CA1227205A - Sulphonylisothioureidopyrimidine derivative - Google Patents
Sulphonylisothioureidopyrimidine derivativeInfo
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- CA1227205A CA1227205A CA000513443A CA513443A CA1227205A CA 1227205 A CA1227205 A CA 1227205A CA 000513443 A CA000513443 A CA 000513443A CA 513443 A CA513443 A CA 513443A CA 1227205 A CA1227205 A CA 1227205A
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- chlorine
- methyl
- benzenesulphonyl
- fluorine
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Abstract
ABSTRACT OF THE DISCLOSURE
A sulphonylisothioureidopyrimidine derivative of the general formula (VII A) (VII A) in which R1 represents a substituted phenyl radical
A sulphonylisothioureidopyrimidine derivative of the general formula (VII A) (VII A) in which R1 represents a substituted phenyl radical
Description
~7;2~S
This is a divisional application of Canadian patent application number 489,594, filed on Thea August, 1985.
The invention relates -to new sulphonylguanidinopyrimidine derivatives, processes for their preparation and their use as herbicides.
Various guanidine derivatives have been disclosed as potential herbicides in patent specifications (compare DE-AS (German Published Specification) 1,089,210 and East German Patent Specifications 71,016 and Betty have not hitherto achieved relatively great importance as agents for combating weeds and/or regulating plant growth.
Other guanidine derivatives are the subject of prior patents EGOS (European Published Specification) 121,082).
According to the parent application there are provided new sulphonylguanidinopyrimidine derivatives of the general formula (I) , M N __,R4 Al SO N `~' N R5 (I)
This is a divisional application of Canadian patent application number 489,594, filed on Thea August, 1985.
The invention relates -to new sulphonylguanidinopyrimidine derivatives, processes for their preparation and their use as herbicides.
Various guanidine derivatives have been disclosed as potential herbicides in patent specifications (compare DE-AS (German Published Specification) 1,089,210 and East German Patent Specifications 71,016 and Betty have not hitherto achieved relatively great importance as agents for combating weeds and/or regulating plant growth.
Other guanidine derivatives are the subject of prior patents EGOS (European Published Specification) 121,082).
According to the parent application there are provided new sulphonylguanidinopyrimidine derivatives of the general formula (I) , M N __,R4 Al SO N `~' N R5 (I)
2 \ 3 on Shea M represents hydrogen or one equivalent of a metal, 1 represents an optionally substituted phenol radical earn R7 and I are dental or different and represent hydrogen, halogen [in particular fluorine, color--Noah anger bromide cyan, vitro or C1-C4-alkyl [which is optionally substituted by fluorine, chlorine, brom;ne, Sweeney C1-c4-alkoxy-carbonyl~
lo A 23 307 - Foreign countries I
C1-C4-alkylamino-carbonyl, di-(C1-Cb-alkyl)-amino carbonyl, C1-C4-alkoxy, C1-Ch alkylthio, C1-C~-alkylsulph;nyl or C1-C4-alkyl-sulphonyl~, or represent C1-C4-alkoxY C~h;ch is optionally substituted by fluorine, chlorine, bromide, cyan, C1-C~,-alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylthio~ C~-C4-alkylsulph;nyl or C1-C4-alkyl-sulphonyl], or represent C1-C4-alkylthio, C1-C~-alkylsulphinyl or C1-C4-alkylsulphonyl Couch are optionally substituted by fluorine, chlorine, bromide, cyan or C1-C4-alkoxy-carbonyl~, or represent C1-C~-alkylamino-sulphonyl, d;-(C1-C4-alkyl)-am;no-sulphonyl, C1-C4-alkoxyamino-sulphonyl, benzyloxy-aminosulphonyl, C1-C4-alkoxy-C1-C4-alkyl-aminosulphonyl, or represent phenol or phonics, or represent C1-C4-alkoxy-sulphonyl, or represent C2-C6-alkenyl which is optionally substituted by fluorine chlorine, bromide, cyan, C1-C4-alkoxy-carbonyl, carboxyl or phenol, c2-c6-alk;nYl Shea us optionally substituted by fluorine chlorine, bromide, cyan or C1-C4-alkoxy-carbonyl~, c3-C6-alkenoxY
Couch is optionally substituted by fluorine, chlorine, bromide, cyan or c1-c4-alkoxY-carbonyl]~
C3-C6-alkenylthio which is optionally subset-tuned by fluorine, chlorine, bromide, cyan or Cl-c4-alkoxy-carbonyl~ C1-C6-alkoxy-carbonyl which us optionally substituted by fluorine, chlorine, brom;ne, cyan or C1-C4-alkoxy~, C3-C6-cycloalkoxy-carbonyl, cl-c~-alkYlth;ocarbonyl wish us optionally substituted by fluorine, chlorine bromide cyan or C1-C4-alkoxy-carbonyl~, amino-carbonyl, C1-C4-alkylamino-carbonyl, dip tC1-C4-alkyl)-amino-carbonyl, Cl-C4-alkoxy-aminocarbonyl, C3-C4-alkenyloxy-amino carbonyl, benzyloxyaminocarbonyl, C1-C4-alkoxy-C1-C4-lo A 23 307 - Foreign countries I
alkyl-amino-carbonyl, d;methylhydraz;nocarbonyl, dimethylhydrazinosulphonyl, c3-c6-a~kinYlo~y or C3-C6-alkynylthio;
or in Shea, furthermore, R1 represents an optionally substituted bouncily radical SHEA-whereon R9 and R10 are identical or different and repro-sent hydrogen, halogen Couch as, in particular, fluorine, chlorine or bromide Sweeney vitro, C1-Colloquial which is optionally substituted by fluorine andlor chlorine], C1-C4-alkoxy tush is optionally substituted by fluorine and/or chlorine, C1-c4-alkoxy-carbonyl~ C1-C4-alkyl-trio, c1-C4-alkYlsUlPhinYl~ C1-C4-alkYl-sulphonyl or di-(C1-C4-alkyl)-am;nosulphonyl;
and on Shea, furthermore, R2 represents hydrogen, C1-C4-alkyl or a sulphonyl radical R11-S02-wherein R11 represents C1-C12-alkyl Couch is optionally substituted by fluorine, chlorine, brom;ne, cyan, Nero C~-C4-alkoxy-carbonyl, C1-C4-alkylam;no-carbonyl~ d;-(C1-C4-alkyl)-am;no-carbonyl~
C1-C4-alkoxy~ C1-C4-alkylth;o, C1-C4-alkyl-sulph;nyl or C1-C4-alkylsulphonyl], C1-C12-alkoxy which is optionally substituted by fluorine, chlorine, brom;ne, cyan, Nero C1-C4 alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylth;o, C1-C4-alkylsulph;nyl or C1-C4-alkyllsulphonyl], Cz~C12-alkenyl C~h;ch us optionally substituted by fluorine, chlorine, brom;ne, cyan, Nero C1~
lo A_ 3 307 - Foreign countries_ ~27~
C4-a~koxy, C1-C4-aLkylth;o or phenol, ~2-C12-alkenyloxy which is optionally substituted by fluorine, chlorine, brom;ne, cyan, vitro, C1-C~-alkoxy, C1-C4-alkylthio or phenol, C1-Cg~
alkylamino, di-(C1-C4-alkyl)-amino, C3-C6-cyclo-alkyl-amino or di-(C3-C6-cYcloalkyl)-amino which are optionally substituted by fluorine, chlorine, bromide, Sweeney vitro, phenol, phonics, C1-C4-alkoxy, C1 C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl], C2-C8-alkenYlamino [which is optionally substituted by fluorine, chlorine, bromide, cyan, vitro or phenol, phenol-amino or benzylam;no [Shea are optionally subs;-tuned by fluorine, chlorine, bromide, C1-C4-alkyl9 trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoro-alkoxy, C1-C4-alkylthio, C1-C~-alkylsulphinyl, C1-C~-alkylsulphonyl, cyan, vitro and/or C1-c4-alkoxY-carbonyl]~ bouncily Which us optionally substituted by fluorine, chlorine, bromide, cyan, vitro, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy-carbonyl~ C1-C4-alkoxy or di-(C1-C4-alkyl)-am;no-sulphonyl~ or an optionally subset-tuned phenol radical R
- wherein R13 R12 and R13 are dental or different and have the meanings given above for R7 and I but are not identical to R7 and R8 on each individual case;
and in which, furthermore R3 represents the radical -û-R14, 30 whereon R14 represents Cl-c1z-alkyl [which us optionally substituted by fluorine, chlorine, bromide, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C~-C4-alkylsulphonyl], or represents C3-C6-cycloalkyl~ C3-C6 cycle alkyl-C1-C2-alkyl~ c3-c6-alkenyl Couch us lo A 23 307 - Foreign countries I I
optionally substituted by fluorine, chlorine or bromide C3-C6-alk;nyl, C1-C4-alkoxy carbonyl-C1-C2~
alkyd, aminocarbonylmethyl, C1-C4-aLkylamino-carbonyl-methyl or di-(C1-C4-alkyl)-amino-carbonyl-methyl, or represents phenol, bouncily, or ben~hydryl or phenethyl Shea are optionally substituted by fluorine, chlorine, vitro, cyan, C1-C4-alkyl, Cl-C4-alkoxy or C1-C4-alkoxy-carbonyl];
or in which, furthermore, R3 represents the radical -N
Rl6 wherein R15 represents hydrogen or C1-C4-alkyl and R16 represents hydrogen or C1-C4 alkyd [which is optionally substituted by fluorine, chlorine, bromide, cyan, C1-C~-alkoxy or C1-C4~alkoxy-carbonyll, or represents C3-c6-cycloalkyl~ or represents phenol, bouncily or phenethyl which are optionally substituted by fluorine, chlorine, bromide, cyan, vitro, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl]~ or represents C1-C4-alkyl-carbonyl, C~-C4-alkoxy-carbonyl, C1-C4-alkyl-sulphonyl or phenylsulphonyl Couch is optionally substituted try fluorine, chlorine, bromide, cyan, vitro or methyl;
and on uh;ch, furthermore - in the case where R2 repro-sets a sulphonyl radical R11-S02-earn R11 has the above mentioned meaning -R3 also represents hydrogen; 0 and in which, furthermore, I represents hydrogen, fluorine, chlorine brom;ne or C1-C~-alkyl Couch is optionally substituted by fluorine and/or chlorine], or rep-resents C1 c4-alkoxy Couch is optionally sub-lo A 23 307 - Foreign countries 2'7~S
stituted by fluorine and/or chlorine, or represents C1-C4-alkylthio Couch us optionally substitu-ted by fluorine and/or chlorine];
R5 represents hydrogen, fluorine, chlorine, S bromide or C1-Ct~alkyl Couch is optionally substituted by fluorine and/or chlorine, or rep-resents cyan, formal, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl and R6 represents hydrogen, C1-C4-alkyl which us optionally substituted by fluorine Andre chlorine], or represents C1-C4-alkoxy Couch is optionally substituted by fluorine and/or chlorine, or represents amino, C1-C4-alkylamino or d;-tC1-C4-alkyl)-amino - Thea the proviso thee R4 and R6 do not Somali-tonsil represent methyl.
1:1 adduces of compounds of the formula (I) with strong acids, have also now teen found, the following come pounds being excluded: the possum salt of N'-t4,6-20 d;methoxy-pyrimidin-2-yl)-N"-methoxy-N"'-~2-trifluurea-methoxy benzenesulphonyl)-guanidine, N'-(4-methoxy-6-methyl~pyrimidin-2-yl)-N"-pimethylamino-N"'-t2-metthy-benzenesulphonyl)-guanidine, N'-~4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N"'-~2-chloro-benzenesuulphon-yl~-guan;d;ne and N'-(4-methoxy-6-methyl-pyrim;din~Z~Y~)~
'N"-dimethylam;no-N"'-~2-chloro-benzenesulphonyl)--undone.
If M represents hydrogen, the general formula I) repro-sets the individual tautomers of the formulae VIA) and JIB) z to NO US VIA) R2 ~R3 . C N pi ( If) N
lo A 23 307 - Foreign countries I
in Shea R1 R2 R3 R4, R5 and R6 have the above mentioned meanings, and mixtures of the tautomers (IA) and tip).
S The mixing ratio (IA)/(IE~) depends on factors which determine the state of aggregation, such as, for example, the temperature, solvent and concentration.
In the case where, on addition t-o M, R2, too, represents hydrogen, a further tautomeric form (IT) is possible:
\ C / ON ~R6 (IT) N
~R3 According to a further aspect of the parent application the new sulphonylguanidinopyrimidine derivatives of the formula I) are obtained by a process in which (a) in the case where M represents hydrogen and R represents R -S02 guanidinopyrimidine derivatives of the formula (II) \ H I R4 HO R5 ill) g No R6 on which R3, R4, R5 and R6 have the above mentioned meanings, are reacted with sulphon;c acid chlorides of the formula (III) R1-S02 Of (III) on Shea R1 has the above mentioned meaning, in the presence of acid acceptors and if appropriate on the presence of d;luents; or lo A 23 307 Foreign countries ___ ~2Z~dZ~S
(b) in the case where M represents hydrogen and R2 rep-resents hydrogen or C1-C4-alkyl, the sulphonyLguani-d;nopyrimidine derivatives obtainable by the process desk cried above under (a), of the formula RID) H ' N R4 RYAN No/ R5 tidy C / N I
N
R1-5~2 o'er in Shea R1 R4 R5, I and R14 have the above mentioned meanings, are reacted with amino compounds of the formula (IVY) /R2 (IV) HO
in which R
R2 represents hydrogen or C1-c4-alkyl and R3 has the above mentioned meaning, or ugh hydrochloride of amino compounds of the formula IVY), 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 rep resents a sulphonyl radical of the formula R1 1 Sue_ wherein R11 has the above mentioned meaning, sulphonylguanidinopyrimidine derivatives of the formula (If) Rl-SQ2-N No/ R5 I / N~<R6 N (If) H I
lo A 23 307 Foreign countries ~L2;~'7 in which R1, R3, R4, R5 and R6 have the above mentioned meanings, are reacted with sulphonic acid chlorides of the formula (V) R11-50z-Cl (V) in which R11 has the above mentioned meaning, in the presence of acid acceptors and it appropriate in the presence of delineates; or id) likewise in the case where M represents hydrogen and R2 represents a sulphonyl radical of the formula ROY-wherein R11 has the abovement;oned meaning, sulphonylguan;d;nopyrimidine derivatives of the formula (VI) , H; N R4 Ho `' No/ R5 (VI) R11-502 \R3 in Shea R3, R4, R5, R6 and R11 have the above-mentioned meanings, are reacted with sulphonic acid chlorides of the formula ~III) R1-S02-Cl (III) lo A 23 307 - Foreign countries _ I
- Jo -in which R1 has the above mentioned meaning, on the presence of acid acceptors and if appropriate in the presence of delineates; or (e) in the case where M represents hydrogen and R2 rep-resents hydrogen or C1-C4-alkyl, sulphonylisothio-ureidopyrimidine derivatives of the formula (YIP) Al 50 N `- / N~/~R5 (VII) \R17 on which R1, R4, R5 and R6 have the abovement;oned meanings and R17 represents C1-c4~alkyl or bouncily, are reacted with amino compounds of the formula (IV) I (IV) HO
in which R
R2 represents hydrogen or C1-C~-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 metal, the compounds obtainable by the processes desk cried above under (a), (by, (c), (d) and (e), of the formula (I), in which M represents hydrogen and R1, R2, R3, R4, R5 and R6 have the above mentioned meanings, are reacted with metal hydroxides, hydrides or alkanolates or with organometallic compounds, if appropriate in the presence of delineates; or (g) on the case where 1:1 adduces of compounds of the formula (I) with strong acids are to be prepared, come pounds of the formula (I) in which M represents hydrogen lo A 23 307 - Foreign countries and R , R , R , R , R and R have the ahovementioned meanings, are reacted with strong acids, if appropriate in the presence of delineates.
The new sulphonylguanidinopyrimidine derivatives of the formula (I) and their addicts with strong acids are distinguished by a powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) exhibit a considerably better herbicidal action than the already known guanidines of the same type of action.
According to the present divisional invention -there is provided a sulphonylisothioureidopyrimidine derivative of the general formula (VII A) R4 C 6 (VII A) R
in which R represents a substituted phenol radical wherein R represents Cl-C4-alkylthio, Cl-C4-alkyl-sulphinyl or Cl-C4-alkylsulphonyl, or Cl-C4-fluoroalkoxy, R represents hydrogen, fluorine, chlorine, bromide or Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkylthio [which is optionally substituted by fluorine and/or chlorine, to - ha -R represents hydrogen, fluorine, chlorine, bromide or Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents cyan, formal, Cl-C4-alkylcarbonyl or Cl-C4-alkoxy-carbnYl, R represents hydrogen, or represents Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represents amino, Cl-C4-alkylamino or di-(Cl-C4-alkyl)-amino - with the proviso that R and R do not simultaneously represent methyl - and R represents Cl-C4-alkyl or bouncily.
These compounds are useful in process (e) above as intermediates in -the synthesis of the sulphonylguanidinopyrimidine compounds of the parent application.
According to another aspect of this divisional application there is further provided a process for the preparation of a sulphonylisothioureidopyrimidine derivative of the formula (VII A) as defined above, which process comprises reacting an N-sulphonyl-imino-di-thiocarbonic acid ester of the formula (XV A) R -SO NO (XV A) in which R and R have the meanings given above, with an aminopyrimidine of the formula (XI) .R4 HEN R (XI) R
r - fib -in which R , R and R have the meanings given above, if required, in the presence of a base and, if required, in the presence of a delineate, and, when the reaction has ended, diluting the mixture with water and acidifying with a strong acid.
Preferred compounds of this divisional application are compounds wherein R represents methylthio isopropyl-thio, deflower-methoxy, trifluoromethoxy, methylsulphonyl, R represents methyl, methoxy, ethics, hydrogen, chlorine or methylthio, R represents hydrogen or chlorine and R represents methyl, ethyl, methoxy, ethics, diEluoromethoxy, dimethylamino or hydrogen.
Particularly preferred compounds of this divisional application are compounds wherein R7 represents methylthio, R
represents methyl or methoxy, R represents hydrogen, R represents methyl or methoxy and R represents methyl.
he invention of the parent application preferably relates to compounds of the formula (I) in which M represents hydrogen or one equivalent of sodium, potassium or calcium, R represents an optionally substituted phenol radical wherein R 7 and R8 are identical or different and represent hydrogen, fluorine, chlorine, bromide, cyan, vitro or methyl [which is optionally -- tic --substituted by Fluorine chlorine, ennui, Cl-C3-alkoxyearbonyl, Cl-C3-alkoxy, C1-C3-alkylthio, Cl-C3-alkylsulphinyl or C1-C3-alkylsulphonyl], or represent C1-C2-alkoxy [which is optionally substituted by fluorine, chlorine, cyan, Cl-C3-alkoxy-carbonyl, Cl-C3-alkoxy, Cl-C3-alkylthio, Cl-C3-alkylsulphinyl or Cluck-al.kylsulphonyl], or represent Cl-C3-alkylthio, Cl-C3-alkylsulphinyl or Cl-C3-alkylsulphonyl [which are optionally substituted by fluorine, chlorine, cyan or Cl-C3-alkoxy-carbonyl], or represent di-(Cl-C3-alkyl)-amino-sulphonyl, Cl-C3-alkoxy-methylamino-sulphonyl, phenol or phonics, ~2;2~5 or represent C1-C4-alkoxy-carbonyl [which is optionally substituted by f Lowry no, sheller no, Brigham no, cyan or C1-C3-alkoxy~ C3-C6-cycloalkoxy-carbonyl, C1-C~-alkylthio-carbonyl, di-~C1-C3-alkyl)-amino-carbonYl or C1-C3-alkoxymethylamino-carbonyl, or represent C2-C4-alkenyl Couch is optionally substituted by fluorine, chlorine, cyan or C1-C3-alkoxy-carbonyl];
or in which, furthermore, R1 represents an optionally substituted bouncily radical (I SHEA-whereon R9 and R10 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 R11-S02-wherein R11 represents C1-Cg-alkyl Couch is optionally substituted by fluorine, chlorine or cyan], C1-: C8-alkoxy which is optionally substituted by fluorine, chlorine or cyan], C2-C8-alkenyl C~h;ch is optionally substituted by fluorine, chlorine, cyan or phenol, C2-C8-alkenyloxy Which us optionally substituted by fluorine, chlorine, cyan or phenyl~p C1-CO-alkylamino, C3-C6-cycloalkylamino or d;-(C1-C3-alkyl)-amino Couch are optionally substituted by fluorine, chlorine, cyan, phenol, phonics or C1_c2_ alkoxy~, c2-c6-alkenylamino Which is optionally Lea 23 307 - Foreign countries .~2~7 substituted by fluorine, chlorine, cyan or phenol], phenylamino or benzylami~o Couch are optionally substituted by fluorine, chlorine, bromide, C1-Colloquial, trifluoromethyl, C~-C3-alkoxy, S C1-C2-fluoroalkoxy, Cl-C3-alkylthio, C1-C3-alkylsulphinylO C1-C3-alkylsulphonyl~ cyan, vitro and/or C1-C3 alkoxy-carbonyl], bouncily Couch is optionally substituted by fluorine, chlorine, cyan, vitro, methyl, methoxy and/or C1-C2-alkoxy-carbonyl] or an optionally subset-outed phenol radical R12 wherein R1~
R~2 and R13 are identical or different and have the meanings given above as preferred for R7 and R8, but are not identical to R7 and R8 in each individual case;
and in which, furthermore R3 represents the radical -û-R14, wherein ~14 represents C~-c8-alkyl Couch is optionally : substituted by fluorine or chlorine], or represents C3-C6-alkenyl Couch 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, vitro, methyl methoxy or C1-C2-alkoxy-carbonyl];
or in which, furthermore, R3 represents the radical -N
\ R 1 6 wherein R15 represents hydrogen or methyl and R16 represents hydrogen or C1-C3-alkyl Which is optionally substituted by fluorine, chlorine, Sweeney C1~C2-alkoxy or c1-c2-alkoxy-carbonyl]
lo A 23 307 - Foreign countries _ I ho or represents C3-c6-cycloalkYl, phenol bouncily or phenethyl Quiche is optionally substituted by fluorine, chlorine, bromide, vitro, cyan, C1-C2-Cole, C1 C2 alkoxy or C1-C2-alkoxy-carbonyl], or represents acutely, methoxycarbonyl, Bunyan-suLphonyl or toluenesulphonyl;
and in which, furthermore R4 represents hydrogen chlorine or methyl Which us optionally substituted by fluorine and/
or chlorine, or represents C1-C2-alkoxy [which is optionally substituted by fluorine and/or chlorine, or represents C1-Cz-alkylthio [which is optionally substituted by fluorine and/or chlorine], R5 represents hydrogen, fluorine, chlorine, brow mine, methyl, acutely or C1-C2-alkoxy-carbonyl and R6 represents C1-C3-alkyl [which is optionally substituted by fluorine and/or chlorine], or rep-resents C~-C3-alkcxy [which is optionally substituted by fluorine and/or chlorine, or rep-resents amino, C1-C3-alkylamino or di-~C1-C3-alkyl)-amino - with the proviso that R and R do not simultaneously represent methyl.
The invention of the parent application 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 trifluoroacetic acid, with alkanesulphonic acids which have up to 4 carbon atoms and are optionally substituted by fluorine or chlorine, or with Bunsen - or naphthalene-sulphonic acids, which are optionally substituted by fluorine, chlorine, bromide or methyl.
The invention of the parent application particularly relates to compounds of the formula (I) in which lo A 23 307 - Foreign countries M represents hydrogen or one equivalent o-f sodium, potassium or calcium, R1 represents a substituted phenol raid eel Wrier wherein R7 represents fluorine, chlorine, bromide, methyl, tr;fluoromethyl, methoxy, difluoromethoxy, in-fluoromethoxy, C1-C3-alkylthio, C1-C3-aLkyl-sulphinyl, C~-C3-alkylsulphonyl, dimethylamino-sulphonyl~ diethylaminosulphonyl, N-methoxy-N-methyl-amino-sulphonyl, phenol, C1-C4-alkoxy-carbonyl, difluoromethylthio or trifluoromethylthio and R8 represents hydrogen;
and in which, furthermore, R2 represents hydrogen, methyl or a sulphonyl radical : R11-wherein R11 represents C1-C4-alkyl Cnhich is optionally substituted by fluorine or chlorine or represents C1-C4-alkylam;no or di-(C1-C2-alkyl)-amino which are optionally substituted by fluorine or represents an optionally substituted phenol radical wherein R12 R12 and R13 are identical or different and represent hydrogen fluorine, chlorine, bromide, cyan, vitro, methyl, tr;fluoromethyl, C1-C2-alkoxy [which is optionally substituted by flour-ire, chlorine, cyan or C1-C3-alko%y-carbonyl~, C1-C3-alkylthio, C1-C3-alkylsulphinyl or C1-C3-alkylsulphonyl [which are optionally substituted by fluorine and/or chlorine], dimethylaminosulphonyl, diethylaminosulphonyl~
lo A 23 307 - Foreign countries N-methoxy-N-methylaminosulphonyl, phenol or C1 C4-alkoxy-carbonyl Couch is optionally substituted by fluorine, chlorine, cyan or C1-C2-alkoxy], and in which, furthermore, S R3 represents the radical -O'ER
wherein R14 represents C1-C~-alkyl Which is optionally substituted by chlorine] or represents C3-C~-alkenyl Quiche is optionally substituted by chlorine], or represents C1-C2-alkoxy-carbonyl-methyl, phenol, phenethyl or bouncily Quiche is optionally substituted by fluorine, chlorine, vitro, cyan, methyl, methoxy or C1-C2-alkoxy-carbonyl~, or in which, furthermore, R3 represents the radical -N \
wherein R15 represents hydrogen or methyl and R16 represents hydrogen, C1-C3-alkyl, C3-C6-cyclo-alkyl, phenol, acutely, methoxycarbonyl, benzenesulphonyl or toluenesulphonyl;
and in which, furthermore, R4 represents hydrogen, chlorine or C1-C2-alkoxy Which is optionally substituted by flour-ire and/or chlorine], R5 represents hydrogen, methoxycarbonyl, ethoxycarbonyl or acutely and R6 represents C1-C2-alkyl Couch is optionally substituted by fluorine and/or chlorine or Of-C2-alkoxy Couch is optionally substituted by fluorine and/or chlorine, and - in the case where M represents hydrogen - the 1:1 adduces of the compounds defined above with hydrochloric acid, sulfuric acid, trifluoroacetic acid, methanesul-phonic acid, benzenesulphonic acid and toluenesulphonic acid.
lo A 23 307 - Foreign countries I
The compounds mentioned individually above are also excluded from the preferred and particularly pro-furred range.
