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Патент USA US2374335

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Patented Apr.‘ '24, 1945
2,374,335 _~
UNTED STATES
' PATENT OFFlCE
2,374,335‘
'
TRIAZOLE DERIVATIVES
Gaetano F. D’Alelio, Pitts?eld, Mass.,'assignor to
General ‘Electric Company, a corporation of
New York
1 No Drawing. Application December 26, 1942,
Serial No. 470,220
,
(oi. 260-308)
14 Claims. >
where R, R’ and Z have the same meanings as
given above with reference to Formula I.
tives. The invention especially is concerned with
I Illustrative examples of divalent radicals that
the production of new and useful acylaminoaryl
Z in the above formulas may represent are: di
amino triazoles. '
'
5 valent aromatic, e. g., phenylene, xenylene, naph
This invention relates to new chemical com
pounds and more particularly to triazole deriva
thylene, etc.; divalent aliphatic-substituted aro
matic, e. g., 2,4-tolylene, ethyl 2,5-phenylene, iso
The triazole derivatives of this invention may
be represented by the following general formula:
propyl 3,4-phenylene, l-butyl 2.,4-naphthylene,
1,4-dimethyl 2,3-phenylene, etc.; radicals that - -
10 may be classed either as divalent aliphatic-sub
stituted aromatic or as divalent aromatic-sub
stituted aliphatic and wherein the-free bond of
where R represents a member of the class con-'7
the aromatic nucleus is attached to the acylamino
sisting of hydrogen and monovalent hydrocarbon
radical, e. g., 4,alpha-tolylene, 3,beta-phenylene
radicals, R’ represents a monovalent hydrocarbon 15 ethyl, 4,alpha-xylylene, 2,gamma-phenylenebutyl,
radical, and Z represents a member of the class
etc. ; and their homologues, as well as those .di-_
valent radicals with one 'or_-more of their nuclear
consisting of divalent aromatic and nuclearly 'sub-A
stituted, more particularly nuclearly halogenated,
hydrogen atoms replaced by a substituerit, e. en,
acyl, allgvl, alkenyl, hydroxy, alkoxy, aryloxy,
Illustrative examples of monovealent hydrocar-v 2o carboalkoxy, carboaroxy, sulfamyl, an acylamino
aromatic hydrocarbon radicals.
'
bon radicals that R and R’ in the above formula
may represent are: aliphatic (e. g., methyl, ethyl,
emit-r’)
propyl, isopropyl, butyl, secondary butyl, isobutyl,
butenyl, amyl, isoamyl, hexyl, octyl, allyl, meth
grouping in addition to the single acylamino
allyl, crotyl, etc), including cycloaliphatic (e. g"
grouping shown, for example, in Formula I, etc.'
cyclopentyl, cyclopentenyl, cyelohexyl, cyclo 25 ‘Specific
examples of substituted divalent radicals
hexenyl,‘ cycloheptyl, etc.); aryl (e. g., phenyl, di
that
Z
may
represent are chlorophenylene, bromo-v
phenyl or xenyl, naphthyl, anthracyl, etc);
phenylene, chloroxenylene, chloronaphthylene,
aliphatic-substituted aryl (e. g., tolyl, xylyl, ethyl
' chlorotolylene, bromotolylene, ethoxyphenylene,
' phenyl, propylphenyl, isopropylphenyl, allylphen
actophenylene, actoxyphenylene, aminophen
yl, z-butenylphenyl, propenylphenyl, tertiary 3° ylene,
carboethoxyphenylene, sulfamylphenyl
butylphenyl, methylnaphthyl, etc.); and aryl
ene, carbophenoxyphenylene, hydroxyphenylene',
substituted aliphatic (e. g.', benzyl, cinnamyl,
phenoxyphenylene, methylphenylene (tolylene),
'phenylethyl, phenylpropyl, etc.) . Preferably R
allylphenylene, etc.’ Preferably Z is phenylene or
represents hydrogen, in which case the com
pounds correspond to the following general
35
tolylene.
