Note: Descriptions are shown in the official language in which they were submitted.
1228~57
The invention relates to new sulphonylguanidinotriazine
derivatives, processes for their preparation and their use as
herbicides.
A divisional application, divided out of this application
relates to new sulphonyl-iso-thioureido-triazine derivatives of
the formula VIVA (hereinafter defined) and to their preparation.
The compounds of formula VIVA are intermediates useful in preparing
the herbicidally active compounds of the present invention.
Various guanidine derivatives have been disclosed as
potential herbicides from patent specifications (compare DE-AS
(German Published Specification) 1,089,210 and East German Patent
Specifications 71,016 and 84,530), but they have not hitherto
achieved relatively great importance as agents for combating weeds
and/or regulating plant growth. Other guanidine derivatives are
known (compare DEMOS (German Published Specification) 3,344,455).
According to one aspect of the present invention there
is provided new sulphonylguanidinotriazine derivatives of the
general formula (I) R4
Rl-SO2-N \ / N I/ N
I R5 (I)
/ N \
R2 \ R3
in which
M represents hydrogen or one equivalent of a metal,
Al represents an optionally substituted phenol radical
I'
~2283S7
wherein
R6 and R7 are identical or different and represent
hydrogen, halogen (such as, in particular, fluorine, chlorine,
and/or bromide), cyan, vitro or Cl-C4-alkyl (which is optionally
substituted by fluorine, chlorine, bromide, cyan, Cl-C4-alkoxy-
carbonyl, C1-C4-alkylamino-carbonyl, di-(Cl-C4-alkyl)-amino-
carbonyl, Cl-C4-al.koxy,
- lo -
;
` 1228357
- 2 -
C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-
C4-alkyl-sulphonyl), or represent C1-C4-alkoxy
(which is optionally substituted by fluorine,
chlorine, bromide, cyan, C1-C4-alkoxy-carbonyl,
C1-C4-alkXY~ C1-C4-alkylthio, C1-C4-alkyl-
sulphinyl or C1-c4-alkylsulphonyl)~ or represent
C1-C4-aLkylthjo~ C1-c4-alkYlsulphinyl~ or
represent C1-c4-alkylsulphonyl (whir are optionally
substituted by fluorine, chlorine, bromide, cyan or
C1-c4-alkoxy-carbonyl)~ or represent C1-C4-
alkylamino-sulphonyl, di-(C1-C4-alkYl)-amino-
sulphonyl, C1-C4-alkoxyamino-sulphonyl, benzyloxy~
aminosulphonyl or C1-C4-alkoxy-C1-C4~alkYl-
aminosulphonyl, or represent phenol or phonics, or
represent C1-C4-alkoxysulphonyl, or represent
C~-c6-alkenyl (which is optionally substituted by
fluorine, chlorine, bromide, cyan, C1-C4-alkoxy-
carbonyl, carboxyl or phenol), or represent C2-C6-
alkinyl (which is optionally substituted by fluorine,
chlorine, bromide, c / C1-C4 alkoxY car y
or represent Schick (which is optionally
substituted by fluorine, chlorine, bromide, cyan or
C1-C4-alkoxycarbonyl), or represent C3-C6-
alkenylthio (which is optionally substituted by
I fluorine, chlorine, bromide, cyan or C1-C4-alkoxy-
carbonyl), or represent C1-c6-alkoxy-carbonyL
(which is optionally substituted by fluorine, chlorine,
bromide, cyan or C1-C4-alkoxy)~ or represent C3-
C6-cycloalkoxy-carbonyl, or represent C1-C6-
alkylthio-carbonyl (which is optionally substituted by
fluorine, chlorine, bromide, cyan or C1-C4-alkoxy-
carbonyl), or represent aminocarbonyl, C1-C4-
alkylamino-carbonyl, di-(c1-c4-alkyl)-amino-
carbonyl, C1-C4-alkoxyamino-carbonyl, C3-C4-
alkenyloxy-amino-carbonyl, benzyloxyamino-carbonyl,
lo A 23 308 - Foreign Countries
` - 3 - 1228~57
C1~C4~alkoXY~C1~C4-alkyl-amino-carbonyl,
dimethyl-hydrazino-carbonyl, or dimethyl-hydrazino-
sulphonyl, or represent C3-C6-alkinyloxy or C3-
C6-alkinylthio,
or in which, furthermore,
R1 represents an optionally substituted bouncily radical
B
SHEA-
R9
wherein
R8 and R9 are identical or different and represent
hydrogen, halogen (such as, in particular,
fluorine, chlorine or bromide), cyan, vitro, C1-
colloquial (which is optionally substituted by
fluorine and/or chlorine), C1-C4-alkoxy which is
optionally substituted by fluorine and/or color-
fine), C1-C4-alkoxycarbonyl, Cl-C4-alkylthio,
C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl or
di~(C1-C4-alkyl)-aminosulphonyl;
and in which, furthermore,
R2 represents hydrogen, C1-c4-alkyl or a
AL sulphonyl radical R10-so2
wherein
R10 represents C1-C12-alkyl (which is
optionally substituted by fluorine, chlorine,
bromide, cyan, vitro, C1-C4-alkoxy-carbonyl,
C1-C4-alkylamino-carbonyl, di-(C1-C4-
alkyl)-amino-carbonyl, C1-c4-alkoxy~ C1-C4-
alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkYl
sulphonyl), or represents C1-C12-alkoxy (which
is optionally substituted by fluorine, chlorine,
bromide, cyan, vitro, C1-C4-alkoxycarbonyl,
C1-C4-alkXY~ Cl~C4-alkylth joy C1-C4-alkyl-
sulphinyl or C1-C4-alkylsulphonyl)~ or represents
C2-C12-alkenyl (which is optionally substituted
lo A 23 308 - Foreign Countries
_ 4 _ ~22~57
by fluorine, chlorine, bromide, cyan, vitro, C1-
C4-alkoxy, C1-C4-alkYlthio or phenol), or
represents C~-c1z-alkenyloxy which is
optionally substituted by fluorine, chlorine,
bromide, cyan, vitro, C1-C4-alkoxy, C1-C4-
alkylthio or phenol), or represents C1-C8~
alkylamino, di~(C1-c4-alkyl)-amino~ C3-C6-
cycloalkylamino or di-(C3-C6-cycloalkyl)-amino
(which are optionally substituted by fluorine,
chlorine, bromide, cyan, vitro, phenol, phonics,
C1-c4-alkoxy, C1~C4-alkylthio~ C1-C4-
alkylsulphinyl or c1-c4-alkylsulphonyl)~ or
represents C2-c~-alkenylamino (which is
optionally substituted by fluorine, chlorine,
bromide, cyan, vitro or phenol), or represents
phenylamino or benzylamino (which are optionally
substituted by fluorine, chlorine, bromide, C1-
Colloquial, trifluoromethyl, C1-C4-alkoxy,
C1-C2-f~UOrOaLkOXY, C1-c4-alkylthio~ C1-
C4~alkY~sUlPhinY~, C1-c4-a~kylsulphony~
cyan, vitro and/or C1-c4-alkoxy-carbonyl)~ or
represents bouncily (which is optionally substituted
by fluorine, chlorine, bromide, cyan, vitro, C1-
Colloquial, trifluoromethyl, C1-C4-alkoxY-
carbonyl, Cl-c4-alkoxy or di-(c1-c4-alkyl)-
aminosulphonyl), or represents an optionally subset-
tuned phenol radical
R1l
R12
wherein
R11 an R12 are identical or different and have the
meanings given above for R6 and R7, but are not ides-
tidal to R6 and R7 in each individual case;
and in which, furthermore,
R3 represents the radical -o'er,
lo A 23 308 - Foreign Countries
12283S7
-- 5
wherein
R13 represents C1-C12-alkyl (which is optionally
substituted by fluorine, chlorine, bromide, C1-C4-
alkoxy~ C1-C4-alkYlthiO, Cl-c4-alkylsulphinyl
or C1-C4-alkylsulphonyl), or represents C3-C6-
cycloalkyl, C3-c6-cycloalkyl-c1-c2-alkyl~ C3-
c6-alkenYl (which is optionally substituted by
fluorine, chlorine or bromide), C3-C6-alkinyl,
C1-C4-alkoxy-carbonyl-C1-C2~alkyl~ amino-
I carbonyl-methyl, C1-c4-alkylamino-carbonyl-methyl
or di-(cl-c4-alkyl)-amino-carbonyl-methyl~ or
represents phenol, bouncily or phenethyl which are
optionally substituted by fluorine, chlorine, vitro,
cyan, Cl-c4-alkyl~ C1-C4-alkoxy or C1-
c4-alkoxycarbonyl)i
or in which, furthermore, R14
R3 represents the radical -No
R15
wherein
R14 represents hydrogen or C1-C4-alkyl and
I R15 represents hydrogen, C1-C4-alkyl (which is
optionally substituted by fluorine, chlorine, brow
mine, cyan, C~-C4-alkoxy or C1-C4-alkoxy-carbo-
nil), or represents C3-C~-cycLoalkyl, or repro-
sets phenol, bouncily or phenethyl (which are opt
tonally substituted by fluorine, chlorine, brow
mine, cyan, vitro, C1-C4-alkyl, C1-C4-alkoxy
or C1-C4-alkoxy-carbonyl), or represents C1-C4-
alkyl-carbonyl, C1-C4-alkoxy-carbonyl, C1-C4-
alkyl-sulphonyl, or phenylsulphonyl (which is optionally
I substituted by fluorine, chlorine, bromide, cyan,
vitro or methyl);
or in which, furthermore - in the case where R2 represents a
sulphonyl radical
RUSS
- lo A I 308 - Foreign Countries
i228357
-- 6 --
wherein
R1~ has the above mentioned meaning -
R3 also represents hydrogen;
and in which, furthermore,
R4 represents fluorine, chlorine, bromide, cycle-
propel or C1-C4-alkyl (which is optionally subset-
tuned by fluorine and/or chlorine), or represents
C1-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), or represents C1-C4-
MU alkylthio (which is optionally substituted by
fluorine and/or chlorine), or represents C1-C4-
alkyd- or di-(c1-c4-alkyl)-amino (which are option-
ally substituted by fluorine) and
R5 represents fluorine, chlorine, bromide, cycle-
propel, C1-c4-alkyl (which is optionally subset-
tuned by fluorine and/or chlorine), or represents
C1-c4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), or represents C1-C4-
alkylthio (which is optionally substituted by
fluorine and/or chlorine), or represents C1-C4-
alkyd- or di~(C1-C4-alkyl)-amino (which are
optionally substituted by fluorine),
and 1:1 adduces of compounds of the formula (I) with
strong acids, have now been found, the following compounds
being excluded: N'-(4-methoxy-6-methyl-s-triazin-2'yl)-
h"-dimethylamino-N"'-(2-difluoromethoxy-benzenesullphonyl)-
guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N"-methoxy-
N",h"'-bis-(2-trifluoromethyl-benzenesulphonyl)-guundone,
N'-(4-dimethylamino-6-methyl-s-triazin-Z-yl)-N"-meethics-
MU ~"'-(2-methyl-benzenesulphonyl)-guanidine and N'-(4-di-
methylamino-6-methyl-s-triazin-2-yl)-N"-dimethylamMinoan"'-
(2-methyl-benzenesulphonyl)-guanidine.
If I represents hydrogen, the general formula (I)
represents the individual tautomers of the formulae (IA)
and (IT)
lo A us 30~ - Foreign Countries
lZ28:357
-- 7 --
R 1 - 5 0 .. - N NH </ ON
G I\ / N=~R5 ( I A )
\ 3
R 1 - S 2 - NH N I N
N No R5 (It)
R2 \R3
in which
R1, R2, R3, R4 and R5 have the above mentioned
5 meanings,
and mixtures of the tautomers (IA) and (IT).
The mixing ratio IAMB depends on factors
which determine the state of aggregation, such as, for
example, the temperature, solvent and concentration.
In the case where R2 also represents hydrogen,
in addition to M, another tautomeric form (IT) is possible:
N~R4
Rl-502-NH NO
C/ N~R5 tic
in which R3
R1, R3, R4 and R5 have the above mentioned meanings.
to The new sulphonylguanidinotriazine derivatives of the
formula I) are obtained by a process in which
(a) in the case where M represents hydrogen, guanidinotri-
amine derivatives of the formula IT
H ' No; R4
C/ No R5 (II)
/ \ 3
lo A 23 308 - Foreign Countries
12~8357
-- 8 --
in which
R3, R4 and R5 have the above mentioned meanings,
are reacted with sulphonyl chlorides of the formula
(III )
Al -Seiko Tao )
in which
R1 has the above mentioned meaning,
in the presence of acid acceptors and if appropriate in
the presence of delineates; or
(b) in the case where M represents hydrogen and R2 repro-
sets hydrogen or C1-C4-alkyl~ the sulphonylguanidino~
treason derivatives obtainable by the process described
above under (a), of the formula (ID)
` H No R4
N No 5 (ID)
Al -S02 . -Rl 3
in which
R1, R4, R5 and R13 have the above mentioned
meanings,
are reacted with amino compounds of the formula (IV)
MU R2 (IV)
HO ~R3
in which
I represents hydrogen or C1-C4-alkyl and
R3 has the above mentioned meaning,
or with hydrochloride of amino compounds of the formula
(IV), if appropriate in the presence of acid acceptors and
if appropriate in the presence of delineates; or
(c) in the case where M represents hydrogen and R2 repro-
sets an optionally substituted sulphonyl radical
R1~_S02_
lo A 23 30B - Foreign Countries
1228357
_ 9 _
wherein
Rho has the above mentioned meaning,
sulphonylguanidinotriazine derivatives of the formula (If)
Rl-502-N HO I/ N (If)
H' N I
in which
R1, R3, R4 and R5 have the above mentioned
meanings,
are reacted with sulphonyl chlorides of the formula
(V)
R10-S02-Cl (V)
in which
R10 has the above mentioned meaning
in the presence of acid acceptors and if appropriate in
the presence of delineates; or
(d) also in the case where M represents hydrogen and
I represents an optionally substituted sulphonyl
radical
R1 Sue_
wherein
R10 has the above mentioned meaning,
sulphonylguanidinotriazine derivatives of the formula (VI)
OH ,' No R
RlO_So~ R3
lo A 23 3~8 - Foreign Countries
- 1 o - ~2~8~57
in which
R3, R4, R5 and R10 have the above mentioned
meanings,
are reacted with sulphonyl chlorides of the formula
( I I I )
Rl-SOz~C l ~III)
in which
R1 has the above mentioned meaning,
in the presence of acid acceptors and if appropriate in
the presence of delineates; or
(e) in the case where M represents hydrogen and RZ repro-
sets hydrogen or C1-C4-alkyl, sulphonylisothioureido-
Rosen derivatives of the formula (VII)
I N=CR5 (VII)
s
\R16
in which
R1, R4 and R5 have the above mentioned meanings
and
R16 represents C1-C4-alkyl or bouncily,
are reacted with amino compounds of the formula tip)
Ho (IV)
in which
RZ represents hydrogen or C1-C4-alkyl-and
R3 has the above mentioned meaning
if appropriate in the presence of delineates; or
(f) in the case where M represents one equivalent of a me-
tat, the compounds obtainable by the processes described
above under (a), tub), (c), id) and (e) of the formula tip
in which if represents hydrogen and R1, RZ, R3, R4 and R5
have the above mentioned meanings, are reacted with metal
hydroxides, hydrides or alkanolates or with organometallic
lo A 2-S 3~8 - Foreign Countries
I :8~5~7
- 11 -
compounds, if appropriate in the presence of delineates; or
(go in the case where 1:1 adduces of compounds of the for
mute (I) with strong acids are to be prepared, compounds
of the formula (I) in which M represents hydrogen and R1,
R2, R3, R4, and R5 have the above mentioned meanings,
are reacted with strong acids, if appropriate in the pros-
once of delineates.
The new sulphonyLguanidinotriazine derivatives of
the formula (I) and their addicts with strong acids are0 distinguished by a powerful herbicidaL activity.
Surprisingly, the new compounds of the formula (I)
exhibit a considerably better herbicidaL action than
already known guanidines of the same type of action.