If, for example, 2-fluoro-benzenesulphonyl chloride and N'-t4-methoxy-6-methyl-pyrimidin-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:
F I H ) N SHEA
2 I- 502C l HO ~--~ No N
-2 Hal OF NO 3 N
I
If, for example, N'-t4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-guanidine and phenylhydrazine are used as starting substances for process variant (b), the course of the reaction can be outlined by the following equation:
I N~)COCNF2 I) / ` OUCH Q 52 NASH 3 lo A 23 307 - Foreign countries (~52-N~ NO
NH
NH ~!~
If, for example, ~'-(4,6-dimethoxy-pyr;midin-2-5 yl)-N"-benzyloxy-N"'-(2-chloro-phenylmethylsulphonnil)-guanidine and 2-trifluoromethane-sulphonyl chloride are used as starting substances for process variant (c), the course of the reaction can be outlined by the following equation:
clue J OUCH
H OUCH
lo A 23 307 - Foreign countries - HO I C N OUCH
If, for example, N'-~4-ethoxy-6-methyl-pyrimidin-2-yl)-N" methoxy-N"-(2-ethoxycarbonyl-benzenesulphonyl)-guanidine and 2-dimethylaminosulphonyl-benzenesulphonyl chloride are used as starting substances for process variant (d), the course of the reaction can be outlined by the following equation:
, H N SHEA 502-N~CH3)2 HO\; ON j- 5 2 - C 1 SO / KOCH
COOK
SOz-N~CH3)2 - Hal Suzanne Swiss OKAY
COOK
If, for example, N'-t4-methoxy-6-methyl-pyrimi-din-2-yl)-N"-t2-methyl-benzenesulphonyl)-S-me~hyl--is-Thor and N,N-dimethylhydrazine are used as starting substances for process variant (e), the course of the reaction can be outlined by the following equation:
lo A 23 307 - Foreign countries .
SHEA ' H I N SHEA
N `-' No H2NN(CH3)2 \ SHEA
SHEA H ' N SHEA
N
H N(CH3~2 If, for example, N'-(4,6-dimethoxy-pyrimid;n-2-yl)~N"-isopropoxy-N"'-(2-methoxycarbonyl-phenylmetthylsul-phonyl~-guanidine and potassium ethanol ate are used as starting substances for process variant (f), the course of the reaction can be outlined by the following equation:
COUCH OH,\ N OUCH COOK
CHOSEN No C Nash - HAYAKAWA
H OCH(CH3~2 I
COUCH N OUCH
I OUCH
H OCH(CH3~2 If, for example, N'-~5-acetyl-4-methyl-pyrimidin-2-yl)-N"~methoxy-N"-(2~chloro-benzenesulphonyl)-N""'-(2-difluoromethoxy-benzenesulphonyl)~guanidine and methane-sulphonic acid are used as starting substances for pro-lo A 23 307 - Foreign countries 72~
cuss variant (9), the course of the reaction can be out-lined by the following equation:
OCHF2 , H ) N SHEA
~502-N N~/~COCH3 SHEA
/ \ O C H
Of OCHF2 I H Jo N SHEA
\ C / No X SHEA
N
Of Formula (II) provides a general definition of the S guanidinopyr;midine derivatives to be used as starting substances for process variant (a). In formula tip), R3, R4, R5 and R6 preferably and particularly have the same meanings as are given above as preferred or as par-titularly preferred in the context of the definition of the subst;tuents of formula (I).
Examples which may be mentioned of starting sub-stances of the formula (II) are: N'-(4-methyl-pyrimidin-yule)-, N'-(4-ethyl-pyr;m;d;n-2-yl)-, N'-(4-methoxy-6-methyl-pyr;m;din-2-yl)-, N'-(4-ethoxy-6-methyl-pyrimidin-2 ye)-, N'-(4-propoxy-6-methyl-2-yl)-, N'-(4-isopropoxy-6-methyl-pyrimid;n-2-yl) , N'-(4-chloro-6-methoxy-pyr;midin-yule)-, N'-(b-chloro-6-ethoxy-pyr;mid;n-2 ye)-, No chLoro-6-d;methyLam;no-pyr;m;d;n-2-yl)-, N'-(4-methyl-6-methylth;o-pyr;m;din-2-yl)-9 N'-(4,6-d;me~hoxy-pyrimidin-yule)-, N'-(b-d;fluoromethoxy-6 methyl-pyr;m;d;n-2-yl)-and N'-t4-dimethylamino-6-methyl-pyrimid;n-2-yl)-N"-methoxy-guan;dine, -N"-ethoxy-guanidine, -N"-propoxy-guanidine, -N"-isopropoxy-guanidine~ -N"-butoxy-guanidine, -N"-isobutoxy-guanidine, -N"-sec.-butoxy-yuan;d;ne, -N"-lo A 23 3û7 - Foreign countries ~2Z72~
pentoxy-guanidine, -N"-isopentoxy-guanidine, -N"-hexyl-oxy-guanidine, -N"~octyloxy-guanidine, -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"-methoxy-carbonylmethoxy-guanidine, -N"-ethoxy-carbonyl-methoxy-guanidine, -N"-(1-methoxycarbonyl-ethoxy)-guanidine, No ethoxycarbonyl-ethoxy)-guanidine, -N"-dimethyl-aminocarbonyl-methoxy-guanidine, -N"-(2-phenyl-ethoxy)-guanidine, -N"-phenoxy-guanidine, -N"-(4-methyl-benzyl-oxy)-guanidine, -N"-(4-fluoro-benzyloxy)-guanidine, -N"-(4-chloro-benzyloxy)-guanidine, -N"-(4-nitro-benzyloxy)-guanidine, -N"-(2,6-dichloro-benzyloxy)-guanidine, -N"-~4-methoxycarbonyl~benzyloxy)-guanidine and No ethoxycarbonyl-benzyloxy-guanidine.
The starting substances of the formula (II) form the subject of prior patents (compare EGOS (European Published Specification 121,082); however, new compounds are those of the formula (II), in which (a) R4 represents chlorine, R5 represents hydrogen and R6 represents C1-C4-alkoxy which is optionally substituted by fluorine and/or chlorine], C1-C4-alkylamino or di-(C1-C4-alkyl)-amino;
: or in which (b) R4 represents C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine], R5 represents hydrogen and R6 represents C1-C4-alkoxy which is substituted by fluorine and/or chlorine, or represents C1-C4-alkylamino of di-(C1-C4-alkyl)-amino;
or in which (c) R4 and R5 represent hydrogen and R6 represents C2-C3-alkYl;
lo A 23 307 - Foreign countries ~.22~
and in each case R3 has the above mentioned meaning.
The guanidinopyrimidine derivatives of the formula (II) - and hence also the new compounds of the formulae (Ida), Jib and (Sir) which are defined above under to), by and lo) - are obtained by a process on which cyanoaminopyrimi dine derivatives of the formula (VIII) N R4 (VIII) N--<R6 in which R4, R5 and R6 have the abovement;oned meanings, are reacted with amino compounds of the formula (IX) 1ûH2N-R3 (IX) on which R3 has the above mentioned meaning, or with hydrochloride thereof, of appropriate in the presence of d;luents, such as, for example, ethanol, is-propanol 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 cyanoaminopyr;m;dine derivatives of the for-mute (VIII) form the subject of prior patents (compare PUS (European Published Specification) 121,082); however, new compounds are those of the formula (VIII) on which (a) R4 represents chlorine, R5 represents hydrogen and I represents C1-C4-alkoxy C~h;ch is optionally substituted by fluorine and/or chlorine], C1-C4-alkylamino or di~(C1-C4-alkyl)-amino;
or in Shea lo A 23 307 - Foreign countries ye I
- I -(b) R4 represents C1~C4-alkyl Couch is optionally substituted by fluorine and/or chlorine], R5 represents hydrogen and R6 represents C1~C4-alkoxY which is substituted by fluorine andtor chlorine, or represents C1-C4-alkylamino or di-(C1-C4-alkyl)-amino;
or in which (c) R4 and R4 represent hydrogen and R6 represents C2~C3-alkyl.
The compounds of the formula (VIII) - and hence also the new compounds of the formulae (Vow), (VIIIb) and (Yoke) Shea are defined above under (a), (b) and (c) - are essentially obtained by the following synthesis routes:
(a) by reaction of alkali metal or alkaline earth metal salts of cyanamide - such as, for example, sodium cyan-aside or calcium cyanamide - with chloropyrimidines of the formula (X) Clue/ R5 (X) in which R4, R5 and R6 have the above mentioned meanings, if appropriate in the presence of inert delineates, such as, for example, ethanol, acetone, acetonitriLe or dip ~ethylformamide, at temperatures between ûC and 100C.
After the mixture has been concentrated and the residue has been dissolved in water, the cyanoaminopyrimidine derivatives of the formula (YO-YO) can be precipitated by acidification for example with hydrochloric acid, and isolated by filtration with suction.
Alternatively, cyanoaminopyrimidine derivatives of the formula (VIII) are obtained aye) in the case where R4 and/or R6 represent hydroxyl, by reaction of cyanoguanidine ("dicyanodiamide") with suitable ~-dicarbony( compounds - or derivatives thereof -lo A 23 307 - Foreign countries .
3L~27%~3~
such as, for example, 1,1~dimethoxy-3-oxo-butane, methyl acetoacetate or ethyl acetoacetate (compare J.
Pratt. Chum. 77 (1908), 542 and J. Chum. Sock 1948, 586) or dim ethyl Mullen or deathly malonate (compare German Patent Specification 158,591).
The 2-cyanoamino-4-hydroxy-6-methyl- or -Dow hydroxy-pyrimidines obtained from acetoacetic acid esters or Malone acid esters can be converted into correspond-no 2-cyanoam;no-4-alkoxy-6-methyl- or -4,6-d;alkoxy-pyr;m;d;nes on a known manner by reaction with alky~atingagents, such as, for example, dim ethyl sulfite or deathly sulfite, of appropriate on the presence of d;luents, such as for example, water, methanol, ethanol, n- or ;so-propanol, acetone, Dixon or d;methylform-amid, and on the presence of ac;d-b;nd;ng agents, such as, for example, sodium hydroxide or potassium hydroxide or sodium carbonate or potassium carbonate. To avoid N-alkylat;on, acylation is carried out, if appropriate, with an assaulting agent, such as, for example, acetic 2û android or acutely chloride, and, after the alkylat;on, the product us desolated again with aqueous acids or bases.
In another alternative process, cyanoam;nopyrimi dyne derivatives of the formula (VIII) are obtained by a process on Shea (a) am;nopyr;m;d;nes of the formula taxi) N -I
HEN R5 (XI) in which R4, R5 and R6 have the above mentioned meanings, are reacted with carbonyl isothiocyanates of the formula (XII) o Rl~-C-N=C=S (XII) lo A 23 3n7 - Foreign countries -I
on which R18 represents ethics or phenol, if appropriate in the presence of an inert delineate, such as, for example, acetone acetonitrile or Tulane, at S temperatures between 0C and 100C, the carbonylthio-ureas thereby formed, of the formula tXIII>
R 1 8 _ C - NH - if - NH ~/~ R 5 ( X I I I
in which I R5, R6 and R1~ have the above mentioned 1û 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 soul-lion, if appropriate in the presence of an organic sol-vent, such as, for example, tetrahydrofuran or Dixon, at temperatures between 0C and 12ûC, and the Theresa obtained as crystals after acidification, for example with hydrochloric acid, of the formula (XIV) If N R4 (XIV) ON - C - OH ~/~ R
on which R4, R5 and R6 have the above mentioned meanings, are isolated by filtration with suction and reacted with metal compounds which can bond hydrogen sulfide, such as, for example, with lead-II acetate, copper-II acetate, mercury-II acetate or iron-II acetate, in the presence of aqueous alkali metal or alkaline earth metal hydroxide 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 lit-lo A 23 307 - Foreign countries irate is acidified with an acid, such as, for example, acetic acid.
The products of the formula (VOW thereby obtained as crystals can be isolated by filtration with suction.
The starting substances for the preparation pro-cusses described above under tax), (a) and (a) for the cyanoaminopyrimidine derivatives of the formula (VIII) are known and/or can be prepared by processes which are known per so.
These substances include the chloropyrimidines of the formula (X) (compare J. Chum. Sock (C) 1966, 2031;
Chum. Harm. Bull. 11 (1963), 1382-1388 and Arch Harm.
295 (1962), 649-657), the aminopyrimidines of the formula 15 (XI) (compare Chum. Harm. Bull 11 (1963), 1382-1388);
J. Chum. Sock 1946, 81 and US. Patent Specification 4,299,960) and the carbonyl isothiocyanates of the for-mute (XII) (compare J. Heterocycl. Chum. 5 (1968), 837 and US. Patent Specification 4,160,037).
The amino compounds of the formula (IX) also to be used as starting substances are likewise already known and/or 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.
25 Sock 1930, 228 and Help. Chum. Act 45 (1962), 1387).
Formula (III) provides a general definition of the sulphonic acid chlorides also to be used as starting substances for process variant (a). In formula (III), R1 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 to).
Examples which may be mentioned of starting sub-stances of the formula (III) are: sheller-, sheller-, sheller-, 2,5-d;chloro-, flyer-, flyer-, Brigham, Brigham-, nutria-, nutria-, Sweeney-, 2-methyl-, 4-lo A 23 307 - Foreign countries -~2~7 methyl-, 2-chloromethyl-, 2-trifluoromethyl-, 2-methoxy-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-methylthiomethyl-, 2-methylsulphinylmethyl-, 2-methyl-sulphonylmethyl-, 2-dimethylaminosulphonyl-, deathly-aminosulphonyl-, phenol-, 2-methoxycarbonyl-, ethics-carbonyl-, 2-propoxycarbonyl-, 2-isopropoxycarbonyl-, 2-butoxycarbonyl-, 2-dimethylaminocarbonyl-, deathly-aminocarbonyl-, phonics 2-methyl-5-chloro-, sheller-5 trifluoromethyl-, 2-methylsulphonyl-, 2-ethylsulphonyl-, 2-chloro-4-trifluoromethoxy, 3-chloro-4-trifluoromethoxy-, 2-trifluoromethoxy-5-chloro-, 3,5-dichloro-, 2-difluoromethyl-trio- and 2-trifluoromethylthiobenzenesulphonyl chloride, and also methane-, chloromethane-, trifluoromethane-, ethanes-, 2-chloroethane-, ethene-, propane-, butane-, per-fluorobutane- and perfluoro-octane-sulphonyl chloride;
methyl-, ethyl-, propel, isopropyl-, cyclohexyl-, dim ethyl-and diethyl-sulphamic acid chloride and (Z-chloro-phenyl)-, (Z-cyano-phenyl)- and ~2-methoxycarbonyl-phenyl)-methane-sulphonyl chloride.
The sulphonic acid chlorides of the formula (III) are known and/or can be prepared by processes which are known per so (compare J. Org. Chum. 33 (1968), 2104; J.
Org. Chum. 25 (1960), 1824; DE-AS (German Published Spew suffocation) 2,308,262; EGOS (European Published Specific 25 cations) Z3,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; and US. Patent Spew c;fications 2,929,820, 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 R1S03H or 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 color-ides phosgene or benzotrichloride, if appropriate in the lo A 23 307 - Foreign countries presence of catalysts such as, for example, pardon or dimethylformamide, and if appropriate using inert dill-ens, such as, for example ethylene chloride, sheller form, aceton;trile, chlorobenzene and/or sulpholane, at temperatures between -20C and icky, preferably between 0C and ~100C; after dilution with water, the sulk phonic acid chlorides - Where these are obtained as crystals - can be isolated by filtration with suction or purified by extraction with a water-immiscible solvent, such as, for example, ethylene chloride, deathly ether or hexane, washing and drying of the extracts, concentra-lion and recrystallization or distillation; or to) in a manner which is known per so (compare J. Org.
Chum. 25 (1960), 1824; DEMOS (German Published Specific-lion) 2,308,262 and EGOS (European Published Specific-lion) 59,241), by reaction of corresponding amino come pounds R1-NH2 with sodium nitrite and hydrochloric acid, if appropriate in the presence of acetic acid, at - temperatures between -10C and ~20C, preferably between -5C and 110C, and subsequently (in situ) with sulk pour dioxide or a salt of sulfurs acid, such as, for example, sodium sulfite or sodium bisulphite, in the presence of a copper compound, such as, for example, copper chloride or copper sulfite - as a catalyst, at temperatures between ûC and 80C, preferably between 10C and 60C.
Working up can be effected in the customary manner; on dilution with water, the sulphonic acid chlorides are in general obtained as crystals and can be isolated by filtration with suction. However, they can also be extracted from the aqueous dispersion with a sol-vent which is virtually immiscible with water such as, for example, ethylene chloride or deathly ether, dried and purified by vacuum distillation.
Formula (ID) provides a general definition of the sulphonylguanidinopyrimidine derivatives to be used as lo A 23 307 - Foreign countries I
- I -starting substances for process variant (b). In formula (ID), I R4, R5, R6 and R14 preferably and part-ocularly 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 ox compounds of the formula RID) are: N'-(4-chloro-6-methoxy-pyrimidin-2-yl)-N"-methoxy N,,N"'-bis-(2-chloro-benzenesulphonyl)-, -N",N"'-bis-~2-bromo-benzenesulphonyl)-, -N",N"'-bis-(Z-1û ~luoro-benzenesulphonyl)-, -N",N"'-bis-(2-methyl-benzene-sulphonyl)-,-N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-,, -N-",N"'-bis-bis(2-methoxy-benzenesulphonyl)-, -N",N"'-bis-(2-phenyl-benzenesulphonyl)- and -N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-guanidine, N'-(4-methyl-pyrimi~in-2-yl)-15 N"-methoxy-N","'-bis-(Z-chloro-benzenesulphonyl)-,, NUN
bis-(2-methoxycarbonyl-benzenesulphonyl~ N",N"'-bis-(2-difluoromethoxy-benzene-sulphonyl)-, -N",N"'-bis-(2-diethyLaminosulphonyl-benzene-sulphonyl)-, -N",N"'-bis-(2-bromo-benzenesulphonyl)-, -N",N"'-bis-(2-tr;fluorome~hylthio-I benzenesulphonyl)-, -N",N"'-bis-(2-phenoxy-benzenesulphonyl)-and-N",N"'-b;s-~2-methyl-sulphonyl-benzenesulphonyl)--guanidine, N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N",N""'-bus-(2-chloro-benzenesulphonyl)-, -N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-difluoromethoxy-benzene-sulphonyl)-,-N",N"'-bis-(2-trifluoromethoxy-benzenesulphonyl)--, -N",N"'-bis-(2-dimethylaminosulphonyl-benzenesulphHoneywell)-, -N",N"'-bis-(2-methylthio-benzenesulphonyl)-, -N",N"'-bis-(2-ethoxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-phenyl-benzenesulphonyl)-, -N",N"'-bis-~2-cyclopropyloxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-trifluoromethylsulPhonYl-benzenesulphonyl)-, -N",N"'-bis-(2-nitro-benzenesulphonyl)-and -N",N"'-bis-(2-cyano-benzenesulphonyl-guanidine), N~-(4-methoxy-6-methyl-pyrimidino2-yl)-N"-methoxy~NUN
bis-(2-chloro-benzenesulphonyl)-, -N"~N"'-bis-(2-methoxy-carbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-methylsulphonyl-benzenesulphonyl)-, ~N",N"'-bis-(2-methylthio-benzenesulphonyl)-, lo A 23 307 - Foreign countries I
-Nl~Nl~-bis-(2-trifluoromethoxy-benzenesulphonyl)--I NUN
bis-(2-ethoxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-, -N",N"'-bis-(2-isopropyl~
thio-benzenesulphonyl)-, -N",N"'-bis-(2-N-methoxy-N-methyl-S aminosulphonyl benzenesulphonyl)-, -N",N"'-bis-(2-tr;fluoro-methylthio-benzenesulphonyl)-, -N",N"'-bis-S2,5-dichloro-benzenesuLphonyl)-, -N",N"7-bis-(2-phenoxy-benzenesulphonyl)-and -N",N"'-bis-(2-phenyl-benzenesulphonyl-guanidine, N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-N"--methoxy-N",N"'-bis-(2-ethoxycarbonyl-benzenesuLphonyl)-, NUN
bis-(2-bromo-benzenesulphonyl)-, -N",N"'-bis-(2-methyl-sulphonylmethyl-benzenesulphonyl)-, -N",N"'-bis-(2-trifluoro-methylthio-benzenesulphonyl)-, -N",N"'-bis-(2-methoxy-benzene-sulphonyl)-, -N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-and-N",N"'-b;s-(2-chloro-benzenesulphonyl)-guanidine..
The compounds of the formula (ID) can be prepared by the process described above under (a).
Formula (IVY) provides a general definition of the amino compounds also to be used as starting substances in process variant (b). In formula (IV), R2 and R3 prefer-ably and particularly have the same meanings as have been 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, phenylhydrazine, 0-methyl-hydroxylamine, 0-ethyl-hydroxyl-amine, 0,N-dimethylhydroxylamine and propel-, issue-propel-, bottle-, 0-sec~-butyl-, ponytail-, issue-ponytail 0-sec.-pentyl-, exile-, 0-isohexyl-, 0-hotly-, 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)-, sheller-bottle)-, 0-methoxycarbonylmethyl-, 0-ethoxycarbonylmethyl-, 0-(1-methoxycarbonyl)-ethyl-, I ethoxycarbonyl)-ethyl-, 0-aminocarbonylmethyL-, 0-(2-phenyl-ethyl)-, phenol-, lo A 23 307 - Foreign countries 0 t4-methyl-benzyl)-~ 0-(4-fluoro-benzYl)-, sheller-bouncily)-, 0-(4-nitro-benzyl)-, 0-(2,6-dichloro-benzyl)-, 0-(4-methoxycarbonyl-benzyl)- and 0-t4-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. Bull. 15 ~1967), 345; pull. Sock Chimp France 1958, 66~; Synthesis 1976, ~j82; J.Chem. Sock 1930, 228 and Help. Chimp Act 45 t1962), 1387).
Formula (If) provides a general definition ox the sulphonylguanidinopyrimidine derivatives to be used as starting substances in process variant (c). In formula (If), R1, R3, R4, R5 and R6 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 subs~ituents of formula (I).