'
‘
'
The new compounds of this invention may be
used, for example, as pharmaceuticals, insecti
4
- cides, fungicides, plasticizers and as intermediates
in the preparation of‘ derivatives thereof, e. g.,
40 ureido, ‘acyl, hydrazino, ‘carbamyl, amidine,
methylol, methylene, etc., derivatives of them
_ where Z and R’ have the same meanings as given
dividual compound embraced by Formula I, These
above with reference to Formula I. However,
‘there also may be produced in accordance with the
new compounds are especially valuable in the
present‘ invention chemical compounds , corre
sponding to the following general formulas:
III
'- ‘N—-N—R
‘
‘
preparation of synthetic resinous ;compositions..
45‘ Thus, they may be condensed’ with, for instance,
aldehydes, including- polymeric aldehydes, hy
droxy-aldehydes and/aldehyde-addition products,
to yield condensation products having particular
utility in the plastics and coating arts.' Such
IV
50 condensation products are more fully described
and are speci?cally claimed in my copending all
plication Serial‘ No. 470,219, ?led concurrently
herewith and assigned to the same assignee as
the present invention.
66
.
,
Various methods may be employed‘ to produce
2
2,374,335
Ethyl hydrazine
Propyl hydrazine
Isobutyl hydrazine
Phenyl hydrazine
Allyl hydrazine
Propenyl hydrazine
Cyclohexyl hydrazine
Tolyl hydrazines
Xylyl, hydrazines
Phenethyl hydrazine
Ethylphenyl hydrazines
Octyl hydrazine
Naphthyl hydrazines
the chemical compounds of this invention. I pre
fer to prepare them by effecting reaction under
‘heat between a hydrazine corresponding to the
‘ general formula
-
where R has the'same meaning as given above
with reference to Formula -I, and an acylaminoaryl
biguanide corresponding to the general formula
VI
NE
NH
_
0
‘
NH,-<l§-Nn_t|:-NH-z_NR-t'J-R'
where R, R’ and Z have the same-I meanings as
given above with reference to Formula. I. This
Illustrative examples of acylaminoaryl bi
reaction is carried out under conditions such as 15
guanides that may be employed, depending upon
will result in the formation of ammonia, or, if
the particular end-‘product desired, are:
an acid is present, an ammonium salt as a by
product of the reaction. This reaction may be
Acetylaminophenyl biguanides (acetamidophenyl
represented by the following general equation:
:20
biguanides), including ortho-(acetylamino)
phenyl biguanide, meta-(acetylamino) phenyl
biguanide and para-jacetylamino) phenyl bi
guanide
'
*Acetylaminotolyl biguanides, which may be rep
resented by the formula
25
Or, when the reaction is carried out in. the
IX
presence of an acid effective in binding the am
monia liberated during the reaction, it may be
represented by the following general equation: 30
Acetylaminoxylyl biguanides
Acetylaminonaphthyl biguanides
35 Acetylaminoxenyl biguanides, which may be rep
resented by the formula
‘
Fox) 1
In Equations VII and VIII, R,‘ R’ and Z have _ 40
the same meanings as given above with refer
ence to Formula I, and HA (Equation VIII)
represents an acid, which may be either or
ganic. orv inorganic but which preferably is in
organic. Illustrative examples of organic and 45
inorganic acids that may be used to bind the
ammonia in the form of a salt are oxalic, acetic,
hydrochloric, hydrobromic,_ sulfuric, etc. -The
reaction advantageously is carried out in an
aqueous solution containing an inorganic‘ acid. 50
However, other solvents or mixtures of solvents
or by the formula
0
XI-
I|~IH
I|\|IH 7
(QNH- ill -cH, .
H,N-d-NH-c-Nn-< ' >
may be used, e. g‘.,"a1c0h01s, ethers, dioxane,
benzene, etc. The reaction may be carried out
under a variety of temperature and pressure 'con- .
ditions. Ordinarily the ‘reaction is e?ected at 55
Propanoylaminophenyl biguanides
Butanoylaminophenyl biguanides
Bu'tanoylaminotolyl biguanides
atmospheric pressure under re?ux at the boil- . ‘ Isobutanoylaminoxylyl biguanides
Propenoylaminophenyl biguanides
ing temperature of the reaction mess.