The invention preferably relates to compounds of
the formula (I)
in which
represents hydrogen or one equivalent of sodium,
potassium or calcium,
R1 represents an optionally substituted phenol
MU radical R6
wherein
R6 and R7 are identical or different and repro-
sent hydrogen, fluorine, chorine, bromide, cyan,
I vitro or methyl (which is optionally substituted
by fluorine, chlorine, cyan, C1-C3-aLkoxy-carbo-
Noah C1-Cs~aLkOXY~ C1~C3-aLkyLthjo~ C1-C3-
alkyLsuLphinyL or C1-c3-alkylsulphonyL)~ or rep-
resent C1-c~-alkoxy (which is optionally sub-
I stituted by fluorine, chlorine, cyan, c1-c3-alkoxY
carbonyl, C1-c3-alkOxy~ C1-C3-alkylthio, I
Cs-alkyLsulphinyl or C1-C3-aLkYlsuLphonyl), or
represent C1-C3-alkyLthio, C1-C3-alkyLsulphinyl
or C1-C3-aLkyLsuLphonyl (which are optionally
lo A 23 308 - Foreign Countries
~21~357
- 12 -
substituted by fluorine, chlorine, cyan or C1-
C3-alkoxy-carbonyl), or represent Dick-
C3-alkyl)-aminosulphonyl, C1-C3-alkoxy-
methyl-aminosulphonyl, phenol or phonics, or
represent C1-C4-alkoxy-carbonyl (which is
optionally substituted by fluorine, chlorine,
brom;ne, cyan or C1-C3-alkoxy), C3-C6-
cycloalkyloxy-carbonyl, C1-C4-alkYlthio-
carbonyl, di-(C1-C3-alkyl)-amino-carbonyl or
C1-C3-alkoxy-methylamino-carbonyl or no-
present C2-C4-alkenyl (which us optionally
substituted by fluorine, chlorine, cyan or C1-
C3-alkoxy-carbonyl);
or in which, furthermore,
R1 represents an optionally substituted bouncily
radical R8
SHEA--
wherein R9
R8 and R9 are identical or different and represent
hydrogen, fluorine, chlorine, cyan, vitro, methyl,
methoxy or C1-C3-alkoxy-carbonyl;
and in which, furthermore,
R2 represents hydrogen, methyl or a sulphonyl
radical
R10-S02_
wherein
R10 represents C1-C8-alkyl (which is optionally
substituted by fluorine, chlorine or cyan), or
. represents C1-C8-alkoxy (which us optionally
substituted by fluorine, chlorine or cyan), or
represents C2-C8-alkenyl (which is optionally
substituted by fluorine, chlorine, cyan or phenol),
or represents C2-C8-alkenyloxy (which is
optionally substituted by fluorine, chlorine, cyan
lo A 23 308 - Foreign Countries
~228357
- 13 -
or phenol), or represents C1-C6-alkylamino, C3-C6-
cycloalkylamino or di-(C3-C6-alkyl)-amino (which are
optionally substituted by fluorine, chlorine, cyan,
phenol, phonics or C1-C2-alkoxy), or represents
C2-C6-alkenylamino (which is optionally subset-
tuned by fluorine, chlorine, cyan or phenol), or
represents phenylamino or benzylamino (which are
optionally substituted by fluorine, chlorine, bromide,
C1-C4-alkyl, trifluoromethyl, C1-C3-alkoxy,
C1-C2-fluoroalkoxy, C1-C3-alkylthio, C1-
alkylsulphinyl, C1-C3-alkylsulphonyl, cyan,
vitro and/or C1-C3-alkoxy-carbonyl), or represents
bouncily (which is optionally substituted by fluorine,
chlorine, cyan, vitro, methyl, methoxy and/or C1-
C2-alkoxy-carbonyl), or represents an optionally
substituted phenol radical
Al
R12
wherein
R11 and R12 are identical or different and have the
preferred meanings given above for R7 and R8, but
are not identical to R7 and R8 in each individual
case;
and in which, furthermore,
R3 represents the radical -o'er,
wherein
R13 represents C1-C8-alkyl which is optionally
substituted by fluorine or chlorine), or represents
C3-C6-alkenyl which is optionally substituted by
chlorine), or represents C1-C3-alkoxy-carbonyl-
C1-C2-alkyl, phenol, phenethyl or bouncily which
is optionally substituted by fluorine, chlorine
lo A 23 308 - Foreign Countries
` - 14 - 1228357
vitro, methyl, methoxy or C1-C2-alkoxy-carbonyl);
or in which, furthermore,
R3 represents the radical
/Rl4
-N
R15
wherein
R14 represents hydrogen or methyl and
5 represents hydrogen, C1-C3-alkyl (which is
optionally substituted by fluorine, chlorine,
I cyan, C1-C~-alkoxy or C1-C2-alkoxY-carbonyl),
or represents C3-c6-cyc~oa~ky~ phenol, bouncily or
phenethyl (which is optionally substituted by
fluorine, chlorine, bromide, vitro, cyan,
C1-C2-alkyl, C1-C~-alkoxy or C1-C2-alkoxy-car-
bony), or represents acutely, methoxycarbonyl,
benzenesulphonyl or toluenesu~phonyl;
and in which, furthermore,
R4 represents fluorine, chlorine, cyclopropyl or
methyl (which is optionally substituted by flu-
fine and/or chlorine), or represents C1-C3-alkoxy
(which is optionally substituted by fluorine and/
or chlorine), or represents C1-C3-alkylthio
(which is optionally substituted by fluorine and/
or chlorine), or represents C1-C3-a~ky~- or di-(C1-C3-
I alkyl)-amino (which are optionally substituted by
fluorine) and
US represents fluorine, chlorine, cyclopropyl
or methyl (which is optionally substituted by
fluorine and/or chlorine), or represents C1-C3-
I alkoxy (which is optionally substituted by flu-
fine and/or chlorine), or represents C1-C~-alkyl-
trio (which is optionally substituted by fluorine
and/or chlorine), or represents C1-C3-alkyl- or dip
lo A I 308 - Foreign Countries
- 15 - 12~8~57
(C1-C3-alkyl)-amino (which are optionally sub-
stituted by fluorine),
the compounds mentioned individually above being excluded.
The invention furthermore preferably relates to
1:1 adduces of compounds of the formula (I) - as defined
above, wherein M represents hydrogen - with hydrogen
halide acids, such as hydrogen chloride, hydrogen bromide
and hydrogen iodide, with sulfuric acid or triflers-
tic acid, with alkanesulphonic acids which have up to 4
I carbon atoms and are optionally substituted by fluorine
or chlorine, or with Bunsen- or naphthalene- sulphonic
acids, which are optionally substituted by fluorine, Shelley-
fine, bromide or methyl.
The invention particularly relates to compounds
of the formula (I)
in which
I represents hydrogen or one equivalent of sodium,
potassium or calcium,
R1 represents a substituted phenol radical
211 R~7 6
wherein
I represents fluorine chlorine, bromide, methyl,
trifluoromethyl, methoxy, difluoromethoxy, in-
fluoromethoxy, C1-C3-alkylthio, C1-C3-alkylsul
I phenol, c1-c3-alkYlsulphonyl~ dimethylaminosul-
phony, diethylaminosulphonyl, methoxymethylamino-
sulphonyl, phenol C1-C4
alkoxy-carbonyl, difluoromethylthio or trifler-
methylthio and
R7 represents hydrogen;L and in which, furthermore,
R2 represents hydrogen, methyl or a sulphonyl
radical
lo A 23 I - Foreign Countries
- 16 - i2~8357
ROY_
wherein
R10 represents Cl-c4-aLkyL (which is
optionally substituted by fluorine or chlorine),
or represents C1-C4-aLkyLamino or Dick-
C-~alkyl)-amino (which are optionally sub-
stituted by fluorine), or represents an optionally
substituted phenol radical
R l lo
12
ill wherein
R11 and R12 are identical or different and repro-
sent hydrogen, fluorine, chlorine, bromide, cyan,
vitro, methyl, trifluoromethyl, C1-C2-alkoxy
(which is optionally substituted by fluorine, Shelley-
fine, cyan or C1-C3-alkoxy-carbonyl), C1-
C3-aLkylthio~ C1-C3-alkylsulphinyL or C1-C3-
alkylsulphonyl (which are optionally substituted by
fluorine and/or chlorine), dimethylaminosulphonyl,
diethylaminosulphonyl, N-methoxy-N-methylamino-
MU sulphonyl, phenol or C1-C4-alkoxy-carbonyl (which .
is optionally substituted by fluorine, chlorine,
cyan or C1-C2-alkoxy~,
and in which, furthermore,
R3 represents the radical -o'er,
25 wherein
R13 represents C1-C4-alkyl~ C3-C4-alkenyl,
C1-C4-alkoxy-carbonyl-methyl, phenol, phenethyl
or bouncily (which is optionally substituted by
fluorine, chlorine, vitro, cyan, methyl, methoxy
MU or methoxycarbonyl), -
or in which, furthermore,
R3 represents the radical
lo A us MU - Foreign Countries
` - 17 - 12~8~7
R14
~R15
wherein
R~4 represents hydrogen or methyl and
R15 represents hydrogen, C1-C-S-alkYl~ C3-C6-
cycloalkyl, phenol, acutely, methoxycarbonyl, bent
zenesulphonyl or toLuenesulphonyl;
and in which, furthermore,
R4 represents methyl, methoxy, ethics, methylthio,
ethylthio, methyl amino, ethyl amino, dimethylamino
or diethylamino and
R5 represents methyl, methoxy, ethics, methylthio,
ethylthio~ methyl amino, ethyl amino, dimethylamino
or aiethylamino,
- the compounds mentioned individually above being exile-
dyed - and - in the case where M represents hydrogen - the
1:1 adduces of the compounds defined above with hydrochloric
acid, sulfuric acid, trifluoroacetic acid, methanesulpho-
nix acid, benzenesulphonic acid and toluenesulphonic acid.
the compounds mentioned individually above are also
excluded in the preferred and particularly preferred range.
If, for example, 2-fluoro-benzenesulphonyl Shelley-
ride and Nl-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-ethoxy-
guanidine are used as starting substances for process
variant (a), the course of the reaction can be outlined
by the following equation:
2 Scholl No C
H C2H5
lo A US I - Foreign Countries
- 18 122~3357
- 2 Hal C No OUCH
/ \
If, for example, N'-(4-methoxy-6-methylthio-s~tri-
azin-2-yl)-N"-methoxy-N",N"'-bis-(~-trifluoromethyyl-ben-
zenesulphonyL)-guanidine and phenyLhydrazine are used as
S starting substances for process variant (b), the course
of the reaction can be outlined by the following equation:
S 2 - N NH I ON
~52 OUCH
I<
CF3 _
H2NNH
>
- SO - NASH
OF
S 2 - N NH 4 ON
NH
NO
If, for example, N'-(4,6-dimethoxy-s-triazin-2-yl)-
N"-benzyLoxy-~ (2-chlorophenylmethylsulphonyl)-guanidine
I and 2-trifluoromethanesulphonic acid chloride are used
Lo A 23 3~8 - Foreign Countries
~2~8~S7
- 19 --
as starting substances for process variant (c), the course
of the reaction can be outlined by the following equation:
N 3 CF3-5O2-Cl
H OUCH
1 H N OUCH
I N OUCH
- Hal CF352 OUCH
If, for example, N'-(4-ethoxy-6-methyl-s-triazin~
2-yl)-N"-methoxy-N"-(2-ethoxycarbonyl~benzenesulphHoneywell
guan~dine and 2-dimethylaminosulphonyl-benzenesulphonyl
chloride are used as starting substances for process vary-
ant (d), the course of the reaction can be outlined by the
following equation:
I OH, ON SHEA
I N OOZE synch
N
SO OUCH
COOK
SOz-N(CH3~2
OH N SHEA
C N OOZE
- Hal No
C COO 2H5
lo A I ~08 - Foreign Countries
12;~ ~33~7
- Jo
If, for example, N'-(4-methoxy~6~methyl~s~triazin~
2-yl)-N"-(2-methyl-benzenesulphonyl)-S-methyl-isotThor
and h,N-dimethylhydrazine are used as starting substances
for process variant (e), the course of the reaction can
be outlined by the following equation:
SHEA H ' N SHEA
C OUCH + H2NN(CH312
So
SHEA
C N SHEA
- HSCH3 No
H N~CH3)2
If, for example, N'-(4,6-dimethoxy-s-triazin~2~yl)~
N"-isopropoxy-N"'-~2~methoxycarbonylphenyLmethylsuulphonyl)~
guanldine and potassium ethanol ate are used as starting
I substances for process variant (f), the course of the reaction can be outlined by the following equation:
COUCH ` H ON OUCH
N
H OCH~CH3)2
COUCH G, No OUCH
COOK I No OUCH
- HAYAKAWA ON
H OCH(CH3)2
lo A I 3~8 - Foreign Countries
- 21 - 12~8357
If, for example, N'-(4-methylamino-6-methylthio-
s-triaz;n-2-yl)-N"-methoxy-N"-(2-chloro-benzenesullphonyl)-
N"'-(2-difluoromethoxy-benzenesulphonyl)-guanidineeland
methanesulphonic acid are used as starting substances for
process variant tug), the course of the reaction can be
outlined by the following equation:
fishwife H N NHCH3
I N SC + SHEA
SO / KOCH
\ / ON
C SHEA X CHIHUAHUAS
SO \ OUCH
Formula (II) provides a general definition of the
guanid;notriazine derivatives to be used as starting sub-
MU stances for process variant (a). In formula (II), R3,R4 and R5 preferably and particularly have the same
meanings as are given above as preferred or as portico-
laxly preferred in the context of the definition of the
substituents of formula (I).
Examples which may be mentioned of starting
substances of the formula tip) are: N'-(4,6-dimethyl-
s-triazin-2-yl)-, N'-(4-methoxy-6-methyl-s-triazin-
yule)-, N'-(4-ethoxy-6-methyl-s-triazin-2-yl)-, N'-
(4,6-dimethoxy-s-triazin-2-yl)-, N'-(4,6-diethoxy-s-
triazin-2-yl)-, N'-(4-ethoxy-6-methoxy-s-triazin-2-
ye)-, N'-(4-methyl-6-methylthio-s-triazin-2-yl)-,
lo A 23 308 - Foreign Countries
12~8357
- 22 -
N'-(4-ethylth;o-6-methyl-s-triazin-2-yl)-, N'-(4-methoxy-
6-methylthio-s-triazin-2-yl)-, N'-(4-ethoxy-6-methylthio-
s-triazin-2-yl)-~ N'-(4-ethylthio-6-methoxy-s-triazin-2-
ye)-, N'-(4-ethoxy-6-ethylthio-s-triazin-2-yl)-, N'-(4,6-
bis-methylthio-s-triazin-2-yl)-, N'{4,6- bis-ethylthio-s-
triazin-2-yl)-, N'-(4-methyl-6-methylamino-s-triazin-2-
ye)-, N'-(4-ethylamino-6-methyl-s-tr;azin-2-yl)-, No
dimethylamino-6-methyl-s-triazin-2-yl)-, N'-(4-diethyl-
amino-6-methyL-s-triazin-2-yl)-, N'-(4-methoxy-6-methyl-
amino-s-triazin-2-yl)-, N'-(4-ethylamino-6-methoxy-s-tri-
azin-2-yl)-, N'-(4-dimethylamino-6-methoxy-s-triazin-2-yl)-,
N'-(4-diethylamino-6-methoxy-s-triazin-2-yl)-, No
ethoxy-6-methylamino-s-triazin-2-yl)-, Nighthawks-
ethylamino-s-triazin-2-yl)-, N'-(4-dimethylamino-6-ethoxy-
s-triazin-2-yl)-, N'-(4-diethylamino-6-ethoxy-s-triazin-
yule)-, N'-(4-methylamino-6-methylthio-s-triazin-2-yl)-,
N'-(4-ethylamino-6-methylthio-s-triazin-2-yl)-, N'-t4-di-
methylamino-6-methylthio-s-triazin-2-yl)-, N'-(4-diethyl-
amino-6-methylthio-s-triazin-2-yl)-, N'-(4-ethylthio-6-
methylamino-s-triazin-2-y~)-, N'-(4-dimethylamino-6-ethyl-
thio-s-triazin-2-yl)- and N'-(4-diethylamino-6-ethylthio-
s-triazin-2-yl)-N"-methoxy-guanidine, -N"-ethoxy-guan-
iodine, -N"-propoxy-guanidine, -N"-isopropoxy-guanidine,
-N"-butoxy-guanidine, -N"-isobutoxy-guanidine, -N"-sec.-
butoxy-guanidine, -N"-pentoxy-guanidine, -N"-isopentoxy-
guanidine, -N"-hexyloxy-guanidine, -N"-octyloxy-guan-
iodine, -N"-allyloxy-guanidine, -N"-(2-chloro-ethoxy)-
guanidine, -N"-(2-fluoro-ethoxy)-guanidine, -N"-(2-chloro-
propoxy)-guanidine, -N"-(2-fluoro-propoxy)-guanidine,
-N"-(3-chloro-propoxy)-guanidine, -N"-(4-chloro-butoxy)-
guanidine, -N"-methoxycarbonylmethoxy-guanidine, -N"-
ethoxy-carbonyl-methoxy-guanidine, -N"-(1-methoxy-carbo-
nyl-ethoxy)-guanidine, -N"-(1-ethoxy-carbonyl-ethoxy)-
guanidine, -N"-dimethylamino-carbonyl-methoxy-guanidine,
-N"-(2-phenyl-ethoxy)-guanidine, -N"-phenoxy-guanidine,
-N"-(4-methyl-benzyloxy)-guanidine, -N"-(4-fluoro-benzyloxy)-
lo A 23 308 - Foreign Countries
1228357
- 23
- guanidine, -N"-t4-chloro-benzyloxy)-guanidine, No
nitro-benzyloxy)-guanidine, -N"-~2,6-dichloro-benzyloxy)-
guanidine, -N"-(4-methoxycarbonyl-benzyloxy)~guanidine
and -N"-(4-ethoxycarbonyl-benzyloxy)-guanidine.