Examples which may be mentioner of compounds of the formula (If) are: N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methox`y-N"'-(2-chloro-benzenesulphonyl)-guaniddine -N"'-(3-chloro-benzenesulphonyl)-, -N"'-(4-chloro-benzene-sulphonyl)-, -N"'-(2-fluoro-benzenesulphonyl)-, No fluoro-benzenesulphonyl~-, -N"'-(2-bromo-benzenesulphonyl)-, -N"'-(4-bromo-benzenesulphonyl)-~ -N"'-t2-cyano-benzene-sulphonyl)-, -N"'-(Z-nitro-benzenesulphonyl)-, -N"'-t4-ni~ro-benzenesulphonyl)-, -N"'-tZ-methyl-benzenesulphon-ye)-, -N"'-t4-methyl-benzenesulphonyl)-, -N"'-(2-chloro-methyl-benzenesulphonyl)-, -N"'-(2-trifluoromethyl-ben-zenesulphonyl)-, -N"'-t2-methoxy-benzenesulphonyl)-, -N"'-(4-methoxy-benzenesulphonyl)~, -N"'-(2-methylthio-3û benzenesulphonyl)-, -N"'-(2-difluoromethoxy-benzene-sulphonyl)-, -N"'-t2-trifluoromethoxy-benzenesulphonyl)-, -N"'-t2-methylthiomethyl-benzenesulphonyl)-, N"'-t2-dimethylamino-sulphonyl-benzenesulphonyl)-, -N"'-t2-phenyl-benzenesulphonyl)-, -N"'-t2-methoxysulphonyl-benzenesulphonyl)-, -N"'-t2-methoxycarbonyl-benzene~
sulphonyl)-, -N"'-(2-ethoxycarbonyl-benzenesulphonyl)-, ye A 23 307 - Foreign countries ~22~7~
-N"'-t2-propoxycarbonyl-benzenesuLphonyl)-, No methylaminocarbonyl-benzenesulphonyl)-, -Knothole-aminocarbonyl-benzenesulphonyl)-, -N"'-(2-propylanino-carbonyl-benzenesulphonyl)-, -N"'-(2-methoxyaminocarbon-S yl-benzenesulphonyl)-, -N"'-(2-ethoxyaminocarbonyl-benzenesulphonyl)-, -N"'-(2-propoxyaminocarbonyl-benzene-sulphonyl)-, -N"'-(2-dimethylaminocarbonyl-benzenesulphon-ye)- and -N"'-(2-diethylaminocarbonyl-benzenesulphonyl)-guanidine; and furthermore N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-ethoxy-N"'-benzenesulphonyl-, -N"'-(2-chloro-benzenesulphonyl)-, -N"'-(3-chloro-benzenesulphonyl)-, ~N"'-(4-chloro-benzenesulphonyl)-, -N"'-(2,4-dichLoro-benzenesulphonyl)-, -N"'-(2,5-dichloro-benzenesulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulphonyl)-, -N"'-(2-tri-fluoromethoxy-benzenesulphonyl)-, -N"'-(2-methylthio-benzenesulphonyl)-, -N"'-(2-methyl-benzenesulphonyl)-, -N"'-(Z-methylthiomethyl-benzenesulphonyl)-, -N"'-(2-di-methylaminosulphonyl-benzenesulphonyl)-, -N"'-(2-methoxy-sulphonyl-benzenesulphonyl)-, -N"'-(2-methoxycarbonyl-benzenesulphonyl)-, -N"'-(2-ethoxycarbonyl-benzenesul-phony)-, -N"'-t2-methylaminocarbonyl-benzenesulphonyl)-, N"'-(2-ethylaminocarbonyl-benzenesulphonyl)-, No methoxyaminocarbonyl-benzenesulphonyl)- and No dimethylaminocarbonyl-benzenesulphonyl)-guanidine;; and furthermore N'-(4,6-dimethoxy-pyr;m;d;n-2-yl)-N"-propoxy-, -N"-;sopropoxy-, ~N"-butoxy, -N"-isobutoxy-, -N"-sec.-buttocks-, -N"-pentoxy-, -N"-hexyloxy-, -N"-octyloxy-, -N"-allyloxy-, -N"-crotyloxy-, -N"-(3-chloro-propoxy)-, -N"-methoxycarbonyl-methoxy-, -N"-ethoxycarbonyl-methoxy--N"-t1-methoxycarbonyl-e~hoxy)-, -N"-(1-ethoxycarbonyl-ethics)-, -N"-(2-phenyl-ethoxy)-, -N"-phenoxy-, -N"-benzyloxy-, -h"-(4-methyl-benzyloxy)-, -N"-(4-fluoro-benzyloxy)-, -N"-(4-chloro-benzyloxy)-, -N"-(4-nitro-benzyloxy)-, -N"-(2,6-dichloro-benzyloxy)-, No methoxycarbonyl-benzyloxy)- and -N"-(4-ethoxycarbonyl-benzyloxy)-, -N"'-(2-chloro-benzenesulphonyl)-guanidine lo A 23 307 - Foreign countries t72~S
and-N"'-(2-methoxycarbonyl-benzenesulphonyl)-guanidinno;
and furthermore N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy~N"'-(2-chloro-benzenesulphonyl)-, No methyl-benzenesulphonyl)-O N"'-(2-methylthio-benzene-sulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulphonyl)-and-N"l-(2-trifluoromethoxy-benzenesulphonyl)-guanidiire;
and furthermore N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-and N'-(4-methyl-pyrimidin-2-yl)-N"-methoxy-N"'-(2-chloro-benzenesulphonyl)~guanidine;
and furthermore N'-(4-chloro-6-methoxy-pyrimidin-2-yl)-N"-methoxy-No chloro-benzenesulphonyl)-, -N"'-(2-methoxycarbonyl-benzene-sulphonyl)-, -N"'-~2-difluoromethylthio-benzenesulphonyl)-and -N"'-(2-dimethylaminosulphonyl-benzenesulphonyl)-guan;d;ne;and furthermore N'-(4-chloro-6-ethoxy-pyrimidin-2-yl)-N"-ethoxy-N""'-to-bromo-benzenesulphonyl)-, -N"'-(2-phenylbenzenesulphonyl)-, -N"'-(2-dimethylaminocarbonyl-benzenesulphonyl)-, -N"'-(2-methylthiomethyl-benzolsulphonyl)-, -N"'-(2-phenoxy-benzenesulphonyl)- and -N"'-(isopropoxy-benzenesulphonyl)-guanidine;
and furthermore N'-(4-chloro-6-d;methylamino-pyrimidin-2-yl)-N"-meethics-N"'-(2-fluoro-benzenesulphonyl)-, -N"'-(2-difluoromethylthio-benzenesulphonyl)-, -N"'-(2-methyl-benzenesulphonyl)-, -N"'-(Z-ethoxycarbonyl-benzenesulphonyl)- and -N"'-(2-cyano-benzenesulphonyl)-guanidine;
and furthermore 30 N'-(4-methyl-6-methylthio-pyrimid;n-2-yl)-N"-allylloxy-N"'-(2-chloro-benzenesulphonyl)-, -N"'-(Z-isopropoxy-ben~ene-sulphonyl)-, -N"'-(2-phenoxy-benzenesulphonyl)-, No methylsulphonyl-benzenesulphonyl)- and -N"'-(2-cyclopropyl-oxycarbonyl-benzenesulphonyl~-guanidine;
and furthermore N'-(4-dimethylamino-6-methyl-pYrimidin-2-yl)-N~ sour _ A 23 307 - Foreign countries I -N"'-(2-chLoro-ben~enesulphonyl)-, -N"'-(2-chlorodifluoro-methyl-benzenesulphonyl)-, ~N"'-(2-N-methoxy-N-methyl-amino-sulphonyL-ben~enesulphonyl)-, -N"'-~2-phenyl-benzenesulphony~)-and-N"'-(2-isopropylthio-benzenesulphonyl)-guan;dine;;
S and furthermore N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-N"--methoxy-carbonyl-N"'-(2-methyl-benzenelsulphonyl)-, -N"'-t2-diethyl-aminosulphonyl-benzenesulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulphonyl)-, -N"'-~2-nitro-benzenesulphonyl)-, -N"'-(2-methylthio-benzenesulphonyl)- and -Nighthawks-carbonyl-benzenesulphonyl)-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 suLphonic acid chlorides also to be used as starting sub-stances in process variant (c). In formula (V), R11 preferably and particularly has the same meaning as is given above as preferred or as particularly pro-furred in the context of the definition of the substitu-ens of formula I).
The sulphon;c acid chlorides which have been mentioned above as examples of compounds of the formula (II) can apply as examples of the starting substances of the formula (V).
The sulphonic acid chlorides of the formula (V) are known and/or can be prepared by processes ire are known per so compare the literature and synthesis routes for the compounds of the formula (III~ - above).
Formula (VI) provides a general definition of the sulphonylguanid;nopyrimidine derivatives to be used as starting substances for process variant Ed). In formula (VI), R3, R4, R5, R6 and R11 preferably and portico-laxly 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).
Examples which may be mentioned of compounds of the formula (VI) are: No methyl-pyrimidin-2-yl)-, I'-lo A 23 307 Foreign countries I
t4-methoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-chloro-6-methoxy-pyrimidin-2-yl) , N'-(~-chloro 6-ethoxy-pyrimidin-2-yl)-, N'-t4-chloro-6-dimethylamino-pyrimidin-2-yl)~, N'-(4-methyl-6-methylthio-pyrimidin-2-yl)-, N'-(4-dimethylamino-6-methyl-pyrimidin-yule)-, N'-(4,6-dimethoxy-pyrimidin-2-yl)- and N'-(4-difluoro-methoxy-6-methyl-pyrimidin-Z-yl)-N"-methoxy-~ -N"-methoxy-, -Nighthawks-, -N"-isopropoxy-, -N"-propoxy-, -N"-butoxy-, -N"-isobutoxy-, -N"-sec.-butoxy-, Spent ox-, -N"-octyloxy-, -N"-allyloxy-, -N"-(3-chloro-prop-ox)-, -N"-methoxycarbonylmethoxy-, -N"-ethoxycarbonyl-methoxy-, -N"-(2-phenyl-ethoxy)-, -N"-benzyloxy-, -N"-t4-methyl-benzyloxy)-, -N"-(4-fluoro-benzyloxy)-, -N"-t4-chloro-benzyloxy)-~ -N"-(4-nitro-benzyloxy)- and No methoxycarbonyl-benzyloxy)-, -N"-benzenesulphonyl-, -N"-(2-chloro-benzenesulphonyl)-, -N"-(3-chloro-benzenesul-phony)-, -N"-(4-chloro-benzenesulphonyl)-, -N"-t2-fluoro-benzenesulphonyl)-, -N"-(4-fluoro-benzenesulphon-ye)-, -N"-(2-bromo-benzenesulphonyl)-, -N"-(2-cyano-2û benzenesulphonyl)-, -N"-(2-n;tro-benzenesulphonyl)-, -N"-(4-nitro-benzenesulphonyl)-, -N"-(2-methyl-benzenesul-phony)-, -N"-(4-methyl-benzenesulphonyl)-, -N"-(2-tri-fluoromethyl-benzenesulphonyl)-, -N"-(2-methoxy-benzene-sulphonyl)-, -N"-(4-methoxy-benzenesulphonyl)-, No methylthio-benzenesulphonyl)-, -N"-(2-difluoromethoxy-benzenesulphonyl)-, -N"-(2-trifluoromethoxy-benzenesul-phony)-, -N"-~2-methylthiomethyl-benzenesulphonyl)-, -N"-(2-d;methylam;nosulphonyl-benzenesulphonyl)-, -N"-t2-phenyl-benzenesulphonyl)-, -N"-(2-methoxysulphonyl-benzenesulphonyl)-, -N"-(2-methoxycarbonyl-benzenesul phony)-, -N"-t2-ethoxycarbonyl-benzenesulphonyl)-, -N"-(2-propoxycarbonyl-benzenesulphonyl)-, -N"-(2-methyl-methoxy-amino-carbonyl-benzenesulphonyl)-, Nod methylamino-carbonyl-benzenesulphonyl)- and -N"-(2-di-ethylamino-carbonyl-benzenesulphonyl)-guanidine.
The sulphonylguanidinoPYrimidine derivatives ox lo A 23 307 - Foreign countries ~;~2~1[35i the formula (VI) are new and can be prepared by a process analogous to process (a) by reaction of guanidinopyrimi-dine derivatives of the formula tip) with approximately equimolar amounts of sulphon;c acid chlorides of the formula (V).
Formula Tao) provides a general Dionysian of the sulphonic acid chlorides also to be used as starting substances on process variant I In formula (III), R1 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 subst;tuents of the formula (I).
Examples of the sulphon;c acid chlorides of the formula (III) and their preparation process here have already been described above on connection ugh the desk Cretan of the starting substances for process (a).
Formula (VII) provides a general definition of the sulphonyl;soth;oure;dopyr;midine derivatives to be used as starting substances on process variant (e). In 2û formula (VII), R1, R4, R5 and R6 preferably and particularly have the same meanings as are given above as preferred or as particularly preferred on the context of the definition of the substituents of formula (I), and R17 preferably and particularly represents methyl.
Examples which may be mentioned of compounds of the formula (VII) are: N'-(4-chloro-6-methylth;o-pyr;m;d;n-yule)-, N'-(4-methyl-pyrimidin-2-yl)-, N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-, N'-t4-ethoxy-6-methyl-pyrim;d;n-yule)-, N'-(4-chloro-o-methoxy-pyrimidin-2-yl)-, No chloro~6-ethoxy-pyrimidin-2-yl)-, N'-(4-chloro-6-dimethyl-amino-pyrimidin-2-yl)-, N'-(4-methyl-6-methylthio-pyrimidin-yule)-, Ni-(4-dimethylamino-6-methyl-pyrimidin-2-yl)-, N'-(4,6-dimethoxy-pyrimidin-2-yl)- and N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-, -N"-(2-fluoro-benzenesulphonyl)-, -N"-(2-chloro-benzenesulphonyl)-, -N"-(2-bromo-benzenesulphon-ye)-, -N"-t2-methyl-benzenesulphonyl)-, -N"-(2-methoxy-lo A Z3 307 - Foreign countries carbonyl-benzenesulyhonyl)-, -N"- (2-ethoxycarbonyl-benzenesulphonyl)-, -N"-~2-propoxycarbonyl-benzcnesulphonyl) -, -N"- (2-isopropoxycarbonyl-benzenesul-phony) -, -N"- (2-phenyl-benzenesulphonyl) -, -N"-(2-trifluoromethyl-benzene-sulphonyl)-, -N"- (2-difluoromethoxy-benzenesulphonYl)- and -N"-(2-trifluoro-methoxy-benzenesulphonyl)-S-methyl-isothiourea.
The sulphonylisothioureidopyrimidine derivatives of the formula (VII) are known and/or can be prepared by processes which are known per so (compare EGOS (European Published Specification) 5,986).
It is to be noted however, that compounds of the formula (VII), in Itch Al represents a phenol radical substituted in ortho-position by Cluck-fluoroalkoxy, C,-CA-alkylthio, Cl-C~-alkylsulphinyl or Cl-C4-alkyl-sulphonyl, and in which R4, R5, R8 and R17 have the above-mentioned meanings, are not ye-t known. These new compounds may be presented by formula (VII A) and are the subject of this divisional patent application.
The compounds of the formula (VII and VII A) are obtained by a process in which N-sulphonyl-imino-dithiocarbonic acid esters of the formula (XV) or (XV A) as appropriate, R -SNUCK (XV or XV A) in which Al and R have the above mentioned meanings, as appropriate, are reacted with aminopyrimidines of the formula (XI) N
ON I/ R5 (XI) \ R
in which R , R and R have the above mentioned meanings, if appropriate in the ~7;~5 - I -presence of bases, such as, for example, sodium hydrides or potassium left.-butylate, and if appropriate in the presence of delineates, such as, for example, tetrallydrofuran, Dixon or dimethylformamide, at temperatures between 0C and 100C and, when the reaction has ended, the mixture is diluted with water and acidified with a strong acid, such as, for example, hydrochloric aria, and the products of the formula (VII ion VII A) obtained as crystals are isolated by filtration with suction.
The process for preparing a compound of the formula (VII A) by reacting a compound of the formula (XV A) with a compound of the formula (XI) comprises one aspect of the subject of this divisional application.
s Formula (XV) provides a general definition of the N-sulphonyl-;mino-dithiocarbonic acid esters required here as starting substances. In formula (XV), R1 and R17 preferably and particularly have the same meanings as are given above as preferred or as particularly characterized in the context of the definition of the substituents for formula (I) or formula (VII).
Examples which may be mentioned of compounds of the formula (XV) are: S,S-dimethyl N-(2-fluoro-benzene-sulphonyl-, N-(2-chloro-benzenesulphonyl-, N-(2-bromo-benzenesulphonyl)-, N-(2~methyl-benzenesulphonyl)-, No methoxycarbonyl-benzenesulphonyl)-, N-(2-ethoxycarbonyl-benzenesulphonyl)-, No propoxycarbonyl-benzenesulphon-ye)-, N (2-isopropoxycarbonyl-benzenesulphonyl)-, No phenyl-benzenesulphonyl)-O No trifluoromethyl-benzene-sulphonyl)-, N-(2-difluoromethoxy-benzenesulphonyl)-, N-(2-trifluoromethoxy-benzenesulphonyl)-, N-(2-trifluoromethylthio-benzenesulphonyl)-, N-(2-difluoro-methylthio-benzenesulphonyl)-, N-(2-phenoxy-benzenesul-phony)-, N-(2-cyclopropyloxycarbonyl-benzenesulphonyl)-, N-(2-methylthio-benzenesulphonyl)-, N-(2-isopropylthio-benzenesulphonyl)-, N-(2-trifluoromethylsulphonyl-benzene-sulphonyl)-, N-(2-dimethylaminosulphonyl-benzenesulphonyl)-~N-(Z-N-methoxy-N-methylaminosulphonyl-benzenesulpphony)-, N-(2-cyano-benzenesulphonyl)-, N-~2-nitro-benzenesulphonyl)-, N-t2-dimethylaminocarbonyl-benzenesulphonyl)- and No methylsulphonylmethyl-benzenesulphonyl)-im;no-d;th;ocarbonate.
The N-sulphonyl-imino-dithiocarbonic acid esters of the formula TV) are known andtor can be prepared by processes which are known per so (compare Comma Per. 99 (1966), 2885 and EP-ûS (European Published Specification) S,~86).
The compounds of the formula (XV) are obtained by a process in which sulphonic acid asides of the formula ~XVI) lo A I 307 - Foreign countries _ .. .. . . . . . . ....
~22~
R1-SOzcNH2 (XVI) on which R1 has the above mentioned meanings, are reacted with carbon disulphide on the presence of a strong base, such as, for example, sodium hydroxide, and, if appropriate, in the presence of delineates, such as, for example, water and dimethylformamide, at temperatures between 0C and 100C and subsequently (in situ) with an alkylating agent of the formula (XVII) X-R17 (XVII) on Shea R17 has the above mentioned meaning and X represents chlorine, bromide or iodine, at temperatures between 0C and 100C~
The products of the formula (XV) obtained as crystals after dilution of the mixture with water can be isolated by filtration with suction.
Formula (XVI) provides a general definition of the sulphonic acid asides required as starting substances.
In formula (XVI), 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 compounds of the formula (XVI) are: 2-trifluoromethylthio-, deflower-methylthio-, phonics-, 2-cyclopropoxycarbonyl-, 2-methyl-trio-, 2-isopropylthio~, 2-trifluoromethylsulphonyl-, 2-d;methylaminocarbonyl-, 2-dimethylaminosulphonyl-, Sweeney-, flyer sheller Brigham-, 2-methyl-, 2-methoxy-carbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl-, 2-isopropoxycarbonyl-, phenol-, 2-trifluoromethyl-, 2-difluoromethoxy- and 2-trifluoromethoxy-, 2-N-methoxy-N
lo A 23 307 - Foreign countries ~2~7~5 *, methylaminosulphonyl~, nutria- and 2-methylsulphonylmethyl-benzenesulphonamide D
The sulphonic acid asides of the formula (XVI~
are known and/or can be prepared by processes which are known per so (compare EGOS (European Published Specific-lions) 23,422, 30~14D, 35,893, 44,807, 44,80~, 44,809, 51,466, 6~,804, 7û,041 and 70,802; US. Patent Specific-lion ~,372,778 and Oh. Org. Kim Jo Org. Chum. USSR] 8 (1972), 1023~1026 English 1032-1034]).
These compounds are obtained in a manner which is known per so by reacting sulphonic acid chlorides of the formula (III) - above - with ammonia, if appropriate on the presence of d;luents, such as for example, dip ethyl ether, tetrahydrofuran or water, at temperatures between 0C and kiwi The products of the formula (XVI) thereby obtained as crystals can be isolated by filtration Thea suction.
Examples of suitable starting substances of the formula Tao) and preparation methods for these are given above in the description of the starting substances for process (a).
Examples which may be mentioned of starting sub-stances of the formula (XVII) are: methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide and ethyl iodide, and bouncily chloride and bouncily bromide.
The compounds of the formula (XVII) are known.
Formula I provides a general definition of the aminopyrimidines also to be used as starting substances.
In formula (XI), R4, R5 and R6 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 compounds of the formula (XI) are: 4-chloro-6-methoxy-, sheller-ethics-, 4-chloro-6-dimethylamino-, 4-methyl-6-methylthio-, lo A 23 307 - Foreign countries ... . . .. . ... .. .. . . . . . . . . . . ... .. .
I
, 4-dimethylam;no-6-methyl-, 4-d;fluoromethoxy-6-methyl-, 4,6-d;methoxy-~ 4-methoxy-6-methyl-, 4-ethoxy-6-methyl-and 4-methyl-2 amino-pyrim;d;ne.
The aminopyrimidines of the formula (XI) are known and/or can be prepared by processes which are known per so (compare J. Chum. Sock 1946, 81; Chum. Harm. Bull.
11 (1963), 1382-1388, US. Patent pacification ~,299,960; EGOS (European Published Spec;f;cation) 19,811; AUTOS Austrian Published Spec;ficat;on) 8,316,181 and EGOS European Publishes Specification 70 804).
Formula (IV) provides a general definition of the amino compounds also to be used as starting substances in process variant (e). In formula (lo), 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 pro-furred in the context of the definition of the subset ens for formula (I).
Examples of suitable starting substances of the formula (IV) and literature references for these are given above on 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 substances for process (~) - M rep-resents hydrogen and R1, R2, R3, R4, R5 and R6 prefer-ably and particularly have the same meanings as are given above as preferred or as particularly preferred on the context of the definition of the substations for formula (I).
The compounds of the formula (I) to be used as starting substances for process (f) can be prepared by the processes described under (a), (b), (c), (d) and (e).
Examples which may be mentioned of the metal hydroxides, hydrides and alkanolates or organometallic lo A 23 307 - Foreign countries ~.2~7~
compounds to be used 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 ate and potassium ter.-butanolate, and bottle-lithium and isopropyl-magnesium chloride.
Formula with the proviso that M represents hydrogen - provides a general definition of the compounds to be used as starting substances on process variant (9).
In formula (I), where this relates to the compounds to be used as starting substances for process go - M represents hydrogen and R1, RZ, R3, R4, R5 and R6 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 subst;tuents for 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 (9). 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 sub-stituted by fluorine or chlorine, such as, for example, methanesulphonic acid, ethanesulphonic acid, sheller-methanesulphonic acid, 2-chloroethanesulphonic acid and tr;fluoromethanesulphonic acid, and trifluoroacetic acid, and furthermore benzenesulphonic acid, p-toluenesulphonic acid, naphthalene-1-sulphonic acid, naphthalene-Z-sul-phonic acid and naphthalene-1,4-, -1,5-, -1,6-, -2,6- and -2,7-d;sulphonic acid.
Process (a) for the preparation of the new compounds of the formula (I) is preferably carried out using delineates. Possible d;luents are virtually all the inert organic solvents, but prefer-ably aprotic polar solvents. These include optionally lo A 23 307 - Foreign countries .
~2;2~
substituted hydrocarbons, such as, for example, ethylene chloride, chloroform, 1,2-dichloroethane, Tulane, zillion and chlorobenzene, nitrites, such as, for example, acetonitrile and prop;onitr;le, ethers, such as, for example, 1,2-dimethoxyethane, tetrahydrofuran and Dixon, and d;methylformamide, dimethylacetamide, dimethylsulph-oxide, sulpholane, pardon and 2-methyl-5-ethyl-pyr;dine.
Virtually all the acid-binding agents which are usually employed can be used as acid acceptors in pro-cuss pa). These include, in particular, alkali metal and alkaline earth metal hydroxides, alkali metal and alga-line earth metal hydrides, organometallic compounds, such as butyl-lithium, and furthermore aliphatic, aromatic or heterocyclic amine, such as trimethylamine, triethyl-amine, N,N-dimethylaniline, N,N-dimethyl-benzylamine, diazabicyclooctane (DICK), diazabicyclononene (DUN), diazabicycloundecene (DUB), pardon, 2-methyl-5-ethyl-pardon 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 -80 and ~100C, preferably between -30C and +50C. Process (a) according to the invention is in general carried out under normal pressure.
For carrying out process to), in general between 1 and 5 moles, preferably between 2 and 3 moles, of sulk phonic acid chloride of the formula (III) are employed per mole of guanidinopyrimidine derivative of the formula (If).
The reaction components are usually brought to-getter 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 a water-immiscible solvent, such as, for example, methyl-one chloride, chloroform or Tulane, if appropriate after distilling off volatile components, and the organic phase lo A I 307 - Foreign countries .. .. . .
~2~t7~
is washed it water, dried, filtered and concentrated The products ox the formula (I) which remain in the nest-due are made to crystallize by digestion with organic solvents, such as, for example, deathly ether, ethyl acetate, ethanol or isopropanol, and, if appropriate, are purified by recrystallization.
Process (b) is prefer-ably carried out using delineates. Possible delineates are virtually all the inert organic solvents. These include, on particular, alcohols, such as methanol, ethanol and n-or i-propanol, ethers, such as tetrahydrofuran~ Dixon and 1,2-dimethoxyethane, esters, such as methyl acetate and ethyl acetate, nitrites, such as, for example, asset-nitrite or propionitrile, and dimethylformamide and water.
Acid-binding agents which do not have nucleon fluky properties uh;ch noticeably compete with those of the amino compounds ox the formula (IV) can be employed as acid acceptors in process (b). Acid acceptors of this type which may be mentioned are alkali metal and alkaline earth metal carbonates, such as, for example, potassium carbonate and calcium carbonate, tertiary amine, such as, for example, triethylamine, NUN-dimethylaniline and N,N-dimethylbenzylamine, and nitrogen-containing heterocyclic compounds, such as, for Z5 example, pardon, diazab;cyclooctane (DICK) and d;azab;cycloundecene (DUB).
The reaction temperature can be varied within a substantial range in process (b). In general, the react lion us carried out between 0C and 150C, preferably between 10C and 100C. Process (b) is in general carried out under normal pressure.
For carrying out process (b), in general between 1 and 10 moles, preferably between 2 and 5 moles, of amino compound of the formula (IV) or hydrochloride thereof are employed per mole of -the compound of the formula (ID).
lo A 23 307 - Foreign countries ~X;;~2~
- I -In general, the compound of the formula (ID) is with the delineate at 20C or with gentle cooling and the amino compound of the formula (IV) or the hydrochloride thereof and, if appropriate, a suitable acid acceptor are added. The reaction mixture is then in general stirred at room temperature or elevated temperature until the reaction has ended.
working up can be carried out by customary methods. If the products of the formula (I) are obtained 1û as crystals from the reaction mixture, they can be is-fated by filtration with suction. Otherwise - if approp-rite after concentration - the mixture is diluted with utter and extracted with a solvent which is virtually water-immiscible, such as, for example, ethylene color-ides The products of the formula (I) can be obtained in pure form by Washing the extraction solution with water, drying, filtering, concentrating the filtrate and no-crystallizing the residue.
Process (c) is prefer-ably carried out using d;luents. Possible delineates are virtually all the inert organic solvents, but preferably aprotic polar solvents, such as have been mentioned above on connection with the description of process (a) accord-in to the invention.
Virtually all the acid-binding agents which are usually employed can be used as acid acceptors in process I These include, in particular, the acid-binding agents mentioned above in connection with the description of process (a).
3û The reaction temperatures can be varied within a substantial range in process I In general, the react lion is carried out between -80C and ~100C, preferably between -30C and ~50C. Process I is in general carried out under normal pressure.
For carrying out process (c), in general between 1 and 2 moles, preferably between 1.1 and 1.5 moles, of lo A 23 307 - Foreign countries s - by -sulphonic acid chloride of the formula (V) are employed per mole of sulphonylguanidinopyrimidine derivative of the formula tie).
The procedure and working up for process I can be analogous to that for process (a).
Process (d) is prefer-ably carried out using dullness. 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-no to the invention.
Virtually all the acid-binding agents which are usually employed can be used as acid acceptors in process Ed). These include in particular, the acid-binding agents mentioned above in connection with the description of process (a) according to the invention The reaction temperatures can be varied within a substantial range on process (d). In general, the react ton us carried out between -80C and +100C, preferably between -30C and ~50C. Process (d) is in general carried out under normal pressure.
In carrying out process (d), in general between 1 and 2 moles, preferably between 1.1 and 1.5 moles, of sulphonic acid chloride of the formula (III) are employed per mole of sulphonylguanidinopyrimidine derivative of the formula (YIP).