The acid represented by HA in Equation VIII
may constitute one of the starting materials, to
Propenoylaminonaphthyl biguanides '
' Cyclopentanoylaminophenyl biguanides
gather with the hydrazine and the acylaminoaryl 60 vBenzoylaminophenyl biguanides
biguanide. Or, if desired, the acid may be in
troduced into the reaction mixture in other
Acetylamino-(chloro)~-phenyl biguanides, which
, may be represented by the formula.
forms. For example, a Part of the acid may be
employed in a free or solution state and a. part
in the form of a‘ mono salt of the acylaminoaryl 65
biguanide or of the hydrazine; or, a part ‘of the
acid may be used in the form of a mono salt
of the hydrazine and a part in the form of a
mono salt of the acylaminoarylbiguanide. '
‘
Illustrative examples of hydrazines that vmay
be used, depending upon the» particular end
product desired, are: \
V
-
_
__
I
Hydrazine (or hydrazine hydrate)
Methyl hydrazine
_ = 1'
Acetylamino-(bromo) -phenyl biguanides
Propanoylamino-(chloroT-tolyl biguanides
Acetylamino- (iodo) -phenyl biguanides
,Acetylamino- (?uoro) -p_henyl biguanides
"
3v
Toiuylaminoxenyl biguan'ides,_ which may be
represented by the formula
(Para-acetamido phenyl) biguanide hydro
chloride
I -
‘-
'
135.2
Hydrazine hydrate (in 34.5 parts water)-.. 25.0 v
Concentrated aqueous solution of hydro
,chloric acid (approx.'38% HCl) _____ __
OH;
XIII
48.0
Water
200.0
were heated together under reflux at the‘ boil
' ing temperature of the massfor 18 hours, after
or by the formula
which the solution was evaporated to dryness-to
yield a gummy. semi-crystalline mass. This
mass was dissolved in boiling ethyl alcohol. The
on,
Us“?
alcohol-insoluble material, mostly ammonium
chloride,
was removed vby ?ltration. 'I'he.?ltrate
15
was vtreated with ’a de-colorizing carbon to de—
colorize it.» after which it was concentrated by
evaporation.‘ While still hot, ether was added
vto the concentrated‘?ltrate until a solid bezan
to precipitate from the solution. The solution
(N-methyl acetylaminophenyl) biguanides .
(N-ethyl , propanoylai‘nino
ethylphenyl)
guanides
‘
20 was chilled to obtain a maximum yield of
(N-isobu'tyl benzoylamino methylnaphthyl) bi
guanides
_
p
.
—
~-
.
,solid precipitate comprising (para-acetamido
‘
anilino) amino 1.2,4-triazoles. The product was
removed from the solution by ?ltration and dried.
The dried material had a melting point of about
200° _C. with some indication of decomposition at
(N-cyclopentyl benzoylamino phenyl) bizu'anides'
(N-phenvl methylcyclopentanoylamino chloro-.
phenyl) biguanides, which may be‘ represented
by the formula
v
‘
this temperature.
‘
The corresponding‘ortho and meta derivatives
are‘ prepared by using 135.2 parts of (oi-tho;
acetamido phenyl) bi'guanide- hydrochloride o'r
(meta-acetamido phenyl) biguanide Mal-'0',
30
chloride instead of 135.2 parts of
(para.
acetamido phenyl) biguanidev hydrochloride.
I
_1,2,4-triazoles' are ‘prepared in essentially'the -
(N-xenyl acetylamino bromotolyl) biguanides,
same manner as described under Example 1 with
which may be represented by the formula j
xvi
the exception that 23 parts of methyl hydra
‘ zine are used in place of 25 parts of hydrazine
.