The starting substances of the formula (II) are
known compare DEMOS (German Published Specification)
3,334,455).
The guanidinotriazine derivatives of the formula
(II) are obtained by a process in which cyanoaminotriazine
derivatives of the formula (YO-YO)
< (VI I I )
No R5
in which
R4 and R5 have the above mentioned meanings,
are reacted with amino compounds of the formula (IX)
HzN-R3 (IX)
in which
R3 has the above mentioned meaning,
or with hydrochloride thereof, if appropriate in the pro-
since of delineates, such as, for example, ethanol, isopropa-
I not or buttonhole at temperatures between 20C and 150C,
preferably between 50C and 120C, and, if appropriate,
the reaction products are treated with acid acceptors,
such as, for example, ammonia, sodium hydroxide solution
or sodium carbonate.
The cyanoaminotriazine derivatives of the formula
(VIII) are known (compare DEMOS (German Published Spew
suffocation) 3,334,455).
The compounds of the formula (~III) are essentially
lo A 23 308 - Frown Countries
12~8357
- 24
obtained by the following synthesis routes:
aye) by reactions of alkali metal or alkaline earth metal
salts of cyanamide - such as, for example, sodium cyan-
mode or calcium cyanamide - with chlorotriazines of the
formula (X)
- N R4
Of I/ N (X)
No R5
in which
R4 and R5 have the above mentioned meanings,
if appropriate in the presence of inert delineates, such as,
for example, ethanol, acetone, acetonitrile or dim ethyl-
formamide, at temperatures between 0C and 100C. After
the mixture has been concentrated and the residue has been
dissolved in water, the cyanoaminotriazine derivatives of
the formula (VIII) can be precipitated by acidification,
for example with hydrochloric acid, and isolated by lit-
traction with suction.
Alternatively, cyanoaminotriazine derivatives of
the formula (VIII) are obtained by a process in which
(a) aminotriazines of the formula (XI)
I No R4
H2N4 N (XI )
N R5
in which
R4 and R5 have the above mentioned meaning,
are reacted with carbonyl isothiocyanates of the formula
tXII)
O
R17-C-N=C=s (XII)
in which
R17 represents ethics or phenol,
lo A 23 I - Foreign Countries
- 25 1228~57
if appropriate in the presence of inert delineates, such
as, for example, acetone, acetonitrile or Tulane, at
temperatures between 0C and 100C, the carbonyl-
Theresa thereby formed of the formula (XIII)
R 1 7 _ C - NH - C - NH ON ( X I I I )
No R5
in which
R4, R5 and R17 have the above mentioned meanings,
are isolated by filtration with suction, if appropriate
after concentration of the mixture, and are reacted with
aqueous alkali metal or alkaline earth metal hydroxide
solutions, such as, for example, sodium hydroxide solution,
if appropriate in the presence of an organic solvent, such
as, for example, tetrahydrofuran or Dixon, at tempera
lures between 0C and okay an the Theresa obtained
in crystalline form after acidification, for example with
hydrochloric acid, of the formula (XIV)
H2N-C-NH ON ~XIV)
N R5
in which
R4 and R5 have the above mentioned meanings,
are isolated by filtration with suction and reacted with
metal compounds which can bind hydrogen sulfide, such as,
for example, with Lydia) acetate, Cooper) acetate, men-
query) acetate or iron) acetate, in the presence of
aqueous alkali metal or alkaline earth metal hydroxide
25 solutions, such as, for example, sodium hydroxide soul-
lion, at temperatures between 20C and 100C, the mixture
is filtered, when the reaction has ended, and the filtrate
is acidified with an acid, such as, for example, acetic
acid.
The products of the formula (YO-YO) thereby ox-
lo A 23 30~ - Foreign Countries
12;;~8357
- 26 -
twined as crystals can be isolated by filtration with-
suction.
The chlorotriazines of the formula (X), aminotri-
azines of the formula I and carbonyl isoth;ocyanates
of the formula (XII) to be used as starting substances for
the preparation processes described above under (a) and
(a) for the cyanoaminotriazine derivatives of the for-
mute (VIII) are known and/or can be prepared by processes
which are known per so (compare US. Patent Specification
3,154,547 and US. Patent Specification 4,160,037).
In another alternative process, cyanoaminotri-
amine derivatives of the formula (VIII) are obtained
when
(a) dichlorotriazines of the formula (Pa)
Nil
Of I/ N
N R5 (Pa)
in which
R5 has the abovement;oned meaning,
are reacted with alkali metal salts or alkaline earth
metal salts of cyanamide, such as, for example, with
disod;um cyanamide, on the presence of a fluent such
as, for example, water, at temperatures between -10C
and +50C, and the resulting metal salt of the moo-
chloro-cyanoaminotriazine of the formula (Vow)
(Vow)
N:~CR5
lo A 23 308 - Foreign countries
- 27 - 1228357
on which
R5 has the meaning given above,
is converted to the free monochloro-cyanoam;notriazine
of the formula (Vow) with an acid, such as, for
example, hydrochloric acid.
The corresponding cyanoaminotriazines of the
formula tVIII), in which R4 represents alkoxy,
alkylthio, alkylamino or dialkylamino, can be prepared
from the monochloro-cyanoaminotriazines of the formula
(Vow) by reaction with alcohols or alkanethiols or
with monoalkyl- or dialkylamines.
In a further alternative process, cinnamon-
treason derivatives of the formula (VIII) are
obtained if
(a) aminotriazines of the formula (XI)
HEN I/ N (XI)
in which
R4 and R5 have the above mentioned meaning,
are reacted with cyanogen chloride CLAN in the
presence of a base, such as, for example, bottle-
lithium, and in the presence of a delineate, such as
tetrahydrofuran, at temperatures between 0C and
50C, and when the reaction is complete, the mixture
is evaporated down and the residue is diluted with
water and acidified.
The amino compounds of the formula (IX) also to
be used as starting substances are likewise known and
lo A 23 308 - Foreign countries
- 28 - 12~8357
can be prepared by processes which are known per so
(compare Chum. Harm. Bull. 15, (1967), 345; Bull.
Sock Chimp France 1958, 664; Synthesis 1976, 682; J.
Chum. Sock 193U, 228 and Help. Chimp Act 45,
(1962), 1387).
Formula (III) provides a general definition of the
sulphonyl chlorines also to be used as starting sub-
stances for process variant (a). In formula (III), R1
preferably and particularly has the same meaning as is
given above as preferred or as particularly preferred in
the context of the definition of the substituents of
formula (I).
Examples which may be mentioned of starting sub-
stances of the formula (III) are: sheller-, sheller-,
sheller-, 2,5-dichloro-, flyer-, flyer-, Brigham-,
Brigham-, nutria-, nutria-, Sweeney-, 2-methyl-, 4-
methyl-, 2-chLoromethyl-, 2-trifluoromethyl-, 2-methoxy-,
2-djfluoromethoxy-, 2-trifluoromethoxy-, 2-methylthio-,
2-methy~thiomethyl-, 2-methylsulphinylmethyl-, 2-methyl-
sulphonylmethyl-, 2-dimethylaminosulphonyl-, deathly-
aminosulphonyl-, phenol-, 2-methoxycarbonyl-, ethics-
carbonyl-, 2-propoxycarbonyl-, 2-isopropoxycarbonyl-, 2-
butoxycarbonyl-, 2-dimethylaminocarbonyl-, 2-diethylamino-
carbonyL-, phonics-, 2-methyl-5-chloro-, 2-chloro-5-tri-
fluoromethyl-, 2-methylsulphonyl-, 2-ethylsulphonyl-, Z-
chLoro-4-trifluoromethoxy-, 3-chloro-4-trifluoromethoxy-, 2-
trifluoromethoxy-5-chloro- and 3,5-dichloro-benzenesulpho-
nil chloride; (2-chloro-phenyl)-, (2-cyano-phenyl)- and
(2-methoxycarbonyl-phenyl)-methanesulphonyl chloride; and
also methane-, chloromethane-, trifluoromethane-, ethanes-,
2-chloroethane-, ethene-, propane-, butane-, perfluorobutane-
and perfluorooctanesulphonyl chloride and methyl-, ethyl-,
propel-, isopropyl-, cyclohexyl-, dim ethyl- and deathly-
sulphamyl chloride.
The sulphonyl chlorides of the formula (III)
are known and/or can be prepared by processes which are
lo A 23 308 - Foreign Countries
- 29 - 1228~57
known per so compare J. Org. Chum. 33 (1968), 2104; J.
Org. Chum. 25 t1960), 1824; DE-AS German Published Specie
ligation) 2,308,262; EGOS (European Published Specific-
lions) 23,140, 23,141, 23,422, 35,893, 48,143, 51,466,
64,322, 70,041, 44,808 and 44,809; and US. Patent Specie
fixations ~,929,82U, 4,282,242, 4,348,220 and 4,372,778
and Anger. Chum. 93 (1981), 151).
These compounds are essentially obtained by the
following two synthesis routes:
(1) by reaction of the corresponding sulphonic acids
R1-S03-H or of alkali metal or alkaline earth metal salts
thereof with halogenating agents, such as, for example,
phosphorus-V chloride phosphorus pentachloride), pros-
furl chloride phosphorus oxychloride), thinly Shelley-
ride, phosgene or benzotrichloride, if appropriate in the presence of catalysts, such as, for example, pardon or
dimethylformamide~ and if appropriate using inert delineates,
such as, for example, ethylene chloride, chloroform,
acetonitrile, chlorobenzene and/or sulpholane, at tempera-
I lures between -OKAY and +150C, preferably between C
and +100C; after dilution with water, the sulphonyl
chlorides - where these are obtained as crystals - can be
isolated by filtration with suction or purified by extract
lion with a water-immiscible solvent, such as, for example,
ethylene chloride, deathly ether or hexane, washing and
drying of the extracts, concentration and recrystallize-
lion or distillation; or also Org.
(2) in a manner which is known per so (compare J.VChem.
25 (1960), 1824; DEMOS (German Published Specification)
I 2,308,2~2 and EGOS (European Published Specification)
59,241)~ by reaction of corresponding amino compounds
R1-NH2 with sodium nitrite and hydrochloric acid, if
appropriate in the presence of acetic acid, at tempera-
lures between -ltJC and +20C, preferably between -5C
and +10C, and subsequently (in situ) with Selfware
dioxide or a salt of sulfurs acid, such as, for example,
lo A 23 308 - Foreign Countries
12;~8357
- 30 -
sodium bisulphite, in the presence of a copper compound,
such as, for example, copper chloride or copper sulfite,
as a catalyst, at temperatures between 0C and 80C,
preferably between 1~C and 60C.
Working up can be carried out in the usual manner:
on dilution with water, the sulphonyl chlorides are
in general obtained as crystals and can be isolated by
filtration with suction. However, they can also be ox-
treated from the aqueous dispersion with a solvent which
I is virtually water-immiscible, such as, for example, me-
ethylene chloride or deathly ether, dried and purified by
vacuum distillation.
Formula (ID) provides a general definition of the
sulphonylguanidinotriazine derivatives to be used as
starting substances for process variant (by. In formula
(ID, R1, R4, R5 and R13 preferably and particularly
have the same meanings as are given above as preferred or
as particularly preferred in the context of the define-
lion of the substituents of formula (I).
I Examples which may be mentioned of the compounds
of the formula (ID) are: N'-(4,6-dimethoxy-s-triazin-2-
yl)-N"-methoxy-N", _N"'-bis-(2-trifluoromethyl-benzenesul-
phonyl)-guanidine, N'-~4-diethylamino-6-methoxy-s-triazin-~-
yl)-N"-methoxy-N",N"'-bis-(2-chloro-benzenesulphonnil)-
guanidine and N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-
methoxy-N",N"'-bis-(2^chloro-benzenesulphonyl)-guaaniline.
The compounds of the formula (ID) can be prepared
by the process described above under (a).
Formula tip) provides a general definition of the
I amino compounds to be used as starting substances in
process variant (b). In formula (IV), R2 and R3 preferably
and particularly have the same meanings as are given above
as preferred or as particularly preferred in the context
of the definition of the substituents of formula (I).
Examples which may be mentioned of starting sub-
stances of the formula (IV) are: N,N-dimethylhydrazine,
lo A 23 3~8 - Foreign Countries
12~8357
- 31
phenylhydrazine, 0-methyl-hydroxylamine~ (J-ethyl-hydroxyl-
amine, Us dimethylhydroxylamine~ and propel-, 0-isopro-
ply-, li-butyl-~ 0-isobutyl-, 0-sec.-butyl-, ponytail-, 0-
isopentyl-, 0-sec.-pentyl-, exile-, 0-isohexyl-, 0-hep-
5 twill-, 0-isoheptyl-, 0-octyl-, 0-isooctyl-, allele-, 0-
crotyl-, 0-(2-chloro-ethyl)-~ 0-(2-fluoro-ethyl)-, 0-(2-
chloro-propyl)-, 0-(3-chloro-propyl)-, 0-(4-chloro-butyl)-,
U-methoxycarbonylmethyl-~ 0-~thoxycarbonylmethyl-, 0-(1-
methoxycarbonyl)-ethyl-, 0-(1-ethoxycarbonyl)-ethyl-, 0-
10 aminocarbonylmethyl-, 0-(2-phenyl-ethyl)-, phenol-, 0-
(4-methyl-benzyl)-, 0-(4-fluoro-benzyl)-, 0-(4-chloro-ben-
Zulu)-, 0-(4-nitro-benzyl)-, ~-(2,6-dichloro-benzyl)-, 0-
(4-methoxycarbonyl-benzyl)- and li-(4-ethoxycarbonyl-benzyl)-
hydroxylamine.
Amino compounds of the formula (IV) are known and
can be prepared by processes which are known per so (coy-
pare Chum. Harm. pull. 15 (1967), 345; Bull. Sock Chimp
France 1958, 664; Synthesis 1976, 6~2; J. Chum. Sock 193~,
228 and Help. Chimp Act 45 (1962), 1387).
I Formula IT provides a general definition of the
sulphonylguanidinotriazine derivatives to be used as
starting substances in process variant (c). In formula
(If), R1, R3, R4 and R5 preferably and particularly
have the same meanings as are given above as preferred or
25 as particularly preferred in the context of the definition
of the substituents of formula (I).