The procedure and working up in process (d) can be analogous to that in process (a).
Process (e) is prefer- -3û ably carried out using d;luents. Possible delineates are virtually all the inert organic solvents, but preferably aprotic polar solvents. These include, in particular, tetrahydrofuran, Dixon, 1,2-dimethoxyethane, asset-nitrite, acetone, methyl ethyl kitten, methyl isobutyl kitten, dimethylformamide, dimethylacetamide and dim ethyl-sulphoxide.
lo A 23 307 - Foreign countries The reaction temperature can be varied within a substantial range in process (e). In general, the reaction is carried out between OKAY and 150~C, preferably between 10C and 100C. Process (e) is in general carried out under normal pressure or slightly reduced pressure.
For carrying out process (e), in general between l and lo moles, preferably between l and 5 moles, of amino compound of the formula (IV) are employed per mole of sulphonylisothioureidopyrimidine derivative of the formula (VII) which group includes compounds of the formula (VII A) which are the subject of this divisional application.
In general, the sulphonylisothioureidopyrimidine derivatives of the formula (VII) (including those of formula (VII A)) and the delineate are taken and -the amino compound of the formula (IV) is metered in. The reaction mixture is then stirred until the reaction has ended.
The products of the formula (I) 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 (f) is preferably 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 iso-propanol, ethers, such as, for example, tetrahydrofuran, Dixon and 1,2-dimethoxyethane, esters, such as, for 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 reaction is carried out between -20C and ~50C, preferably between 0C and 30C. Process (f) is in general carried out under normal pressure.
For carrying out process (f), in general between 0.9 and 1.2 moles, preferably between 0.95 and 1.1 moles, of metal compound are 72~
employed per mole of the compound of the formula (I).
In general, the compounds of the formula (I) and the delineate are taken and - of appropriate with gentle external cooling - the metal compound - of appropriate dissolved on the delineate - us metered in. The reaction mixture us stirred until the reaction has ended. The salt-like products of the formula (I) are in general obtained as crystals and can be isolated by filtration with suction.
Process (g) is prefer-ably carries out using delineates Possible delineates are virtually all the inert organic solvents. These include, in particular, alcohols, such as methanol, ethanol and n- or ;so-propanol, ethers, such as tetrahydrofuran, Dixon and 1,2-dimethoxyethane, esters such as methyl acetate and ethyl acetate, and kittens, such as acetone, methyl ethyl kitten and methyl ;sobutyl kitten.
If the acids used as starting substances are employed in aqueous solution, it may also be advantageous to use acetic android as the delineate.
The reaction temperature can be varied within a substantial range in process (9). In general, the react lion is carried out between -20C and ~5ûC, preferably between 0C and 30C. Process (g) is in general carried out under normal pressure.
For carrying out process (9), in general between 1 and 10 moles, preferably between 1 and 5 moles, of a strong acid are employed per mole of the compound of the formula (I).
In general, the compounds ox the formula (I) and the delineate are taken and - if appropriate with gentle external cooling - the strong acid is metered on. The reaction mixture us stirred until the reaction has ended.
The 1:1 adduces are in general obtained as crystals and can be isolated by filtration with suction.
The active compounds according to the invention lo A 23 307 - Foreign countries _ 27;;~
can be used as defoliants, desiccants, agents for desk trying broad-leaved plants and, especially, as weed-killers. Eye weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds can be used, for example, on connection with the follow-no plants:
Dicotyledon Leeds of the genera: Synapse, Lepidium, Gallium, Styler, Mutterer Anthems, Galinsoga, Sheehan-podium, Utica, Seneca, Amaranths, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cur-swum, Keywords, Sonchus, Selenium, Rewrap, Rotate, Lender-Noah, Lam;um, Veronica, Abutilon, Emex, Dotter Viola, Galeopsis, Palaver and Sinatra.
cotyledon cultures of the genera: Gossypium, Gleason, Beta, Caucus, Fossils, Possum, Selenium, L;num, Ipomoea, Via Nicotiana, Lycopers;con, Arachis, risque, lag-tuna, Cucum;s and Cucurbita.
Monocotyledon weeds of thy genera: Echinochloa, Satyr, Panicum, Jotter Phlegm, Poe, Fistic, Eleusine, Bra-Shari, Lolium, Brahms, Arena, Cyprus, Sorghum, Ago-pylon, Sundown, Monkery, Fimbr;styl;s, Sag;ttaria, Eleochar;s, Scripps, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrost;s, Alopecurus and Opera.
Monocotyledon cultures of the genera: Ours, Zeal Tryout-gum, Hordeum, Arena, Scale, Sorghum, Pan;cum, Saccharum, Bananas, Asparagus and Alma.
However, the use of the active compounds 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 lo A 23 307 - Foreign countries ~Z~72~
on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating Leeds in preen-nil cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, and for the selective combating of Leeds in annual gut-lures.
The active compound scan be used for selectively combating monocotyledon and dicotyledon Leeds on monocotyledon and dicotyledon crops, such as, for example, cotton, rice, cereals and maize.
The active compounds can be converted to the cuss tumor formulations, such as solutions, emulsions, wet-table powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated Thea active compound and very fine capsules in polymeric substances.
These formulations are produced on 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 emulsify-in agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as Audi-fiery solvents. As liquid solvents, there are suitable the main: aromatics, such as zillion, Tulane or alkyd naphthalenes, chlorinated aromatics and chlorinated elf-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 lo A 23 307 = Foreign countries 31Z2~
Bunnell or glycol as jell as their ethers and esters, kittens, such as acetone, methyl ethyl kitten, methyl isobutyl kitten or cyclohexanone, strongly polar solvents, such as d;methylformamide and d;methylsulphox;de, as well as water.
As solid carriers there are suitable: for example ammon;um salts and ground natural minerals, such as kayo-lens, clays, talc, chalk quartz, at~apulg;te, montmor;l-lunate or d;atomaceous earth, and ground synthetic miner-1û also such as highly disperse stoic acid, alumna ands;licates, as solid carriers for granules there are suit-able: for example crushed and fractionated natural rocks such as Calcutta marble, pumice, sepiolite and dolomite, as jell as synthetic granules of inorganic and organic meals and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as Emil-sifting and/or foam-form;ng agents there are suitable:
for example non-ion;c and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty ZOO alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as jell as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methyl cellulose.
Adhesives such as carboxymethylcelluLose and natural and synthetic polymers in the form of powders, granules or lotuses, such as gum Arabic, polyvinyl Alcoa hot and polyvinyl acetate, as well as natural phosphor lipids, such as cephalins and lecithins, and synthetic phospholipids, can be used on the formulations. Further additives can be mineral and vegetable owls.
It us possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian glue, and organic distaffs, such as alizarin distaffs, ago distaffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, lo A 23 307 - Foreign countries I._ I I
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 0.5 and 90%.
The active compounds according to the invention, as such or in the form of their formulations, can also be used, for conbat;ng Leeds, as mixtures with known herb-aides, finished formulations or tank mixes being possible.
For the mixtures come known herbicides, such as, for example, N-(2-benzothiazolyl)-N,N'-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(4-isopropyl-phenyl)-~ dimethylurea, Amman dimethylethyl)-3-methylthio-1,2,4-triazin-5-~4H)-oone, 4-amino-6-(1,1-dimethylethyl)-3-ethylthio-1,2,4-triaassign-(one, 1-amino-6-ethylthio-3-(2,2-d;methylpropyl)-1,3,5-~riazine-2,~-(1H,3H)-dione, 4-amino-3-methyl-6-phenyl-1,2,4-tr;az;n-5-(4H)-one, 2-chloro-4-ethylamino-6-isopropyl-am;no treason, the R-enant;omer of (tr;methyls;lyl)-methyl 2-C4-(3,5-d;chloropyr;dyl-2-I oxy)-phenoxy~-propionate, the R-enantiomer of (2-benzyloxy~-ethyl 2-~4-(3,5-dichloropyridyl-Z-oxy)-phenoxy]-propionate, 2,4-d;chlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)-propionic acid, 4-chloro-2-methyl-phenoxy-acetic acid, 2-(2-methyl-4-chlorophenoxy)-pro-phonic acid, 3,5-diiodo-4-hydroxy-benzonitrile, Dow-broom 4-hydroxy-benzonitrile and diphenyl ethers and phenylpyr;dazines, such as, for example, peridots. Sun-praisingly, some mixtures also show a synergistic action.
Mixtures with other Nolan active compounds, such as fungicides, insecticides, acar;c;des, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, on the form of their formulations or on the use forms prepared therefrom by further dilution, such as Rhodes Lowe-Chinese suspensions, emulsions, powders, pastes and grant lo A 23 307 - Foreign countries I
- I -vies. They are used in the customary manner, or 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.
he amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.001 and 15 kg of active compound per Hector of soil surface, preferably between 0.05 and 10 kg per ha.
The examples which follow exemplify the inventors ox the parent and divisional applications, as appropriate.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Preparation Examples Example 1 Of N__cOC~3 _502_N~ Nay KOCH
. Of (Process (a)) 10.1 9 ~0.048 mole) of 2 chloro-benzenesulphonyl chloride are added to a solution of 4.5 9 (0.02 mole) of N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-guaniiodine on 30 ml of pardon at -10C. The reaction mixture is stirred at 20C for two days. After addition of a further 1.5 g of 2-chloro-benzenesulphonyl chloride, the mixture is stirred at 20C for a further 24 hours. At a maximum temperature of 40C, the mixture is concern-treated, the residue is taken up in ethylene chloride and the mixture it washed with I strength hydrochloric acid.
lo A 23 307 - Foreign countries The organic phase us dried, filtered and concentrated.
The oily residue is made lo crystallize with isopropanol.
2.65 9 (23X of theory) of N'-(4,6-dimethoxy-pyr;midin-2-yl)-N"-methoxy-N",N"'-bis (2-chloro-benzene-sulphonyl)-guanid;ne of melting point 164-165C are obtained.
Example 2 ONE / NO
H N~CH~)2 process (b)) A mixture of 5.8 9 (0.01 mole) of N'-(4,6-di-methoxy-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-csheller-benzenesulphonyl)-guanidine, 1.5 9 (0.0Z5 mole) of NUN-d;methylhydrazine, 20 ml of ethanol and 10 ml of water is heated at the boiling point under reflex for one hour.
The product obtained as crystals after cooling the mix-lure is isolated by filtration with suction and wreckers-tallied from ethyl acetate.
1.3 9 (31% of theory) of N'-(4,6-dimethoxy-pyr;midin-2-yl)-N"-dimethylamino-N"'-(2-chloro-bennzene-2û sulphonyl)-guan;d;ne of melting point 190C are obtained.
Example 3 ON
H OUCH
(Process ye)) A mixture of 16.0 9 (0.04 mole) of N'-(4-methoxy-25 6-methyl-pyrimidin-2-yl)-N"-(2-methylthio-benzenescellophane-yl)-S-methyl-isothiourea, 4.0 9 (0.û85 mole) of 0-methyl-lo A 23 307 - Foreign countries ~;~Z7~6~S
hydroxylam;ne and 80 ml of Dixon is stirred at 30C
to 33C for 15 hours. The mixture us then concentrated, the residue is made to crystallize by trituration with ethanol and the product is isolated by filtration with 5 suction.
8.4 9 t53~ of theory) of N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N"'-(2-methylthio-benzeone-sulphonyl)-guan;dine of melting point 134C are obtained.
Example 502N(C~3)2 _502-N~- / NH4 x SHEA
SYNCH
(Process tug)) A mixture of 5.4 9 (û.0075 mole) of N'-(4,6-dimethoxy-pyr;midin-2-yl)-N"-methoxy-N",N"'-bis-(22-d;methylam;nosulphonyl-benzenesulphonyl)-guanidinee, 0.75 9 (0.0075 mole) of methanesulphonic acid and 10 ml of acetone us stirred at 20C for 24 hours. The products obtained as crystals us then isolated by filtration with suction.
1.6 9 ~26% of theory) of the 1:1 adduce of N'-20 ~4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N"~N"'-bbus-tdimethylaminosulphonyl-ben~enesulphonyl)-guanidinno and methanesulphonic acid of melting point 145C are obtained.
The following compound is obtained analogously:
lo A 23 307 Foreign countries -I
Example 5 502N(CH3~2 t H No X H2504 502N~CH3)2 : Melting point: 155C
The compounds of the formula (I) lusted in the following Table 1 can be prepared by the processes desk cried by way of example in the preceding examples:
M / N ,R4 R1-502-N ` No R5 I) / N
lo A 23 307 - Foreign countries ~L227~d~g~
c I, C'` N N Us I
C It 0 t`
J .
a o Of I: X 2 O O O O O O
I:;
I; :~: 3 S I 2 I I
. 5 X T
O O H t,) I_ U
I; l l l l l l I
Roy O o o o z:
I;
to I, Noah N Lo N N
O O O O O O
O Us O Us N
I
O O lo O -I O --J
' _ E O Of) I o I X _ _.
LO
lo A 23 307- Foreign countries I
o c I
O
.
to to to I to O O O O O O
a l l l l l l Us to; y T T :~:
O O O O O
a:;
I X
O O O O O O
N I IN Z1~ a N
I: ~[~3 c N
_ 5 Zen QJ
_ o JO (o z N _ --lo A 23 307- Oregon countries 2~5 I
I
I In O or _, _ _ _ a o a.
S T
I
O O O O
I I T
Us T X T 3 t'lrq to o O U T
I; I I I I I
I ) T
o o o Q o o it; l l l l l l N I.) N Z to O O O N O
_ Us O Us O Us c Tao N
X
C O 'I I O
O O O O
U ~0~0~
I Q
_ E
x Z -- -- N N
lo A 23 307- Foreign countries , ~;2;;~7;2~i _.
.
r N
_ .
O
Q
lo A 23 307 - Foreign countries I
C1-C4-alkylamino-carbonyl, di-(C1-Cb-alkyl)-amino carbonyl, C1-C4-alkoxy, C1-Ch alkylthio, C1-C~-alkylsulph;nyl or C1-C4-alkyl-sulphonyl~, or represent C1-C4-alkoxY C~h;ch is optionally substituted by fluorine, chlorine, bromide, cyan, C1-C~,-alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylthio~ C~-C4-alkylsulph;nyl or C1-C4-alkyl-sulphonyl], or represent C1-C4-alkylthio, C1-C~-alkylsulphinyl or C1-C4-alkylsulphonyl Couch are optionally substituted by fluorine, chlorine, bromide, cyan or C1-C4-alkoxy-carbonyl~, or represent C1-C~-alkylamino-sulphonyl, d;-(C1-C4-alkyl)-am;no-sulphonyl, C1-C4-alkoxyamino-sulphonyl, benzyloxy-aminosulphonyl, C1-C4-alkoxy-C1-C4-alkyl-aminosulphonyl, or represent phenol or phonics, or represent C1-C4-alkoxy-sulphonyl, or represent C2-C6-alkenyl which is optionally substituted by fluorine chlorine, bromide, cyan, C1-C4-alkoxy-carbonyl, carboxyl or phenol, c2-c6-alk;nYl Shea us optionally substituted by fluorine chlorine, bromide, cyan or C1-C4-alkoxy-carbonyl~, c3-C6-alkenoxY
Couch is optionally substituted by fluorine, chlorine, bromide, cyan or c1-c4-alkoxY-carbonyl]~
C3-C6-alkenylthio which is optionally subset-tuned by fluorine, chlorine, bromide, cyan or Cl-c4-alkoxy-carbonyl~ C1-C6-alkoxy-carbonyl which us optionally substituted by fluorine, chlorine, brom;ne, cyan or C1-C4-alkoxy~, C3-C6-cycloalkoxy-carbonyl, cl-c~-alkYlth;ocarbonyl wish us optionally substituted by fluorine, chlorine bromide cyan or C1-C4-alkoxy-carbonyl~, amino-carbonyl, C1-C4-alkylamino-carbonyl, dip tC1-C4-alkyl)-amino-carbonyl, Cl-C4-alkoxy-aminocarbonyl, C3-C4-alkenyloxy-amino carbonyl, benzyloxyaminocarbonyl, C1-C4-alkoxy-C1-C4-lo A 23 307 - Foreign countries I
alkyl-amino-carbonyl, d;methylhydraz;nocarbonyl, dimethylhydrazinosulphonyl, c3-c6-a~kinYlo~y or C3-C6-alkynylthio;
or in Shea, furthermore, R1 represents an optionally substituted bouncily radical SHEA-whereon R9 and R10 are identical or different and repro-sent hydrogen, halogen Couch as, in particular, fluorine, chlorine or bromide Sweeney vitro, C1-Colloquial which is optionally substituted by fluorine andlor chlorine], C1-C4-alkoxy tush is optionally substituted by fluorine and/or chlorine, C1-c4-alkoxy-carbonyl~ C1-C4-alkyl-trio, c1-C4-alkYlsUlPhinYl~ C1-C4-alkYl-sulphonyl or di-(C1-C4-alkyl)-am;nosulphonyl;
and on Shea, furthermore, R2 represents hydrogen, C1-C4-alkyl or a sulphonyl radical R11-S02-wherein R11 represents C1-C12-alkyl Couch is optionally substituted by fluorine, chlorine, brom;ne, cyan, Nero C~-C4-alkoxy-carbonyl, C1-C4-alkylam;no-carbonyl~ d;-(C1-C4-alkyl)-am;no-carbonyl~
C1-C4-alkoxy~ C1-C4-alkylth;o, C1-C4-alkyl-sulph;nyl or C1-C4-alkylsulphonyl], C1-C12-alkoxy which is optionally substituted by fluorine, chlorine, brom;ne, cyan, Nero C1-C4 alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylth;o, C1-C4-alkylsulph;nyl or C1-C4-alkyllsulphonyl], Cz~C12-alkenyl C~h;ch us optionally substituted by fluorine, chlorine, brom;ne, cyan, Nero C1~
lo A_ 3 307 - Foreign countries_ ~27~
C4-a~koxy, C1-C4-aLkylth;o or phenol, ~2-C12-alkenyloxy which is optionally substituted by fluorine, chlorine, brom;ne, cyan, vitro, C1-C~-alkoxy, C1-C4-alkylthio or phenol, C1-Cg~
alkylamino, di-(C1-C4-alkyl)-amino, C3-C6-cyclo-alkyl-amino or di-(C3-C6-cYcloalkyl)-amino which are optionally substituted by fluorine, chlorine, bromide, Sweeney vitro, phenol, phonics, C1-C4-alkoxy, C1 C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl], C2-C8-alkenYlamino [which is optionally substituted by fluorine, chlorine, bromide, cyan, vitro or phenol, phenol-amino or benzylam;no [Shea are optionally subs;-tuned by fluorine, chlorine, bromide, C1-C4-alkyl9 trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoro-alkoxy, C1-C4-alkylthio, C1-C~-alkylsulphinyl, C1-C~-alkylsulphonyl, cyan, vitro and/or C1-c4-alkoxY-carbonyl]~ bouncily Which us optionally substituted by fluorine, chlorine, bromide, cyan, vitro, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy-carbonyl~ C1-C4-alkoxy or di-(C1-C4-alkyl)-am;no-sulphonyl~ or an optionally subset-tuned phenol radical R
- wherein R13 R12 and R13 are dental or different and have the meanings given above for R7 and I but are not identical to R7 and R8 on each individual case;
and in which, furthermore R3 represents the radical -û-R14, 30 whereon R14 represents Cl-c1z-alkyl [which us optionally substituted by fluorine, chlorine, bromide, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C~-C4-alkylsulphonyl], or represents C3-C6-cycloalkyl~ C3-C6 cycle alkyl-C1-C2-alkyl~ c3-c6-alkenyl Couch us lo A 23 307 - Foreign countries I I
optionally substituted by fluorine, chlorine or bromide C3-C6-alk;nyl, C1-C4-alkoxy carbonyl-C1-C2~
alkyd, aminocarbonylmethyl, C1-C4-aLkylamino-carbonyl-methyl or di-(C1-C4-alkyl)-amino-carbonyl-methyl, or represents phenol, bouncily, or ben~hydryl or phenethyl Shea are optionally substituted by fluorine, chlorine, vitro, cyan, C1-C4-alkyl, Cl-C4-alkoxy or C1-C4-alkoxy-carbonyl];
or in which, furthermore, R3 represents the radical -N
Rl6 wherein R15 represents hydrogen or C1-C4-alkyl and R16 represents hydrogen or C1-C4 alkyd [which is optionally substituted by fluorine, chlorine, bromide, cyan, C1-C~-alkoxy or C1-C4~alkoxy-carbonyll, or represents C3-c6-cycloalkyl~ or represents phenol, bouncily or phenethyl which are optionally substituted by fluorine, chlorine, bromide, cyan, vitro, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl]~ or represents C1-C4-alkyl-carbonyl, C~-C4-alkoxy-carbonyl, C1-C4-alkyl-sulphonyl or phenylsulphonyl Couch is optionally substituted try fluorine, chlorine, bromide, cyan, vitro or methyl;
and on uh;ch, furthermore - in the case where R2 repro-sets a sulphonyl radical R11-S02-earn R11 has the above mentioned meaning -R3 also represents hydrogen; 0 and in which, furthermore, I represents hydrogen, fluorine, chlorine brom;ne or C1-C~-alkyl Couch is optionally substituted by fluorine and/or chlorine], or rep-resents C1 c4-alkoxy Couch is optionally sub-lo A 23 307 - Foreign countries 2'7~S
stituted by fluorine and/or chlorine, or represents C1-C4-alkylthio Couch us optionally substitu-ted by fluorine and/or chlorine];
R5 represents hydrogen, fluorine, chlorine, S bromide or C1-Ct~alkyl Couch is optionally substituted by fluorine and/or chlorine, or rep-resents cyan, formal, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl and R6 represents hydrogen, C1-C4-alkyl which us optionally substituted by fluorine Andre chlorine], or represents C1-C4-alkoxy Couch is optionally substituted by fluorine and/or chlorine, or represents amino, C1-C4-alkylamino or d;-tC1-C4-alkyl)-amino - Thea the proviso thee R4 and R6 do not Somali-tonsil represent methyl.
1:1 adduces of compounds of the formula (I) with strong acids, have also now teen found, the following come pounds being excluded: the possum salt of N'-t4,6-20 d;methoxy-pyrimidin-2-yl)-N"-methoxy-N"'-~2-trifluurea-methoxy benzenesulphonyl)-guanidine, N'-(4-methoxy-6-methyl~pyrimidin-2-yl)-N"-pimethylamino-N"'-t2-metthy-benzenesulphonyl)-guanidine, N'-~4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N"'-~2-chloro-benzenesuulphon-yl~-guan;d;ne and N'-(4-methoxy-6-methyl-pyrim;din~Z~Y~)~
'N"-dimethylam;no-N"'-~2-chloro-benzenesulphonyl)--undone.
If M represents hydrogen, the general formula I) repro-sets the individual tautomers of the formulae VIA) and JIB) z to NO US VIA) R2 ~R3 . C N pi ( If) N
lo A 23 307 - Foreign countries I
in Shea R1 R2 R3 R4, R5 and R6 have the above mentioned meanings, and mixtures of the tautomers (IA) and tip).
S The mixing ratio (IA)/(IE~) depends on factors which determine the state of aggregation, such as, for example, the temperature, solvent and concentration.
In the case where, on addition t-o M, R2, too, represents hydrogen, a further tautomeric form (IT) is possible:
\ C / ON ~R6 (IT) N
~R3 According to a further aspect of the parent application the new sulphonylguanidinopyrimidine derivatives of the formula I) are obtained by a process in which (a) in the case where M represents hydrogen and R represents R -S02 guanidinopyrimidine derivatives of the formula (II) \ H I R4 HO R5 ill) g No R6 on which R3, R4, R5 and R6 have the above mentioned meanings, are reacted with sulphon;c acid chlorides of the formula (III) R1-S02 Of (III) on Shea R1 has the above mentioned meaning, in the presence of acid acceptors and if appropriate on the presence of d;luents; or lo A 23 307 Foreign countries ___ ~2Z~dZ~S
(b) in the case where M represents hydrogen and R2 rep-resents hydrogen or C1-C4-alkyl, the sulphonyLguani-d;nopyrimidine derivatives obtainable by the process desk cried above under (a), of the formula RID) H ' N R4 RYAN No/ R5 tidy C / N I
N
R1-5~2 o'er in Shea R1 R4 R5, I and R14 have the above mentioned meanings, are reacted with amino compounds of the formula (IVY) /R2 (IV) HO
in which R
R2 represents hydrogen or C1-c4-alkyl and R3 has the above mentioned meaning, or ugh hydrochloride of amino compounds of the formula IVY), 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 rep resents a sulphonyl radical of the formula R1 1 Sue_ wherein R11 has the above mentioned meaning, sulphonylguanidinopyrimidine derivatives of the formula (If) Rl-SQ2-N No/ R5 I / N~<R6 N (If) H I
lo A 23 307 Foreign countries ~L2;~'7 in which R1, R3, R4, R5 and R6 have the above mentioned meanings, are reacted with sulphonic acid chlorides of the formula (V) R11-50z-Cl (V) in which R11 has the above mentioned meaning, in the presence of acid acceptors and it appropriate in the presence of delineates; or id) likewise in the case where M represents hydrogen and R2 represents a sulphonyl radical of the formula ROY-wherein R11 has the abovement;oned meaning, sulphonylguan;d;nopyrimidine derivatives of the formula (VI) , H; N R4 Ho `' No/ R5 (VI) R11-502 \R3 in Shea R3, R4, R5, R6 and R11 have the above-mentioned meanings, are reacted with sulphonic acid chlorides of the formula ~III) R1-S02-Cl (III) lo A 23 307 - Foreign countries _ I
- Jo -in which R1 has the above mentioned meaning, on the presence of acid acceptors and if appropriate in the presence of delineates; or (e) in the case where M represents hydrogen and R2 rep-resents hydrogen or C1-C4-alkyl, sulphonylisothio-ureidopyrimidine derivatives of the formula (YIP) Al 50 N `- / N~/~R5 (VII) \R17 on which R1, R4, R5 and R6 have the abovement;oned meanings and R17 represents C1-c4~alkyl or bouncily, are reacted with amino compounds of the formula (IV) I (IV) HO
in which R
R2 represents hydrogen or C1-C~-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 metal, the compounds obtainable by the processes desk cried above under (a), (by, (c), (d) and (e), of the formula (I), in which M represents hydrogen and R1, R2, R3, R4, R5 and R6 have the above mentioned meanings, are reacted with metal hydroxides, hydrides or alkanolates or with organometallic compounds, if appropriate in the presence of delineates; or (g) on the case where 1:1 adduces of compounds of the formula (I) with strong acids are to be prepared, come pounds of the formula (I) in which M represents hydrogen lo A 23 307 - Foreign countries and R , R , R , R , R and R have the ahovementioned meanings, are reacted with strong acids, if appropriate in the presence of delineates.