-
II
Example 2
'l-methyl (para-acetamido anilino) amino
35
hydrate.
If?“
'
Example 3
l-phenyl _(para-acetamido anilino) amino
1,2,4-triazoles are prepared in essentially the
45 same‘manner as described under Example 1
.with the exception that 54 parts of phenyl hy
drazine
‘ are ‘used instead of 25 parts of hydra
zine
hydrate.v
,
I
'
'
p
Example 4
('Para-propanamido anilino) amino l.2,4¢tri
. azoles are produced in essentially‘ the same man
ner_- as ‘described under Example 1 withthe ex
Ethylbenzoylaminophenyl biguanides.
ception that 142.2 parts of (para-p'ropanamido
V
'phenyl) ‘biguanide hydrochloride, which alsom'ay
The acylaminoaryl'biguanides used in practic- ’
‘ ing the present invention are prepared, for exam
. be named (para-propanoylamino phenyl) bigua-
nide of hydrochloride, are used in place of 135.2
ple, by e?ecting reaction between biguanide or di- - . parts of (para-acetamid'ophenyl)“ biguanide hy- .
cyandlamide ~(cyanoguanidine) and an acyl
aminoaryl amine, ‘preferably in the presence of
an inorganic acid.
.In order that those skilled in ‘the .art better '
may understand how- the'present invention may
be carried into e?ectgthe following examples are
given by way ofa'illustration and not by way oi’
limitation. All part/‘fare by weight.
'
‘'
,Era'mple 1
drochloride..
'
60
r
a
,
Example _5
1
same manner as described under Example 1 with
the exception that 142.2 parts of »[(N'-methyl
para-acetamido)_ phenyl] biguanide ,hydroohlo-f
ride are used instead-oi‘ 135.2 parts or‘ (para
acetamido phenyl) I biguanide hydrochloride.
amino 1,2.4-triazoles,
'More speci?c examples of compounds ‘embraced
by Formula I that may beproduced in accordance
which also may be named (para-acetylamino
with the present, invention arelisted below:
phenvlamino) amino 1.2, __.-t1_'iazoles,. oriv'(para
acetylamino‘ anilino). amino.v 1,2,4-triazoles, or
l-metl'rvl. (ortho-acetamido anilino) amino 1,2,4
(para-acetamido .phenylamino') 1 ‘amino 1,2,4_-tri
azoles.v
.
[(N-methyl 'para-aceta‘mido) anilino] a' o
1,2,4-triazoles are prepared in essentiall the
This example illustrates the preparation of v
' (paraacetamido anilino)
‘
.
‘
.
triazoles
.
'
'
,
'
- ,l-methyl (meta-acetainldo anilino) amino 1,2,4
'
175' t'riazoles
2,374,836
4
L-prepyl (acetamide toluide) amine 1,2,4-tri
l-phenyl (ortho-acetamido aniline) amino 1,2,4
triazoles'
azeles
I
triazoles
'
-
l-isebutyl (benzamide'aniline) amine 1,2,4-tri
l-phenyl (meta-acetamide aniline) amine 1,2,4
azoles
l-propenyl (benzamido aniline) amino-1,2,4-tri
,
(Orthe-propanamido aniline) amino 1,2,4-trl
azoles
> azoles, which may be represented by the ter- .
.
l-cyclopentyl (acetamido aniline) amino 1,2,4
mula
triazoles
XVII
10
L \Ni
-
1~pheny1 (methylbenzamido xylidine) amino
1,2,4-triazoles
l-methyl [(N-methyl acetamide) aniline] amine
1,2,4-triaz‘oles, which may be represented by the
formula
_
-
(Meta-prepanamido aniline) amine 1,2,4-tri
azeles
_
(Acetamido teluide) amine 1,2,4-triazoles, which
may
represented by the formula
20 vl-benzyl
['(N-ethyl acetamide)‘, aniline] amine
1,2,4-triazeles
(Acetamide chlero aniline) amino 1,2,4-triazoles
(Acetamido bremo aniline) amine 1,2,4-triazeles
25
l-ethyl (acetamido aniline) amino 1,2,4-triazoles
l-methyl (acetamido teluido) amino 1,2,4-tri
azoles
'
triazoles
-
30
'
(Propanamido toluide) amine 1,2,4-triazeles
(Butanamido teluido) amino 1,2,4-triazeles
XIX
CH;
mg
triazeles
I
[(N-phenyl acetamide) aniline] amino 1,2,4-tri
azeles
v
.