Examples which may be mentioned of the compounds
of the formula (If) are: N'-(4,6-dimethyl-s-triazin-2-yl)-,
N'-(4-methoxy-6-methyl-s-triazin-2-yl)-, Nighthawks-
30 methyl-s-triazin-2-yl)-, N'-(4,6-dimethoxy-s-triazin-2-
ye)-, N'-(4,6-diethoxy-s-triazin-2-yl)-, Nighthawks-
methoxy-s-triazin-2-yl)-, N'-(4-methyl-6~methylthio-s~
treasonously)-, N'-(4-ethylthio-6-methyl-s-triazin-2-
y l)-, N'(4-methoxy-6-methylthio-s-triazin-Z-yl)-, N'-
35 (4-ethoxy-6-methylthio-s-triazin-2-yl)-, No
ethylthio-6-methoxy-s-triazin-2-yl)-, Nighthawks
lo A 23 30~ - Foreign Countries
1228357
- 32 -
6-ethylthio-s-triazin-Z-yl)-, N'-(4,6-bis-methylth;o-s-
triazin-2-yl)-, N'-(4,6-bis-ethylthio-s-triazin-2-yl)-,
N'-(4-methyl-6-methylamino-s-triazin-2-yl)-, Knothole-
amino-6-methyl-s-triazin-2-yl)-, N'-(4-dimethylamino-6-
methyl-s-triazin-2-yl)-, N'-(4-diethylamino-6-methyl-s-
triazin-2-yl)-, N'-(4-methoxy-6-methylamino-s-triazin-2-
ye)-, N'-(4-ethylamino-6-methoxy-s-triazin-2-yl)-, No
dimethylamino 6-methoxy s-triazin-2-yl)-, N'-(4-diethyl-
amino-6-methoxy-s-triazin-2-yl)-, N'-(4-ethoxy-6-methyl-
amino-s-triazin-2-yl)-, N'-(4-ethoxy-6-ethylamino-s-tria-
z;n-2-yl)-, N'-(4-dimethylam;no-6-ethoxy-s-tr;azin-2-yl)-,
N'-(4-diethylamino-6-ethoxy-s-triazin-2-yl)-, No
methyl amino 6-methylthio-s-triazin-2-yl)-, Knothole-
amino-6-methylthio-s-triazin-2-yl)-, N'-(4-dimethylamino-
6-methylthio-s-triazin-2-yl)-, N'-(4-diethylamino-6-
methylthio-s-triazin-2-yl)-, N'-(4-ethylthio-6-methyl-
amino-s-tr;azin-2-yl)-, N'-(4-dimethylamino-6-ethylthio-
s-tr;az;n-2-yl)- and N'-(4-d;ethylamino-6-ethylthio-s-
triaz;n-2-yl)- N"-methoxy-, -Nighthawks-, -N"-propxy-,
-N"-;sopropoxy-, -N"-butoxy-, -N"-isobutoxy-, -N"-sec.-
buttocks-, -N"-pentoxy-, -N"-hexyloxy-, -N"-octyloxy-, -N"-
allyloxy-, -N"-crotyloxy-, -N"-t3-chloro-propoxy)-, -N"-
methoxycarbonyl-methoxy-, -N"-ethoxycarbonylmethoxy,
-N"-(1-methoxycarbonyl-ethoxy)-, -N"-(1-ethoxycarbonyl-
ethics)-, -N"-(2-phenyl-ethoxy)-, -N"-phenoxy-, Ben
zyloxy-, -N"-(4-methyl-benzyloxy)-, N"-(4-fluoro-benzyl-
ox)-, -N"-(4-chloro-benzyloxy)-, -N"-(4-n;tro-benzyloxy)-,
-N"-(2,6-d;chloro-benzyloxy)-, -N"-(4-methoxycarbonyl-ben-
zyloxy)- and -N"-(4-ethoxycarbonyl-benzyloxy)-, Ben
zenesulphonyl-, -N"'-(2-chloro-benzenesulphonyl)-, No
chloro-benzenesulphonyl)-, -N"'-(4-chloro-benzenesulpho-
nil)-, -N"'-(2-fluoro-benzenesulphonyl)-, -N"'-(4-fluoro-
benzenesulphonyl)-, -N"'-(2-bromo-benzenesulphonyl)-, -
N"'-(4-bromo-benzenesulphonyl)-, -N"'-(2-cyano-benzene-
sulphonyl)-, -N"'-(2-nitro-benzenesulphonyl)-, -N"'-
35 (4-nitro-benzenesulphonyl)-,~-N"'-(2-methyl-benzenno-
lo A 23 308 - Foreign Countries
12;~83~7
- 33 -
sulphonyl)-, -N"'-(4-methyl-benzenesulphonyl)-, No
chloromethyl-benzenesulphonyl)-, -N"'-~2-trifluoromethyl-
benzenesulphonyl)-, -N"'-~2-methoxy-benzenesulphonyl)-,
-N"'-(4-methoxy-benzenesulphonyl)-, -N"'-(2-methylthio-ben-
zenesulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulpho-
nil)-, -N"'-(2-trifluoromethoxy-benzenesulphonyl)-, No
methylthio-methyl-benzenesulphony~)-, -N"'-(2-dimethylami-
no-sulphonyl-benzenesulphonyl)-, -N"'-(2-phenyl-benzene-
sulphonyl)-, -N"'-(2-methoxysulphonyl-benzenesulphonyl)-,
-N"'-(2-methoxycarbonyl-benzenesulphonyl)-, -Nighthawks-
carbonyl-benzenesulphonyl)-, -N"'-(2-propoxycarbonyl-ben-
zenesulphonyl)-, -N"'-t2-methylaminocarbonyl-benzenesul-
phony)-, -N"'-(2-ethylaminocarbonyl-benzenesulphonyl)-,
-N"'-(2-propylaminocarbonyl-benzenesulphonyl)-, No
methoxyaminocarbonyl-benzenesulphonyl)-, -Nighthawks-
aminocarbonyl-benzenesulphonyl)-, -N"'-(2-propoxyaminocar-
bonyl-benzenesulphonyl)-, -N"'-(2-dimethylaminocarbonyl-
benzenesulphonyl)- and -N"'-(2-diethylaminocarbonyl-ben-
zenesulphonyl)-guanidine.
The compounds of the formula (If) can be prepared
by the processes described above under (a) and (b).
Formula (V) provides a general definition of the
sulphonyl chlorides also to be used as starting sub-
stances on process variant (c). In formula (V), R10
preferably and particularly has the same meaning as us
given above as preferred or as particularly preferred in
the context of the definition of the substituents of
formula (I).
The sulphonyl chlorides which have been men-
toned above as examples of compounds of the formula (Iamb apply as examples of the starting substances of the
formula (V).
The sulphonyl chlorides of the formula (V)
are known andtor can be prepared by processes which are
known per so (compare the literature and synthesis routes
for the compounds of the formula (III) above).
lo A 23 308 - Foreign Countries
_ 34 _ 1228357
Formula (VI) provides a general definition of the
sulphonylguanidinotriazine derivatives to be used as
starting substances for process variant (d). In formula
TV), R3 , R4, R5 and R10 preferably and portico-
laxly have the same meanings as are given above as pro-
furred or as particularly preferred in the context of the
definition of the substituents of formula (I).
Examples which may be mentioned of the compounds
of the formula TV) are: N'-(4,~-dimethyl-s-triazin-2-
I ye)-, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-, No
ethoxy-6-methyl-s-triazin-2-yl)-~ N'-(4,6-dimethoxy-s-
triazin-2-yl)-, N'-(4,6-diethoxy-s-triazin-2-yl)-, No
ethoxy-6-methoxy-s-triazin-2-yl)-, N'-(4-methyl-6-methyl-
thio-s-triazin-2-yl)-, N'-(4-ethylthio-6-methyl-s-tria-
zanily)-, N'-(4-methoxy-6-methylthio-s-triazin-2-yl)-,
N'-(4-ethoxy-6-methylthio~s-triazin~2-yl)~, Knothole-
thio-6-methoxy-s-triazin-2-yl)-, N'~(4~ethoxy-6~ethyl-
thio-s-triazin-2-yl)-, N'-(4,6-bis-methylthio-s-tri~
assign)-, N'-(4,6-bis-ethylthio-s-triazin-2-yl)-, N'-
(4-methyl-6-methylamino-s-triazin-2-yl)-, N'-(4-ethylamino-
6-methyl-s-triazin-2~yl)~, N'-(4-dimethylamino-6-methyl-
s-triazin-2-yl)-, N'-(4-diethylamino-6-methyl-s-triazin-
yule)-, N'-(4-methoxy-6-methylamino-s-triazin-2-yl)-, N'-
(4-ethylamino-6-methoxy-s-triazin-2-yl)-~ N'-(4-dimethyl-
amino-6-methoxy-s-triazin-2-yl)-, N'-(4-diethylamino~6-
methoxy-s-triazin-2-yl)-, N'-(4-ethoxy-6-methylamino-s-
triazin-2-yl)-, N'-(4-ethoxy-6-ethylamino-s-triazin-2-
ye)-, N'-(4-dimethylamino-6-ethoxy-s-triazin-2-yl)-, N'-
(4-diethylamino-6-ethoxy-s-triazin-2-yl)-, N'-(4-methyl-
AL amino-6-methylthio-s-triazin-2-yl)-, N'-(4-ethylamino-6-
methylthio-s-triazin-2-yl)-, N'-(4-dimethylamino-6-methyl-
thio-s-triazin-2-yl)-, N'-(4-diethylamino-6-methylthio-s-
triazin-2-yl)-, N'-(4-ethylthio-6-methylamino-s-triazin-
yule)-, N'-(4-dimethylamino-6-ethylthio-s-triazin~2~yl)~
and N'-(4~diethylamino-6-ethylthio-s-triazin-2~yl)-
N"-methoxy-, -Nighthawks-, -N"-propoxy-, -N"-isopropoxy-,
lo A 23 I - Foreign Countries
_ 35 _ 1228357
-N"-butoxy-, -N"-isobutoxy-, -N"-sec.-butoxy-, -N"-pentyloxy-,
-N"-hexyloxy-, -N"-octyloxy-, -N"-allyloxy~, -N"-t3-chloro-
propoxy)-, -N"-methoxycarbonylmethoxy-, -N"-ethoxycarbonyl~
methoxy-, -N"-~Z-phenyl-ethoxy)-, -N"-benzyloxy-, No
methyl~benzyloxy)-, -N"-(4-fluoro-benzyloxy)-, No
chloro-benzyloxy)-, -N"-(4-nitro-benzyloxy)- and No
methoxycarbonyl-benzyloxy)-, N"-benzenesulphonyl-, -N"-
(2-chloro-benzenesulphonyl)-~ -N"-(4-chloro-benzenesulphonyl)-,
-h"-(2-fluoro-benzenesulphonyl)-, -N"-(4-fluoro-benzene-
sulphonyl)-, -h"-(2-bromo-benzenesulphonyl)-, -h"-(3-chloro-
benzenesulphonyl)-, -N"-(2-cyano-benzenesulphonyL)-, -N"-
(2-nitro-benzenesulphonyl)-, -N"-(4-nitro-benzenesulpho-
nil)-, -N"-(2-methyl-benzenesulphonyL)-, -N"-(4~methyL-
benzenesuLphonyl)-, -N"-(2-chloromethyl-benzenesulphonyl)-,
-N"-(2-trifluoromethyL-benzenesulphonyl)-, -N"-(2-methoxy-
benzenesuLphonyl)-, -N"-(4-methoxy-benzenesulphonyL)-,
-N"-(2-methylthio-benzenesulphonyl)-, -N"-(2-difLuorome-
thoxy-benzenesulphonyl)-~ -N"-(2-trifluoromethoxy-benzene-
sulphonyl)-, -N"-(2-methylthiomethyl-benzenesulphonyl)-, -N"-
(2-dimethylamino-sulphonyl-benzenesulphonyl)-~ -N"-(Z-phenyl-
benzenesulphonyl)-, -N"-(methoxysulphonyl-benzenesulpho-
nil)-, -h"-(2-methoxycarbonyl-benzenesuLphonyL)-, No
ethoxycarbonyl-benzenesulphonyl)-, -N"-(2-propoxycarbonyl-
benzenesuLphonyl)-, -N"-C2-(N-methyl-N-methoxy-amino-carbonyl-
benzenesulphonyl]-, -N"-(2-dimethylaminocarbonyl-benzene-
sulphonyl)- and -N"-(2-diethylaminocarbonyl-benzenesul-
phonyl)-guanidine.
The sulphonylguanidinotriazine derivatives of the
formula (VI) are new and can be prepared by a process
analogous to process (a) by reacting guanidinotriazine
derivatives of the formula (II) with somewhat equimolar
amounts of sulphonyl chlorides of the formula (V).
Formula (III) provides a general definition of the
sulphonyl chlorides also to be used as starting sub-
stances in process variant (d). In formula Tao), R1preferably and particularly has the same meaning as is
lo A 23 30~ - Foreign Countries
36 _ i228357
given above as preferred or as particularly preferred in
the context of the definition of the substituents of
formula I}).
Examples of the sulphonyl chlorides of the
formula (III) and their preparation processes for this have
already been given above in connection with the descrip-
lion of the starting substances for process (a).
Formula VOW) provides a general definition of the
sulphonylisothioureidotriazine derivatives to be used as
I starting substances in process variant I In formula
(VII), R1, R4 and R5 preferably and particularly have
the same meanings as are given above as preferred or as
particularly preferred in the context of the definition
of the substituents of the formula (I), and R16 preferably
and also particularly represents methyl.
Examples which may be mentioned of the compounds
of the formula (VOW are: N'-(4,b-dimethyl-s-triazin-2-
ye)-, N'-(4-methoxy-6-methyl-s-triazin-Z-yl)~, No
ethoxy-6-methyl~s-triazin-2-yl)-, N'-(4,6-dimethoxy-s-
I triazin-2-yl)-, N'-(4,6-diethoxy-s~triazin-2-y~)-, No
ethoxy-6-methoxy-s-triazin-2-yl)-, N'-(4-methyl-6-methyl-
thio-s-triazin-2-yl)-~ N'-(4-ethylthio-6-methyl-s-tria-
zanily)-, N'-(4-methoxy-6-methylthio-s-triazin-Z-yl)-,
N'-(4-ethoxy-6-methylthio-s-triazin-2-yl)-, Knothole-
thio-o-methoxy-s-triazin-2-yl)-, N'-(4-ethoxy-6~ethylthio~
s-triazin-2-yl)-, N'-(4,6-bis-methylthio-s-triazin-
yule N'-(4,6-bis-ethylthio-s-triazin-Z-yl)-, N'-
(4-methyl-6-methylamino-s-triazin-2-yl)-, N'-(4-ethylamino-
6-methyl-s-triazin-2-yl)-, N'-(4-dimethylamino-6-n1ethyl-
I s-triazin-2-yl)-, N'~(4-diethylamino-6~methyl-s-triazin-
yule)-, h'-(4-methoxy-6-methylamino-s-triazin-2-yl)-, N'-
(4-ethylamino-6-methoxy-s-triazin-2-yl)-, N'-~4-dimethyl-
amino-o-methoxy-s-triazin-2-yl)-, N'-(diethylamino-6-
methoxy-s-triazin-2-yl)-, N'~(4~ethoxy-6-methylamino~s-
triazin-2-yl)-, N'-(4-ethoxy-6-ethylamino-s-triazin-2-yl)-,
N'-(4-dimethylamino-6-ethoxy-s-triazin-Z-yl)-~ N'-(4-di-
lo A US 3~8 - Foreign Countries
~228357
ethylamino-6-ethoxy-s-triazin-2-yl)-, N'-(4-methylamino-6-methyl-
thio-s-triazin-2-yl)-, N'-(4-ethylamino-6-methylthio-s-triazin-2-
ye)-,N'-(4-dimethylamino-6-methylthio-s-triazin-2-yl)-,, No
diethylamino-6-methylthio-s-triazin-2-yl)-, N'-(4-ethylthio-6-
methylamino-s-triazin-2-yl)-, N'-(4-dimethylamino-6-ethylthio-s-
triazin-2-yl)- and N'-(4-diethylamino-6-ethylthio-s-triazin-2-
yl)-N"-(2-fluoro-benzenesulphonyl)-, -N"-(2-chloro-benzenesul-
phony)-, -N"-(2-bromo-benzenesulphonyl)-, -N"-(2-methyl-benzene-
sulphonyl)-, -N"-(2-methoxy-benzenesulphonyl)-, -N"-(2-methoxy-
carbonyl-benzenesul.phonyl)-, -N"-(2-ethoxy-carbonyl- benzene-
sulphonyl)-, -N"-(2-propoxycarbonyl-benzenesulphonyl)-, -N"-
~2-isopropoxycarbonyl-benzenesulphonyl)-, -N"-(2-phenyl-benzene-
sulphonyl)-, -N"-(2-trifluoromethyl-benzenesulphonyl)-, No
difluoromethoxy-benzenesulphonyl)- and -N"-(2-trifluoromethoxy-
benzenesulphonyl)-S-methyl-isothiourea.