The new sulphonylguanidinopyrimidine derivatives of the formula (I) and their addicts with strong acids are distinguished by a powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) exhibit a considerably better herbicidal action than the already known guanidines of the same type of action.
According to the present divisional invention -there is provided a sulphonylisothioureidopyrimidine derivative of the general formula (VII A) R4 C 6 (VII A) R
in which R represents a substituted phenol radical wherein R represents Cl-C4-alkylthio, Cl-C4-alkyl-sulphinyl or Cl-C4-alkylsulphonyl, or Cl-C4-fluoroalkoxy, R represents hydrogen, fluorine, chlorine, bromide or Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkylthio [which is optionally substituted by fluorine and/or chlorine, to - ha -R represents hydrogen, fluorine, chlorine, bromide or Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents cyan, formal, Cl-C4-alkylcarbonyl or Cl-C4-alkoxy-carbnYl, R represents hydrogen, or represents Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represents amino, Cl-C4-alkylamino or di-(Cl-C4-alkyl)-amino - with the proviso that R and R do not simultaneously represent methyl - and R represents Cl-C4-alkyl or bouncily.
These compounds are useful in process (e) above as intermediates in -the synthesis of the sulphonylguanidinopyrimidine compounds of the parent application.
According to another aspect of this divisional application there is further provided a process for the preparation of a sulphonylisothioureidopyrimidine derivative of the formula (VII A) as defined above, which process comprises reacting an N-sulphonyl-imino-di-thiocarbonic acid ester of the formula (XV A) R -SO NO (XV A) in which R and R have the meanings given above, with an aminopyrimidine of the formula (XI) .R4 HEN R (XI) R
r - fib -in which R , R and R have the meanings given above, if required, in the presence of a base and, if required, in the presence of a delineate, and, when the reaction has ended, diluting the mixture with water and acidifying with a strong acid.
Preferred compounds of this divisional application are compounds wherein R represents methylthio isopropyl-thio, deflower-methoxy, trifluoromethoxy, methylsulphonyl, R represents methyl, methoxy, ethics, hydrogen, chlorine or methylthio, R represents hydrogen or chlorine and R represents methyl, ethyl, methoxy, ethics, diEluoromethoxy, dimethylamino or hydrogen.
Particularly preferred compounds of this divisional application are compounds wherein R7 represents methylthio, R
represents methyl or methoxy, R represents hydrogen, R represents methyl or methoxy and R represents methyl.
he invention of the parent application preferably relates to compounds of the formula (I) in which M represents hydrogen or one equivalent of sodium, potassium or calcium, R represents an optionally substituted phenol radical wherein R 7 and R8 are identical or different and represent hydrogen, fluorine, chlorine, bromide, cyan, vitro or methyl [which is optionally -- tic --substituted by Fluorine chlorine, ennui, Cl-C3-alkoxyearbonyl, Cl-C3-alkoxy, C1-C3-alkylthio, Cl-C3-alkylsulphinyl or C1-C3-alkylsulphonyl], or represent C1-C2-alkoxy [which is optionally substituted by fluorine, chlorine, cyan, Cl-C3-alkoxy-carbonyl, Cl-C3-alkoxy, Cl-C3-alkylthio, Cl-C3-alkylsulphinyl or Cluck-al.kylsulphonyl], or represent Cl-C3-alkylthio, Cl-C3-alkylsulphinyl or Cl-C3-alkylsulphonyl [which are optionally substituted by fluorine, chlorine, cyan or Cl-C3-alkoxy-carbonyl], or represent di-(Cl-C3-alkyl)-amino-sulphonyl, Cl-C3-alkoxy-methylamino-sulphonyl, phenol or phonics, ~2;2~5 or represent C1-C4-alkoxy-carbonyl [which is optionally substituted by f Lowry no, sheller no, Brigham no, cyan or C1-C3-alkoxy~ C3-C6-cycloalkoxy-carbonyl, C1-C~-alkylthio-carbonyl, di-~C1-C3-alkyl)-amino-carbonYl or C1-C3-alkoxymethylamino-carbonyl, or represent C2-C4-alkenyl Couch is optionally substituted by fluorine, chlorine, cyan or C1-C3-alkoxy-carbonyl];
or in which, furthermore, R1 represents an optionally substituted bouncily radical (I SHEA-whereon R9 and R10 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 R11-S02-wherein R11 represents C1-Cg-alkyl Couch is optionally substituted by fluorine, chlorine or cyan], C1-: C8-alkoxy which is optionally substituted by fluorine, chlorine or cyan], C2-C8-alkenyl C~h;ch is optionally substituted by fluorine, chlorine, cyan or phenol, C2-C8-alkenyloxy Which us optionally substituted by fluorine, chlorine, cyan or phenyl~p C1-CO-alkylamino, C3-C6-cycloalkylamino or d;-(C1-C3-alkyl)-amino Couch are optionally substituted by fluorine, chlorine, cyan, phenol, phonics or C1_c2_ alkoxy~, c2-c6-alkenylamino Which is optionally Lea 23 307 - Foreign countries .~2~7 substituted by fluorine, chlorine, cyan or phenol], phenylamino or benzylami~o Couch are optionally substituted by fluorine, chlorine, bromide, C1-Colloquial, trifluoromethyl, C~-C3-alkoxy, S C1-C2-fluoroalkoxy, Cl-C3-alkylthio, C1-C3-alkylsulphinylO C1-C3-alkylsulphonyl~ cyan, vitro and/or C1-C3 alkoxy-carbonyl], bouncily Couch is optionally substituted by fluorine, chlorine, cyan, vitro, methyl, methoxy and/or C1-C2-alkoxy-carbonyl] or an optionally subset-outed phenol radical R12 wherein R1~
R~2 and R13 are identical or different and have the meanings given above as preferred for R7 and R8, but are not identical to R7 and R8 in each individual case;
and in which, furthermore R3 represents the radical -û-R14, wherein ~14 represents C~-c8-alkyl Couch is optionally : substituted by fluorine or chlorine], or represents C3-C6-alkenyl Couch 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, vitro, methyl methoxy or C1-C2-alkoxy-carbonyl];
or in which, furthermore, R3 represents the radical -N
\ R 1 6 wherein R15 represents hydrogen or methyl and R16 represents hydrogen or C1-C3-alkyl Which is optionally substituted by fluorine, chlorine, Sweeney C1~C2-alkoxy or c1-c2-alkoxy-carbonyl]
lo A 23 307 - Foreign countries _ I ho or represents C3-c6-cycloalkYl, phenol bouncily or phenethyl Quiche is optionally substituted by fluorine, chlorine, bromide, vitro, cyan, C1-C2-Cole, C1 C2 alkoxy or C1-C2-alkoxy-carbonyl], or represents acutely, methoxycarbonyl, Bunyan-suLphonyl or toluenesulphonyl;
and in which, furthermore R4 represents hydrogen chlorine or methyl Which us optionally substituted by fluorine and/
or chlorine, or represents C1-C2-alkoxy [which is optionally substituted by fluorine and/or chlorine, or represents C1-Cz-alkylthio [which is optionally substituted by fluorine and/or chlorine], R5 represents hydrogen, fluorine, chlorine, brow mine, methyl, acutely or C1-C2-alkoxy-carbonyl and R6 represents C1-C3-alkyl [which is optionally substituted by fluorine and/or chlorine], or rep-resents C~-C3-alkcxy [which is optionally substituted by fluorine and/or chlorine, or rep-resents amino, C1-C3-alkylamino or di-~C1-C3-alkyl)-amino - with the proviso that R and R do not simultaneously represent methyl.
The invention of the parent application 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 trifluoroacetic acid, with alkanesulphonic acids which have up to 4 carbon atoms and are optionally substituted by fluorine or chlorine, or with Bunsen - or naphthalene-sulphonic acids, which are optionally substituted by fluorine, chlorine, bromide or methyl.
The invention of the parent application particularly relates to compounds of the formula (I) in which lo A 23 307 - Foreign countries M represents hydrogen or one equivalent o-f sodium, potassium or calcium, R1 represents a substituted phenol raid eel Wrier wherein R7 represents fluorine, chlorine, bromide, methyl, tr;fluoromethyl, methoxy, difluoromethoxy, in-fluoromethoxy, C1-C3-alkylthio, C1-C3-aLkyl-sulphinyl, C~-C3-alkylsulphonyl, dimethylamino-sulphonyl~ diethylaminosulphonyl, N-methoxy-N-methyl-amino-sulphonyl, phenol, C1-C4-alkoxy-carbonyl, difluoromethylthio or trifluoromethylthio and R8 represents hydrogen;
and in which, furthermore, R2 represents hydrogen, methyl or a sulphonyl radical : R11-wherein R11 represents C1-C4-alkyl Cnhich is optionally substituted by fluorine or chlorine or represents C1-C4-alkylam;no or di-(C1-C2-alkyl)-amino which are optionally substituted by fluorine or represents an optionally substituted phenol radical wherein R12 R12 and R13 are identical or different and represent hydrogen fluorine, chlorine, bromide, cyan, vitro, methyl, tr;fluoromethyl, C1-C2-alkoxy [which is optionally substituted by flour-ire, chlorine, cyan or C1-C3-alko%y-carbonyl~, C1-C3-alkylthio, C1-C3-alkylsulphinyl or C1-C3-alkylsulphonyl [which are optionally substituted by fluorine and/or chlorine], dimethylaminosulphonyl, diethylaminosulphonyl~
lo A 23 307 - Foreign countries N-methoxy-N-methylaminosulphonyl, phenol or C1 C4-alkoxy-carbonyl Couch is optionally substituted by fluorine, chlorine, cyan or C1-C2-alkoxy], and in which, furthermore, S R3 represents the radical -O'ER
wherein R14 represents C1-C~-alkyl Which is optionally substituted by chlorine] or represents C3-C~-alkenyl Quiche is optionally substituted by chlorine], or represents C1-C2-alkoxy-carbonyl-methyl, phenol, phenethyl or bouncily Quiche is optionally substituted by fluorine, chlorine, vitro, cyan, methyl, methoxy or C1-C2-alkoxy-carbonyl~, or in which, furthermore, R3 represents the radical -N \
wherein R15 represents hydrogen or methyl and R16 represents hydrogen, C1-C3-alkyl, C3-C6-cyclo-alkyl, phenol, acutely, methoxycarbonyl, benzenesulphonyl or toluenesulphonyl;
and in which, furthermore, R4 represents hydrogen, chlorine or C1-C2-alkoxy Which is optionally substituted by flour-ire and/or chlorine], R5 represents hydrogen, methoxycarbonyl, ethoxycarbonyl or acutely and R6 represents C1-C2-alkyl Couch is optionally substituted by fluorine and/or chlorine or Of-C2-alkoxy Couch is optionally substituted by fluorine and/or chlorine, and - in the case where M represents hydrogen - the 1:1 adduces of the compounds defined above with hydrochloric acid, sulfuric acid, trifluoroacetic acid, methanesul-phonic acid, benzenesulphonic acid and toluenesulphonic acid.
lo A 23 307 - Foreign countries I
The compounds mentioned individually above are also excluded from the preferred and particularly pro-furred range.
If, for example, 2-fluoro-benzenesulphonyl chloride and N'-t4-methoxy-6-methyl-pyrimidin-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:
F I H ) N SHEA
2 I- 502C l HO ~--~ No N
-2 Hal OF NO 3 N
I
If, for example, N'-t4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-guanidine and phenylhydrazine are used as starting substances for process variant (b), the course of the reaction can be outlined by the following equation:
I N~)COCNF2 I) / ` OUCH Q 52 NASH 3 lo A 23 307 - Foreign countries (~52-N~ NO
NH
NH ~!~
If, for example, ~'-(4,6-dimethoxy-pyr;midin-2-5 yl)-N"-benzyloxy-N"'-(2-chloro-phenylmethylsulphonnil)-guanidine and 2-trifluoromethane-sulphonyl chloride are used as starting substances for process variant (c), the course of the reaction can be outlined by the following equation:
clue J OUCH
H OUCH
lo A 23 307 - Foreign countries - HO I C N OUCH
If, for example, N'-~4-ethoxy-6-methyl-pyrimidin-2-yl)-N" methoxy-N"-(2-ethoxycarbonyl-benzenesulphonyl)-guanidine and 2-dimethylaminosulphonyl-benzenesulphonyl chloride are used as starting substances for process variant (d), the course of the reaction can be outlined by the following equation:
, H N SHEA 502-N~CH3)2 HO\; ON j- 5 2 - C 1 SO / KOCH
COOK
SOz-N~CH3)2 - Hal Suzanne Swiss OKAY
COOK
If, for example, N'-t4-methoxy-6-methyl-pyrimi-din-2-yl)-N"-t2-methyl-benzenesulphonyl)-S-me~hyl--is-Thor and N,N-dimethylhydrazine are used as starting substances for process variant (e), the course of the reaction can be outlined by the following equation:
lo A 23 307 - Foreign countries .
SHEA ' H I N SHEA
N `-' No H2NN(CH3)2 \ SHEA
SHEA H ' N SHEA
N
H N(CH3~2 If, for example, N'-(4,6-dimethoxy-pyrimid;n-2-yl)~N"-isopropoxy-N"'-(2-methoxycarbonyl-phenylmetthylsul-phonyl~-guanidine and potassium ethanol ate are used as starting substances for process variant (f), the course of the reaction can be outlined by the following equation:
COUCH OH,\ N OUCH COOK
CHOSEN No C Nash - HAYAKAWA
H OCH(CH3~2 I
COUCH N OUCH
I OUCH
H OCH(CH3~2 If, for example, N'-~5-acetyl-4-methyl-pyrimidin-2-yl)-N"~methoxy-N"-(2~chloro-benzenesulphonyl)-N""'-(2-difluoromethoxy-benzenesulphonyl)~guanidine and methane-sulphonic acid are used as starting substances for pro-lo A 23 307 - Foreign countries 72~
cuss variant (9), the course of the reaction can be out-lined by the following equation:
OCHF2 , H ) N SHEA
~502-N N~/~COCH3 SHEA
/ \ O C H
Of OCHF2 I H Jo N SHEA
\ C / No X SHEA
N
Of Formula (II) provides a general definition of the S guanidinopyr;midine derivatives to be used as starting substances for process variant (a). In formula tip), R3, R4, R5 and R6 preferably and particularly have the same meanings as are given above as preferred or as par-titularly preferred in the context of the definition of the subst;tuents of formula (I).
Examples which may be mentioned of starting sub-stances of the formula (II) are: N'-(4-methyl-pyrimidin-yule)-, N'-(4-ethyl-pyr;m;d;n-2-yl)-, N'-(4-methoxy-6-methyl-pyr;m;din-2-yl)-, N'-(4-ethoxy-6-methyl-pyrimidin-2 ye)-, N'-(4-propoxy-6-methyl-2-yl)-, N'-(4-isopropoxy-6-methyl-pyrimid;n-2-yl) , N'-(4-chloro-6-methoxy-pyr;midin-yule)-, N'-(b-chloro-6-ethoxy-pyr;mid;n-2 ye)-, No chLoro-6-d;methyLam;no-pyr;m;d;n-2-yl)-, N'-(4-methyl-6-methylth;o-pyr;m;din-2-yl)-9 N'-(4,6-d;me~hoxy-pyrimidin-yule)-, N'-(b-d;fluoromethoxy-6 methyl-pyr;m;d;n-2-yl)-and N'-t4-dimethylamino-6-methyl-pyrimid;n-2-yl)-N"-methoxy-guan;dine, -N"-ethoxy-guanidine, -N"-propoxy-guanidine, -N"-isopropoxy-guanidine~ -N"-butoxy-guanidine, -N"-isobutoxy-guanidine, -N"-sec.-butoxy-yuan;d;ne, -N"-lo A 23 3û7 - Foreign countries ~2Z72~
pentoxy-guanidine, -N"-isopentoxy-guanidine, -N"-hexyl-oxy-guanidine, -N"~octyloxy-guanidine, -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"-methoxy-carbonylmethoxy-guanidine, -N"-ethoxy-carbonyl-methoxy-guanidine, -N"-(1-methoxycarbonyl-ethoxy)-guanidine, No ethoxycarbonyl-ethoxy)-guanidine, -N"-dimethyl-aminocarbonyl-methoxy-guanidine, -N"-(2-phenyl-ethoxy)-guanidine, -N"-phenoxy-guanidine, -N"-(4-methyl-benzyl-oxy)-guanidine, -N"-(4-fluoro-benzyloxy)-guanidine, -N"-(4-chloro-benzyloxy)-guanidine, -N"-(4-nitro-benzyloxy)-guanidine, -N"-(2,6-dichloro-benzyloxy)-guanidine, -N"-~4-methoxycarbonyl~benzyloxy)-guanidine and No ethoxycarbonyl-benzyloxy-guanidine.
The starting substances of the formula (II) form the subject of prior patents (compare EGOS (European Published Specification 121,082); however, new compounds are those of the formula (II), in which (a) R4 represents chlorine, R5 represents hydrogen and R6 represents C1-C4-alkoxy which is optionally substituted by fluorine and/or chlorine], C1-C4-alkylamino or di-(C1-C4-alkyl)-amino;
: or in which (b) R4 represents C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine], R5 represents hydrogen and R6 represents C1-C4-alkoxy which is substituted by fluorine and/or chlorine, or represents C1-C4-alkylamino of di-(C1-C4-alkyl)-amino;
or in which (c) R4 and R5 represent hydrogen and R6 represents C2-C3-alkYl;
lo A 23 307 - Foreign countries ~.22~
and in each case R3 has the above mentioned meaning.
The guanidinopyrimidine derivatives of the formula (II) - and hence also the new compounds of the formulae (Ida), Jib and (Sir) which are defined above under to), by and lo) - are obtained by a process on which cyanoaminopyrimi dine derivatives of the formula (VIII) N R4 (VIII) N--<R6 in which R4, R5 and R6 have the abovement;oned meanings, are reacted with amino compounds of the formula (IX) 1ûH2N-R3 (IX) on which R3 has the above mentioned meaning, or with hydrochloride thereof, of appropriate in the presence of d;luents, such as, for example, ethanol, is-propanol 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 cyanoaminopyr;m;dine derivatives of the for-mute (VIII) form the subject of prior patents (compare PUS (European Published Specification) 121,082); however, new compounds are those of the formula (VIII) on which (a) R4 represents chlorine, R5 represents hydrogen and I represents C1-C4-alkoxy C~h;ch is optionally substituted by fluorine and/or chlorine], C1-C4-alkylamino or di~(C1-C4-alkyl)-amino;
or in Shea lo A 23 307 - Foreign countries ye I
- I -(b) R4 represents C1~C4-alkyl Couch is optionally substituted by fluorine and/or chlorine], R5 represents hydrogen and R6 represents C1~C4-alkoxY which is substituted by fluorine andtor chlorine, or represents C1-C4-alkylamino or di-(C1-C4-alkyl)-amino;
or in which (c) R4 and R4 represent hydrogen and R6 represents C2~C3-alkyl.
The compounds of the formula (VIII) - and hence also the new compounds of the formulae (Vow), (VIIIb) and (Yoke) Shea are defined above under (a), (b) and (c) - are essentially obtained by the following synthesis routes:
(a) by reaction of alkali metal or alkaline earth metal salts of cyanamide - such as, for example, sodium cyan-aside or calcium cyanamide - with chloropyrimidines of the formula (X) Clue/ R5 (X) in which R4, R5 and R6 have the above mentioned meanings, if appropriate in the presence of inert delineates, such as, for example, ethanol, acetone, acetonitriLe or dip ~ethylformamide, at temperatures between ûC and 100C.
After the mixture has been concentrated and the residue has been dissolved in water, the cyanoaminopyrimidine derivatives of the formula (YO-YO) can be precipitated by acidification for example with hydrochloric acid, and isolated by filtration with suction.
Alternatively, cyanoaminopyrimidine derivatives of the formula (VIII) are obtained aye) in the case where R4 and/or R6 represent hydroxyl, by reaction of cyanoguanidine ("dicyanodiamide") with suitable ~-dicarbony( compounds - or derivatives thereof -lo A 23 307 - Foreign countries .
3L~27%~3~
such as, for example, 1,1~dimethoxy-3-oxo-butane, methyl acetoacetate or ethyl acetoacetate (compare J.
Pratt. Chum. 77 (1908), 542 and J. Chum. Sock 1948, 586) or dim ethyl Mullen or deathly malonate (compare German Patent Specification 158,591).
The 2-cyanoamino-4-hydroxy-6-methyl- or -Dow hydroxy-pyrimidines obtained from acetoacetic acid esters or Malone acid esters can be converted into correspond-no 2-cyanoam;no-4-alkoxy-6-methyl- or -4,6-d;alkoxy-pyr;m;d;nes on a known manner by reaction with alky~atingagents, such as, for example, dim ethyl sulfite or deathly sulfite, of appropriate on the presence of d;luents, such as for example, water, methanol, ethanol, n- or ;so-propanol, acetone, Dixon or d;methylform-amid, and on the presence of ac;d-b;nd;ng agents, such as, for example, sodium hydroxide or potassium hydroxide or sodium carbonate or potassium carbonate. To avoid N-alkylat;on, acylation is carried out, if appropriate, with an assaulting agent, such as, for example, acetic 2û android or acutely chloride, and, after the alkylat;on, the product us desolated again with aqueous acids or bases.
In another alternative process, cyanoam;nopyrimi dyne derivatives of the formula (VIII) are obtained by a process on Shea (a) am;nopyr;m;d;nes of the formula taxi) N -I
HEN R5 (XI) in which R4, R5 and R6 have the above mentioned meanings, are reacted with carbonyl isothiocyanates of the formula (XII) o Rl~-C-N=C=S (XII) lo A 23 3n7 - Foreign countries -I
on which R18 represents ethics or phenol, if appropriate in the presence of an inert delineate, such as, for example, acetone acetonitrile or Tulane, at S temperatures between 0C and 100C, the carbonylthio-ureas thereby formed, of the formula tXIII>
R 1 8 _ C - NH - if - NH ~/~ R 5 ( X I I I
in which I R5, R6 and R1~ have the above mentioned 1û 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 soul-lion, if appropriate in the presence of an organic sol-vent, such as, for example, tetrahydrofuran or Dixon, at temperatures between 0C and 12ûC, and the Theresa obtained as crystals after acidification, for example with hydrochloric acid, of the formula (XIV) If N R4 (XIV) ON - C - OH ~/~ R
on which R4, R5 and R6 have the above mentioned meanings, are isolated by filtration with suction and reacted with metal compounds which can bond hydrogen sulfide, such as, for example, with lead-II acetate, copper-II acetate, mercury-II acetate or iron-II acetate, in the presence of aqueous alkali metal or alkaline earth metal hydroxide 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 lit-lo A 23 307 - Foreign countries irate is acidified with an acid, such as, for example, acetic acid.
The products of the formula (VOW thereby obtained as crystals can be isolated by filtration with suction.
The starting substances for the preparation pro-cusses described above under tax), (a) and (a) for the cyanoaminopyrimidine derivatives of the formula (VIII) are known and/or can be prepared by processes which are known per so.
These substances include the chloropyrimidines of the formula (X) (compare J. Chum. Sock (C) 1966, 2031;
Chum. Harm. Bull. 11 (1963), 1382-1388 and Arch Harm.
295 (1962), 649-657), the aminopyrimidines of the formula 15 (XI) (compare Chum. Harm. Bull 11 (1963), 1382-1388);
J. Chum. Sock 1946, 81 and US. Patent Specification 4,299,960) and the carbonyl isothiocyanates of the for-mute (XII) (compare J. Heterocycl. Chum. 5 (1968), 837 and US. Patent Specification 4,160,037).
The amino compounds of the formula (IX) also to be used as starting substances are likewise already known and/or 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.
25 Sock 1930, 228 and Help. Chum. Act 45 (1962), 1387).
Formula (III) provides a general definition of the sulphonic acid chlorides also to be used as starting substances for process variant (a). In formula (III), R1 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 to).
Examples which may be mentioned of starting sub-stances of the formula (III) are: sheller-, sheller-, sheller-, 2,5-d;chloro-, flyer-, flyer-, Brigham, Brigham-, nutria-, nutria-, Sweeney-, 2-methyl-, 4-lo A 23 307 - Foreign countries -~2~7 methyl-, 2-chloromethyl-, 2-trifluoromethyl-, 2-methoxy-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-methylthiomethyl-, 2-methylsulphinylmethyl-, 2-methyl-sulphonylmethyl-, 2-dimethylaminosulphonyl-, deathly-aminosulphonyl-, phenol-, 2-methoxycarbonyl-, ethics-carbonyl-, 2-propoxycarbonyl-, 2-isopropoxycarbonyl-, 2-butoxycarbonyl-, 2-dimethylaminocarbonyl-, deathly-aminocarbonyl-, phonics 2-methyl-5-chloro-, sheller-5 trifluoromethyl-, 2-methylsulphonyl-, 2-ethylsulphonyl-, 2-chloro-4-trifluoromethoxy, 3-chloro-4-trifluoromethoxy-, 2-trifluoromethoxy-5-chloro-, 3,5-dichloro-, 2-difluoromethyl-trio- and 2-trifluoromethylthiobenzenesulphonyl chloride, and also methane-, chloromethane-, trifluoromethane-, ethanes-, 2-chloroethane-, ethene-, propane-, butane-, per-fluorobutane- and perfluoro-octane-sulphonyl chloride;
methyl-, ethyl-, propel, isopropyl-, cyclohexyl-, dim ethyl-and diethyl-sulphamic acid chloride and (Z-chloro-phenyl)-, (Z-cyano-phenyl)- and ~2-methoxycarbonyl-phenyl)-methane-sulphonyl chloride.
