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Патент USA US2406591

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Patented Aug. 27, 1946
2,406,591
UNITED STATES PATENT I OFFICE
2,406,591
‘ vMIXTURES OF ISOMERIC TRIAZOLE DERIV
ATIVES AND PROCESS OF PREPARING THE
SAME
Gaetano F. D’Alelio, Northampton, Mass, assign
or to General Electric Company, a corporation
of New York '
No Drawing. Application August 31, 1944,
- Serial No. 552,202
,
,7
,
12 Claims.
1
(01. 260—308)
.
~
2
This invention relates to the production of new
tion of the triazole nucleus. However, there also
and useful compositions comprising a mixture of
isomeric compounds, more particularly isomeric
triazole derivatives. Speci?cally the invention is
concerned with compositions comprising a mix
ture of isomers represented by A and B, each
may be produced in accordance with the present
invention a mixture ofisomers represented by
A and B, each of which corresponds to the gen
eral formula
>
of which corresponds to the’general formula
10
or wherein each isomer of the mixture corre
sponds to the general formula
where R represents a member of the class con
sisting of hydrogen and monovalent hydrocar
bon radicals, in isomer A the ~—NH2 grouping
being attached to the carbon atom in the 3
position of the triazole nucleus and in isomer B
to the carbon atom in the 5 position of the tri
azole nucleus.
Illustrative examples of monovalent hydrocar
bon radicals that R in the above formula may
represent are: aliphatic (e. g., methyl, ethyl, pro-V
pyl, isopropyl, butyl, sec-butyl, isobutyl, butenyl,
In Formulas III and IV, R has the same mean
ing as given above with reference to Formula I
and the —NI-I2 grouping of each isomer is at
tached to ‘the triazole nucleus as hereinbefore
tyl, etc), including cycloaliphatic (e. g., cyclo
mentioned with reference to Formulas I and II.
pentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,
, The mixtures of isomeric compounds of this
cycloheptyl, etc); aryl (e. g.,"phenyl, biphenylyl 30 invention may be used, for example, as phar
amyl, isoamyl, hexyl, octyl, allyl, methallyl, cro
or xenyl, naphthyl, anthracyl, etc); aliphatic
substituted aryl (e. g., tolyl, xylyl, ethylphenyl,
propylphenyl, isopropylphenyl, allylphenyl, 2
butenylphenyl, propenylphenyl, tert.-butylphen
yl, methylnaphthyl, etc); and aryl-substituted
aliphatic (e. g., benzyl, cinnamyl,-phenylethyl,
phenylpropyl, etc). Preferably R represents hy
drogen, in which case each of the isomers A and
B in the mixture corresponds to the general
maceuticals, insecticides, fungicides, plasticizers
‘ and as intermediates in the preparation of mix
tures of derivatives of the isomers, e. g., ureido,
hydrazino, acyl, carbamyl, methylol, methylene,
35 etc, derivatives.
These new isomeric mixtures,
without separation of the individual isomers, are
especially valuable in the preparation of syn
thetic resinous compositions. Thus, they may be
condensed with, for instance, aldehydes, includ
ing polymeric aldehydes, hydroxyaldehydes and
aldehyde-addition products, to yield condensation
products having particular utility in the plastics
and coating arts.
Such reaction products are
more fully described and are speci?cally claimed
45 in my copending application, Serial No. 552,201,
?led concurrently herewith'and assigned to the
same assignee as the present invention.
