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Патент USA US2403790

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Patented July 9, 1946
' ‘2,403,790
UNITED STATES, PAT ENT 'iOF-FICE
’
12,403,790
METHOD ‘OFIPREPARING , ‘DIAzIN-E
‘V
DERIVATIVE '
Gaetano F. DfAlelio and James:wp?iierwota;
Pitts?eld, Mass, 'as'signors : “"Géiiéial Elec- " '
tric Company, a corporatior'iof New York‘ ,
No Drawing‘... Application September I, 1942,
-
7 Serial No. 456,929
'
c
1 Claim. (01. 2604451’)
2
This invention relates, to the preparation’ of ‘- one'o'r more of their hydrogen atoms substituted
diazine derivatives-Which: areembraced by the‘
by, for example, a halogen, .more particularly
following general formula:
chlorine, ‘bromine, ?uorine or iodine. Speci?c
I
.
,
'
'
1
C\
ll
0
N
V
V
-.
A
In the above formula 12 represents an integer-arid
is at least I- and not more ‘than 2,-R1representsa' '
member, of the class consisting of hydrogen ‘and
monovalenthydrocarbon and substituted hydro-~
V :ITL-GNI‘HRM
examples of halogeno-substituted hydrocarbon
radicals that R in. the’ above formula may rep
resent are: chloromethyl, chloroethyl, chloro
phenyl, dichlorophenyl, ethyl chlorophenyl, ch10
carbon-radicals, more particularly halo-hydrocar= 15 rocyclohexyl, phenyl-r chloroethyl, bromoethyl, I
bon radicals, and Z represents a member of the
bromopropyl, \?‘uorophenyll, liodophenyl, \bromo
class consisting of oxygen and sulfur. Morer'par
ticularly the invention is concerned with ‘certain
toly'l,‘etc. ' .Preferab-ly'R 'is hydrogen. ‘ However,
there also may be ‘produced in» accordance with
new and useful improvements in a-method of
the present invention compounds such, for in
Illustrative examples of radicals that R in For- '
Where n (Formula II), R and Z (Formulas II, III
mula I may represent are: aliphatic (e. g;, methyl, I 45 and IV) have the same meanings
as
v
ethyl, propyl, isopropyl, butyl; 's’econdary‘but'yl,
isobutyl, butenyl, amyl, isoamyl, 'hexyl', etc.),"'iri-‘
eluding cycloaliphatic (e; g., cyclopentyl,‘ cycloe"
pentenyl, cyclohexyl; jcyclohexenyl, cycloheptyl,
etc.) ; aryl (e. g.,'phenyl, diphenyl or Xenyl, naph
with reference to Formula I.
given above
c
h '
The compounds embraced by Formula I maybe
used, for example, as pharmaceuticals; plasti
cizers,fungicides, bactericides, insecticides,»_a_s ad
ditives to petroleum products, as an intermedi
thyl, etc.); aliphatic-substituted‘ aryl (e. g.,.toly1, 50 ate in the preparation of dyes, drugs, textile as
xylyl, ethylphenyl, propylphenyl, isopropylphenyl,“ sistants and other chemical compounds, for in
allylphenyl, Z-butenylphenyl, tertiary-butylphen
stanc'e‘as .an intermediatein- producing deriva
yl, etc.) ; aryl-substituted aliphatic (e. g., benzyl,
tives thereof such asureido, hydrazine, carbainyl,
cinnamyl, phenylethyl, phenylpropyl, etc.) ; and. amidine,=inethylol, methylene, ‘etcl, derivatives of
their?homologueai as well as those groupsiwithr 55 --the individual compound represented byrtrmina
2,403,790
l4 ,
3
2-mercapto 4,6-di-cyc1opentylamino) 5-ethyl py
I. These compounds are especially valuable in
the preparation of synthetic resinous composi
tions.
rimidine
2-mercapto 4,6-dianilino pyrimidine
Z-mercapto 4,6-ditoluido 5-iodophenyl pyrimi
Thus, they may be condensed with, for
example, aldehydes, including polymeric alde
hydes, hydroxyaldehydes and aldehyde-addition
products to yield condensation products having
dine
2-mercapto 4,6-dixy1idino pyrimidine
2-mercapto 4,6-di-(phenethylamino)
particular utility in the plastics and coating arts.