The sulphonic acid chlorides of the formula (III) are known and/or can be prepared by processes which are known per so (compare J. Org. Chum. 33 (1968), 2104; J.
Org. Chum. 25 (1960), 1824; DE-AS (German Published Spew suffocation) 2,308,262; EGOS (European Published Specific 25 cations) Z3,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; and US. Patent Spew c;fications 2,929,820, 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 R1S03H or 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 color-ides phosgene or benzotrichloride, if appropriate in the lo A 23 307 - Foreign countries presence of catalysts such as, for example, pardon or dimethylformamide, and if appropriate using inert dill-ens, such as, for example ethylene chloride, sheller form, aceton;trile, chlorobenzene and/or sulpholane, at temperatures between -20C and icky, preferably between 0C and ~100C; after dilution with water, the sulk phonic acid chlorides - Where these are obtained as crystals - can be isolated by filtration with suction or purified by extraction with a water-immiscible solvent, such as, for example, ethylene chloride, deathly ether or hexane, washing and drying of the extracts, concentra-lion and recrystallization or distillation; or to) in a manner which is known per so (compare J. Org.
Chum. 25 (1960), 1824; DEMOS (German Published Specific-lion) 2,308,262 and EGOS (European Published Specific-lion) 59,241), by reaction of corresponding amino come pounds R1-NH2 with sodium nitrite and hydrochloric acid, if appropriate in the presence of acetic acid, at - temperatures between -10C and ~20C, preferably between -5C and 110C, and subsequently (in situ) with sulk pour dioxide or a salt of sulfurs acid, such as, for example, sodium sulfite or sodium bisulphite, in the presence of a copper compound, such as, for example, copper chloride or copper sulfite - as a catalyst, at temperatures between ûC and 80C, preferably between 10C and 60C.
Working up can be effected in the customary manner; on dilution with water, the sulphonic acid chlorides are in general obtained as crystals and can be isolated by filtration with suction. However, they can also be extracted from the aqueous dispersion with a sol-vent which is virtually immiscible with water such as, for example, ethylene chloride or deathly ether, dried and purified by vacuum distillation.
Formula (ID) provides a general definition of the sulphonylguanidinopyrimidine derivatives to be used as lo A 23 307 - Foreign countries I
- I -starting substances for process variant (b). In formula (ID), I R4, R5, R6 and R14 preferably and part-ocularly 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 ox compounds of the formula RID) are: N'-(4-chloro-6-methoxy-pyrimidin-2-yl)-N"-methoxy N,,N"'-bis-(2-chloro-benzenesulphonyl)-, -N",N"'-bis-~2-bromo-benzenesulphonyl)-, -N",N"'-bis-(Z-1û ~luoro-benzenesulphonyl)-, -N",N"'-bis-(2-methyl-benzene-sulphonyl)-,-N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-,, -N-",N"'-bis-bis(2-methoxy-benzenesulphonyl)-, -N",N"'-bis-(2-phenyl-benzenesulphonyl)- and -N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-guanidine, N'-(4-methyl-pyrimi~in-2-yl)-15 N"-methoxy-N","'-bis-(Z-chloro-benzenesulphonyl)-,, NUN
bis-(2-methoxycarbonyl-benzenesulphonyl~ N",N"'-bis-(2-difluoromethoxy-benzene-sulphonyl)-, -N",N"'-bis-(2-diethyLaminosulphonyl-benzene-sulphonyl)-, -N",N"'-bis-(2-bromo-benzenesulphonyl)-, -N",N"'-bis-(2-tr;fluorome~hylthio-I benzenesulphonyl)-, -N",N"'-bis-(2-phenoxy-benzenesulphonyl)-and-N",N"'-b;s-~2-methyl-sulphonyl-benzenesulphonyl)--guanidine, N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N",N""'-bus-(2-chloro-benzenesulphonyl)-, -N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-difluoromethoxy-benzene-sulphonyl)-,-N",N"'-bis-(2-trifluoromethoxy-benzenesulphonyl)--, -N",N"'-bis-(2-dimethylaminosulphonyl-benzenesulphHoneywell)-, -N",N"'-bis-(2-methylthio-benzenesulphonyl)-, -N",N"'-bis-(2-ethoxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-phenyl-benzenesulphonyl)-, -N",N"'-bis-~2-cyclopropyloxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-trifluoromethylsulPhonYl-benzenesulphonyl)-, -N",N"'-bis-(2-nitro-benzenesulphonyl)-and -N",N"'-bis-(2-cyano-benzenesulphonyl-guanidine), N~-(4-methoxy-6-methyl-pyrimidino2-yl)-N"-methoxy~NUN
bis-(2-chloro-benzenesulphonyl)-, -N"~N"'-bis-(2-methoxy-carbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-methylsulphonyl-benzenesulphonyl)-, ~N",N"'-bis-(2-methylthio-benzenesulphonyl)-, lo A 23 307 - Foreign countries I
-Nl~Nl~-bis-(2-trifluoromethoxy-benzenesulphonyl)--I NUN
bis-(2-ethoxycarbonyl-benzenesulphonyl)-, -N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-, -N",N"'-bis-(2-isopropyl~
thio-benzenesulphonyl)-, -N",N"'-bis-(2-N-methoxy-N-methyl-S aminosulphonyl benzenesulphonyl)-, -N",N"'-bis-(2-tr;fluoro-methylthio-benzenesulphonyl)-, -N",N"'-bis-S2,5-dichloro-benzenesuLphonyl)-, -N",N"7-bis-(2-phenoxy-benzenesulphonyl)-and -N",N"'-bis-(2-phenyl-benzenesulphonyl-guanidine, N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-N"--methoxy-N",N"'-bis-(2-ethoxycarbonyl-benzenesuLphonyl)-, NUN
bis-(2-bromo-benzenesulphonyl)-, -N",N"'-bis-(2-methyl-sulphonylmethyl-benzenesulphonyl)-, -N",N"'-bis-(2-trifluoro-methylthio-benzenesulphonyl)-, -N",N"'-bis-(2-methoxy-benzene-sulphonyl)-, -N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-and-N",N"'-b;s-(2-chloro-benzenesulphonyl)-guanidine..
The compounds of the formula (ID) can be prepared by the process described above under (a).
Formula (IVY) provides a general definition of the amino compounds also to be used as starting substances in process variant (b). In formula (IV), R2 and R3 prefer-ably and particularly have the same meanings as have been 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, phenylhydrazine, 0-methyl-hydroxylamine, 0-ethyl-hydroxyl-amine, 0,N-dimethylhydroxylamine and propel-, issue-propel-, bottle-, 0-sec~-butyl-, ponytail-, issue-ponytail 0-sec.-pentyl-, exile-, 0-isohexyl-, 0-hotly-, 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)-, sheller-bottle)-, 0-methoxycarbonylmethyl-, 0-ethoxycarbonylmethyl-, 0-(1-methoxycarbonyl)-ethyl-, I ethoxycarbonyl)-ethyl-, 0-aminocarbonylmethyL-, 0-(2-phenyl-ethyl)-, phenol-, lo A 23 307 - Foreign countries 0 t4-methyl-benzyl)-~ 0-(4-fluoro-benzYl)-, sheller-bouncily)-, 0-(4-nitro-benzyl)-, 0-(2,6-dichloro-benzyl)-, 0-(4-methoxycarbonyl-benzyl)- and 0-t4-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. Bull. 15 ~1967), 345; pull. Sock Chimp France 1958, 66~; Synthesis 1976, ~j82; J.Chem. Sock 1930, 228 and Help. Chimp Act 45 t1962), 1387).
Formula (If) provides a general definition ox the sulphonylguanidinopyrimidine derivatives to be used as starting substances in process variant (c). In formula (If), R1, R3, R4, R5 and R6 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 subs~ituents of formula (I).
Examples which may be mentioner of compounds of the formula (If) are: N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methox`y-N"'-(2-chloro-benzenesulphonyl)-guaniddine -N"'-(3-chloro-benzenesulphonyl)-, -N"'-(4-chloro-benzene-sulphonyl)-, -N"'-(2-fluoro-benzenesulphonyl)-, No fluoro-benzenesulphonyl~-, -N"'-(2-bromo-benzenesulphonyl)-, -N"'-(4-bromo-benzenesulphonyl)-~ -N"'-t2-cyano-benzene-sulphonyl)-, -N"'-(Z-nitro-benzenesulphonyl)-, -N"'-t4-ni~ro-benzenesulphonyl)-, -N"'-tZ-methyl-benzenesulphon-ye)-, -N"'-t4-methyl-benzenesulphonyl)-, -N"'-(2-chloro-methyl-benzenesulphonyl)-, -N"'-(2-trifluoromethyl-ben-zenesulphonyl)-, -N"'-t2-methoxy-benzenesulphonyl)-, -N"'-(4-methoxy-benzenesulphonyl)~, -N"'-(2-methylthio-3û benzenesulphonyl)-, -N"'-(2-difluoromethoxy-benzene-sulphonyl)-, -N"'-t2-trifluoromethoxy-benzenesulphonyl)-, -N"'-t2-methylthiomethyl-benzenesulphonyl)-, N"'-t2-dimethylamino-sulphonyl-benzenesulphonyl)-, -N"'-t2-phenyl-benzenesulphonyl)-, -N"'-t2-methoxysulphonyl-benzenesulphonyl)-, -N"'-t2-methoxycarbonyl-benzene~
sulphonyl)-, -N"'-(2-ethoxycarbonyl-benzenesulphonyl)-, ye A 23 307 - Foreign countries ~22~7~
-N"'-t2-propoxycarbonyl-benzenesuLphonyl)-, No methylaminocarbonyl-benzenesulphonyl)-, -Knothole-aminocarbonyl-benzenesulphonyl)-, -N"'-(2-propylanino-carbonyl-benzenesulphonyl)-, -N"'-(2-methoxyaminocarbon-S yl-benzenesulphonyl)-, -N"'-(2-ethoxyaminocarbonyl-benzenesulphonyl)-, -N"'-(2-propoxyaminocarbonyl-benzene-sulphonyl)-, -N"'-(2-dimethylaminocarbonyl-benzenesulphon-ye)- and -N"'-(2-diethylaminocarbonyl-benzenesulphonyl)-guanidine; and furthermore N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-ethoxy-N"'-benzenesulphonyl-, -N"'-(2-chloro-benzenesulphonyl)-, -N"'-(3-chloro-benzenesulphonyl)-, ~N"'-(4-chloro-benzenesulphonyl)-, -N"'-(2,4-dichLoro-benzenesulphonyl)-, -N"'-(2,5-dichloro-benzenesulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulphonyl)-, -N"'-(2-tri-fluoromethoxy-benzenesulphonyl)-, -N"'-(2-methylthio-benzenesulphonyl)-, -N"'-(2-methyl-benzenesulphonyl)-, -N"'-(Z-methylthiomethyl-benzenesulphonyl)-, -N"'-(2-di-methylaminosulphonyl-benzenesulphonyl)-, -N"'-(2-methoxy-sulphonyl-benzenesulphonyl)-, -N"'-(2-methoxycarbonyl-benzenesulphonyl)-, -N"'-(2-ethoxycarbonyl-benzenesul-phony)-, -N"'-t2-methylaminocarbonyl-benzenesulphonyl)-, N"'-(2-ethylaminocarbonyl-benzenesulphonyl)-, No methoxyaminocarbonyl-benzenesulphonyl)- and No dimethylaminocarbonyl-benzenesulphonyl)-guanidine;; and furthermore N'-(4,6-dimethoxy-pyr;m;d;n-2-yl)-N"-propoxy-, -N"-;sopropoxy-, ~N"-butoxy, -N"-isobutoxy-, -N"-sec.-buttocks-, -N"-pentoxy-, -N"-hexyloxy-, -N"-octyloxy-, -N"-allyloxy-, -N"-crotyloxy-, -N"-(3-chloro-propoxy)-, -N"-methoxycarbonyl-methoxy-, -N"-ethoxycarbonyl-methoxy--N"-t1-methoxycarbonyl-e~hoxy)-, -N"-(1-ethoxycarbonyl-ethics)-, -N"-(2-phenyl-ethoxy)-, -N"-phenoxy-, -N"-benzyloxy-, -h"-(4-methyl-benzyloxy)-, -N"-(4-fluoro-benzyloxy)-, -N"-(4-chloro-benzyloxy)-, -N"-(4-nitro-benzyloxy)-, -N"-(2,6-dichloro-benzyloxy)-, No methoxycarbonyl-benzyloxy)- and -N"-(4-ethoxycarbonyl-benzyloxy)-, -N"'-(2-chloro-benzenesulphonyl)-guanidine lo A 23 307 - Foreign countries t72~S
and-N"'-(2-methoxycarbonyl-benzenesulphonyl)-guanidinno;
and furthermore N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy~N"'-(2-chloro-benzenesulphonyl)-, No methyl-benzenesulphonyl)-O N"'-(2-methylthio-benzene-sulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulphonyl)-and-N"l-(2-trifluoromethoxy-benzenesulphonyl)-guanidiire;
and furthermore N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-and N'-(4-methyl-pyrimidin-2-yl)-N"-methoxy-N"'-(2-chloro-benzenesulphonyl)~guanidine;
and furthermore N'-(4-chloro-6-methoxy-pyrimidin-2-yl)-N"-methoxy-No chloro-benzenesulphonyl)-, -N"'-(2-methoxycarbonyl-benzene-sulphonyl)-, -N"'-~2-difluoromethylthio-benzenesulphonyl)-and -N"'-(2-dimethylaminosulphonyl-benzenesulphonyl)-guan;d;ne;and furthermore N'-(4-chloro-6-ethoxy-pyrimidin-2-yl)-N"-ethoxy-N""'-to-bromo-benzenesulphonyl)-, -N"'-(2-phenylbenzenesulphonyl)-, -N"'-(2-dimethylaminocarbonyl-benzenesulphonyl)-, -N"'-(2-methylthiomethyl-benzolsulphonyl)-, -N"'-(2-phenoxy-benzenesulphonyl)- and -N"'-(isopropoxy-benzenesulphonyl)-guanidine;
and furthermore N'-(4-chloro-6-d;methylamino-pyrimidin-2-yl)-N"-meethics-N"'-(2-fluoro-benzenesulphonyl)-, -N"'-(2-difluoromethylthio-benzenesulphonyl)-, -N"'-(2-methyl-benzenesulphonyl)-, -N"'-(Z-ethoxycarbonyl-benzenesulphonyl)- and -N"'-(2-cyano-benzenesulphonyl)-guanidine;
and furthermore 30 N'-(4-methyl-6-methylthio-pyrimid;n-2-yl)-N"-allylloxy-N"'-(2-chloro-benzenesulphonyl)-, -N"'-(Z-isopropoxy-ben~ene-sulphonyl)-, -N"'-(2-phenoxy-benzenesulphonyl)-, No methylsulphonyl-benzenesulphonyl)- and -N"'-(2-cyclopropyl-oxycarbonyl-benzenesulphonyl~-guanidine;
and furthermore N'-(4-dimethylamino-6-methyl-pYrimidin-2-yl)-N~ sour _ A 23 307 - Foreign countries I -N"'-(2-chLoro-ben~enesulphonyl)-, -N"'-(2-chlorodifluoro-methyl-benzenesulphonyl)-, ~N"'-(2-N-methoxy-N-methyl-amino-sulphonyL-ben~enesulphonyl)-, -N"'-~2-phenyl-benzenesulphony~)-and-N"'-(2-isopropylthio-benzenesulphonyl)-guan;dine;;
S and furthermore N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-N"--methoxy-carbonyl-N"'-(2-methyl-benzenelsulphonyl)-, -N"'-t2-diethyl-aminosulphonyl-benzenesulphonyl)-, -N"'-(2-difluoromethoxy-benzenesulphonyl)-, -N"'-~2-nitro-benzenesulphonyl)-, -N"'-(2-methylthio-benzenesulphonyl)- and -Nighthawks-carbonyl-benzenesulphonyl)-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 suLphonic acid chlorides also to be used as starting sub-stances in process variant (c). In formula (V), R11 preferably and particularly has the same meaning as is given above as preferred or as particularly pro-furred in the context of the definition of the substitu-ens of formula I).
The sulphon;c acid chlorides which have been mentioned above as examples of compounds of the formula (II) can apply as examples of the starting substances of the formula (V).
The sulphonic acid chlorides of the formula (V) are known and/or can be prepared by processes ire are known per so compare the literature and synthesis routes for the compounds of the formula (III~ - above).
Formula (VI) provides a general definition of the sulphonylguanid;nopyrimidine derivatives to be used as starting substances for process variant Ed). In formula (VI), R3, R4, R5, R6 and R11 preferably and portico-laxly 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).
Examples which may be mentioned of compounds of the formula (VI) are: No methyl-pyrimidin-2-yl)-, I'-lo A 23 307 Foreign countries I
t4-methoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-chloro-6-methoxy-pyrimidin-2-yl) , N'-(~-chloro 6-ethoxy-pyrimidin-2-yl)-, N'-t4-chloro-6-dimethylamino-pyrimidin-2-yl)~, N'-(4-methyl-6-methylthio-pyrimidin-2-yl)-, N'-(4-dimethylamino-6-methyl-pyrimidin-yule)-, N'-(4,6-dimethoxy-pyrimidin-2-yl)- and N'-(4-difluoro-methoxy-6-methyl-pyrimidin-Z-yl)-N"-methoxy-~ -N"-methoxy-, -Nighthawks-, -N"-isopropoxy-, -N"-propoxy-, -N"-butoxy-, -N"-isobutoxy-, -N"-sec.-butoxy-, Spent ox-, -N"-octyloxy-, -N"-allyloxy-, -N"-(3-chloro-prop-ox)-, -N"-methoxycarbonylmethoxy-, -N"-ethoxycarbonyl-methoxy-, -N"-(2-phenyl-ethoxy)-, -N"-benzyloxy-, -N"-t4-methyl-benzyloxy)-, -N"-(4-fluoro-benzyloxy)-, -N"-t4-chloro-benzyloxy)-~ -N"-(4-nitro-benzyloxy)- and No methoxycarbonyl-benzyloxy)-, -N"-benzenesulphonyl-, -N"-(2-chloro-benzenesulphonyl)-, -N"-(3-chloro-benzenesul-phony)-, -N"-(4-chloro-benzenesulphonyl)-, -N"-t2-fluoro-benzenesulphonyl)-, -N"-(4-fluoro-benzenesulphon-ye)-, -N"-(2-bromo-benzenesulphonyl)-, -N"-(2-cyano-2û benzenesulphonyl)-, -N"-(2-n;tro-benzenesulphonyl)-, -N"-(4-nitro-benzenesulphonyl)-, -N"-(2-methyl-benzenesul-phony)-, -N"-(4-methyl-benzenesulphonyl)-, -N"-(2-tri-fluoromethyl-benzenesulphonyl)-, -N"-(2-methoxy-benzene-sulphonyl)-, -N"-(4-methoxy-benzenesulphonyl)-, No methylthio-benzenesulphonyl)-, -N"-(2-difluoromethoxy-benzenesulphonyl)-, -N"-(2-trifluoromethoxy-benzenesul-phony)-, -N"-~2-methylthiomethyl-benzenesulphonyl)-, -N"-(2-d;methylam;nosulphonyl-benzenesulphonyl)-, -N"-t2-phenyl-benzenesulphonyl)-, -N"-(2-methoxysulphonyl-benzenesulphonyl)-, -N"-(2-methoxycarbonyl-benzenesul phony)-, -N"-t2-ethoxycarbonyl-benzenesulphonyl)-, -N"-(2-propoxycarbonyl-benzenesulphonyl)-, -N"-(2-methyl-methoxy-amino-carbonyl-benzenesulphonyl)-, Nod methylamino-carbonyl-benzenesulphonyl)- and -N"-(2-di-ethylamino-carbonyl-benzenesulphonyl)-guanidine.
The sulphonylguanidinoPYrimidine derivatives ox lo A 23 307 - Foreign countries ~;~2~1[35i the formula (VI) are new and can be prepared by a process analogous to process (a) by reaction of guanidinopyrimi-dine derivatives of the formula tip) with approximately equimolar amounts of sulphon;c acid chlorides of the formula (V).
Formula Tao) provides a general Dionysian of the sulphonic acid chlorides also to be used as starting substances on process variant I In formula (III), R1 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 subst;tuents of the formula (I).
Examples of the sulphon;c acid chlorides of the formula (III) and their preparation process here have already been described above on connection ugh the desk Cretan of the starting substances for process (a).
Formula (VII) provides a general definition of the sulphonyl;soth;oure;dopyr;midine derivatives to be used as starting substances on process variant (e). In 2û formula (VII), R1, R4, R5 and R6 preferably and particularly have the same meanings as are given above as preferred or as particularly preferred on the context of the definition of the substituents of formula (I), and R17 preferably and particularly represents methyl.
Examples which may be mentioned of compounds of the formula (VII) are: N'-(4-chloro-6-methylth;o-pyr;m;d;n-yule)-, N'-(4-methyl-pyrimidin-2-yl)-, N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-, N'-t4-ethoxy-6-methyl-pyrim;d;n-yule)-, N'-(4-chloro-o-methoxy-pyrimidin-2-yl)-, No chloro~6-ethoxy-pyrimidin-2-yl)-, N'-(4-chloro-6-dimethyl-amino-pyrimidin-2-yl)-, N'-(4-methyl-6-methylthio-pyrimidin-yule)-, Ni-(4-dimethylamino-6-methyl-pyrimidin-2-yl)-, N'-(4,6-dimethoxy-pyrimidin-2-yl)- and N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-, -N"-(2-fluoro-benzenesulphonyl)-, -N"-(2-chloro-benzenesulphonyl)-, -N"-(2-bromo-benzenesulphon-ye)-, -N"-t2-methyl-benzenesulphonyl)-, -N"-(2-methoxy-lo A Z3 307 - Foreign countries carbonyl-benzenesulyhonyl)-, -N"- (2-ethoxycarbonyl-benzenesulphonyl)-, -N"-~2-propoxycarbonyl-benzcnesulphonyl) -, -N"- (2-isopropoxycarbonyl-benzenesul-phony) -, -N"- (2-phenyl-benzenesulphonyl) -, -N"-(2-trifluoromethyl-benzene-sulphonyl)-, -N"- (2-difluoromethoxy-benzenesulphonYl)- and -N"-(2-trifluoro-methoxy-benzenesulphonyl)-S-methyl-isothiourea.
The sulphonylisothioureidopyrimidine derivatives of the formula (VII) are known and/or can be prepared by processes which are known per so (compare EGOS (European Published Specification) 5,986).
It is to be noted however, that compounds of the formula (VII), in Itch Al represents a phenol radical substituted in ortho-position by Cluck-fluoroalkoxy, C,-CA-alkylthio, Cl-C~-alkylsulphinyl or Cl-C4-alkyl-sulphonyl, and in which R4, R5, R8 and R17 have the above-mentioned meanings, are not ye-t known. These new compounds may be presented by formula (VII A) and are the subject of this divisional patent application.
The compounds of the formula (VII and VII A) are obtained by a process in which N-sulphonyl-imino-dithiocarbonic acid esters of the formula (XV) or (XV A) as appropriate, R -SNUCK (XV or XV A) in which Al and R have the above mentioned meanings, as appropriate, are reacted with aminopyrimidines of the formula (XI) N
ON I/ R5 (XI) \ R
in which R , R and R have the above mentioned meanings, if appropriate in the ~7;~5 - I -presence of bases, such as, for example, sodium hydrides or potassium left.-butylate, and if appropriate in the presence of delineates, such as, for example, tetrallydrofuran, Dixon or dimethylformamide, at temperatures between 0C and 100C and, when the reaction has ended, the mixture is diluted with water and acidified with a strong acid, such as, for example, hydrochloric aria, and the products of the formula (VII ion VII A) obtained as crystals are isolated by filtration with suction.
The process for preparing a compound of the formula (VII A) by reacting a compound of the formula (XV A) with a compound of the formula (XI) comprises one aspect of the subject of this divisional application.
s Formula (XV) provides a general definition of the N-sulphonyl-;mino-dithiocarbonic acid esters required here as starting substances. In formula (XV), R1 and R17 preferably and particularly have the same meanings as are given above as preferred or as particularly characterized in the context of the definition of the substituents for formula (I) or formula (VII).
Examples which may be mentioned of compounds of the formula (XV) are: S,S-dimethyl N-(2-fluoro-benzene-sulphonyl-, N-(2-chloro-benzenesulphonyl-, N-(2-bromo-benzenesulphonyl)-, N-(2~methyl-benzenesulphonyl)-, No methoxycarbonyl-benzenesulphonyl)-, N-(2-ethoxycarbonyl-benzenesulphonyl)-, No propoxycarbonyl-benzenesulphon-ye)-, N (2-isopropoxycarbonyl-benzenesulphonyl)-, No phenyl-benzenesulphonyl)-O No trifluoromethyl-benzene-sulphonyl)-, N-(2-difluoromethoxy-benzenesulphonyl)-, N-(2-trifluoromethoxy-benzenesulphonyl)-, N-(2-trifluoromethylthio-benzenesulphonyl)-, N-(2-difluoro-methylthio-benzenesulphonyl)-, N-(2-phenoxy-benzenesul-phony)-, N-(2-cyclopropyloxycarbonyl-benzenesulphonyl)-, N-(2-methylthio-benzenesulphonyl)-, N-(2-isopropylthio-benzenesulphonyl)-, N-(2-trifluoromethylsulphonyl-benzene-sulphonyl)-, N-(2-dimethylaminosulphonyl-benzenesulphonyl)-~N-(Z-N-methoxy-N-methylaminosulphonyl-benzenesulpphony)-, N-(2-cyano-benzenesulphonyl)-, N-~2-nitro-benzenesulphonyl)-, N-t2-dimethylaminocarbonyl-benzenesulphonyl)- and No methylsulphonylmethyl-benzenesulphonyl)-im;no-d;th;ocarbonate.
