (CH.sub.2).sub.3
OH Red. 343 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH (CH.sub.2).sub.2
OCH.sub.3 Red. 344 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3 Red. 345 (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OH (CH.sub.2).sub.3 OCH.sub.3 Red. 346 H
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH Yellowish red. 347 ##STR174##
CH.sub.2CH.sub.2OH Red. 348 " (CH.sub.2).sub.3 OH Red. 349 "
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH Red. 350 ##STR175##
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH Red. 351 " (CH.sub.2).sub.2
OH Red. 352 " (CH.sub.2).sub.3 OH Red. 353 ##STR176##
(CH.sub.2).sub.3 OH Red. 354 ##STR177## (CH.sub.2).sub.2 OH Red.
355 ##STR178## (CH.sub.2).sub.2O(CH.sub.2).sub.2 OH Red. 356
##STR179## CH.sub.2CH.sub.2OH Red.
__________________________________________________________________________
The Examples described in the above Tables are prepared by always
first introducing the radical R.sup.1.
EXAMPLE 357
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.degree. to 100.degree. 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
EXAMPLE 358
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.degree. 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.degree. C with decomposition.
The free base of the formula: ##STR183## is obtained from the salt
by a conventional method.
TABLE 6
__________________________________________________________________________
##STR184## Melting Number R.sup.1 R.sup.2 point, .degree. C.
__________________________________________________________________________
359 C.sub.6 H.sub.5 C.sub.6 H.sub.5 128-130 360 ##STR185##
##STR186## 178 361 CH.sub.3 CH.sub.3 140-150 362 CH(CH.sub.2).sub.2
CH(CH.sub.3).sub.2 118-120 363 C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7
(n) 122-123 364 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 77 365
C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) 97 366 C.sub.6 H.sub.13 (n)
C.sub.6 H.sub.13 (n) Oil 367 ##STR187## ##STR188## 193 368 H H 225
369 ##STR189## ##STR190## 175 370 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2C.sub.6 H.sub.5 170 371 CH.sub.2CH.sub.2C.sub.6 H.sub.5
CH.sub.2CH.sub.2C.sub.6 H.sub.5 110 372 C.sub.2 H.sub.5 C.sub.2
H.sub.5 .sup.1 205 373 C.sub.6 H.sub.5 C.sub.4 H.sub.9 (n) 115 374
C.sub.6 H.sub.5 H (.sup.2) 375 C.sub.4 H.sub.9 (n) H 100 376
C.sub.2 H.sub.5 C.sub.6 H.sub.5 218-220 377 CH.sub.2 CH.sub.2
C.sub.6 H.sub.5 H 100 378 ##STR191## ##STR192## Ca.60 379 H
CH.sub.2CH.sub.2C.sub.6 H.sub.5 Ca.100,.sup.1 188 380 C.sub.8
H.sub.17 (n) H Oil 381 C.sub.14 H.sub.29 H Ca.90-105 382 H
##STR193## Tar 383 ##STR194## H Tar 384 CH.sub.2CH.sub.2CN
CH.sub.2CH.sub.2CN 170-176 385 CH.sub.2CH.sub.2CN
CH.sub.2CH.sub.2C.sub.6 H.sub.5 Ca.120 386 H (CH.sub.2).sub.5 CN
142
__________________________________________________________________________
.sup.1 Hydrochloride. .sup.2 Tarry: becomes solid after prolonged
standing.
Table 7 ______________________________________ ##STR195## Shade
when coupled with Ex. X R.sup.1 R.sup.2 ##STR196##
______________________________________ 387 CH.sub.3 H CH.sub.2
CH.sub.2 OH Yellowish red. 388 CH.sub.3 H (CH.sub.2).sub.3 OH " 389
CH.sub.3 H ##STR197## " 390 CH.sub.3 H CH.sub.2 CH.sub.2 C.sub.6
H.sub.5 " 391 C.sub.3 H.sub.7 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH
Bluish red. 392 C.sub.3 H.sub.7 C.sub.6 H.sub.5 (CH.sub.2).sub.3 OH
" 393 C.sub.3 H.sub.7 C.sub.6 H.sub.5 (CH.sub.2).sub.2
O(CH.sub.2).sub.2 OH " 394 C.sub.3 H.sub.7 ##STR198##
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH " 395 C.sub.3 H.sub.7 "
CH.sub.2 CH.sub.2 OH " 396 C.sub.3 H.sub.7 " (CH.sub.2).sub.3 OH "
397 H C.sub.6 H.sub.5 (CH.sub.2).sub.3 OH "
______________________________________
EXAMPLE 398
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.degree. 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.degree.-10.degree. 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.degree. C.
EXAMPLE 399
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.degree. 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.degree. C is obtained.
168 parts of this powder is mixed with about 170 parts of
.beta.-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-.beta.-hydroxyethylaminopyridine.
A greenish yellow dye may be obtained by coupling with diazotized
2-aminobenzonitrile.
TABLE 8
__________________________________________________________________________
##STR202## Shade when coupled with No. R.sup.1 R.sup.2 X ##STR203##
__________________________________________________________________________
400 H CH.sub.3 CN Golden yellow. 401 H C.sub.2 H.sub.5 CN " 402 H
C.sub.3 H.sub.7 CN " 403 H C.sub.2 H.sub.4 OCH.sub.3 CN " 404 H
C.sub.2 H.sub.4 OCH.sub.3 CONH.sub.2 Yellowish red. 405 H C.sub.3
H.sub.6 OCH.sub.3 CONH.sub.2 " 406 H C.sub.3 H.sub.6 OCH.sub.3 CN
Golden Yellow. 407 H C.sub.4 H.sub.9 (n) CN Yellow orange. 408 H
C.sub.4 H.sub.9 (n) CONH.sub.2 Yellowish red. 409 H CH.sub.2
CHCH.sub.2 CN Golden yellow. 410 H ##STR204## CONH.sub.2 Yellowish
red. 411 H ##STR205## CN Orange. 412 H ##STR206## CONH.sub.2 Red.
413 ##STR207## CH.sub.2 CH.sub.2 OH CONH.sub.2 Red. 414 ##STR208##
(CH.sub.2).sub.3 OH CONH.sub.2 Red. 415 CH.sub.2 CH.sub.2 OH
##STR209## CONH.sub.2 Red. 416 ##STR210## CH.sub.2 CH.sub.2 OH
CONH.sub.2 Red. (M.P. 150-153.degree. C.)
__________________________________________________________________________
* * * * *