Such condensation products are more fully de
_
'
- 2-mercapto
scribed and are speci?cally claimed in our co
10
pending application Serial No. 461,770,1‘iled Oc
tober 12, 1942, and assigned to the same assignee
5-butyl
pyrimidine
4,6-di-(ethy1phenylamino)
5-tolyl
pyrimidine‘ '
‘4-mercapto 2,6-di-(methylamino) 5-methy1 py
as the present invention. These compounds also
rimidine
v
2-mercapto ,.4,6-di<(chloroethylamino) pyrimi
may be compounded with rubber, both natural and
synthetic, to modify the propertiesfof the rubber.‘
Maine
7
For instance, they may be used to accelerate or
I- _2-mercapto 4,6—di-(bromoxy1idino) 5-chloroethyl
otherwise facilitate the vulcanization of natural
2-mercapto, 4,6-diamino 5-bromotoly1 pyrimidine
pyrimidine
and synthetic rubbers. Instead of using the com; ‘
< 2-mercapto 4,6-di-(iodoani1ino) pyrimidine
pounds in the form shown in Formulall, they
may be used in the form of their salts in such ap
plications as above'mentioned by way of illus
Z-mercapto 4-al1y1amino ?-butylamino pyrimi
dine
_
»
‘
4-mercapto 2,6-di-(methylamino) pyrimidine
tration.
Z-mercapto 4,6-di-(methylamino) 5-methyl py
Various methods may be employed to produce
the chemical compounds embraced by Formula
I. We prefer to prepare them by effecting reac
rimidine
‘
‘l-mercapto 2,6-di-(methy1amino) 5-pheny1 py
tion, in the presence of a hydrohalide acceptor,
between (1) a mercapto- diamino [(——NHR)2]_
pyrimidine corresponding to the general formula A g
rimidine
‘
2-mercapto 4-chloroethy1amino 6—methylamin0
pyrimidine
'
2-mercapto 4,6-dianilino 5-buty1 pyrimidine
2-mercapto 4-Xeny1amino 5-cyclohexenyl ?-ami
. no pyrimidine
30
Z-toluidb 4-mercapto 5-cyclopenty1 ‘ti-amino py
rimidine
~
-
-
v
‘
7
I
2-mercapto 4,6-di-(propylamino) pyrimidine
’
2-allylamino 4-mercapto ?-chloroanilino pyrimi
Where R has the same meaning as given above
with reference to Formula I and (2) a di-(halo
alkyl) ether corresponding to the general formula
VI
XCnR27l'—Z-—C7LR21LX
Where X represents a halogen atomyand n, Z
dine
-
2-penty1amino 4-mercapto S-phenyl G-amino py
rimidine
v
3
‘
v
'
2-dichloroanilino 4-mercapto ‘5-toly1 ?-propyl
amino pyrimidine
v
2-cycloheptylamino é-mercapto G-butylamino py
and R have the same meanings as given above
rimidine
with reference to Formula I, the reactants being
Z-mercapto 4-(3’-butenylamino) ?-isopropylami
employed in the ratio of at least two mols oi the
mercapto diamino pyrimidine of (1) per mol of
‘
no pyrimidine
It will‘be noted , '
Illustrative examples of di-(haloalkyl) ethers
that when R in- Formula VI represents hydro- -> .
that may be used, depending upon the particular
end-product desired, are:
the di-(haloalkyl) ether or (2).
gen, the compound may be represented by the
formula
‘ ' 1' Di- (chloromethyl) ether
Di-(bromomethyl) ether
Illustrative examples of mercapto diamino 50 ' Di- ( alpha-chloroethyl) ether
> Di-(alpha-bro-moethyl) ether
[(-NHR)2] diazines that may be employed, de
pending upon the 'desired end-product, are: 1
' Di-(beta-chloroethyl) ether
‘ _Di-_(beta-br0moethyl) ether
n -
2-mercapto, 4,6 diamino pyrimidine
4-mercapto 2,6-diamino pyrimidine (G-mercapto
ZA-diamino pyrimidine)
2-mercapto 4,6-diamino 5-methyl pyrimidine
ll-mercapto 2,6-diamino 5-ethy1 pyrimidine
Z-mercapto 4,6-diamino 5-pheny1 pyrimidine
Z-mercapto é-bromotoluido G-benzylamino py-.