Some of the sulphonylisothioureidotriazine derivatives
of the formula (VII) are known and/or can be prepared by processes
which are known so (compare EGOS (European Published
Specification) 5,986).
It is to be noted however, that compounds of the formula
(VII), in which Al represents a phenol radical substituted in
ortho-position by Cl-C4-fluoroalkoxy, Cl-C4-alkylthio, Cluck-
alkylsulphinyl or Cl-C4-alkylsulphonyl, and in which R4, R5 and
R16 have the above mentioned meanings, are not yet known and are
the subject of the divisional application.
According to one aspect of the invention of the
divisional application there is provided a sulphonylisothioureido-
treason derivative of the general formula (VIVA)
- 37 -
12~:8357
N
R -SWEENEY , N I/ N
I R5 (VIVA)
R 6
in which
Ala represents a substituted phenol radical
ROY
wherein
ROY represents Cl-C4-fluoroalkoxy, Cl-C4-alkylthio,
Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl;
R4 represents fluorine, chlorine, bromide, cyclopropyl
or Cl-C4-alkyl (which is optionally substituted by fluorine or
chlorine), or represents Cl-C4-alkoxy (which is optionally
substituted by fluorine or chlorine), or represents Cl-C4-alkylthio
(which is optionally substituted by fluorine or chlorine), or
represents Cl-C4-alkyl- or di-(Cl-C4-alkyl)-amino (which are
optionally substituted by fluorine);
R5 represents fluorine, chlorine, bromide, cyclopropyl,
Cl-C4-alkyl (which is optionally substituted by fluorine or
chlorine), or represents Cl-C4-alkoxy (which is optionally
substituted by fluorine or chlorine), or represents Cl-C4-alkylthio
(which is optionally substituted by fluorine or chlorine), or
represents Cl-C4-alkyl- or di-(Cl-C4-alkyl)-amino (which are
optionally substituted by fluorine); and
_ aye -
isle
R16 represents Cl-C4-alkyl or bouncily.
According to a further aspect of the invention of the
divisional application there is provided a process for the
preparation of sulphonylisothioureidotriazine derivative of the
formula (VIVA) as defined above, which process comprises reacting
an N-sulphonyl-imino-dithiocarbonic acid ester of the formula (EVA)
SR16
S 2 (EVA)
SO 6
in which
Ala and R16 have the meanings given above, with an
aminotriazine of the formula (XI)
R4
N
HEN I/ N (XI)
N I 5
in which
R4 and R5 have the meanings given above, and, when the
reaction has ended, diluting the mixture with water and acidifying
with a strong acid.
The compounds of the formula (VII) are obtained by a
process in which N-sulphonyl-imino-dithiocarbonic acid esters
of the formula (XV)
SR16
Al -SO 2 NO ( XV )
SR16
in which
,:
- 37b -
835~
Al and R16 have the above mentioned meanings, are
reacted with aminotriazines of the formula (XI)
HEN I/ N (XI)
N I 5
in which
R4 and R5 have the above mentioned meanings,
- 37c -
38 _ 12~8357
if appropriate in the presence of bases, such as, for
example, sodium hydrides or potassium tert.-butyLate, and
if appropriate in the presence of delineates such as, for
example, tetrahydrofuran, Dixon or dimethylformamide,
at temperatures between C and 100C, and, when the
reaction has ended, the mixture is diluted with water and
acidified with a strong acid, such as, for example, hydra-
caloric acid, and the products of the formula (VII) ox-
twined as crystals are isolated by filtration with suction.
AL Formula (XV) provides a general definition of the
N-sulphonyl-imino-dithiocarbonic acid esters required here
as starting substances. In formula (XV), R1 and R16
preferably end particularly have the same meanings as are
given above as preferred or as particularly preferred
in the context of the definition of the substituents of
formula (I) or formula (VII ) .
Examples which may be mentioned of the compounds
of the formula TV are: S,S-dimethyl N-(2-fluoro-ben-
zenesulphonyl)-, h-(2-chloro-benzenesulphonyl)-, No
2b bromo-benzenesulphonyl)-, N-(2-methyl-benzenesulphonyl)-,
N-(2-methoxycarbonyl-benzenesulphonyl)-, N-(2-ethoxycar-
bonyL-benzenesulphonyl)-, N-(2-propoxycarbonyl-benzene-
sulphonyl)-, N-(2-isopropoxycarbonyl-benzenesulphonyl)-,
N-(2~phenyl-benzenesulphonyl)~, N-(2-trifluoromethyl-ben-
zenesulphonyl)-; N-(2-difluoromethoxy-benzenesulphonyl)-
anN-(2-trifluoromethoxy-benzenesulphonyl)-iminodithito-
carbonate.
The N-sulphonyl-iminodithiocarbonic acid esters
of the formula (XV) are known and/or can be prepared by
I processes which are known per so (compare Chum. Ben. 99
(1900), 2~5 and EGOS (European Published Specification)
o ) .
The compounds of the formula (XV) are obtained by
a process in which sulfonamides of the formula (XVI)
R1-SO~-NH2 (XVI)
in which
lo A 23 SOS - Foreign Countries
12~8357
_ I _
R1 has the above mentioned meaning,
are reacted with carbon disulphide in the presence of a
strong base, such as, for example, sociium hydroxide, and
if appropriate in the presence of delineates, such as, for
example, water an dimethy~formamide, at temperatures bet-
wren UC and 1UuC, and then (in situp with an alkylating
agent of the formula (ZOO)
X-R16 (XVII)
in which
R16 has the above mentioned meaning and
represents chlorine, bromide or iodine,
at temperatures between 0C and 1U0C.
The products of the formula (XV) obtained as cry-
slats after dilution of the mixture with water can be is-
US fated by filtration with suction.
Formula (XVI) provides a general definition of thesulphonamides required as starting substances. In formula
(ZOO), R1 preferably and particularly has the same
meaning as given above as preferred or as particularly
AL preferred in the context of the definition of the
substituents of formula (I).
Examples which may be mentioned of the compounds
of the formula (ZOO) are: flyer-, sheller Brigham-,
methyl 2-methoxycarbonyl-~ Z-ethoxycarbonyl-, 2-pro-
US poxycarbonyl-, 2-isopropoxycarbonyl-, phenol-, try-
fluoromethyl-, 2-difluoromethoxy- and 2-trifluoromethoxy-
benzenesulphonamide.
The sulfonamides of the formula (ZOO) are
known and/or can be prepared by processes which are known
30 per so compare EGOS European Published Specifications)
Z3,4~2, 3U,140, ~5,893, owe, 44,~0h, 44,~09, 51,466,
owe, 70,041 and USE; US. Patent Specification
4,3?2,77~ an Oh. Org. Kim. [J. Org. Chum. USSR] 8 (1972),
1U~3-1026 English 1032-1U34]).
These compounds are obtained in a manner which is
known per so, by reacting sulphonyl chlorides of the
lo A us 30~ - Foreign Countries
- MU - 1228357
formula (Ill) - above - with ammonia, if appropriate in
the presence of delineates, such as, for example, deathly
ether, tetrahydrofuran or water, at temperatures between
LJOC and 10~C. The products of the formula (ZOO)
S thereby obtained as crystals can be isolated by filtration
with suction
Examples of suitable starting compounds of the
formula Tao) and preparation methods for these are given
above in the description of the starting substances for
I process (a).
Examples which may be mentioned of the starting
substances of the formula (ZOO) are: methyl chloride,
methyl bromide, methyl iodide, ethyl chloride, ethyl brow
mile and ethyl iodide, and bouncily chloride and bouncily
bromide.
The compounds of the formula (ZOO) are known.
Formula (XI) provides a general definition of the
aminotriazines also to be used as starting substances. In
formula (ZOO, R4 and US preferably and particularly have
the same meanings as are mentioned above as preferred or
as particularly preferred in the context of the definition
of the substituents of formula (I).
Examples which may be mentioned of the compounds
of the formula (XI) are: 4,6-dimethyl-, 4-methoxy-6-me-
thy-, 4-ethoxy-6-methyl-, 4,6-dimethoxy-, 4,6-diethoxy-,
4-ethoxy-6-methoxy-, 4-methyl-6-me~hylthio-, 4-ethylthio-
methyl-, 4-methoxy-6-methylthio-, 4-ethoxy-6-methylthio-,
4-ethylthio-6-methoxy-, 4-ethoxy-6-ethylthio-, Boyce-
methylthio-, 4,6-bis~ethylthio-, 4-methyl-o-methylamino-,
I 4-ethylamino-6-methyl-, 4-dimethylamino-6-methyl-, Dow-
ethylamino-o-methyl-, 4-methoxy-6-methylamino-, 4-ethyl-
amino-6-methoxy-, 4-dimethylamino-6-methoxy-, deathly-
amino-6-methoxy-, 4-ethoxy-6-methylamino-, ethics-
ethyl amino-, 4-dimethylamino-6-ethoxy-, 4~diethylamino~6-
ethics-, 4-methylamino-6-methylthio-, 4-ethylamino-6-
methylthio-, 4-dimethylamino~6~methylthio~,
lo A I 3U8 - Foreign Countries
12~8~57
- 41 - 23189-6066
4-diethylamino-6-methylthio-, 4-ethylthio-6-methylamino-,
4-dimethylamino-6-ethylthio and 4-diethylamino-6-ethylthio-2-amino-
s-triazine.
The aminotriazines of the formula (XI) are known and/or
can be prepared by processes which are known per so.
Formula (IV) provides a general definition of the amino
compounds also to be used as starting substances in process van-
ant (e). In formula (IV), R2 preferably represents hydrogen or
methyl, in particular hydrogen, and R3 preferably and particularly
has the same meaning as is given above as preferred or as
particularly preferred in the context of the definition of the
substituents for formula (I).
Examples of suitable starting substances of the formula
(IV) and literature references for these are given above in the
description of the starting substances for process (b).
Formula (I) - with the proviso that M represents hydrogen
- provides a general definition of the compounds to be used as
starting substances in process variant (f). In formula (I) -
where this relates to the compounds to be used as starting sub-
stances for process (f) - M represents hydrogen and Al, R2, R3, R4
and R5 preferably and particularly have the same meanings as are
given above as preferred or as particularly preferred in the
context of the definition of the substituents of formula (I).
The compounds of the formula (I) to be used as starting
substances for process (f) can be prepared by the processes desk
cried under (a), (b), (c), (d) and (e).
Examples which may be mentioned of the metal hydroxides,
hydrides and alkanolates and organometallic compounds to be used
1228357
- 42 - 23189-6066
in process (f) are: the hydroxides of lithium, sodium, potassium,
magnesium and calcium, the hydrides of lithium, sodium and calcium,
sodium methanol ate and ethanol ate, potassium methanol ate, ethanol
late and potassium tert.-butanolate, and butyl-lithium and is-
propyl-magnesium chloride.
Formula (I) - with the proviso that M represents
hydrogen - provides a general definition of the compounds to be
used as starting substances in process variant (g). In formula
(I) - where this relates to the compounds to be used as starting
substances for process (g) - M represents hydrogen and Al, R2, R ,
R4 and R5 preferably and particularly have the same meanings as
are given above as preferred or as particularly preferred in the
context of the definition of the substituents of formula (I).
The compounds of the formula (I) to be used as starting
substances for process (g) can be prepared by the processes
described under (a), (b), (c), (d) and (e).
Strong acids are used as starting substances in process
(g). These are preferably hydrogen halide acids, such as hydrogen
chloride, hydrogen bromide or hydrogen iodide, and furthermore
sulfuric acid or alkanesulphonic acids which have up to 4 carbon
atoms and are optionally substituted by fluorine or chlorine, such
as, for example, methanesulphonic acid, ethanesulphonic acid,
chloromethanesulphonic acid, 2-chloroethanesulphonic acid and in-
fluoromethanesulphonic acid, trifluoroacetic acid and furthermore
benzenesulphonic acid, p-toluenesulphonic acid, naphthalene-l-
sulphonic acid, naphthalene-2-sulphonic acid and naphthalene-1,4-,
-1,5-, -1,6-, -2,6- and -2,7-disulphonic acid.
Process (a) according to the invention for the prepare-
lion of the new compounds of the formula (I) is preferably carried
8;~S7
- aye - 23189-6066
out using delineates. Possible delineates are virtually all the inert
organic solvents, but preferably aprotic polar solvents. These in-
elude optionally substituted hydrocarbons, such as, for example,
ethylene chloride, chloroform, 1,2-dichloroethane, Tulane,
zillion and chlorobenzene, nitrites, such as acetonitrile and
propionitrile, ethers, such as, for example,
` _ 43 _ 1228357
1~2-dimelhoxyethane~ tetrahy~rofuran and dnoxane, and I-
methylformamiae, dimethylacetam1~e, dim ethyl suLphoxide,
sulpholane, pardon and 2-methyl-5-ethyL-pyridine.
Virtually all the acid-binding agents which are
usually employed can be used as acid acceptors in pro-
cuss (a). These include, in particular, alkali metal and
alkaline earth metal hydroxides, alkali metal and alkaline
earth metal Horace, organometallic compounds, such as
butyl-lithium, and furthermore aliphatic, aromatic or
MU heterocyclic amine, such as trimethylamine, triethylamine,
h,N-dimethylar,iline, ~,N-dimethyl-benzylamine, Disobeys-
clooctane (DABCO), diazabicyclononene (DUB), diazabicyclo-
undecene (DUB), pardon, 2-methyl-5-ethyl-pyridine and
4-dimethylamino-pyridine.
The reaction temperatures can be varied within a
substantial range in process (a). In general, the react
lion is carried out between -I and +10~C, preferably
between -I and +5~C. Process (a) according to the
invention is in general carried out under normal pressure.
For carrying out process (a), in general between
1 and 5 moles, preferably between 2 an 3 moles, of sulk
phony chloride of the formula Tao) are employed per
mole of guanidinotriazine derivative of the formula (II).
The reaction components are usually brought to-
tether at room temperature or with external cooling and the reaction mixture is stirred until the reaction has
ended.
The new compounds are worked up and isolated by
customary methods. The mixture is shaken with water and
So a water-immiscible solvent, such as, for example, methyl
tone chloride, chloroform or Tulane, if appropriate after
the volatile components have been distilled off, and the
organic phase is washed with water, dried, filtered and
concentrated The products of the formula (It which no-
main in the residue are made to crystallize by digestion with organic solvents, such as, for example, deathly ether,
lo A 23 3~8 - Foreign Countries
-
12~8~57
- 44 -
ethyl acetate, ethanol or isopropanol, and, if appropriate,
are purified by recrystallization.
Process (b) according to the invention is prefer-
ably carried out using delineates. Possible delineates are
virtually all the inert organic solvents. These include,
in particular, alcohols, such as methanol, ethanol and n- or
i-propanol, ethers, such as tetrahydrofuran, Dixon and
1,~-dimethoxyethane, esters, such as methyl acetate and
ethyl acetate, nitrites, such Astor example, acetonitrile
I or propionitrile, and dimethylformamide and water.
Acld-binding agents winch do not have nucleophilic
properties which noticeably compete with those of the
amino compounds of the formula (IV) can be used as acid
acceptors in process (b). As acid acceptors of this type
US there may be mentioned alkali metal and alkaline earth me-
tat carbonates, such as, for example, potassium carbonate
and calcium carbonate, tertiary amine, such as, for
example, triethylamine, ~i,N-dimethylaniline and India
methylbenzylamine and nitrogen-containing heterocyclic
I compounds, such as, for example, pardon, diazabicyclo-
octane (DABC0) and diazabicycloundecene DUB
The reaction temperature can be varied within a
substantial range in process (b). In general, the react
lion is carried out between bC and 150C, preferably
I between 1~C and 10~C. Process (b) according to the
invention is in general carried out under normal pressure.
For carrying out process (b) according to the in-
mention, in general between 1 and MU moles, preferably
between and 5 moles, of amino compound of the formula
I (IV) or hydrochloride thereof are employed per mole of the
compound of the formula (ID).
In general, the compound of the formula (ID) and
the delineate are taken at 2~1C or with gentle cooling, and
the amino compound of the formula (IV) or the hydrochloride
I thereof and, if appropriate, a suitable acid acceptor are
added. The reaction nlixture is then in general stirred
lo A 8 - Foreign Countries
_ 45 _ 12~8357
at room temperature or elevated temperature until the no-
action has ended.
Working up can be carried out by customary methods.