The N-sulphonyl-imino-dithiocarbonic acid esters of the formula TV) are known andtor can be prepared by processes which are known per so (compare Comma Per. 99 (1966), 2885 and EP-ûS (European Published Specification) S,~86).
The compounds of the formula (XV) are obtained by a process in which sulphonic acid asides of the formula ~XVI) lo A I 307 - Foreign countries _ .. .. . . . . . . ....
~22~
R1-SOzcNH2 (XVI) on which R1 has the above mentioned meanings, are reacted with carbon disulphide on the presence of a strong base, such as, for example, sodium hydroxide, and, if appropriate, in the presence of delineates, such as, for example, water and dimethylformamide, at temperatures between 0C and 100C and subsequently (in situ) with an alkylating agent of the formula (XVII) X-R17 (XVII) on Shea R17 has the above mentioned meaning and X represents chlorine, bromide or iodine, at temperatures between 0C and 100C~
The products of the formula (XV) obtained as crystals after dilution of the mixture with water can be isolated by filtration with suction.
Formula (XVI) provides a general definition of the sulphonic acid asides required as starting substances.
In formula (XVI), 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 compounds of the formula (XVI) are: 2-trifluoromethylthio-, deflower-methylthio-, phonics-, 2-cyclopropoxycarbonyl-, 2-methyl-trio-, 2-isopropylthio~, 2-trifluoromethylsulphonyl-, 2-d;methylaminocarbonyl-, 2-dimethylaminosulphonyl-, Sweeney-, flyer sheller Brigham-, 2-methyl-, 2-methoxy-carbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl-, 2-isopropoxycarbonyl-, phenol-, 2-trifluoromethyl-, 2-difluoromethoxy- and 2-trifluoromethoxy-, 2-N-methoxy-N
lo A 23 307 - Foreign countries ~2~7~5 *, methylaminosulphonyl~, nutria- and 2-methylsulphonylmethyl-benzenesulphonamide D
The sulphonic acid asides of the formula (XVI~
are known and/or can be prepared by processes which are known per so (compare EGOS (European Published Specific-lions) 23,422, 30~14D, 35,893, 44,807, 44,80~, 44,809, 51,466, 6~,804, 7û,041 and 70,802; US. Patent Specific-lion ~,372,778 and Oh. Org. Kim Jo Org. Chum. USSR] 8 (1972), 1023~1026 English 1032-1034]).
These compounds are obtained in a manner which is known per so by reacting sulphonic acid chlorides of the formula (III) - above - with ammonia, if appropriate on the presence of d;luents, such as for example, dip ethyl ether, tetrahydrofuran or water, at temperatures between 0C and kiwi The products of the formula (XVI) thereby obtained as crystals can be isolated by filtration Thea suction.
Examples of suitable starting substances of the formula Tao) and preparation methods for these are given above in the description of the starting substances for process (a).
Examples which may be mentioned of starting sub-stances of the formula (XVII) are: methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide and ethyl iodide, and bouncily chloride and bouncily bromide.
The compounds of the formula (XVII) are known.
Formula I provides a general definition of the aminopyrimidines also to be used as starting substances.
In formula (XI), R4, R5 and R6 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 compounds of the formula (XI) are: 4-chloro-6-methoxy-, sheller-ethics-, 4-chloro-6-dimethylamino-, 4-methyl-6-methylthio-, lo A 23 307 - Foreign countries ... . . .. . ... .. .. . . . . . . . . . . ... .. .
I
, 4-dimethylam;no-6-methyl-, 4-d;fluoromethoxy-6-methyl-, 4,6-d;methoxy-~ 4-methoxy-6-methyl-, 4-ethoxy-6-methyl-and 4-methyl-2 amino-pyrim;d;ne.
The aminopyrimidines of the formula (XI) are known and/or can be prepared by processes which are known per so (compare J. Chum. Sock 1946, 81; Chum. Harm. Bull.
11 (1963), 1382-1388, US. Patent pacification ~,299,960; EGOS (European Published Spec;f;cation) 19,811; AUTOS Austrian Published Spec;ficat;on) 8,316,181 and EGOS European Publishes Specification 70 804).
Formula (IV) provides a general definition of the amino compounds also to be used as starting substances in process variant (e). In formula (lo), 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 pro-furred in the context of the definition of the subset ens for formula (I).
Examples of suitable starting substances of the formula (IV) and literature references for these are given above on 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 substances for process (~) - M rep-resents hydrogen and R1, R2, R3, R4, R5 and R6 prefer-ably and particularly have the same meanings as are given above as preferred or as particularly preferred on the context of the definition of the substations for formula (I).
The compounds of the formula (I) to be used as starting substances for process (f) can be prepared by the processes described under (a), (b), (c), (d) and (e).
Examples which may be mentioned of the metal hydroxides, hydrides and alkanolates or organometallic lo A 23 307 - Foreign countries ~.2~7~
compounds to be used 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 ate and potassium ter.-butanolate, and bottle-lithium and isopropyl-magnesium chloride.
Formula with the proviso that M represents hydrogen - provides a general definition of the compounds to be used as starting substances on process variant (9).
In formula (I), where this relates to the compounds to be used as starting substances for process go - M represents hydrogen and R1, RZ, R3, R4, R5 and R6 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 subst;tuents for 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 (9). 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 sub-stituted by fluorine or chlorine, such as, for example, methanesulphonic acid, ethanesulphonic acid, sheller-methanesulphonic acid, 2-chloroethanesulphonic acid and tr;fluoromethanesulphonic acid, and trifluoroacetic acid, and furthermore benzenesulphonic acid, p-toluenesulphonic acid, naphthalene-1-sulphonic acid, naphthalene-Z-sul-phonic acid and naphthalene-1,4-, -1,5-, -1,6-, -2,6- and -2,7-d;sulphonic acid.
Process (a) for the preparation of the new compounds of the formula (I) is preferably carried out using delineates. Possible d;luents are virtually all the inert organic solvents, but prefer-ably aprotic polar solvents. These include optionally lo A 23 307 - Foreign countries .
~2;2~
substituted hydrocarbons, such as, for example, ethylene chloride, chloroform, 1,2-dichloroethane, Tulane, zillion and chlorobenzene, nitrites, such as, for example, acetonitrile and prop;onitr;le, ethers, such as, for example, 1,2-dimethoxyethane, tetrahydrofuran and Dixon, and d;methylformamide, dimethylacetamide, dimethylsulph-oxide, sulpholane, pardon and 2-methyl-5-ethyl-pyr;dine.
Virtually all the acid-binding agents which are usually employed can be used as acid acceptors in pro-cuss pa). These include, in particular, alkali metal and alkaline earth metal hydroxides, alkali metal and alga-line earth metal hydrides, organometallic compounds, such as butyl-lithium, and furthermore aliphatic, aromatic or heterocyclic amine, such as trimethylamine, triethyl-amine, N,N-dimethylaniline, N,N-dimethyl-benzylamine, diazabicyclooctane (DICK), diazabicyclononene (DUN), diazabicycloundecene (DUB), pardon, 2-methyl-5-ethyl-pardon 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 -80 and ~100C, preferably between -30C and +50C. Process (a) according to the invention is in general carried out under normal pressure.
For carrying out process to), in general between 1 and 5 moles, preferably between 2 and 3 moles, of sulk phonic acid chloride of the formula (III) are employed per mole of guanidinopyrimidine derivative of the formula (If).
The reaction components are usually brought to-getter 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 a water-immiscible solvent, such as, for example, methyl-one chloride, chloroform or Tulane, if appropriate after distilling off volatile components, and the organic phase lo A I 307 - Foreign countries .. .. . .
~2~t7~
is washed it water, dried, filtered and concentrated The products ox the formula (I) which remain in the nest-due are made to crystallize by digestion with organic solvents, such as, for example, deathly ether, ethyl acetate, ethanol or isopropanol, and, if appropriate, are purified by recrystallization.
Process (b) is prefer-ably carried out using delineates. Possible delineates are virtually all the inert organic solvents. These include, on particular, alcohols, such as methanol, ethanol and n-or i-propanol, ethers, such as tetrahydrofuran~ Dixon and 1,2-dimethoxyethane, esters, such as methyl acetate and ethyl acetate, nitrites, such as, for example, asset-nitrite or propionitrile, and dimethylformamide and water.
Acid-binding agents which do not have nucleon fluky properties uh;ch noticeably compete with those of the amino compounds ox the formula (IV) can be employed as acid acceptors in process (b). Acid acceptors of this type which may be mentioned are alkali metal and alkaline earth metal carbonates, such as, for example, potassium carbonate and calcium carbonate, tertiary amine, such as, for example, triethylamine, NUN-dimethylaniline and N,N-dimethylbenzylamine, and nitrogen-containing heterocyclic compounds, such as, for Z5 example, pardon, diazab;cyclooctane (DICK) and d;azab;cycloundecene (DUB).
The reaction temperature can be varied within a substantial range in process (b). In general, the react lion us carried out between 0C and 150C, preferably between 10C and 100C. Process (b) is in general carried out under normal pressure.
For carrying out process (b), in general between 1 and 10 moles, preferably between 2 and 5 moles, of amino compound of the formula (IV) or hydrochloride thereof are employed per mole of -the compound of the formula (ID).
lo A 23 307 - Foreign countries ~X;;~2~
- I -In general, the compound of the formula (ID) is with the delineate at 20C or with gentle cooling and the amino compound of the formula (IV) or the hydrochloride thereof and, if appropriate, a suitable acid acceptor are added. The reaction mixture is then in general stirred at room temperature or elevated temperature until the reaction has ended.
working up can be carried out by customary methods. If the products of the formula (I) are obtained 1û as crystals from the reaction mixture, they can be is-fated by filtration with suction. Otherwise - if approp-rite after concentration - the mixture is diluted with utter and extracted with a solvent which is virtually water-immiscible, such as, for example, ethylene color-ides The products of the formula (I) can be obtained in pure form by Washing the extraction solution with water, drying, filtering, concentrating the filtrate and no-crystallizing the residue.
Process (c) is prefer-ably carried out using d;luents. Possible delineates are virtually all the inert organic solvents, but preferably aprotic polar solvents, such as have been mentioned above on connection with the description of process (a) accord-in to the invention.
Virtually all the acid-binding agents which are usually employed can be used as acid acceptors in process I These include, in particular, the acid-binding agents mentioned above in connection with the description of process (a).
3û The reaction temperatures can be varied within a substantial range in process I In general, the react lion is carried out between -80C and ~100C, preferably between -30C and ~50C. Process I is in general carried out under normal pressure.
For carrying out process (c), in general between 1 and 2 moles, preferably between 1.1 and 1.5 moles, of lo A 23 307 - Foreign countries s - by -sulphonic acid chloride of the formula (V) are employed per mole of sulphonylguanidinopyrimidine derivative of the formula tie).
The procedure and working up for process I can be analogous to that for process (a).
Process (d) is prefer-ably carried out using dullness. 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-no to the invention.
Virtually all the acid-binding agents which are usually employed can be used as acid acceptors in process Ed). These include in particular, the acid-binding agents mentioned above in connection with the description of process (a) according to the invention The reaction temperatures can be varied within a substantial range on process (d). In general, the react ton us carried out between -80C and +100C, preferably between -30C and ~50C. Process (d) is in general carried out under normal pressure.
In carrying out process (d), in general between 1 and 2 moles, preferably between 1.1 and 1.5 moles, of sulphonic acid chloride of the formula (III) are employed per mole of sulphonylguanidinopyrimidine derivative of the formula (YIP).
The procedure and working up in process (d) can be analogous to that in process (a).
Process (e) is prefer- -3û ably carried out using d;luents. Possible delineates are virtually all the inert organic solvents, but preferably aprotic polar solvents. These include, in particular, tetrahydrofuran, Dixon, 1,2-dimethoxyethane, asset-nitrite, acetone, methyl ethyl kitten, methyl isobutyl kitten, dimethylformamide, dimethylacetamide and dim ethyl-sulphoxide.
lo A 23 307 - Foreign countries The reaction temperature can be varied within a substantial range in process (e). In general, the reaction is carried out between OKAY and 150~C, preferably between 10C and 100C. Process (e) is in general carried out under normal pressure or slightly reduced pressure.
For carrying out process (e), in general between l and lo moles, preferably between l and 5 moles, of amino compound of the formula (IV) are employed per mole of sulphonylisothioureidopyrimidine derivative of the formula (VII) which group includes compounds of the formula (VII A) which are the subject of this divisional application.
In general, the sulphonylisothioureidopyrimidine derivatives of the formula (VII) (including those of formula (VII A)) and the delineate are taken and -the amino compound of the formula (IV) is metered in. The reaction mixture is then stirred until the reaction has ended.
The products of the formula (I) 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 (f) is preferably 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 iso-propanol, ethers, such as, for example, tetrahydrofuran, Dixon and 1,2-dimethoxyethane, esters, such as, for 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 reaction is carried out between -20C and ~50C, preferably between 0C and 30C. Process (f) is in general carried out under normal pressure.
For carrying out process (f), in general between 0.9 and 1.2 moles, preferably between 0.95 and 1.1 moles, of metal compound are 72~
employed per mole of the compound of the formula (I).
In general, the compounds of the formula (I) and the delineate are taken and - of appropriate with gentle external cooling - the metal compound - of appropriate dissolved on the delineate - us metered in. The reaction mixture us stirred until the reaction has ended. The salt-like products of the formula (I) are in general obtained as crystals and can be isolated by filtration with suction.
Process (g) is prefer-ably carries out using delineates Possible delineates are virtually all the inert organic solvents. These include, in particular, alcohols, such as methanol, ethanol and n- or ;so-propanol, ethers, such as tetrahydrofuran, Dixon and 1,2-dimethoxyethane, esters such as methyl acetate and ethyl acetate, and kittens, such as acetone, methyl ethyl kitten and methyl ;sobutyl kitten.
If the acids used as starting substances are employed in aqueous solution, it may also be advantageous to use acetic android as the delineate.
The reaction temperature can be varied within a substantial range in process (9). In general, the react lion is carried out between -20C and ~5ûC, preferably between 0C and 30C. Process (g) is in general carried out under normal pressure.
For carrying out process (9), in general between 1 and 10 moles, preferably between 1 and 5 moles, of a strong acid are employed per mole of the compound of the formula (I).
In general, the compounds ox the formula (I) and the delineate are taken and - if appropriate with gentle external cooling - the strong acid is metered on. The reaction mixture us stirred until the reaction has ended.
The 1:1 adduces are in general obtained as crystals and can be isolated by filtration with suction.
The active compounds according to the invention lo A 23 307 - Foreign countries _ 27;;~
can be used as defoliants, desiccants, agents for desk trying broad-leaved plants and, especially, as weed-killers. Eye weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds can be used, for example, on connection with the follow-no plants:
Dicotyledon Leeds of the genera: Synapse, Lepidium, Gallium, Styler, Mutterer Anthems, Galinsoga, Sheehan-podium, Utica, Seneca, Amaranths, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cur-swum, Keywords, Sonchus, Selenium, Rewrap, Rotate, Lender-Noah, Lam;um, Veronica, Abutilon, Emex, Dotter Viola, Galeopsis, Palaver and Sinatra.
cotyledon cultures of the genera: Gossypium, Gleason, Beta, Caucus, Fossils, Possum, Selenium, L;num, Ipomoea, Via Nicotiana, Lycopers;con, Arachis, risque, lag-tuna, Cucum;s and Cucurbita.
Monocotyledon weeds of thy genera: Echinochloa, Satyr, Panicum, Jotter Phlegm, Poe, Fistic, Eleusine, Bra-Shari, Lolium, Brahms, Arena, Cyprus, Sorghum, Ago-pylon, Sundown, Monkery, Fimbr;styl;s, Sag;ttaria, Eleochar;s, Scripps, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrost;s, Alopecurus and Opera.
Monocotyledon cultures of the genera: Ours, Zeal Tryout-gum, Hordeum, Arena, Scale, Sorghum, Pan;cum, Saccharum, Bananas, Asparagus and Alma.
However, the use of the active compounds 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 lo A 23 307 - Foreign countries ~Z~72~
on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating Leeds in preen-nil cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, and for the selective combating of Leeds in annual gut-lures.
The active compound scan be used for selectively combating monocotyledon and dicotyledon Leeds on monocotyledon and dicotyledon crops, such as, for example, cotton, rice, cereals and maize.
The active compounds can be converted to the cuss tumor formulations, such as solutions, emulsions, wet-table powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated Thea active compound and very fine capsules in polymeric substances.
These formulations are produced on 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 emulsify-in agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as Audi-fiery solvents. As liquid solvents, there are suitable the main: aromatics, such as zillion, Tulane or alkyd naphthalenes, chlorinated aromatics and chlorinated elf-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 lo A 23 307 = Foreign countries 31Z2~
Bunnell or glycol as jell as their ethers and esters, kittens, such as acetone, methyl ethyl kitten, methyl isobutyl kitten or cyclohexanone, strongly polar solvents, such as d;methylformamide and d;methylsulphox;de, as well as water.
As solid carriers there are suitable: for example ammon;um salts and ground natural minerals, such as kayo-lens, clays, talc, chalk quartz, at~apulg;te, montmor;l-lunate or d;atomaceous earth, and ground synthetic miner-1û also such as highly disperse stoic acid, alumna ands;licates, as solid carriers for granules there are suit-able: for example crushed and fractionated natural rocks such as Calcutta marble, pumice, sepiolite and dolomite, as jell as synthetic granules of inorganic and organic meals and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as Emil-sifting and/or foam-form;ng agents there are suitable:
for example non-ion;c and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty ZOO alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as jell as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methyl cellulose.
Adhesives such as carboxymethylcelluLose and natural and synthetic polymers in the form of powders, granules or lotuses, such as gum Arabic, polyvinyl Alcoa hot and polyvinyl acetate, as well as natural phosphor lipids, such as cephalins and lecithins, and synthetic phospholipids, can be used on the formulations. Further additives can be mineral and vegetable owls.
It us possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian glue, and organic distaffs, such as alizarin distaffs, ago distaffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, lo A 23 307 - Foreign countries I._ I I
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 0.5 and 90%.
The active compounds according to the invention, as such or in the form of their formulations, can also be used, for conbat;ng Leeds, as mixtures with known herb-aides, finished formulations or tank mixes being possible.
For the mixtures come known herbicides, such as, for example, N-(2-benzothiazolyl)-N,N'-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(4-isopropyl-phenyl)-~ dimethylurea, Amman dimethylethyl)-3-methylthio-1,2,4-triazin-5-~4H)-oone, 4-amino-6-(1,1-dimethylethyl)-3-ethylthio-1,2,4-triaassign-(one, 1-amino-6-ethylthio-3-(2,2-d;methylpropyl)-1,3,5-~riazine-2,~-(1H,3H)-dione, 4-amino-3-methyl-6-phenyl-1,2,4-tr;az;n-5-(4H)-one, 2-chloro-4-ethylamino-6-isopropyl-am;no treason, the R-enant;omer of (tr;methyls;lyl)-methyl 2-C4-(3,5-d;chloropyr;dyl-2-I oxy)-phenoxy~-propionate, the R-enantiomer of (2-benzyloxy~-ethyl 2-~4-(3,5-dichloropyridyl-Z-oxy)-phenoxy]-propionate, 2,4-d;chlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)-propionic acid, 4-chloro-2-methyl-phenoxy-acetic acid, 2-(2-methyl-4-chlorophenoxy)-pro-phonic acid, 3,5-diiodo-4-hydroxy-benzonitrile, Dow-broom 4-hydroxy-benzonitrile and diphenyl ethers and phenylpyr;dazines, such as, for example, peridots. Sun-praisingly, some mixtures also show a synergistic action.
Mixtures with other Nolan active compounds, such as fungicides, insecticides, acar;c;des, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, on the form of their formulations or on the use forms prepared therefrom by further dilution, such as Rhodes Lowe-Chinese suspensions, emulsions, powders, pastes and grant lo A 23 307 - Foreign countries I
- I -vies. They are used in the customary manner, or 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.
he amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.001 and 15 kg of active compound per Hector of soil surface, preferably between 0.05 and 10 kg per ha.
The examples which follow exemplify the inventors ox the parent and divisional applications, as appropriate.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Preparation Examples Example 1 Of N__cOC~3 _502_N~ Nay KOCH
. Of (Process (a)) 10.1 9 ~0.048 mole) of 2 chloro-benzenesulphonyl chloride are added to a solution of 4.5 9 (0.02 mole) of N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-guaniiodine on 30 ml of pardon at -10C. The reaction mixture is stirred at 20C for two days. After addition of a further 1.5 g of 2-chloro-benzenesulphonyl chloride, the mixture is stirred at 20C for a further 24 hours. At a maximum temperature of 40C, the mixture is concern-treated, the residue is taken up in ethylene chloride and the mixture it washed with I strength hydrochloric acid.
lo A 23 307 - Foreign countries The organic phase us dried, filtered and concentrated.
The oily residue is made lo crystallize with isopropanol.
2.65 9 (23X of theory) of N'-(4,6-dimethoxy-pyr;midin-2-yl)-N"-methoxy-N",N"'-bis (2-chloro-benzene-sulphonyl)-guanid;ne of melting point 164-165C are obtained.
Example 2 ONE / NO
H N~CH~)2 process (b)) A mixture of 5.8 9 (0.01 mole) of N'-(4,6-di-methoxy-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-csheller-benzenesulphonyl)-guanidine, 1.5 9 (0.0Z5 mole) of NUN-d;methylhydrazine, 20 ml of ethanol and 10 ml of water is heated at the boiling point under reflex for one hour.
The product obtained as crystals after cooling the mix-lure is isolated by filtration with suction and wreckers-tallied from ethyl acetate.
1.3 9 (31% of theory) of N'-(4,6-dimethoxy-pyr;midin-2-yl)-N"-dimethylamino-N"'-(2-chloro-bennzene-2û sulphonyl)-guan;d;ne of melting point 190C are obtained.
Example 3 ON
H OUCH
(Process ye)) A mixture of 16.0 9 (0.04 mole) of N'-(4-methoxy-25 6-methyl-pyrimidin-2-yl)-N"-(2-methylthio-benzenescellophane-yl)-S-methyl-isothiourea, 4.0 9 (0.û85 mole) of 0-methyl-lo A 23 307 - Foreign countries ~;~Z7~6~S
hydroxylam;ne and 80 ml of Dixon is stirred at 30C
to 33C for 15 hours. The mixture us then concentrated, the residue is made to crystallize by trituration with ethanol and the product is isolated by filtration with 5 suction.
8.4 9 t53~ of theory) of N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N"'-(2-methylthio-benzeone-sulphonyl)-guan;dine of melting point 134C are obtained.
Example 502N(C~3)2 _502-N~- / NH4 x SHEA
SYNCH
(Process tug)) A mixture of 5.4 9 (û.0075 mole) of N'-(4,6-dimethoxy-pyr;midin-2-yl)-N"-methoxy-N",N"'-bis-(22-d;methylam;nosulphonyl-benzenesulphonyl)-guanidinee, 0.75 9 (0.0075 mole) of methanesulphonic acid and 10 ml of acetone us stirred at 20C for 24 hours. The products obtained as crystals us then isolated by filtration with suction.
1.6 9 ~26% of theory) of the 1:1 adduce of N'-20 ~4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N"~N"'-bbus-tdimethylaminosulphonyl-ben~enesulphonyl)-guanidinno and methanesulphonic acid of melting point 145C are obtained.
The following compound is obtained analogously:
lo A 23 307 Foreign countries -I
Example 5 502N(CH3~2 t H No X H2504 502N~CH3)2 : Melting point: 155C
The compounds of the formula (I) lusted in the following Table 1 can be prepared by the processes desk cried by way of example in the preceding examples:
M / N ,R4 R1-502-N ` No R5 I) / N
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pa) p-Toluenesulphonic acid salt of Example 7, amorphous, pa) p-Toluenesulphonic acid salt of Example 8, amorphous, 8b) Sulfuric acid salt of Example 8, amorphous.
pa) p-Toluenesulphonic acid salt of Example 9, having a melting point of 175C (decomposition.
9b) Sulphonic acid salt of Example 9, having a melting point of 175C (decomposition).
aye) p-Toluenesulphonic acid salt of Example 22, (oil).
lo A 23 3û7 - Foreign countries : .
` '` it ~7~5 Preparation of starting substances of the formula (II) Example (II-1 ) , H N OUCH
C N owe C H 3 N
H OUCH
A mixture of 36.0 9 (0~2 mole) of cinnamon-
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pa) p-Toluenesulphonic acid salt of Example 7, amorphous, pa) p-Toluenesulphonic acid salt of Example 8, amorphous, 8b) Sulfuric acid salt of Example 8, amorphous.
pa) p-Toluenesulphonic acid salt of Example 9, having a melting point of 175C (decomposition.
9b) Sulphonic acid salt of Example 9, having a melting point of 175C (decomposition).
aye) p-Toluenesulphonic acid salt of Example 22, (oil).
lo A 23 3û7 - Foreign countries : .
` '` it ~7~5 Preparation of starting substances of the formula (II) Example (II-1 ) , H N OUCH
C N owe C H 3 N
H OUCH
A mixture of 36.0 9 (0~2 mole) of cinnamon-
4,6-dimethoxy-pyrimidine, 33.4 9 (0.4 mole) of 0-methyl-hydroxylam;ne hydrochloride and 200 ml of ethanol is heated at the bullying point under reflex for 6 hours.
After addition of a further 16.7 9 (0.2 mole) of 0-methyl-hydroxylamine hydrochloride, the mixture is heated under reflex for a further 6 hours. After cooling, it is filtered over kieselguhr, the filtrate is concentrated and the residue is diluted with 2D0 ml of water. The pi is brought to 7 with dilute sodium hydroxide solution and the product thereby obtained as crystals is isolated by filtration with suction.