[(N-ethyl prepanamido) aniline] amine'1,2,4-tri
(Isebutanamido -xylidino) amino 1,2,4-triazoles,
which may be represented by the formula
_
l-ethylphenyl (acetamido aniline) amino 1,2,4
l-phenyl (acetamide vteluido) ‘amino 1,2,4-tri
azeles
(Prepanamido iode toluide) amine 1,2,4-triazeles
(Butanamide ?uere toluido) amine 1,2,4-triazeles
l-phenethyl (acetamido aniline) amine 1,2,4
azoles
-
85 [(N-prepyl butanamido) teluide] amine 1,2,4
triazoles, which may beg-represented by thefor
CH;
mula
' (Prepenamido 'naphthylamino) amino 1,2,4-tri
azoles
(Cyclopentanamido xenylamino) amino 1,2,4-tri
45 [(N-isebutyl I benzamido)
azeles
(Hexahydrobenzamido aniline) amino 1,2,4-tri
azeles
[(N-cyclepentyl acetamide) aniline] amino 1,2,4
>
(Benzam'ide toluido) amino 1,2,4-triazeles
(Toluamido aniline) amine 1,2,4-triazoles
(Toluamido teluide) amine 1,2,4-triazeles
50
azeles
1,2;4-triazoles
l-methyl [(N-methyl acetamido) naphthylami
(‘3111s
no] amino 1,2,4-triazeles
| lNHC>
I
0-‘
I
\ ¢
N
I
_ ' ~
NB-(?-OH;
‘
'
.0
1,2,4-tria2eles
60
1,2,4-triaze1es
(Dimethylbenzamido ?uore aniline) amine 1,2,4
_
.
‘
It will be understood, of course, by those skilled
65
mula
XXI
amine 1,2,4-triazoles
l-ethyl [(N-phenethyl acetamido) toluido] amine
l-allyl (acetamido aniline) amineLZA-triazeles
~
triazoles, which may be represented by the for-
\
l-telyl [,(N-benzyl acetamido) propyl aniline]
(Benzamido methyl naphthylamine) amino 1,2,4
, triazoles
,
l-phenyl [(N-phenyl acetamide) aniline] amine
I N———-N—H
-e
'
l-methyl [(N-phenyl acetamide) aniline] ‘amide
which may be represented by the formula
H:N——[ I
triazoles
[(N-telyl acetamide) toluidol' amino 1,2,4-tri»
' (Acetamido ethyl aniline) amino 1,2,4-triazeles,
L
amine
[(N-phenyl benzami'do) aniline] amine 1,2,4ltri
(Benzamide aniline) amine 1,2,4-triazeles
azeles
xenylamino]
1,2,4-triazoles
in the art that in the'compounds listed above the
amine grouping may be attached to either the 3
or the 5 carbon atom of the triazele nucleus, the
carbon atom which is not joined to an amine
.
grouping being attached to the aeylaminoaryl
amino grouping; and’, also, that the acylamine
grouping may be attached to any of the reactive
N
carbon atoms of the aromatic nucleus.
‘
What I claim as new and desire to, secure by
(Naphthamide aniline) amino 1,2.4Ftr1azo1es
75
Letters Patent of the United States is: -
5
2,374,935 ’
where R’ represents an alkyl radical and Z rep
1. Chemical compounds corresponding to the
resents 'a divalent aromatic hydrocarbon radical.
general formula
V
'7. Chemical compounds corresponding to the
general formula ‘
where R represents a member of the class con
\ %
N
sisting of hydrogen.'and monovalent hydrocarbon
where R’ represents an alkyl radical and Z rep
resents a phenylene radical.