If the products of the formula (I) are obtained as cry-
5 slats from the reaction mixture, they can be isolated by filtration with suction. Otherwise - if appropriate after
concentration the mixture is diluted with water and ox-
treated with a solvent which is virtually water-immiscible,
such as, for example, ethylene chloride. The products
MU of the formula (I) can be obtained in a pure form by wash-
in the extraction solution with water, crying, filtration,
concentration of the filtrate an recrystallization of the
residue.
Process lo) according to the invention is prefer-
ably carried out using delineates. Possible delineates are
virtually all the inert organic solvents, but preferably
aprot1c polar solvents, such as have been mentioned above
in connection with the description, of process (a) accord-
in to the invention.
MU virtually all the acid-binding agents which are
usually employed can be used as acid acceptors in pro-
cuss (c). These include, in particular, the acid-binding
agents mentioner above in connection with the description
of process (a) according to the invention.
I The reaction temperatures can be varied within a
substantial range in process (c). In general, the react
lion is carried out between -~UC and +1U~C, preferably
between -3UOC and ~5UC. Process (c) is in general
carried out under normal pressure.
I For carrying out process (c), in general between
1 and moles, preferably between 1.1 and 1.5 moles, of
sulphonyl chloride of the formula (V) are employed
per mole of sulphonylguanidinotriazine derivative of the
formula (If).
The procedure and working up in process (c) can
be analogous to process to).
lo A I I - Foreign Countries
- 46 - 12~8357
Process (d) according to the invention is prefer-
ably carries out using ailments. Possible delineates are
virtually all the inert organic solvents, but preferably
aprotic polar solvents, such as have been mentioned above
in connection with the description of process (a) accord-
in to the invention.
All the acid-binding agents which are usually
employed can be used as acid acceptors in process (d).
These induce, in particular, the acid-binding agents men-
I Sheehan above in connection with the description of process according to the invention.
The reaction temperatures can be varied within a
substantial range in process (d). In general, the react
lion is carried out between -8~C and +1~C, preferably
I between -SKYE and +5~C. Process (d) is in general
carried out under normal pressure.
For carrying out process (d), in general between
- 1 and 2 nulls, preferably between 1.1 and 1.5 moles, of
sulphonyl chloride of the formula (III) are employed
I per mole of sulphonylguanidinotriazine derivative of the
formula (I
The procedure and working up in process (d) can
be analogous to process (a).
Process (e) according to the invention is prefer-
I ably carries out using delineates. Possible delineates are virtually all the inert organic solvents, but preferably
aprotic polar solvents. These include, in particular,
tetrahydrofuran, axon, 1,~-dimethoxyethane, acetone-
trite, acetone, methyl ethyl kitten, methyl isobutyl key
I tone, ailnethylformamide~ dimethylacetamide and dimethylsulphoxiae.
The reaction temperature can be varied within a
substantial range in process (e). In general, the react
lion is carried out between C and 15~C, preferably
between 1~C and 1~C. Process (e) is in general car-
fled out under normal pressure or slightly reduced
lo A 23 3~8 - Foreign Countries
- 47 - 1228357
pressure.
For carrying out process (e) according to the in-
mention, in general between 1 and I moles, preferably be-
tweet 1 and 5 moles, of amino compound of the formula
(IV) are employed per mole of sulphonylisothioureidotria-
zinc derivative of the formula IT
In general, the sulphonylisothioureidotriazine de-
rivatives of the formula (VII) and the delineate are taken
and the amino compound of the formula (IV) is metered in.
I The reaction mixture is then stirred until the reaction
has ended. The products of the formula (It are usually
obtained as crystals, after cooling and if appropriate
after acidification, for example with hydrochloric acid,
and can be isolated by filtration with suction.
Process I according to the invention is prefer-
ably carried out using delineates. Possible delineates are
virtually all the inert organic solvents. These include,
in particular, alcohols, such as, for example, ethanol and
n- or lso-propanol, ethers, such as, ion example, twitter-
I hydrofuran, Dixon and 1,2-dimethoxyethane, esters, such
as, ion example, ethyl acetate and methyl acetate, and
nitrites, such as, for example, acetonitrile.
The reaction temperature can be varied within a
substantial range in process (f). In general, the react
US lion is carried out between -2~C and +5~C, preferably
between C and 3~C. Process (f) is in general carried
out under normal pressure.
For carrying out process I according to the in-
venison in general between by and 1.2 moles, preferably
I between ~.95 and 1.1 moles, of metal compound are employed
per mole of the compound of the formula (I).
In general, the compounds of the formula (It and
the delineate are taken and - if appropriate with gentle
external cooling - the metal compound - if appropriate
dissolved in the delineate - is metered in. The reaction
mixture is stirred until the reaction has ended. The
lo A I I - Foreign Countries
I ~228~57
salt-like products of the formula (I) are in general ox-
twined as crystals and can be isolated by filtration with
suction.
Process (g) according to the invention is prefer-
ably carried out using delineates. Possible delineates are
virtually all the inert organic solvents. These include,
in particular, alcohols, such as, for example, methanol,
ethanol and n- or iso-propanol, ethers, such as, for
example, tetrahyarofur3n, Dixon and 1,2-dimethoxy-
I ethanes esters, such as, for example, methyl acetate and ethyl acetate, an kittens, such as acetone, methyl
ethyl kitten and methyl isobutyl kitten.
If the acids used as starting substances are em-
ply in aqueous solution, acetic android can Avon-
I tageously also be used as the ailment.
The reaction temperature can be varied within substantial range in process (9). In general, the react
lion is carried out between -2~C and +5~C, preferably
between C and +~C. process (g) is in general car-
fled out under normal pressure.
For carrying out process (g) according to the in-
mention, in genera between 1 and I moles, preferably 1
an 5 moles, of a strong acid are employed per mole of the
compound of the formula (I).
In general, the compounds of the formula (I) and
the delineate are taken and - if appropriate with gentle ox-
vernal cooling - the strong acid is metered in. The react
lion mixture is stirred until the reaction has ended. The
1:1 abducts are in general obtained as crystals and can
I be isolated by filtration with suction.
The active compounds according to the invention,
can be used as defoliants, desiccants, agents for destroy-
in broad-leaved plants and, especially, as weed killers.
By weeds, in the broadest sense, there are to be understood
I all plants which grow in locations where they are undo-
sired. whether the substances according to the invention
lo A I so - Foreign Countries
- 49 - 1228357
act as total or selective herbicides depends essentially
on the amount used.
The active compounds according to the invention can
be used, for example, in connection with the following plants:
Vicotyledon weeds of the genera: Synapse, Lipid-
I'm, Gallium, Styler, Motorcar, Anthems, Galinsoga,
Chenopodium, Utica, Synch, Amaranths, Portulaca, Ken-
thrum, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,
Cirsium, Keywords, Sonchus, Selenium, Rewrap, Rotate, Lint
AL hernia, Lamium, Veronica, Abutilon, Emex, Dotter, ~iola,Galeopsis, Palaver and Sinatra.
cotyledon cultures of the genera: 60ssypium, Gleason,
Beta, Caucus, Fossils, Possum, Selenium, Linus, Ipomoea,
itch, ~icotiana, Lycopersicon, Arachis, Brusque, lag-
tuna, Cucumis and Cucurbita.~lonocotyledon weeds of the genera: Echinochloa, Satyr,
~anicum, Digit aria, Phlegm, Poe, Fistic, Eleusine, Brush-
aria, Lolium, Browns, Arena, Cyprus, Sorghum, Agropyron,
Sundown, Monkery, FimbristyLis, Sagittaria, Eleocharis,
Lo Syrups, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium,
Agrostis, Alopecurus and Opera.
Monocotyledon cultures of the genera: Ours, Zeal Trill-
gum, H~r~eum, Arena, Scale, Sorghum, Panicum, Saccharum,
Bananas, Asparagus and Gallium.
I However, the use of the active compounds according
to the invention is in no way restricted to these genera,
but also extends in the same manner to other plants.
The compounds are suitable, depending on the con-
cent ration, for the total combating of weeds, for example
I on industrial terrain and rail tracks, and on paths and
squares with or without tree plantings. Equally, the cow-
pounds can be employed for combating weeds in perennial
cultures, for example afforestations, decorative tree
plantings, orchards, vineyards, citrus groves, nut ouch-
ends, banana plantations, coffee plantations, tea plant-
lions, rubber plantations, oil palm plantations, cocoa
lo A I AL - Foreign Countries
28~S7
- MU
plantations, soft fruit plantings and hop fields, and for
the selective combating of weeds in annual cultures.
The active compounds according to the invention can
be used for selectively combating weeps in monocotyLedon and
S dicoty~edon crops, such as, for example, cotton, rice,
cereals and maize. [The active compounds according to the
invention also exhibit a fungicidal action against Pyrrhic-
lane ours in rice.]
The active compounds can be converted to the gusto-
I many formulations, such as solutions, emulsions, wettable
powders, suspensions, powders, dusting agents, pastes,
soluble powders, granules, suspension-emulsion concern-
trades, natural and synthetic materials impregnated with
active compound, and very fine capsules in polar
substances.
These formulations are produced in known manner,
for example by mixing the active compounds with extenders,
that is liquid solvents and/or solid carriers, optionally
with the use of surface-active agents, that is emulsifying
I agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water an an extender,
organic solvents can, for example, also be used as Audi-
diary solvents. As liquid solvents, there are suitable
in the main: aromatics, such as zillion, Tulane or alkyd
I naphthalenes, chlorinated aromatics and chlorinated alit
phatic hydrocarbons, such as chlorobenzenes, chloroethyl-
ones or ethylene chloride, aliphatic hydrocarbons, such
as cyclohexane or paraffins, for example petroleum free-
lions, mineral and vegetable oils, alcohols, such as but-
I not or gawkily as well as their ethers and esters, ketones,such as acetone, methyl ethyl kitten, methyl isobutyl key
tone or cyclohexanone, strongly polar solvents such as
dimethylformamide and dim ethyl sulphoxicle, as well as water.
As solid carriers there are suitable: for example
ammonium salts and round natural minerals, such as kayo-
fins, clays, talc, chalk, quartz, attapulgite,
lo A I by - Foreign Countries
- 51 - 12~8357
montmorillonite or diatomaceous earth, and ground Cynthia-
tic minerals, such as highly disperse silicic acid, alum-
no an silicates, as solid carriers for granules there are
suitable: for example crushed and fractionated natural
rocks such as calcite, marble, pumice, sepiolite and dolor
mite, as well as synthetic granules of inorganic and organ
nix meals, and granules of organic material such as saw-
aunt, coconut shells, maize cobs and tobacco stalks; as
emulsifying and/or foam-~orminy agents there are suitable:
I for example non-ionic and anionic emulsifiers, such as
polyoxyethylene-fatty acid esters, polyoxyethylene-fatty
alcohol ethers, for example alkylaryl polyglycol ethers,
alkylsuLphonates, alkylsulphates, ary~sulphonates as well
as albumin hydrolysation products; as dispersing agents
there are suitable: or example lignin-sulphite waste
liquors and methyl cellulose.
Adhesives such as carboxymethylcellulose and NATO-
fat and synthetic polymers in the form of powders, gray
nulls or lattices, such as gum Arabic polyvinyl alcohol
I and polyvinyl acetate, as well as natural phospholipids
such as cephalins and lecithins, and synthetic phospholi-
pods, can be used in the formulations. Further additives
can be mineral and vegetable oils.
It is possible to use colorants such as inorganic
I pigments, for example iron oxide, titanium oxide and Prows
Sian Blue, and organic distaffs, such as alizarin aye-
stuffs, ago distaffs and metal phthalocyanine distaffs,
and trace nutrients such as salts of iron, manganese,
boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1
and 95 per cent by weight of active compound, preferably
between I and 90X.
The active compounds according to the invention,
as such or in the form of their formulations, can also be
35 used, for combating weeds, as mixtures with known herb-
aides, finished formulations or tank mixes being possible.
lo A I 30~ - Foreign Countries
1228~S7
- 52 -
For the mixtures come known herbicides, such as,
for example, N-(2-benzothiazolyl)-N,N'-dimethylurea, 3-
(3-chloro-4-methylphenyl)-1,1-dimethyl urea, 3-(4-
isopropylphenyl)-1,1-dimethyl urea, Amman-
dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-onno, 4-
amino-6-(1,1-dimethyl-ethyl)-3-ethylthio-1,2,4-triiazin-5-
(one, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-
1,3,5-triazine-2,4-(1H,3H)-dione, 4-amino-3-methyl-6-
phenyl-1,2,4-triazin-5(4H)-one, 2-chloro-4-ethylamino-6-
1û ;sopropyl-amino-1,3,5-tr;azine, the R-enantiomer of
(tr;methylsilyl)-methyl 2-~4-(3,5-dichloro-pyridyl-2-
oxy)-phenoxy]-propionate, the R-enantiomer of (bouncily-
oxy)-ethyl 2-C4-(3,5-dichloropyridyl-2-oxy)-phenoxy~-pro-
pinnate, 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichloro-
phenoxy)-propionic acid, 4-chloro-2-methyl-phenoxy-ace-
tic acid, 2-(2-methyl-4-chloro-phenoxy)-propionic acid,
3,5-diiodo-4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxy-
benzonitrile and diphenyl ethers and phenylpyridazines,
such as, for example, peridots. Surprisingly, some
mixtures also show a synergistic action.
Mixtures with other known active compounds, such
as fungicides, insecticides, acaricides, nematicides, bird
repellents, plant nutrients and agents which improve soil
structure, are also possible.
The active compounds can be used as such, in the
form of their formulations or in the use forms prepared
therefrom by further dilution, such as ready-to-use soul-
lions, suspensions, emulsions, powders, pastes and grant
vies. They are used in the customary manner, for example
by watering, spraying, atomizing or scattering.
The active compounds according to the invention
can be applied either before or after emergence of the
plants.
They can also be incorporated into the soil before
sowing.
The amount of active compound used can vary within
lo A 23 308 - Foreign Countries
~228357
- I -
a substantial range. It depends essentially on the nature
of the desired effect. In general, the amounts used are
between U.UU1 and 15 kg of active compound per Hector of
soil surface, preferably between USE and 10 kg per ha.
S The preparation and use of the active compounds
according to the invention can be seen from the following
examples.
Preparation examples
Example 1
1 Jo
ONE N I/
\
(Process (a))
2.5 9 (0.14 mole) of 2-chloro-benzenesulphonyl
chloride are addle to a mixture, cooled to -7C, of Lowe g
(U.U37 mole) of N'-(4-diethylamino-6-methoxy-s-triazin-2-
yL)-h"-methoxy-guanidine and 70 ml of pardon, with stir-
ring, and the reaction mixture is stirred at 2UC for
3 days. It is then diluted with water and deathly ether.
Tune product thereby obtained as crystals is isolated by
filtration with suction.
MU 15.~ 9 I of theory) of N'-(4-diethylamino-6-
methoxy-s-triazin-2-yl)-N"-methoxy-N",N"'-bis-(2-csheller-
benzenesulphonyl)-guanidine of melting point 133C are
obtained.
Example 2
I H N OH
2 OUCH
lo A 23 huh - Foreign Countries
54 12~8357
(Process (c))
54 9 (U.256 mole) of 2-chloro-benzenesulphonyl
chloride are added drops to a mixture, cooled to -2UOC~
of 97 g Us mole) of h'-(4-methoxy-6-methyl-s-triazin-2-yl)-
5h"-methoxy-li"'-(~-chloro-benzenesu~phonyl)-guaniddine and
30U ml of pardon, with stirring. The reaction mixture
is stirred it 2~C fox lo hours and concentrated. The
residue is taken up in 3UU ml of ethylene chloride and
this solution is washed twice with 15U ml of dilute hydra-
I caloric acid each time, filtered and concentrated. Theproauct obtainer as crystals on trituration of the residue
with ethanol is isolated by filtration with suction.
U 9 oh of theory) of ~'-(4-methoxy-6~methyl-s~
triazin-2-yl)-N"-methoxy-N"-N"'-bis-(2-chloro-benzzenesul-
phonyl~-guanidine of melting point 164C are obtained.
Example 3
N OUCH
H OUCH
(Process (e))
A mixture of 1U.0 9 Us mole) of N'-(4~6-dime-
thoxy-s-triazin-Z-yl)-h"-(2-chloro-benzenesulphonyyules-
methyl-isothiourea, I g (~.065 mole) of U-methyl-hydroxyl-
amine and ml of Dixon s stirred at 2UC for MU hours.
It is then concentrated, the residue is triturated with
ethanol and the product obtained as crystals is isolated
I by filtration with suction.