the --NH2 grouping being ‘attached, in one iso
Various methods may be, employed to produce
mer, to the carbon atom in the 3 position and
the mixture of isomers of this invention. I pre
in the other, to the carbon atom in the 5 posi 50 ferto preparemy new compositions by effecting
‘
2,406,591
4
3
reaction under heat between (1) a hydrazine cor
be used, depending upon the particular end prod
responding to the general formula
uct desired, are:
I-Iydrazine (or hydrazine hydrate)
NHz-NHR
Methyl hydrazine
Ethyl hydrazine
where R has the same meaning as given above
with reference to Formula I and (2) a hydroxy
Propyl hydrazine
Isobutyl hydrazine
V
Phenyl hydrazine
Allyl hydrazine
Propenyl hydrazine
Cyclohexyl hydrazine
aryl biguanide corresponding to the general for
mula
10
[
NE
NE
Tolyl hydrazine
Xylyl hydrazine
Phenethyl hydrazine
Ethylphenyl hydrazine
Octyl hydrazine
Illustrative examples of hydroxyary1 biguanides
at
where R has the same meaning speci?ed above
that may be employed, depending upon the par
with reference to Formula I. This reaction is 20 ticular end product desired, are:
carried out under conditions such as will result
Meta-hydroxyphenyl biguanide
in the formation of ammonia or, if an acid is
Para-hydroxyphenyl biguanide
present, an ammonium salt as a by-product of
(3-methyl ‘l-hydroxyphenyl) biguanide, which
the reaction. The reaction may be represented
also may be named (é-hydroxyphenyl 5-_meth
by the following general equation:
yl) biguanide
(2-methyl 4-hydroxyphepyl) biguanide
(3-hydroxy 4-methylphenyl) biguanide
(3-ethyl 4-hydroxyphenyl) biguanide
(Z-ethyl 3-hydroxyphenyl) biguanide
(B-hydroxy il-propylphenyl) biguanide
(3~isopropyl 4-hydroxyphenyl) biguanide
(3-hydroxy 4-octylphenyl) biguanide
(3-allyl 4-hydroxyphenyl) biguanide
(3-hydroxy 4-propenylphenyl) biguanide
Or, when the reaction is carried out in the pres
(B-phenyl ‘l-hydroxyphenyl) biguanide
(B-hydroxy é-benzylphenyl) biguanide
(3-phenethy1 ‘l-hydroxyphenyl) biguanide
(‘B-cyclopentyl 4-hydroxyphenyl) biguanide
(B-hydroxy é-cyclohexenylphenyl) biguanide
(3-hydroxy 4,5-dimethylphenyl) biguanide
v(ZA-dimethyl 3-hydroxyphenyl) biguanide
(2,6-dimethyl 3'-hydroxyphenyl) biguanide
(4-hydroxy 3,5-dimethylphenyl) biguanide
(3-hydroxy 4,5-diethylphenyl) biguanide
(é-hydroxy 3,5-diethylphenyl) biguanide
all
ence of an acid effective in binding the ammonia
liberated during the reaction, it may be repre
sented by the following generalequation:
The hydroxyaryl biguam'des used in practicing the
present invention are prepared by methods such
as described, for example, in Beilstein Organische
C;
Chemie, 4th ed., 13, 4'78.
'
In order that those skilled in the art better
may understand how the present invention may be
carried into e?ect, the following examples are
given by way of illustration and‘ not by way of
55 ‘limitation. All parts are by weight.
Example 1
This example illustrates the preparation of a
composition comprising a mixture of 3-amino 5
In Equations VII and VIII, R has the same mean.
(para-hydroxyanilino) 1,2,4-triazole and 3
ing as given above with reference to Formula I,
and HA (Equation VIII) represents an acid, which 60 (para-hydroxyanilino) 5-amin0 1,2,4-triazole,
which isomers also may be named, respectively, as
may be either organic or inorganic but which
preferably is inorganic. Illustrative examples of
organic and inorganic acids that may be used to
bind the ammonia in the form of a salt are oxalic,
acetic, hydrochloric, hydrobromic, sulfuric, etc.
3-amino 5-(para-hydroxyphenylamino) 1,2,4-tri
azole and 3-(para-hydroxyphenylamino) 5-amino
- 1,2,4-triazole.
The reaction preferably is carried out in an aque
Para~hydroxyphenyl biguanide hydrochlo
ous solution containing an inorganic acid. How
ever, other solvents or mixtures of solvents may
Hydrazine hydrate (in 34.5 parts water) __
ride _______________________________ __
Parts
114.8
25.0
Concentrated aqueous solution of hydro
be used, e. g., alcohols, ethers, dioxane, benzene,
chloric acid (approx. 38% I-ICl‘) ______ __
96.0
etc. The reaction may be effected under a variety 70
of temperature and pressure conditions. Ordi
were
mixed
with
200
parts
water,
and
the
re
narily the components are caused to react at at
sulting mixture then heated under reflux at the
mospheric pressure under re?ux at the boiling
boiling temperature of the mass for 18 hours.
temperature of the reaction mass.
Illustrative examples of hydrazines that may 7 5 The solid residue obtained by evaporating the re
2,406,591
5
6
phenylamino), 1,2,4-triazole andl-methyl 3
suiting liquid mass to dryness was dissolved» in hot
(2’,6’-dimethyl
ethyl alcohol. Aftercooling, the insoluble ram
monium chloride that separated from the alcohol
3'-hydroxyphenylamino) _
5-‘
amino 1,2,4-triazole
l-ethyl 3-amino 5- (3'-methy1 4'-hydroxyphenyl
solution was removed by ?ltration. ‘The ?ltrate
was decolorized by contacting the heated ?ltrate 5
amino) 1,2,4-triazole and l-ethyl 3-(3'-methyl
4’-hydroxyphenylamino) 5-amino 1,2,4-tri
with a ?nely divided decolorizing carbon. Ether
was added to the decolorized ?ltrate, from which
l-tolyl 3-amino 5- (para-hydroxyanilino) 1,2,4
the decolorizing carbon previously had been re
triazole and l-tolyl 3- (para-hydroxyanilino)
moved, until precipitation began to take place.