Di-(beta-iodoethyl) ether
Di-(alpha-chloroethyl) thioether
55
Di-(alpha-bromoethyl) thioether
Di- (beta-chloroethyl) thioether
_
Chloromethyl beta-chloroethyl ether
Bromomethyl beta-bromoethyl thioether
rimidine
Di-(beta-gchloropropyl) ether
2-toluido ll-mercapto 6-methylamino pyrimidine _
2-mercapto Ll-phenylchloroethylamino 6-phen
ethylamino pyrimidine
Z-mercapto e-chloroanilino G-phenethylamino
pyrimidine
2-mercapto 4-cycloheptylamino ?-isopropylamino
pyrimidine
'
I
2-mercapto 4,6-di-(methylamino) pyrimidine
Z-mercapto 4,6-di-(ethylamino) 5-?uorophenyl
pyrimidine
'
Z-mercapto 4,6-di-(?uoroanilino) pyrimidine
Di-(beta-bromoethyl) thioether
Di-(beta-bromopropyl) ether
Di-(beta-chloropropyl) thioether
Di-(beta-bromopropyl) thioether
65
.
Di-(alpha-phenyl beta-bromomethyl) thioether
Di-(a'lpha-phenyl beta-chloroethyl) ether
Chloromethyl beta-chlorobutyl ether
Chloromethyl beta-chlorobutyl thioether
Di-(alpha-chlorobuten-3-Yl) ether
Di-v(alpha-bromobuten-3-yl) thioether
Various 1 hydrohalide' acceptors may be em
ployed.
We prefer to use a hydrohalide acceptor
2-mercapto ll-propenylamino G-amino pyrimidine
that will react with the mercapto pyrimidine to
Z-mercapto 4,6-di-(benzylamino) 5-_methyl py
75 form ‘a water-soluble salt. Examples of such ac-
2-mercapto 4-methylamino 6-amino pyrimidine
rimidine
'
-
'
-
2303,7901'1
ceptors are the alkali=metalYhydroxides;e;1:5g.l»
sodium hydroxide, potassium " hydroxide,. etc.
Additional examples of hydrohalide acceptors .
that may be used are other inorganic‘ bases; e; ign,
calcium'hydroxide, barium hydroxide‘, ammonium
temperature of the mass for 7 hours. ‘After 0001-: 7
ing', the dprecipitated‘ product comprising
diethyl ether was‘ ?ltered off, washed well with
water to remove s’oluble‘salts and dried.- ' ‘ A yield
hydroxide, etc. ; carbonates of inorganic bases, in
of 158parts'of the puri?ed and dried material
cluding the carbonates of alkali metalsyorganic
was obtained. No attempt was made to recover
amines such as tertiary amines, e.- g.,;trimethyl
any more product from the mother liquor. "
. amine,
dimethyltriethyl
aniline,amine,
quinoline,
tributyl
etc; amine,‘
quaternaryam
pyridine,
, Example 2
10"
monium bases, e. g., tetrameth-yl ammonium'hy; .i
I Beta,beta'-bis-(2,6-diamino pyrimidyl-4 thio): -,
droxide, etc.; and the like.
. .. . .
diethyl ether, which also may be named his- ;
[beta - (2,6 - diamino pyrimidyl-4 thio) ethyll
The reaction between, the mercapto ‘diamino
pyrimidine and the chosen‘ di- (haloalky-l') "ether
ether, is' prepared in essentially the same manner
may be carried out in any suitable manner,-but 15 as described under Example '1 with the exception,
preferably is effected in a suitablesolvent or mix- .