I 9 (57X of theory) of N'-(4,6-dimethoxy-s-tri~
azin-2-yl)-N"-methoxy-N"'-(2-chloro-benzenesulphonnil)-
undone of melting point 15~C are obtained.
lo A Z3 I - Foreign Countries
- 55 _ 1228357
Example 4
N a)
C No OUCH
~50/ OKAY
(process (f))
A mixture of Us 9 (0.~1 mole) of N'-(4-methoxy-
56-methyl-s-triazin-Z-yl)-N"-methoxy-h",N"'-bis-(2--sheller
benzenesulphonyL)-yuanidine~ 54 9 01 mole) of so-
drum methyl ate and 5 ml of methanol is stirred at ~UC
for 1 hour. The product obtained as crystals is then is-
fated by filtration with suction.
MU Us 9 (YO-YO. of theory) of the sodium salt of N'-
(4-methoxy-6-methyl-s-triazin-2-yl)-N"-methoxy-N",Nibs
~2-chloro-benzenesulphonyl)-guanidine of melting point
C are obtained.
Example 5
US H N SHEA x H2504
N
Of
process go
A mixture of 5.7 9 ~.01 mole) of N'-(4-methoxy-
~-methyl-s-triazin-~-yl)-N"-methoxy-N" ,N"'-bis-~2-chloro-
benzenesu~phonyl)~guanidine, 1.0 9 (OWE mole) of concern-
MU treated sulfuric acid and 30 ml of acetone is stirred Attica for 15 hours. The product obtained as crystals is
then isolated by filtration with suction.
5.3 9 (81X of theory) of the 1:1 adduce of No
methoxy-~-methyl-s-triazin-2-yl)-N"-methoxy-N",N"''-bus-
lo A I MU& - Foreign Countries
-
12~:8357
- 56 -
(~-chloro-benzenesulphonyl)-guanidine and sulfuric acid
of melting point 148C are obtained.
The compounds of the formula (I) listed in the
following Table 1 can be prepared by the processes described
by way of example in the preceding Examples:
` No R (I )
No
R2 R3
lo A I Jo - Foreign Countries
_ 5 7
.
,
~17 D I
C _ I J _ _
,, I O O O O
a) o
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1 5 5
N
N N
1 5 I I" 5 urn ON
Z Z O Z Z Z
I
to try
T 5
I
O O
I
I
N
Z O O O O O
I
I I I to I I
N T N No N N
O O O Tao Lo O O
Us O Us OUT O Us Us
N I --I I O I OX O I -- I
O o ' o
O I o It
1 C '
a Q
_ E
D 11~ ' I
_ X O Do I I
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12;; :835~
I
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In
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c L I L
, I O
E N
O I _ _,
to
O O O O
T to
O O G
I; , O O O O O O
I T N N N N S N N
l I.) O O l") O O O O
I O Us IL Us IS. Us O Us O Us Us
N I O to O I O I
N
C N try
., I" T
c I I I
I
D (11 ' I
`` U ZOO I N ' Lo
lo A 23 308- Foreign Countries
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12;~8357
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Jo
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c _ , o
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C I N O
, Jo ., --, _, _ I<
Q O
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I
I I _ Jo 5 5 T
Us
;') 1 5 t'" t" to 5
I; I 0 o 5 5 r N
Z O O O O
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T
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C I
I)
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I I
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X O , 0 O -- N to
1-- US Z , ,_ N N N N
lo A 23 308- Foreign Countries
1228357
_ 60 _
Jo , .
C L
., _ I
I N
_ c
S o
Q
T 5
I S I
O O O O
I .
try
t_) S
o o
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N
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T' if
I ,
,
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C`
I ,
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11 .
I, X O I U ED to
1--UJ Z I N N N N N N
lo A 23 308- Foreign Countries
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12,~8357
7, I .
C o
, . o
_ c i on N i
, S I: S
i
i
S T I or
O O O O . O O
Jo '.
T I) S
it I O I'm I'm O I O
i
ON N N
S = or
it 1 5 I O
O O Z Z Z Z
i
i
I
i 5 I: S
C
O
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N
I
if
I, ill Z ' O ...
lo A 23 308- ion Countries
122~3357
-- 6 2 -- o
o I .
C _ , o
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C I O
N
o
Q. I
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N I 3 5 or
Us I o O o o O O
o O N
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N I C Jo 5
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x O I o . --I
Jo z , or
lo A 23 foreign Countries
l'Z28357
_ 63 _
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or o ' O
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T T ;
T 2 I I 5
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~'~ 5
eye 1 5 N NUN 5 :;:
N
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to x o I N to I'
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1228357
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T 1 N N
I ,(.~ 0 I
N or N N
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to)
to I I T
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N O O O O O Us
T C O I
h . IL --,~ e ho L ~[~
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lo A 23 308- Foreign Countries
1228357
_ 65 _
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s _ s s
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to , o o o o O O
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lo A 23 308- Foreign Countries
- 66 - :1228357
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N
N
C I -- 11~
., I 5
T N
Jo I try to
1 5 _ _ T
so I to Z Z to
I O N N AL N
_ l O O O
_ tot ~0~3 to
x o I to I N try Lo
US Z
lo A 23 frown Countries
1228357
-- 67 --
cur
c -- I
, I
c
a o
I
I
or 5 5 5
if: 1 5 r 5 5 5
O o o o o O
1 5 5 5 5 5
1'" 1 U') N N N
I 5 Jo
N I
O O O
O O O
N
N I N N N to N to N N
; 1 0 0 0 5 0 h o I O
I L us us h us
C aye owe
c , I h
o I; my h I h
,
a
_ E
JO .
at x O I O` O --I
LUG Z
lo A 23 308- Foreign Countries
12283S7
- 68
Jo ,
Lo I
I. o
C _. ,
I,
C
J
-a) o
Q
I T T 2 2 2 2
T I I T
O O O O O O
I I
2 or 5 2
V "I V V to
" ~0~0~
IN IN N TN TN
V V V
I O O O O O O
N N
N
T
N
2 I N I T I T l _ I
I_) N N t,) N Lo N Z N Z N
I O O O O O O O O N O N O
N I O to O Us OUT O Us O Us O Us
V~0V~
115 I N N
, _ N
C , ^ I
T N
C I if) 5 --
O T N `'
I V V V Z Z
I O O . O N N
l ! l O O l O l --I l O l O
no x O N
_. LUG Z
.
lo A 23 308- Foreign Countries
1228~357
6 9
, .
O I
C
.,_
5- ,
T T T I T
I I I I :;:
C: , O O O O O O
I ; T T
N N N
) to N
U
X S S I I
I; I S TN TN N Jo
O O O O O O
I I I
N I to N N
N I I I_) O to N O O O
I I N O Us h O to Us O Us I:
e I L 3 0
., 1 5' or
C -I I O O O
O I L O to O O O
Do . I
X o I I --' N try
_IIJ Z
lo A 23 308- Foreign Countries
i228357
-- 70 '--
_ I
. ,
,
C
O
a: n,
So Jo 5 S, :~:
I T T T T T
I N N N N N N
O O O O O O
T S S S 5
I
T 5 = S S T
I I O O O O O- O
N
N
I Us S
I US
N I I I I I T
t ) N N N t'') N N Z N
N I O O O O O S O N O N O
I; I O Us O Us L Us O Us O Us
O , _ N
._ , I" _
T S
N T
z
I O O Jo N N
I I ~3 '
_ E
X O ,
lo A 23 308- Foreign Countries
12283S7
_ I - 71 -
I
C -- ,
, I
I- C
,
T T X 5
I
T
I I) on T T T
.. I .
I' I I T T T ,~, c
2 IN TN
to
N 11 11 11
T T
N N N
.) T
7
O O
N
N T
I t''-) O Jo
N N Z N to N
, I ohs- O O I O
T
_
I; I h o o ox T
Do O , O --I N 1.
lo A 23 308- Foreign Countries
1228~57
-- 72 --
I) I
-- l
Y C
a) o
Q
2 5 2 2 5
2 5 I 5
O O O O O O
2 2 I 2 5 5
D:; , O O O O O O
,
2 2 2 5 2 or
I: I O O O O O O
N
2 _ ,
2 I N 1 2 I No N
N o N o N to) N 0 2 0
I lo. 0 o o o o o o Lug
N , O O O
._ , N
I
' I
C I Lo
2
2 N 2
` C 0 0 0 2
1 `[~3 go
I
_ E
no ., CUD o -I
X o I ox o o
Z I Jo
lo A 23 Ryan Countries
_ 73- ~228357
,
ago
C _ . .,
.,
C
. . .
a O
S I,
I T T ' 5 or
I
O O O
.,
I
O O O O
I
O O ,. O O O O
N N
2:
N t,) Us
N 1 5 1 -- I I 1 5 I N
N Z N N N I) N to N
N O N O O O O O O O O
I O Us O I O Us Us O Us O U)
O 3 No
., ,
I ^
C I
T , N
C Jo I N N O O T o o
O I: I O O I O I O to O I O
_ E
a I N u)
a x o l O O O O O O
z ,, _,
. _
lo A 23 308- Foreign Countries
.
1 1228357
D 1 7 4
C -- I .
., ,- I
C
' J Jo
O
I
T T T T
I
to T
If ) I T I T T 5
to
I S T T C T Lo
I
N
N N S
i 2 I 3:
N -- N N
to I T T T T Tao
Y. I
O O O O
I . l O l l O
I
N
T
, S I I -- I ' I N l I
I N N Z N N k N , N
N I O O O N O k o T O l O
I O US Us O Us Us
3 my I 0
._ , N
3 1 :~:
C I I)
_ , T z to) k I\
C , o N k T
3 my I 0~3 I
a c
' I Of` D N I
l x O I D C
It ILL Z I
lo A 23 foreign Countries
_ 75 _ 1;228357
I D
I
I
_ Jo I
a O
Q
or
O O O
S
O
I)
[I N
N r) N
I T I 5
O O O O
N
N O
N O Us
O Us I
lo
N I I
L) to t.)
C
O
._ I
I
1~1
r- I I I
I O O
O I O . L O
a
_ E
D
X o I --'
_ ELI Z I -- --' --
.
lo A 23 308- Foreign Countries
- 76 - 12~8357
(pa) 1:1 adduce of Example (2) with p-toluenesulphonic
acid (oil).
(aye) 1:1 adduce of Example (44) with sulfuric acid
(amorphous).
(aye) 1:1 adduce of Example ~45) with sulfuric acid,
having a melting point of 163C.
(aye) 1:1 adduce of Example (49) with sulfuric acid
(amorphous).
lo A 23 308 - Foreign Countries
_ 77 _ 1228357
Preparation of starting compounds of the formula (II)
Example (II-1 )
Ho No OUCH
HO N _(/ \ N
C No N ( C2H5 ) 2
N
H OUCH
A nlixture of 66.5 9 I mole) of cinnamon-
5 diethylamino-6-methoxy-s-triazine, I 9 (0.8 mole) of I-
methylhydroxylarnine hydrochloride and I ml of ethanol
is heated at the boiling point under reflex for 15 hours.
It is then filtered, the filtrate is concentrated, the
residue is taken up in about rnl of water, the mixture
AL is rendered alkaline with sodium hydroxide solution and
the product thereby obtained as crystals is isolated by
filtration with suction.
I 9 (43/. of theory) of N'-(4-diethylamino-6-
methoxy-s-triazin-2-yl)-N"-methoxy-guanidine of melting
point 112C are obtained.
The compounds of the formula (II) listed in the
following Table can be prepared analogously:
` H, No
HO No/ \ N
C N~CR5 (II)
N
H/ \R3
lo A So - Foreign Countries
- I _ 1228~57
Tibet
Example welting
No; R3 R4 R5 point~oC
________________________________________________________
it- 2 OUCH SHEA NHC2H5 117
11- 3 OUCH SHEA NHCH3
5 II- 4 OUCH Of N(C2H5~2
If- 5 C2H5 OUCH N~C2H5)2
If- 6 Ozone SHEA NHC2H5
If- 7 OCH(CH3)2 OUCH NHCH3
If- 8 OCH2-CH=CH2 OUCH N~CH3)2
10 If- 9 Ozone OUCH N~CH3)2
Isle OUCH OUCH N~CH3)2
lo A 23 aye- Foreign Countries
1~28357
Table 2 - Continuation
Example Melting
No R3 R4 R5polnt tic)
1]-11 OCH2COOC2H5 OCH3N(CH3)2
II-12 OUCH SHEA OUCH N~CH3)2
511-13 OUCH SHEA OUCH
11-14 OUCH SHEA OUCH
11-15 OOZE SHEA OUCH 95
II-16 OUCH SHEA NHC2H5122
11-17 OUCH SHEA C2H5
10 11-18 OUCH SHEA C2H5(amorphous)
11-19 ooze SHEA SHEA
lo A 23 308- Foreign Countries
1228357
-
Table 2 - Continuation
Example Melting
No. R3 R4 R5 point DC)
________________________________________________________
11-20 OUCH SHEA SHEA
11-21 OCH2-CH=CH2 SHEA SHEA
511-22 OUCH OUCH OUCH
11-23 OUCH OUCH OUCH
Isle OCH2-C~cH3)3 SHEA SHEA
11-25 OCH2CH2-OCH3 OUCH OUCH
IJ-26 OCH2CH2-Oc2H5 SHEA OUCH
10 11-27 OCH2CH2-ScH3 SHEA C2H5 r
11-28 OCH2CH2-Sc2Hs SHEA SHEA
Toe A 23 3D8- Foreign Countries
. .
1228357
- 81 -
Table 2 - Continuation
Example Melting
No. R3 R4 R5 point
___________________ ___ _ _____________________________
Isle CHICANO OUCH OUCH
Isle OCH2-CH=CHCl SHEA OUCH
5 ~I-31 OUCH 2 SHEA SHEA
II-32 OX ( ) SHEA SHEA
Lo A 23 308- foreign Countries
12~:8357
so
reparation of starting compounds of the formula (III)
Example (I If -1 )
Of
Scholl
295 ml of phosphoryl chloride ("phosphorus ox-
S chloride") are added drops to a mixture of 172 y
Us mole of sodium 2-chloro-benzenesulphonate, 300 ml
of acetoni~riLe and 3UU ml of sulpholane at 2UC to 30C.
The reaction mixture is stirred at 7UC for 4 hours and
then cooled to SAC and diluted with ice-water. After
extraction with petroleum ether, washing of the extraction
solution with water, drying, filtration and concentration,
the product remaining in the residue is purified by vacuum
distillation.
117 9 MU of theory) of 2-chloro-benzenesulphonyl
chloride of boiling point okay mar are obtained.
Example (III-2)
COUCH
clue
75.5 9 (0.5 mole) of methyl ~-aminobenzoate are
dissolved in 170 ml of concentrated hydrochloric acid and
MU 1UU ml of acetic acid. A solution of 34.4 9 of sodium
nitrite in MU ml of water is added drops at UC. After
the reaction mixture has been subsequently stirred for 15
minutes, it is slowly added to a saturated solution, cooled
to C, of Selfware dioxide in 45U ml of acetic acid.
I After the cooling bath has been removed, the mixture is
stirred until the evolution of gas has ended, MU g of cop-
pyre) chloride being introduced in portions. After dill-
lion with ice water extraction with ethylene chloride,
washing of the extraction solution with water, drying,
SO filtration and concentration, the product remaining in the
lo A 23 MU - Foreign Countries
lZ28357
83 -
residue is purified by vacuum distillation.
45 9 ~38Xo of theory) of ~-methoxycarbonyL-ben~ene~
sulphonyl chloride of boiling point 15UC/1.33 mar are
obtained.
The compounds of the formula (III) Listed in the
following Table 3 can be prepared analogously:
R1-SO Jo L (III )
lo A I MU Foreign Countries
1228357
_ 84 _
Table 3
,
Example No. R1 Boiling point/
D reassure
_________ _ _ _____ __ _ __ _~____ .______ ______ _
OUCH (owl, decomposition
III- 3 . on d;st1llatlon) .