. radicals, R’ represents a monovalent, hydrocarbon
radical, and Z represents a member of the class
consisting of divalent aromatic and nuclearly
a. (Ortho-acetamido anilino)
halogenated aromatic hydrocarbon radicals.
2. Chemical compounds corresponding to the
general formula
triazoles.
amino 1,2,4;
v
9. (Meta-acetamido
anilino)
amino
1,2,4
10. (Para-acetamido 'anilino)
amino
1,2,4
15 triazoles.
‘
triazoles.
'
'
11. The method of preparing chemical ‘com
pounds corresponding to 'the general formula
where R represents a member of the class con
20
sisting of hydrogen and monovalent hydrocarbon
radicals, R’ represents a monovalent hydrocarbon
' radical, and Z represents a divalent aromatic hy
drocarbon radical.
where R represents a member of the class con
-
sisting of hydrogen and monovalent hydrocarbon
3. Chemical compounds corresponding to the
general formula
' radicals, R’ represents a monovalent hydrocarbon‘
radical, and Z represents a member of theclass
-
consisting of divalent aromatic and nuclearly>
halogenated aromatic hydrocarbon radicals, said
method comprising effecting reaction under heat
between a hydrazine corresponding to the general
where R represents a member of the class con
sisting of hydrogen and monovalent hydrocarbon I
formula
radicals, R’ represents a monovalent hydrocarbon
radical, and Z represents a divalent aromatic hy
where R has the meaning above given, and an
drocarbon radical.
4. Chemical compounds corresponding to the
general formula
general formula
_
'
ac'ylaminoaryl biguanide corresponding ‘to the
NH
'
NH
.
o
NHi-g-—NH—g-NH—z-NR—<|i-R'
where R, R’ and Z have the meanings above given.
12. A method as in claim 11 wherein the re
action is carried out in the presence of an acid
effective in binding the ammonia liberated during
where R’ represents a monovalent hydrocarbon
radical and Z represents a divalent aromatic hy 45 the reaction.
13.. The method of preparing (para-acetamido
drocarbon radical. .
anilino) amino. 1,2,4-triazoles which comprises
5. Chemical compounds corresponding to the
effecting reaction under heat between (para
acetamido phenyl) biguanide and hydrazine hy
general formula
50 drate in the presence of an acid effective in bind
ing the ammonia liberated during the reaction.
whcre R’ represents a monovalent hydrocarbon
55
radical and Z represents aphenylene radical.
6. Chemical compounds corresponding to the
general formula
14. The method of preparing (para-acetamido
anilino) amino 1,2,4-triazoles which comprises
e?'ecting reaction under heat between (para
acetamido phenyl) biguanide hydrochloride and
hydrazine hydrate, the said reaction being carried
out in an aqueous solution containing hydro
chloric acid in an. amount su?icient to bind the
ammonia liberated during the reaction.
GAETANO F. D’ALELIO.
CERTIFICATE OF CORRECTION.
Patent No. 257L555.
April 21;, 19Li5.
GAE'I‘ANO F. D'ALELIO.
It is hereby certified that error appears in the printed specification
of the above numbered patent requiring correcti on as follows: Page 1, first
column, line 50, between formula III and formula IV insert the word
"and"; and second column, line 50, for "actophenylene, actoxyphenylene"
read —-acetophenylene, acetoxyphenylene--; page 5, first column, lines
27 to 57 inclusive, for that portion of the formula readingv "H511" read
—-H2N--; and second column, line 57, after the syllable "nide" strike out
"of"; page 14., second column, line 19, for "H20" read —-H5C-—; line 55, for
"amido" read —-amino——; and that the said Letters Patent should be read I
with this correction therein that the same may conform to the record of
the case in the Patent Office.
Signed and sealed this 10th day of July, A. D. 1911.5.
Leslie Frazer
(Seal)
Acting Commissioner of Patents.
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