that 142 parts of é-mercapto 2,6-diaminopyrimii
dine are used in place of 142 parts of 2-mercapto
ture of solvents, e. g., water, alcohol, ether, ben
4,6-diamin'o pyrimidine. _
zene, dioxane, etc. Although. various solvents
and solvent mixtures may be‘ employed, forlec'o
nomic reasons and because of their eminent‘ suit 20
Beta,beta'-bis-(4,6-diamino pyrimidyl-2 thio)
ability-we prefer tol use water or a mixture ‘of
diethyl thioether’ is prepared in essentially the
water and alcohol; Theereaction' maybe-car
same manner as described under Example 1 with
ried out undera variety of temperatureiandpres-q
theyexception that 79.5 parts of di-(beta-chloro
sure conditions, for instan'cefat' normal, sub-nor-'
ethyl) thioether are used in place of '7la5parts‘of '
mal or at elevated temperatures and at'atmos'e-I
di-"(beta-chloroethyl) ether. '
ph'eric, sub-atmospheric, ,oru supereatmospheric
..
pressures.
,
,.
I
.
employ an alkali-metalhydroxide as the hydro- '
halide acceptor. ' WhenEa' non-aqueous solution
constitutes the liquid medium in which the re
-
g
'
'
‘
'
v
Beta,beta‘’-bis-(4,6-diamino pyrimidyl-Zl thio).
ethyl isopropyl ether, which also may be named -
beta-’(4,6-diamino pyrimidyl-Z thio) ethyl, beta-f
(4,6-diamino pyrimidyl-Z . thio) isopropyl ether,
action is effected, th'en it isusually desirableto
employ a tertiary amine, e. g.,~pyridine', as them"
drohalide acceptor.
3
Examjole 4 ' 7"
When th'e~..reaction isicarried out .in '
an aqueous solution‘ it. is usually p‘referablefto
Example
is prepared in essentially the same manner as de
scribed under Example 1 withthe exception that _ _.
78.5 parts of beta-chloroethyl beta-chloroiso
-
The above reaction maybe represented by the 35 propyl ether are used instead of 71.5 parts of di
following general equationt' '.
‘ 1
(betaéc'hloroethyl)
In- the above equation}; _:.re,presents1ar halogen.~
atom, and n, R and Z:have the same meanings a g. 1 50
given above with reference to Formula I5;
_ ’
In order that those skilleddnI-the artxbetter.
may understand how the present invention may
This example illustrates the preparation .of
diethyl ether, which‘ also may be named bis-"1
[beta 402,6 - diamino pyrimidyl-Z thio) ethyl]
'
,
_
Parts
.
Approx.
mol ratio
,
Example 5'
Beta,beta’-bis-[4,6-di - (methylamino) pyrim
idyl-2' thio] diethyl ether is prepared in essen
Vmercapto 4,6-di-(methylamino) pyrimidine are
used in place of ‘142 parts of 2-mercapto 4,6-di
amino pyrimidine.
,
beta,beta' - bis - (4,6-diamino -pyrimidyl'-2 thio)
ether.
‘
ample 1 with the exception that 170 parts of 2
given by way of illustration. and not by way of.
limitation. All parts, are by;weig~ht-.
'
7
tially thesame manner as described under Ex
be carried into effect;the»following examples‘are ,
Example 1 '1 55
ether.
'
’
'
'
‘
Example
6
1Beta,beta'-.bis-(4,6-diamino pyrimidyl-Z ' thio)
to dipropyl ether, which also may be named .bis
[beta-‘(4,6-diamino pyrimidyl-Z thio) propyll
ether, is prepared in essentially the same manner
as described under Example 1 with the exception
that 85.5 parts of di-(beta-chloropropyl) ether
are used invplace ofv 71.5 parts of di-(beta-chlo
methyl)
ether.
Similarly
bis - [beta-(4,6 - di
amino pyrimidyl-Z thio) isopropyl] ether is pre
Sodium hydroxide in mixture of 500 parts
pared by using 85.5 parts of di-(beta-chloroiso_
water and 500 parts alcohol ________________ __
40. 0
2
propyl) ether instead of 715 parts of di-(beta
Di-(beta-chloroethyl) ether __________________ __
71. 5
l 70
chloroethyl) ether as in Example 1.