5-amino 1‘,2,4‘-triazole
»
~
The mass Was chilled, and the resulting white, 10
'l-ethyl 3-amino 5-(para-hydroxyanilino) 1,2,4
crystalline material that precipitated was re
triazole and l-ethyl 3- (para-hydroxyanilino)
moved by ?ltration and dried. A yield of 100
5-amino 1,2‘,4-triazole
parts of the dried materialwas obtained. The
l-phenyl B-amino 5-(3'-methyl é'ehydroxy
crystalline product comprising a mixture of' 3
amino 5-(para-hydroxyanilino) 1,2,4-triazole and
phenylamino) 1,2,4-triazole and l-phenyl 3- (3'
methyl 4'-hydroxyphenylamino) 5-amino 1,2,4
B-(para-hydroxyanilino) 5-amino 1,2,4-triazole
azole
melted at 135° to 137°C,
7
t
‘
phenyl biguanide hydrochloride, 96.8 parts of
para-hydroxyphenyl biguanide may be employed, 20
in which case the amount of the concentrated
aqueous solution of hydrochloric acid is increased
-
,
triazole
vInstead of using 1714.8 parts of para-hydroxy
from 96 parts to 192»parts.
'
y
.
'
‘
l-allyl 3-amino 5-(para-hydroxyanilino) 1,2,4
triazole and l-allyl 34(para-hydroxyani1ino) 5
amino 1,2,4-triazole
l-benzyl 3-amino 5- (meta-hydroxyanilino) 1,2,4
triazole and l-benzyl 3-(meta-hydroxyanilino)
5-amino 1,2,4-triazole
>
Example 12
What I claim as new and desire to secure by
A composition comprising a mixture of 3
25
amino 5- (meta-hydroxyanilino) 1,2,4-triazole
and 3-(meta-hydroxyanilino) 5-amino, 1,2,4-tri
Letters Patent of theUnited States is:
1. A composition comprising a mixture of iso
mers represented by A and B, each of which cor
responds to the general formula
azole is produced by the same method described
under Example 1 with the exception that 114.8 30
parts of meta-hydroxyphenyl biguaniderhydro
chloride are used in place of 114.8 parts of para
.hydroxyphenyl biguanide hydrochloride.
.
.
.
Example 3
A composition comprising a mixture of 1 35
phenyl 3-amino S-(para-hydroxyanilino) 1.2,4
where R represents a member of the class con
triazole and l-phenyl 3- (para-hydroxyanilino)
sisting of hydrogen and monovalent hydrocarbon
5-amino 1,2,4-triazole is prepared by thesame
radicals, in isomer A the —NH2~ grouping being
method'set forth under Example 1 with the ex 40 attached to‘ the carbon atom in the 3 position of
ception that 54 parts of phenyl hydrazine are
the triazole nucleus and in isomer B to the carbon
. used instead of 25 parts of. hydrazine hydrate.
atom in the 5 position of the triazole nucleus.
Illustrative examples of other isomeric mix
2. A mixture of isomers represented by A and
tures that may be produced in accordance with
B, each of which corresponds to the general for
the present invention, the individual isomers of 45 mula
which are embraced by Formula I, are mixtures
comprising:
l-methyl
3 - amino
R
'
H N Nu l-—NH-—O/
[ are
lTOH
>O—R
5 - (meta-hydroxyanilino)
1,2,4-triazole and l-methyl 3- (meta-hydroxy
anilino) 5-amino 1,2,4-triazole
l-phenyl 3-amino' 54 (meta-hydroxyanilino) 1,2,4
triazole and l-phenyl 3- (meta-hydroxyanilino)
5-amino 1,2,4-triazole
B-amino 5-(3'-methyl 4'-hydroxyphenylamino)
1,2,4-triazole and 3- (3'-methyl 4’-hydroxy
phenylamino) 5-amino 1;2,4-triazole
Hail |
where R. represents a member of the class con
sisting of hydrogen and monovalent hydrocarbon
5 radicals, in isomer A the —NH2 grouping being
attached to the carbon atom in the 3 position of
the triazole nucleus and in isomer B to the carbon
atom in the 5 position of the triazole nucleus.