III- 4 (melting point:100C)
CF3
I 11- 5 (Of l)
Ill- 6 or 142C/4 mar
III- 7 106C/4 mar
OSSIFY
III- 8 (molting poetic)
,_~OCHF2 (owe, decomposition
_ . III- 9 on d;st;llat;on)
S ON SHEA ) 2
1û Ill-10 (melting poetic)
- . SHEA oily, decomposition
Isle on dist;llat;on)
lo A 23 308- Foreign Countries
~228357
- 85 -
Table 3 -continuation
Example No. R1 Boiling point/pressure
__ _ __ __ __ _ __ _ _ _____________ _____
SCH(CH3)2
IOTA 90C/1.33 mar
CH2502cH3
III-13 molting punt C)
COOK
III-14 155 C/5.32 mar
CH2SOCH3
I I I - 1 5
SHEA
III-16 (melting point:128C)
CHIC 1
III-17
lo A 23 308- Foreign Countries
1228357
- 86 -
Preparation of starting substance of the formula (VI)
Example VOW)
"H, No SHEA
HO No N
C OKAY
/
4.2 9 Tao mole) of 2-chloro-benzenesulphonyl
S chloride are added to a mixture of 6.0 9 (0.02 mole) of
N'-(4-ethoxy-6-methyl-s-tr;az;n-2-yl~-N"-benzyloxyy-
guan;d;ne and 30 ml of pardon which has been cooled to
okay - 5C, and the mixture us stirred for 48 hours at
20C. After the mixture has been concentrated, the
residue us taken up on ethylene chloride, the solution
is washed with ON hydrochloric acid, dried and filtered,
and the filtrate is carefully concentrated.
6.1 9 (64X of theory) of N'-(4'-ethoxy-6-methyl-
s-tr;az;n-2-yl)-N"-benzyloxy-N"-(2-chloro-benzene--
sulphonyl)-guan;d;ne are obtained as an only residue.
The compounds of the formula (VI) which are
lusted on Table 4 below can be prepared analogously:
HO NH No
No R S ( V I )
No
Al -S02 R3
lo A 23 308 - Foreign Countries
12;~8357
-- 87
U)
,
I o
on O I
C
.,. I L
C I O
E
(It O I to
S'` a.
LO
us I .5 I: I to N
I I_) T
O O O I.) O O
to
N S
N to
S N
N
N N N Us
N
I" " N S
O l l O O
to
I S Z
I O --I to I N
o So r So'
a I
a I , N Us
_ E l l l l l l I
I X O I
Z I
.
lo A 23 308- Foreign Countries
.
` 1228357
- 88
Preparation of starting substances of the formula (VII)
Example)
" , No OUCH
SHEA-
11 g ~0.4 mole of sodium hydra (~0/. pure) are
5 added in portions to a suspension of 31.2 9 (OOZE mole) of
2-amino-4,~-dimethoxy-s-triazine in 20C ml of tetrahydro~
Furman at ~UC. After the mixture has been stirred for
12 hours, MU g (0.2 mole) of S',S"-dimethyl N-(2-chloro-
benzenesulphonyL)-imino-dithiocarbonate are added, where-
upon the reaction temperature rises to 60C. the reaction mixture is stirred at 20c for 5 hours, diluted with
~00 ml of water and filtered. After acidification with
concentrated hydrochloric acid, the product crystallizes
and is isolated by filtration with suction.
42 9 OX of theory) of N'-(4,~-dimethoxy-s-tri-
azin-2-yL)-N"- Czech loro-benzenesulphonyl)-S-methyL-iso-
Thor of melting point 176C are obtained.
The compounds of the formula (VII) listed in the
following Table 5 can be prepared analogously:
I,
lo A I I - Foreign Countries
9 - 1228~57
H N R4 (Ill)
S N-/ R5
\R16
Try -I
Example Melting
No. Al R4 R5 R16point(C)
________________________________________________________
VII- I l OUCH OCH3CH3 159
VII- clue SHEA N(CH3)2 SHEA 175
VII- I SHEA OUCH SHEA 148
SHEA
VII- I SHEA OUCH SHEA 167
SHEA
VII- I SHEA 170
SHEA
VII- I SHEA C2H5 SHEA 104
SHEA
10 VII- 3 SHEA SHEA SHEA 119
lo A 23 aye- Foreign Countries
1228357
. - 90
Table S - Continuation
Example Melting
no. Al R4 R5 R16 p`oint(C
Of
Ill- 9 SHEA- SHEA SHEA SHEA 165
VII-10 l SHEA SHEA SHEA 151
OSSIFY
5 Vll-ll SHEA OUCH SHEA to
OCHF2
V11-12 OUCH OUCH SHEA
OCHF2
Vll-13 SHEA OUCH SHEA
-- , SHEA
Vll-14 SHEA OUCH
SYNCH
10 V11-15 SHEA OUCH SHEA
SYNCH
Vll-16 OUCH OUCH SHEA
COOK
V11-17 OUCH OUCH SHEA
lo A 23 30~- Foreign Countries
1228357
_ 91 -
Table 5 - Continuation
- Example Melting
No. Al R4 R5 R16 p`o;nt~C)
_______________ ________________________________________
COOCH~CH3~2
V11-18 OUCH SHEA SHEA
F
Vll-l9 SHEA OUCH SHEA
By
V11-20 SHEA OUCH SHEA
OUCH
5 VII-21 OUCH OUCH SHEA
CF3
VII-22 OUCH SHEA SHEA
VII-23 SHEA OUCH SHEA
SCH~CH3)2
Vll-24 SHEA OUCH SHEA 136
Of
VII-25 g C2H5 OUCH SHEA 132
OSSIFY
lo VII-26 SHEA C2H5 SHEA 103
lo A 23 308- Foreign Countries
1.%28357
- 92 -
Preparation of starting substances of the formula VOW)
Example (VIII-1 )
No ooze
NC - NO N
No -
52.7 9 (0.3 mole) of 2-chloro-4,6-dimethoxy-s-tri-
S amine are added to a solution of 30 9 (0.3 mole) of thedisodium salt of cyanamide in 600 ml of acetone, and the
reaction mixture is heated at the boiling point under no-
flux for 6 hours. After the solvent has been distilled
off, the crystalline residue is dissolved on 250 ml of
water and the solution is acidified with concentrated
hydrochloric acid. The product obtained as crystals is
isolated by filtration with suction.
33 9 (61X of theory) of 2-cyanoamino-4,6-dimethoxy-
s-triazine with a melting point above 300C are obtained.
Example (VIII-2)
(a) NC-N -I ON
No N--~C1
4.5 9 (0.05 mole) of disodium salt of cyanamide 50 ml
of water are added drops to a suspension of 8.2 9 (0.05
mole) of 2,4-dichloro-6-methyl-1,3,5-triazine in 100 ml
20 of ice-water at a temperature of 0C to 5C in such a
way that a pi value of 9.5 is not exceeded. Thereafter,
stirring is continued for another hour at 20C, 40 9
of sodium chloride are added, and stirring is continued
for approx. 0.5 to 1 hour at 20C
After the product has been filtered off with
suction and dried, 9.1 9 (95X of theory) of the sodium
salt of 4-chloro-2-cyanoamino-6-methyl-1,3,5-triazine of
lo A 23 308 - Foreign Countries
1228357
- 93 -
melting point 190C (decomposition) are obtained.
(b)
N SHEA
NC-NH / N
' No
1 ml of concentrated hydrochloric acid is added
to a suspension of 2 9 (0.01 mole) of the sodium salt of
4-chloro-2-cyanoamino-6-methyl-1,3,5-triazine in 50 ml
of water at 0C to 10C. The precipitate formed is
filtered off with suction and dried.
In this manner, 1.3 9 (77% of theory) of
4-chloro-2-cyanoamino-6-methyl-1,3,5-triazine of melting
point 105C (decomposition) are obtained.
lo) N SHEA
NC-N I/ N
No N OOZE
A solution of 3.7 9 (0.16 mole) of sodium in
100 ml of ethanol is added drops to a solution of
29 9 (0.15 mole) of the sodium salt of 4-chloro-2-cyano-
amino-6-methyl-1,3,5-triazine in 500 ml of ethanol in
such a way that a reaction temperature of 30C is not
exceeded. Thereafter, stirring is continued for 3 hours
at 20C, and the mixture is diluted with 400 ml of
ethanol and filtered. The filtrate is concentrated
in vacua, the temperature not exceeding 45C.
In this manner, 29.9 9 (99X of theory) of the
sodium salt of 2-cyanoamino-4-ethoxy-6-methyl-1,3,5-tri-
amine of melting point 200C (decomposition) reobtained.
(d) N SHEA
NC-NH I/ N
N OKAY
lo A 23 308 - Foreign Countries
- 94 _ ~228357
50 ml of 20X. strength hydrochloric acid are
added to a solution of 30.1 9 (0.15 mole) of the sodium
salt of 2-cyanoamino-4-ethoxy-6-methyl-1,3,5-triazine in
300 ml of water at 0C to 10C, and stirring is con-
5 tinted for 15 minutes at 10C. The precipitate is filtered off with suction and dried.
26.5 9 ~98X of theory) of 2-cyanoamino-4-ethoxy-
6-methyl-1,3,5-triazine of melting point 195C (deco-
position) are obtained.
10 (e)
No SHEA
NC-NH~ N
No OOZE
8.5 9 (0.05 mole) of 4-chloro-2-cyanoamino-6-
methyl-1,3,5-triazine are added in portions to a
solution of 2.5 9 (0.11 mole) of sodium in 100 ml of
15 ethanol in such a way that the temperature does not
exceed 35C. Thereafter, stirring is continued for
one hour at 20C, and the mixture is concentrated
in vacua in such a way that the bath temperature does
not exceed 50C. The residue is dissolved in 50 ml
20 of water, and the solution is acidified with 6 ml of con-
cent rated hydrochloric acid. The crystals formed are
filtered off with suction and dried.
8.1 9 (91X of theory) of tsunami nighthawks-
6-methyl-1,3,5-triazine of melting point 195C (deco-
25 position) a no obtained.
The compounds of the formula (VIII) listed in the following Table 6 can be prepared analogously:
No (VIII)
NC-NH N
N~R5
lo A 23 308 - Foreign Countries
122~3S7
- 95
Tab Le. 6.
Exam l e Me L t i no
No. R4 R5 Po;nt~oc)
______. ___ ____________________________________ _______
VIII- 3 OUCH N(C2H5)2 114
VIII- 4 SHEA NHC2H5
5 VIII- 5 OUCH NHCH3 Z10
VIII- 6 Of N~C2H5)2 156
VIII- 7 OUCH SHEA 184
VIII- 8 OCH(CH3)2 SHEA
VIII- 9 SHEA SHEA
10 VIII-10 5C2H5 SHEA
Vowel SCH(CH3)2 SHEA
lo A 23 308-. Foreign Countries
- 96
1228357
Tab to 6 - wont 1 nut i on
Exam to Me Lang
No. R4 R5 point
________________________________________________________
VI I I - 12 NHCH3 SHEA
VI I 1-13 NHCH(CH3)2 SHEA
.
5 VI I I-14 N(CH3)2 SHEA
VIII-15 SHEA SHEA
lo A 23 foreign Countries
_ 97 _ 12283S7
Preparation of starting confounds of the formula (XV)
Example (hV-1) Of
~;2-N=C/
SHEA
8 g Us mole) of sodium hydroxide - dissolved in
15 ml of water - and 6 ml (0.11 mole) of carbon disulphide
are simultaneously added drops (from different dropping
funnels) to a solution of MU 9 (0.1 mole) of sheller-
benzenesulphonamide in 80 ml of dimethylformamide at
2~C After the mixture has been stirred for 1 hour,
MU 13 ml (0.22 mole) of methyl iodide are added drops
and the reaction mixture is stirred at 20C for a further
hour. The product is precipitated by addition of MU ml
of water an is isolated by filtration with suction.
22.1 9 (75'~ of theory) of S',S"-dimethyl No
chloro-benzenesulphonyl)-isothiocarbamate of melting
point 112C are obtained.
The compounds of the formula (XV) listed in the
following Tale 7 can be prepared analogously:
SO 1 6
Rl-502-N=C (XV)
SO l 6
lo A S08 Foreign Countries
1228357
_ I
.
Tubule
Example Melting
No. R1 R16 point DO
__ _ _ __ _ _ _ ____ ________ . _ ____
SHEA
XV- 2 SHEA 103
SHEA
XV- 3 SHEA 143
-
S02CH3
5 XV- 4 SHEA
OSSIFY
XV- 5 SHEA 88
Of
XV- 6 SHEA- SHEA 96
OCHF2
XV- 7 SHEA 112
SNOWSHOE
_ XV- 8 SHEA
10 XV- 9 SHEA 100
XV-10 Of SHEA 94
lo A 23 forgone Countries
.
1228357
_ 99 _
Table 7 - continuation
Example Melting
No. Al R16 point~C~
___~_______ __ _ ____ _ _ _____ __ _ _ __ ___
XV-ll H3C - SHEA 107
XV-12 F SHEA 113
o
5 XV-13 H3C-C-NH SHEA 170
CH2502CH3
XV-14 SHEA
C COO 2H5
XV-15 SHEA
COOCH~CH3)2
XV-16 SHEA
XV-17 SHEA
By
10 XV-18 SHEA
CF3
XV-19 SHEA
lo A 23 308- Foreign Countries
1228357
- 100-
Tubule - continuation
Example Melting
Jo-. R1 R16 po;nt~C)
________________________________________________________
XV-20~ OUCH OH
XV-21 l SHEA
5 XV-22 C2H5 64-66
XV-23 l CH~CH3)2 65-67
SCH~CH3)2
XV-24 SHEA 98
XV-25 Of SHEA a
Lo A 23 308---~oreign Countries
1228357
- 101 -
Preparation of starting substances of the formula tXVI)
Example (XVI-1)
SHEA
52 -NH2
50 ml of concentrated ammonia are added drops
to a mixture of 60 9 (0.27 mole) of 2-methylthiobenzene-
sulphonyl chloride and 60 ml of acetone at 20C to 30C,
with stirring. The reaction mixture is subsequently
stirred at 20C for 1 hour and then poured into 600 ml
of 10X strength sodium hydroxide solution. This solution
is filtered and then acidified with concentrated hydra-
caloric acid. The product thereby obtained as crystals
is isolated by filtration with suction.
19 9 (30X of theory) of 2-methylthio-benzenesul-
phonamide of melting point 149C are obtained
The compounds of the formula (XVI) listed in the
following Table 8 can be prepared by the process described
by way of example in the preceding Example:
R1-S0z-NH2 (XVI)
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Table 8
Example Melting
No. Al put
_______________________________~._______________ _______
SCH~CH3~2
XVI- 2 - - 102
XVI- 3 156
SHEA
XVI- 4 235
502N~CH3)2
XVI- 5 g_ 142
OSSIFY
XVI- 6 186-189
OCHF2
XVI- 7 134
C1
XVI- a SHEA-
CHz502CH3
10 XVI- 9 175
COOK
XVI-10 78
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Table 8 - continuation
Example Melting
No. R1 point tic)
_______ ___ _ _ _ __ _ __ __ _____ _ _____ _ _____
COUCH ( SHEA ) 2
XVI -l 1 Jo
Shekel -
XVI-12 (I
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Example A
Reemergence test/Greenhouse
Solvent: parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active come
pound, 1 oat by weight of active compound is mixed with
the stated amount of solvent, the stated amount of Emil-
sifter is added and the concentrate is diluted with water
to the desired concentration.
I Seeds of the test plants are sown in normal soil
and, after 24 hours, watered with the preparation of the
active compound. It is expedient to keep constant the
amount of water per unit area. Toe concentration of the
active compound in the preparation is of no importance,
only the amount of active compound applied per unit area
being decisive. After three weeks, the degree of damage
to the plants is rated in Jo damage in comparison to the
development of the untreated control. The figures
denote:
Ox. = no action trike untreated control)
10UX = total destruction
In this test, for example, the following compounds
from the preparation examples exhibit an excellent
activity: (2) and I
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Example B
Post-emergence test/~reenhouse
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active come
pound, 1 part by weight of active compound is mixed with
the stated amount of solvent, the stated amount of emulsi~
lien is added and the concentrate is diluted with water to
the desired concentration.
Test plants which have a height of 5 - 15 cm are
sprayed with the preparation of the active compound in such
a way as to apply the particular amounts of active compound
desired per unit area. The concentration of the spray
liquor is so chosen that the particular amounts of active
lo compound desired are applied in ZOO l of water/ha. After
three weeks, the degree of damage to the plants is rated in
damage in comparison to the development of the untreated
control. The figures denote:
= no action (like untreated control)
MU 1UU~ = total destruction
In this test, for example, the following compounds
from the preparation examples exhibit an excellent
activity: (Z), I and I
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