Example 7
The ?rst two components were mixed and a
clear solution obtained. The di-(beta-chloro
Beta,beta’-bis- (2,6-diaminopyrimidyl 1- 4 thio)
2-mercapto 4,6-diamino pyrimidine __________ __
142. 0
2
ethyl) ether was now added and the resulting
dipropyl ether and vbeta,beta'-:bis-(2,6-diamino
mixture was heated under re?ux at the boiling 75 pyrimidyl-4 thio) di-isopropyl ether are prepared
8
7
Alpha; alpha'-bis-(4,6-diamino pyrimidyl-2 thio)
in essentially the same manner as described un
der Example 1 with the exception that 85.5 parts ,
of 'di-(beta-chloropropyl) ether or of- di-(beta
diethyl thioether
.'
.
'
‘
Alpha,alpha'-bisr(4,6-diamino pyrimidyl-Z thio)
diprOpyl ether
‘
l
V
:
Alpha,alpha"-bis-(4,6-diamino pyrimidyl-2 thio)
lpr'opyl butyl ether
v
'
:diethyl thioether
chloroisopropyl) ether are used instead ofl71.5
parts of di- (beta-chloroethyl) ether and 142 parts
of li-mercapto 2,6-diamino pyrimidine are used
in place of 142 parts of 2-mercapto 4,6-‘diamino‘
pyrimidine.
"
Alpha, alpha'ebis- (2,6ediamino pyrimidyl-4 thio)
'
'
'
V
,
v
Alpha,beta'-(4,6'-di'amino pyrimidyl-Z thio) bu
Illustrative examples of other compounds em_
ten-3'-yl butyl ether
braced by Formula I that may be produced in 10
Beta,beta'-bis-[4,6
t-di - (?uoroanilino) pyrimid
accordance with the present invention are listed
y1-2 thioldiethyl etheruql.
below:
Beta,beta'-bis— [2,6-di- (methylamino) pyrimidyl
4 thio] diethyl ether
'
‘ pyrimidyI-Z
Beta,beta’ -bis- [4,6-di-_(ethy1amino)
thio] diethyl ether
7
V
"
'
'
‘ether
-:
'
'
'
'
iAlpha,alpha'-bis-[4,(i- dit- (bromotoluido) pyri
,
midyl-2 thiol dipropyl ether
Beta,beta’-bis-[4,6-di - (propenylamino) pyrimi
dyl-2 thio] diethyl ether
-
Beta,beta'-bis-(4',6-diamino 5-chloromethyl py
rimidyl-2 thio)» beta,beta’-dipheny1 diethyl
‘
'
'
Alpha,beta'-bis-(4,6-diamino 5-iodomethyl py
'
rimidyl-2 thio) ‘diethyl ether
Beta,beta'-bis- [4,6-di- (isobutylamino) pyrimidyl
‘
>
Alpha,:beta' -bis-‘ (4-methylamino ‘ 6 - ‘chloroethyl
2 thio] diethyl ether
amino pyrimidyl-2 thio) beta-phenyl alpha
Beta,beta'-bis- (4,6-diani1ino pyrimidyl-2 thio) di
ethyl ether
' Beta,-beta'-bis-(4,6-dianilino pyri-midyl-Z thio)
diethyl thioether
Beta,beta' -bis- [4,6-di- (methylamino) pyrimidyl
ethyldibutyl thioether'
rimidyle2 thio] diethyl ether
c
pyrimidyl-é‘thio] diethyl-thioether
‘ ‘
'
30'
'
diethyl thioether
Beta,beta'-bis- [2,6-.di- (iodotoluido) E-iodophenyl
pyrimidyl-4 thiol dipropyl ether
v
clohexyl pyrimidyl-2 thiol ‘diethyl ether
’
In a manner similar to that» described 'above
Beta,beta'-bis- [4,6-di- (phenethylamino) pyrimi
dyl-2 thio] diethyl ether
‘
‘
»
35 Beta,beta'-bis-[4,6 - di - icyclohexylamino) 5-cy
Beta,beta'-bis-(2,6-diamino 5-ethyl pyrimidyl-4
thio) diethyl thioether
5 — butyl
pyrimidyl-2 thio] diethyl thioether
Beta,beta’-bis-(4,6-diamino 5-methy1 pyrimidyl
2 thio) diethyl ether ‘
5-chl0ro
phenyl pyrimidy1-2 thio] diethyl ether
Beta,beta'-bis-[4,6 - di v-(chloroanilin'o)
Beta,beta'-bis'-(4,6-ditoluido pyrimidyl-2 thio)
5 - xenyl
‘
Beta,beta'-bis-[4,6 -‘ di - (octylamino) ‘
Beta,beta'-bis-(4,6-dixylidino pyrimidyl-2 thio)
diethyl ether
'
rimidyl-2 thio] dipropylthioether
Beta,betaf -bis_ [2,6-di- (naphthylamino)
Beta,beta'-bis-(4,6-ditoluido pyrimidyl-Q thio)
7
'
Beta,beta’t-bis-[4,6-di-(al1y1amino)
2 thio] diethyl thioether
diethy1 ether
.