3-amino 5- (2’-methyl 4'-hydroxyphenylamino)
1,2,4-triazole and 3—(2'-methyl 4'-hydroxy
v
3. A mixture of isomers represented by A and
phenylamino) 5-amino 1,2,4-triazole
3-amino 5- (2’-ethyl ' 3'-hydroxyphenylamino) ' 60 B, each of which corresponds to the general
formula
1,2,4-triazole and 3-(2'-ethyl 3'-hydroxy
phenylamino) 5-amino 1,2,4-triazole
H
3-amino 5- (3'-phenyl 4'-hydroxyphenylamino)
'
1,2,4-triazole and 3-‘(3'-phenyl_ 4'-hydroxy
R N
HZNQ-I:
‘phenylamino) 5-amino 1,2,4-triazole
3-amino 5- (3’,5'-dimethyl 4'—hydroxyphenyl
amino) 1,2,4-triazo1e and 3-(3',5'-dimethyl 4'
hydroxyphenylamino) 5-amino 1,2,4-triazole
3-amino 5- (2',4'-dimethyl 3'—hydroxyphenyl
amino) 1,2,4-triazole and 3-(2',4'—dimethyl 3'
I
N
fly-(I3
I 1 NH—O/
lon
o—|H
Where R represents a_member of the class con
70 sisting of hydrogen and monovalent hydrocarbon
radicals, in isomer A the —NH2 grouping being
hydroxyphenylamino) 5-amino 1,2,4-triazole V
attached to the carbon atom in the 3 position of
3-amino 5-(3',4’-diethy1 5'-hydroxyphenylamino)
1,2,4-triazole and 3-(3',4'-diethyl 5’—hydroxy
phenylamino) 5-amino 1,2,47triazole
l-methyl 3-amino 5-(2',6’-dimethyl 3’-hydroxy
the triazole nucleus and in isomer B to the car
bon atom in the 5 position of the triazole nucleus.
75
4. A composition comprising a mixture of
2,406,591
8
7
isomers represented by A and B, each of which
corresponds to the general formula
(1) a hydrazine corresponding to the general
formula NHz-NHR where R has the meaning
above given and (2) a hydroxyaryl biguanide cor
responding to the general formula
R
IRE
at
1 0H
in isomer A the —-NHz grouping being attached 10
to the carbon atom in the 3 position of the tri
where R has the meaning speci?ed above.
azole nucleus and in isomer B to the carbon atom
9. A method as in claim 8 wherein the reaction
in the 5 position of the triazole nucleus.
is carried out in the presence of an acid effective
5. A composition comprising a mixture of 3
in binding the armnonia liberated during the re
amino 5-(meta-hydroxyanilino) 1,2,4-triazo1e
action.
and 3-(meta-hydroxyanilino) 5-amino 1,2,4
10. The method of preparing a composition
triazole.
comprising a mixture of 3-amino >5-(para-hy
6. A composition comprising a mixture of 3
amino 5-(para-hydroxyanilino) 1,2,4-triazo1e and
3-(para-hydroxyanilino) S-amino 1,2,4-triazole.
'7. A composition comprising a mixture of 1
phenyl 3-amino 5-(para-hydroxyani1ino) 1,2,4
triazole and l-phenyl 3-(para-hydroxyani1ino)
B-amino 1,2,4-triazole.
8. The method of preparing a composition ~
comprising a mixture of isomers represented by
A and B, each of which corresponds to the gen
eral formula
[
R-N-lg ‘I
L
\N
R
ats 10H
l
m
droxyanilino)
gredients including para-hydroxyphenyl biguan
ide and hydrazine hydrate.
11. The method of preparing a composition
comprising a mixture of 3-amino S-(para-hy
droxyanilino)
tion under heat between ingredients including
1,2,4-triazole and 3-(para-hy
droxyanilino) 5-amino 1,2,4-triazole which com
prises efiecting reaction under heat between
para-hydroxyphenyl biguanide and hydrazine
hydrate in the presence of an-acid eiTective in
binding the ammonia liberated during the reac
tion.
12. The method of preparing a composition
comprising a mixture of 3-amino S-(para-hy
droxyanilino)
where R represents a member of the class con
sisting of hydrogen and monovalent hydrocarbon
radicals, in isomer A the ——NH2 grouping being
attached to the carbon atom in the 3 position
of the triazole nucleus and in isomer B to the
carbon atom in the 5 position of the triazole
nucleus, said method comprising effecting reac
1,2,4-triazole and 3-(para-hy
droxyanilino) S-amino 1,2,4-triazole which com
prises effecting reaction under heat between in
1,2,4-triazole and 3-(para-hy
droxyanilino) 5-amino 1,2,4-triazole which com
prises effecting reaction under heat between
para-hydroxyphenyl biguanide hydrochloride and
hydrazine hydrate, the said reaction being car
ried out in an aqueous solution containing hydro
chloric acid in an amount sufficient to bind the
ammonia liberated during the reaction.
GAETANO F. D’ALELIO.
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