Beta, ' beta’-bis- [4,6-di-'(cyclohexenylamino)
with particular reference to the preparation of
"
Beta;beta’ -bis- ] 4,6-di- (ethylanilino) pyrimidyl-Z V40 :bis-(LB-gdiazinyl thio), that is, bis-(pyrimidyl
thio), dialkyl ethers ‘and thioethers, correspond
thio] diethyl ether
"
-
ing derivatives of 1the 1,2- or vortho-diazines
(pyridazines) ‘and of the 1,4- or para-diazines
Beta,beta’-bis-(4,6-diamino 5-pheny1 pyrimidyl-Z
thio) diethyl ether
(pyrazines) may be prepared.
Beta,beta'-bis- [4,6-di-(methy1amino) 5-ethy1 py-.
rimidy1-2 thio] diethyl ether
Bis-(4,6-diamino pyrimidyl-Z thio) dimethyl
ether
“
‘
45
The method ' 'of_, preparing beta,beta'-bis- (4,6
_
Bisl-(2,6-diamino pyrimidyl-4 thio)
diamino pyrimidy1-2 thio) diethyl ether which
comprises addingdi-(beta-chloroethyl) ether to
.a clear solution obtained ‘by mixing together ap
proximately equal molar ratios of 2-mercapto
dimethyl
ether
Bis- (4,6-diamino pyr'imidyl-Z thio) dimethyl thio
ether
-
Bis-(2,6-diamino pyrimidyl-4 thio) ‘dimethyl “119-
-
ether
Bis-(4,6-diamino 5-methy1 pyrimidyl-Z ‘thio). di-f _"
methyl ether
4,6-diamino pyrimidine and sodium hydroxide
dissolved in a mixture of ‘water and alcohol, the
molar. amount of di-(beta-chloroethyl) ether
P being approximately one-half- that of the molar
amount of 2-mercapto 4,6-diamino pyrimidine,
Bis-(2,6-diamino 5-phenyl pyrimidyl-é thio)‘ dri- :
heating the resulting mixture under re?ux at the
boiling temperature of the mass for a period of
methyl thioether
Bis-[4,6-di-(methy1amino) pyrimidy1-2 thiol di- '
methyl ether
Bis-(4,6-dianilino pyrimidyl-Z thio) dimethyl
ether
'
‘
'
Bis-(4-methylamin0 G-‘anilino pyrimidyl-Z
dimethyl
ether
.
'
'
'
'
-
'
"thio)
.
r
'
Alpha,beta'--bis-(4,6-diamino pyrimidyl-Z thio)
methyl ethyl ether
’
1
'
'
Alpha, alpha'-bi's-(4,6-diamino pyrimidyl-2 thio) ‘
Alpha,
diethyl
a1pha'-bisether
(2,6-diamino
,
pyrimidyl-4
.,
. thio)‘
__
diethyl ether
_
What we claim asnew and desire to secure
by Letters Patent of the United .States is:
a
the order of 7 hours, ?ltering off the precipitate
CO
comprising beta,beta'-bis-(4,6-diamino pyrim
idyl-2 thio) diethyl ether that separates upon
cooling the mass, washing the said precipitate
with water to remove soluble salts, and drying
the Washed material.
GAETANO F. D’ALELIO.
JAMES W. UNDERWOOD.
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