After recrystallization from isopropanol, 16.4 9 (36X of theory) of N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-guanidine of melting point 122C are obtained.
lo A 23 307 - Foreign countries -- Jo -The compounds of the formula (II) lusted on the following Table 2 can be prepared analogously:
Jo i N R4 HO\ No -US tip) N
Table 2 Example Melting No. R3 R4 R5 R6 point I
II-4 -oCH2CH(CH3~2 -OUCH H -OUCH 76 10 II-5 - -OCH2CH=CH2 -OUCH H -OUCH
II-7 -OCH(CH3)2 -OUCH H -OUCH
II-B CH2cH2 -OUCH H -OUCH
II-9 -Ozone) -OUCH H -OUCH
lo A 23 307 - Foreign countries I
Table 2 - continuation Example Melting No. I R4 R5 R6 point t-C]
II-10 -Ozone) -C~3 H -OUCH
Isle clue Nash H -SHEA
Isle -OCH2CH2CH2Cl -OUCH H -OUCH
20 II-14 -ocH2cooc2H5-OCH3 H -OUCH
II-15 -0C3H7~-n) -OUCH H -OUCH
Of lo A 23 307 - Foreign countries ~72~
After addition of a further 16.7 9 (0.2 mole) of 0-methyl-hydroxylamine hydrochloride, the mixture is heated under reflex for a further 6 hours. After cooling, it is filtered over kieselguhr, the filtrate is concentrated and the residue is diluted with 2D0 ml of water. The pi is brought to 7 with dilute sodium hydroxide solution and the product thereby obtained as crystals is isolated by filtration with suction.
After recrystallization from isopropanol, 16.4 9 (36X of theory) of N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-guanidine of melting point 122C are obtained.
lo A 23 307 - Foreign countries -- Jo -The compounds of the formula (II) lusted on the following Table 2 can be prepared analogously:
Jo i N R4 HO\ No -US tip) N
Table 2 Example Melting No. R3 R4 R5 R6 point I
II-4 -oCH2CH(CH3~2 -OUCH H -OUCH 76 10 II-5 - -OCH2CH=CH2 -OUCH H -OUCH
II-7 -OCH(CH3)2 -OUCH H -OUCH
II-B CH2cH2 -OUCH H -OUCH
II-9 -Ozone) -OUCH H -OUCH
lo A 23 307 - Foreign countries I
Table 2 - continuation Example Melting No. I R4 R5 R6 point t-C]
II-10 -Ozone) -C~3 H -OUCH
Isle clue Nash H -SHEA
Isle -OCH2CH2CH2Cl -OUCH H -OUCH
20 II-14 -ocH2cooc2H5-OCH3 H -OUCH
II-15 -0C3H7~-n) -OUCH H -OUCH
Of lo A 23 307 - Foreign countries ~72~
5 Table 2 - continuation Example welting No. R3 R4 R5 R6 Purity C]
II 24 -O-CH2CON(CH3)2 -OUCH H -OUCH
20 11-2~ OCH2scH3 OUCH H -OUCH
II-27 -OUCH Khakis -OUCH H -OUCH
Of 30 II-30 -OUCH -SHEA H -OUCH =1.5645 lo A 23 30~ Foreign countries lo 5 Table 2 - continuation Example Melting No. R3 R4 R5 R6 point [C~
SHEA
Isle C2H5 -SHEA H -OOZE
Isle -OUCH -Of H -OUCH 112 I
11-37 -ooze -Of H -OUCH
II-41 C3H7(~n) -SHEA H -SHEA
11-42 OC4Hg~ n) -SHEA H -N(CH3)2 35 II-44 -OUCH -OUCH H -N~CH3)2 lo A 23 307 - Foreign countries ~2~7~
Table 2 - continuation Example Melting No R3 R4 R5 R6 pox nut t C]
__ _ _ _ .
Isle -OCH2-CH=CH~ -SHEA H -SHEA
Lowe C2H5 -SHEA H H 95 I1-47 -ocH2-cooc2H5 -SHEA H
I1-48 -OUCH -SHEA H H lo 20 11-49 -OUCH -Of H -OOZE
II-50 -ozone -Of H -N~CH3)2 Isle OUCH -Of H -SHEA
Isle ~OCH2CF3 -SHEA H -SHEA
ISSUE -OCH~-CH=CH2 -SHEA H -OCHF~
30 11-54 -OUCH Cook -SHEA H -OOZE
II-56 -O -SHEA H -N(CH3)2 lo A 23 307- foreign countries ~2~;2~5i Tale 2 - continuation -Example Melting No. R3 R4 R5 R6 point I
11-57 -OCH2CH2CH2Cl -Of H -OUCH
Isle -OUCH H H -SHEA 205 : II-61 -OUCH H H -C2H5 9 Isles -OCH2CH2CH2Cl H H -SHEA 102 II-66 -ocH2cH2-oc2H5 H H -SHEA
lo A 23 307~ Foreign countries Table 2 - continuation Example Melting No. R3 R4 I R6 point [C]
11-68 -OCH2CH2-Sc2H5 H H -SHEA
IJ-69 -OCH2-CONh2 H H -SHEA
iI-70 -OCH2-CH-CHCl H H -SHEA
11-71 -OUCH ) 2 H H -SHEA 165 Isle -OX ) 3 H H -SHEA
Isle -OUCH H H H 107-109 : Isle -OCH2-CH=CH2 H H -C2H5 83 lo A 23 307- Foreign countries _ Pro arat;on of Stratton substances of the formula (III) P . 9 _ _ _ Example (III-1 ) _ _ Of 295 ml of phosphoryl chloride phosphorus ox-chloride") are added drops to a mixture of 172 9 (0.8 mole of sodium 2-chloro-benzenesulphonate, 300 ml of acetonitrile and 30û ml of sulpholane at 20C to 30C.
The reaction mixture us stirred at 70C for 4 hours and then cooled to 5C and diluted with ice-water. After extraction with petroleum ether, washing of the extract lion solution with water, drying, filtration and concern-traction, the product which remains in the residue is purified by vacuum distillation.
117 9 (70X of theory) of 2-chloro-benzenesulphonyl chloride of bowling point 110C/1.1 mar are obtained.
Example (III-2) COUCH
I- clue 75.5 9 ~0.5 mole) of methyl 2-aminobenzoate are dissolved on 176 ml of concentrated hydrochloric acid and 100 ml of acetic Acadia A solution of 34.4 9 of sodium nitrite in 70 ml of water is added drops at ûC.
After the reaction mixture has been subsequently stirred for 15 Nazi, it is slowly added to a saturated soul-lion, cooled to 0C~ of Selfware dioxide in 450 ml of acetic acid. After removal of the cooling bath, the mix-lure is stirred until the evolution of gas has ended, 10 9 of copper-II chloride being introduced in portions.
After dilution with ice-water, extraction with ethylene chloride, washing of the extraction solution with water, drying, filtration and concentration, the product which lo A 23 307 - Foreign countries remains on the residue is purified by vacuum d;stillat;on.
45 g t38X of theory) of 2-methoxycarbonyl-benzene-sulphonyl chloride of boiling point 150C/1.33 mar are obtained.
The compounds of the formula Tao) listed on the following Table 3 can be prepared analogously:
R1-S02 Of ~III) Table 3 Example 10 No. R1 Boiling point/pressure Russia 111-3 isle, decomposition on distillation) III-4 remelting point: clue ~,CF3 I I -5 I_ By r o 15 111-6 142 C/4 mar 111-7 106 C/4 mar lo A 23 307 - Foreign countries '72~
Table 3 - continuation Example No. R1 Boiling point/oressure OFF
I11-8 [Molting point: clue ,~OCHF2 15 111-9 (Oil, decomposition on distillation) SO~N~CHB)2 III-10 smelting point: 103C~
SHEA
111-11 (Oil, decomposition on distillation) .
- SCH~CH3)2 12 9û C/1.33 mar ~=~
III-13 molting point: 120C~
COOK
111-14 155 C/5.32 mar lo A 23 ~07- Foreign countries I
Table 3 - continuation Example No. R1 Boiling pointlpressure .
Lowe smelting point:128C~
couch ( SHEA ) 2 Ill Jo COOK -n ) COOK -n ) I I I -20 (I
Jo CONCH
COO
ONE C2H5 ) 2 I I I -23 Smelting point: clue lo Aye 3C17- Foreign countries ~27~5 Table 3 - continuation Example No. Al Boiling point/pressure 1 0 _ _ _ III-24 SKIFF Smelting point: 41-43C~
/ SHEA
SOWN \
SHOWOFF
I I
ON
lo A 23 307- Foreign countries I
Table 3 - continuation Example No. R1 toiling point/pressure COUCH
111-31 SHEA- [Melting point: SUE
ON
151 I It SHEA-. Of 111-~3 I wax-like lo A 23 307- Foreign countries ` i Preparation of start;nQ substances of the formula (VI) Example (VI-1) H / N OUCH
HO No N
COUCH
A solution of 2.8 g 10.012 mole) of 2-methoxy-carbonyl-benzenesulphonyl chloride on 10 ml of twitter-hydrofuran us added to a mixture of 2.3 9 Tao mole) of N'-(4~6-dimethoxy-pyrimiclin-2-yl)-N"-methoxy-guanNadine and 30 ml of tetrahydrofuran a -5C, with stirring.
A solution of 1.3 9 (0.012 mole) of d;azabicyclooctane in 10 ml of tetrahydrofuran is then added drops at -5C
and the mixture is stirred at 20C for 2 hours. After addition of a further 0.5 9 of 2-me~hoxycarbonyl-benzene-sulphonyl chlor;de'and 0.25 9 of diazabicyclooctane, the mixture is stirred at 20C for a further 2 hours. After filtration the filtrate is concentrated, the residue us nude to crystallize with Tulane and the crystals are isolated by filtration with suction.
2.25 9 (57% of theory) of N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N"-(2-methoxycarbonyl-bBunsen-sulphonyl)-guanid;ne of melting point 142-143C are obtained.
The compounds of the formula YO-YO) lusted in the following Table 4 can be prepared analogously:
OH, N 4 HO \ No R5 C N R6 (VI) N
R 1 1 _ S 2/ OR 3 lo A 23 307 - Foreign countries s Jo v v v _ _ _ l l l c u) v ., in v) u o o Of _ _ _ I
c ., J
a s 3: N
Lo _ - $ I
"I I I
X O
I; X :: X
C o o o ., ., I
X S
r O O O O O O
_ E
.0 to .
1~1 X O .
_ ELI ,.
lo A 23 307- Foreign countries .. . , . .. . . ... _ . .. .
I
.
o or I
. _ _ N N
or or: X
Jo I
aye o ::
Utter X
o o o o I I
C I_) J
to a O O.
_ E O I
D I . CO O`
as x o I_ US Z
lo A 23 307- Foreign countries ' I
I, ._ c o .
-a Jo ox Us I X
or N 5 O O O O
I I I I I I
Us r7 I
3: X
Lo c o ,_ (I
I I N I
C X I N :1:
O
I O O O O O
11:; l l l l l Q
_ E I
. _. _ X O
I_ W Z
lo A 23 307- Foreign countries ' . .
I
u o -so Jo L mu U U U
I; O O O O
or; I x or I
C X :~:
I;
o or I I to X
C U U U
O O O O O O
QJ Jo to _.
J N N
I.
JO
us z lo A 23 307_ Foreign countries ~27~
._ o c J
_ [I
I; O _ I, I
Al; or U J I I T
to :: X I o X
O
., I
., O O C
at I
_ x O N N N N N
1~1 Z , I, P
lo A 23 307- Foreign countries __ _ .. ,, . . ... .. . , . , . .. , . _ . . _ ., _ I
_ 99 _ ._ ._ It _ 'o l l Q Lo N
c or ., J
s I
o _.~ g I
C; S 3:
us ., or: x c ., I r or c u o Al o o ., to co I N
.
I X O _ _ 1~1 Z Jo lo A 23 307- Foreign countries repression of starting substances of the ormolu tVII) (A subgroup of these compounds (VII A; see page 38 of -this disclosure) is the subject of this divisional application) Example (VII-l) H j 3 ¦ OUCH
SHEA
A suspension of 8.4 g (0.35 mole) of sodium hydrides (in oil) is added to a mixture of 28.0 g(0.2 mole) of 2-amino-4-methoxy-6-methyl-pyrimidine, with stirring, and the mixture is stirred at 20C for 15 hours. 60 g (0.2 mole) of S',S"-dimethyl N-(2-chloro-benzenesulphonyl)-imino-dithiocarbonatlo are then added in portions to the reaction mixture such that the reaction temperature does not rise above 40C. After the mixture has been stirred a-t ; 20C for 5 hours, 1 of ice-water is added and -the mixture is filtered. The filtrate is acidified with concentrated hydrochloric acid and the product thereby obtained as crystals is isolated by filtration with suction.
67 g (87% o-E theory of N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-(2-chloro-benzenesulphonyl)-S-methylisothHerr of melting point 148C are obtained.
~7~Z7;2~
The compounds of the formula (VII) listed in the following Table S can be prepared analogously:
OH, N R4 R1S02-N \ No US (VOW
\R17 Table S
5 Example Melting No. Al R4 R5 R6 R17 point lo _ SHEA
SHEA
Of 10 VII-4 -OUCH H -OUCH -SHEA aye lo A 23 307 Foreign countries Table 5 - continuation Example Melting No. R1 R4 R5 R6 R17 point [Cj I
OSSIFY
20 Vowel -OUCH H -OUCH -Clue SWISH
SHEA
SENECA
COOK
lo A 23 307- Foreign countries I' .
I
Table 5 - continuation Example Melting No. R1 R4 US R6 R17 Point t'Cj -COOCH(CH3)2 By OUCH
VII-18 -OUCH H -C~3 -SHEA
OSSIFY
30 V11-21 Of -SHEA H -OOZE -SHEA
By V11-22 -Of H -OUCH -SHEA
lo A 23 307- Foreign countries Table S - continuation Example Melting 10 No. Al R4 R5 R6 R17 point [C]
Of VII-23 -Of H -SHEA -SHEA 136 lo OUCH
VOW -Of H -SHEA -SHEA
VOW -Of H -OOZE -SHEA
SKIFF
By 25 VII-27 -Of H -N(CH3)2 Ho VII-28 -Of H -N~CH3)2 -SHEA
ON
;
~CH2scH3 ; 35 VII-30 -SHEA H -SHEA SHEA
lo A 23 307- Foreign countries US
S Table 5 - continuation I.
Example Melting No. I R4 R5 R6 R17 point I
VlI-31 SHEA H -N(CH3)2 -SHEA
OSSIFY
VII-32 SHEA H -N(CH3)2 -SHEA
SCH(CH3)2 Of Vowel SHEA H -OCHF2 -SHEA
r~-~S02N~CH3)2 Vll-36 -SHEA H -OOZE -C2H5 Ho : VII-37 -SHEA H H -C~3 ~_~OCHF2 V11-33 (/ \ -SHEA H N(CH3)2 SHEA
US
lo 23 307- Foreign countries I
5 table 5 - continuation Example Molting No. R R4 R5 R6 R17 point tCi _ Jo C~25CH3 VII-39 -Of H -OUCH -SHEA
ASIA
OSSIFY
VII-41 -SHEA H -OCHF~ -SHEA
Of Of VOW SHEA- -OH -SHEA H -C~3 150 lo A 23 307- Foreign countries noes of the formula (VIII) _ Example (VIII-1 ) NASH
NC - NH
NASH
A solution, heated to 100C, of 24 9 (û.427 mole of potassium hydroxide in 100 ml of water is added to a mixture of 9.2 9 (Owe mole) of 4,6-dimethoxy-pyrimidin-2-yl-thiourea in 70 ml of water at 100C, with stirring.
The mixture is subsequently stirred at 100C for 2 minutes and a solution, warmed to 100C, of 16.2 9 (0.05 mole) of lead-II acetate in 30 ml of water is then added. The mixture is heated under reflex for a further 5 minutes and then cooled to 0C to 5C, and 30 ml of glacial acetic acid are added to the aqueous solution. The pro-duct thereby precipitated as crystals is isolated by filter-lion with suction.
II 24 -O-CH2CON(CH3)2 -OUCH H -OUCH
20 11-2~ OCH2scH3 OUCH H -OUCH
II-27 -OUCH Khakis -OUCH H -OUCH
Of 30 II-30 -OUCH -SHEA H -OUCH =1.5645 lo A 23 30~ Foreign countries lo 5 Table 2 - continuation Example Melting No. R3 R4 R5 R6 point [C~
SHEA
Isle C2H5 -SHEA H -OOZE
Isle -OUCH -Of H -OUCH 112 I
11-37 -ooze -Of H -OUCH
II-41 C3H7(~n) -SHEA H -SHEA
11-42 OC4Hg~ n) -SHEA H -N(CH3)2 35 II-44 -OUCH -OUCH H -N~CH3)2 lo A 23 307 - Foreign countries ~2~7~
Table 2 - continuation Example Melting No R3 R4 R5 R6 pox nut t C]
__ _ _ _ .
Isle -OCH2-CH=CH~ -SHEA H -SHEA
Lowe C2H5 -SHEA H H 95 I1-47 -ocH2-cooc2H5 -SHEA H
I1-48 -OUCH -SHEA H H lo 20 11-49 -OUCH -Of H -OOZE
II-50 -ozone -Of H -N~CH3)2 Isle OUCH -Of H -SHEA
Isle ~OCH2CF3 -SHEA H -SHEA
ISSUE -OCH~-CH=CH2 -SHEA H -OCHF~
30 11-54 -OUCH Cook -SHEA H -OOZE
II-56 -O -SHEA H -N(CH3)2 lo A 23 307- foreign countries ~2~;2~5i Tale 2 - continuation -Example Melting No. R3 R4 R5 R6 point I
11-57 -OCH2CH2CH2Cl -Of H -OUCH
Isle -OUCH H H -SHEA 205 : II-61 -OUCH H H -C2H5 9 Isles -OCH2CH2CH2Cl H H -SHEA 102 II-66 -ocH2cH2-oc2H5 H H -SHEA
lo A 23 307~ Foreign countries Table 2 - continuation Example Melting No. R3 R4 I R6 point [C]
11-68 -OCH2CH2-Sc2H5 H H -SHEA
IJ-69 -OCH2-CONh2 H H -SHEA
iI-70 -OCH2-CH-CHCl H H -SHEA
11-71 -OUCH ) 2 H H -SHEA 165 Isle -OX ) 3 H H -SHEA
Isle -OUCH H H H 107-109 : Isle -OCH2-CH=CH2 H H -C2H5 83 lo A 23 307- Foreign countries _ Pro arat;on of Stratton substances of the formula (III) P . 9 _ _ _ Example (III-1 ) _ _ Of 295 ml of phosphoryl chloride phosphorus ox-chloride") are added drops to a mixture of 172 9 (0.8 mole of sodium 2-chloro-benzenesulphonate, 300 ml of acetonitrile and 30û ml of sulpholane at 20C to 30C.
The reaction mixture us stirred at 70C for 4 hours and then cooled to 5C and diluted with ice-water. After extraction with petroleum ether, washing of the extract lion solution with water, drying, filtration and concern-traction, the product which remains in the residue is purified by vacuum distillation.
117 9 (70X of theory) of 2-chloro-benzenesulphonyl chloride of bowling point 110C/1.1 mar are obtained.
Example (III-2) COUCH
I- clue 75.5 9 ~0.5 mole) of methyl 2-aminobenzoate are dissolved on 176 ml of concentrated hydrochloric acid and 100 ml of acetic Acadia A solution of 34.4 9 of sodium nitrite in 70 ml of water is added drops at ûC.
After the reaction mixture has been subsequently stirred for 15 Nazi, it is slowly added to a saturated soul-lion, cooled to 0C~ of Selfware dioxide in 450 ml of acetic acid. After removal of the cooling bath, the mix-lure is stirred until the evolution of gas has ended, 10 9 of copper-II chloride being introduced in portions.
After dilution with ice-water, extraction with ethylene chloride, washing of the extraction solution with water, drying, filtration and concentration, the product which lo A 23 307 - Foreign countries remains on the residue is purified by vacuum d;stillat;on.
45 g t38X of theory) of 2-methoxycarbonyl-benzene-sulphonyl chloride of boiling point 150C/1.33 mar are obtained.
The compounds of the formula Tao) listed on the following Table 3 can be prepared analogously:
R1-S02 Of ~III) Table 3 Example 10 No. R1 Boiling point/pressure Russia 111-3 isle, decomposition on distillation) III-4 remelting point: clue ~,CF3 I I -5 I_ By r o 15 111-6 142 C/4 mar 111-7 106 C/4 mar lo A 23 307 - Foreign countries '72~
Table 3 - continuation Example No. R1 Boiling point/oressure OFF
I11-8 [Molting point: clue ,~OCHF2 15 111-9 (Oil, decomposition on distillation) SO~N~CHB)2 III-10 smelting point: 103C~
SHEA
111-11 (Oil, decomposition on distillation) .
- SCH~CH3)2 12 9û C/1.33 mar ~=~
III-13 molting point: 120C~
COOK
111-14 155 C/5.32 mar lo A 23 ~07- Foreign countries I
Table 3 - continuation Example No. R1 Boiling pointlpressure .
Lowe smelting point:128C~
couch ( SHEA ) 2 Ill Jo COOK -n ) COOK -n ) I I I -20 (I
Jo CONCH
COO
ONE C2H5 ) 2 I I I -23 Smelting point: clue lo Aye 3C17- Foreign countries ~27~5 Table 3 - continuation Example No. Al Boiling point/pressure 1 0 _ _ _ III-24 SKIFF Smelting point: 41-43C~
/ SHEA
SOWN \
SHOWOFF
I I
ON
lo A 23 307- Foreign countries I
Table 3 - continuation Example No. R1 toiling point/pressure COUCH
111-31 SHEA- [Melting point: SUE
ON
151 I It SHEA-. Of 111-~3 I wax-like lo A 23 307- Foreign countries ` i Preparation of start;nQ substances of the formula (VI) Example (VI-1) H / N OUCH
HO No N
COUCH
A solution of 2.8 g 10.012 mole) of 2-methoxy-carbonyl-benzenesulphonyl chloride on 10 ml of twitter-hydrofuran us added to a mixture of 2.3 9 Tao mole) of N'-(4~6-dimethoxy-pyrimiclin-2-yl)-N"-methoxy-guanNadine and 30 ml of tetrahydrofuran a -5C, with stirring.
A solution of 1.3 9 (0.012 mole) of d;azabicyclooctane in 10 ml of tetrahydrofuran is then added drops at -5C
and the mixture is stirred at 20C for 2 hours. After addition of a further 0.5 9 of 2-me~hoxycarbonyl-benzene-sulphonyl chlor;de'and 0.25 9 of diazabicyclooctane, the mixture is stirred at 20C for a further 2 hours. After filtration the filtrate is concentrated, the residue us nude to crystallize with Tulane and the crystals are isolated by filtration with suction.
2.25 9 (57% of theory) of N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N"-(2-methoxycarbonyl-bBunsen-sulphonyl)-guanid;ne of melting point 142-143C are obtained.
The compounds of the formula YO-YO) lusted in the following Table 4 can be prepared analogously:
OH, N 4 HO \ No R5 C N R6 (VI) N
R 1 1 _ S 2/ OR 3 lo A 23 307 - Foreign countries s Jo v v v _ _ _ l l l c u) v ., in v) u o o Of _ _ _ I
c ., J
a s 3: N
Lo _ - $ I
"I I I
X O
I; X :: X
C o o o ., ., I
X S
r O O O O O O
_ E
.0 to .
1~1 X O .
_ ELI ,.
lo A 23 307- Foreign countries .. . , . .. . . ... _ . .. .
I
.
o or I
. _ _ N N
or or: X
Jo I
aye o ::
Utter X
o o o o I I
C I_) J
to a O O.
_ E O I
D I . CO O`
as x o I_ US Z
lo A 23 307- Foreign countries ' I
I, ._ c o .
-a Jo ox Us I X
or N 5 O O O O
I I I I I I
Us r7 I
3: X
Lo c o ,_ (I
I I N I
C X I N :1:
O
I O O O O O
11:; l l l l l Q
_ E I
. _. _ X O
I_ W Z
lo A 23 307- Foreign countries ' . .
I
u o -so Jo L mu U U U
I; O O O O
or; I x or I
C X :~:
I;
o or I I to X
C U U U
O O O O O O
QJ Jo to _.
J N N
I.
JO
us z lo A 23 307_ Foreign countries ~27~
._ o c J
_ [I
I; O _ I, I
Al; or U J I I T
to :: X I o X
O
., I
., O O C
at I
_ x O N N N N N
1~1 Z , I, P
lo A 23 307- Foreign countries __ _ .. ,, . . ... .. . , . , . .. , . _ . . _ ., _ I
_ 99 _ ._ ._ It _ 'o l l Q Lo N
c or ., J
s I
o _.~ g I
C; S 3:
us ., or: x c ., I r or c u o Al o o ., to co I N
.
I X O _ _ 1~1 Z Jo lo A 23 307- Foreign countries repression of starting substances of the ormolu tVII) (A subgroup of these compounds (VII A; see page 38 of -this disclosure) is the subject of this divisional application) Example (VII-l) H j 3 ¦ OUCH
SHEA
A suspension of 8.4 g (0.35 mole) of sodium hydrides (in oil) is added to a mixture of 28.0 g(0.2 mole) of 2-amino-4-methoxy-6-methyl-pyrimidine, with stirring, and the mixture is stirred at 20C for 15 hours. 60 g (0.2 mole) of S',S"-dimethyl N-(2-chloro-benzenesulphonyl)-imino-dithiocarbonatlo are then added in portions to the reaction mixture such that the reaction temperature does not rise above 40C. After the mixture has been stirred a-t ; 20C for 5 hours, 1 of ice-water is added and -the mixture is filtered. The filtrate is acidified with concentrated hydrochloric acid and the product thereby obtained as crystals is isolated by filtration with suction.
67 g (87% o-E theory of N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-(2-chloro-benzenesulphonyl)-S-methylisothHerr of melting point 148C are obtained.
~7~Z7;2~
The compounds of the formula (VII) listed in the following Table S can be prepared analogously:
OH, N R4 R1S02-N \ No US (VOW
\R17 Table S
5 Example Melting No. Al R4 R5 R6 R17 point lo _ SHEA
SHEA
Of 10 VII-4 -OUCH H -OUCH -SHEA aye lo A 23 307 Foreign countries Table 5 - continuation Example Melting No. R1 R4 R5 R6 R17 point [Cj I
OSSIFY
20 Vowel -OUCH H -OUCH -Clue SWISH
SHEA
SENECA
COOK
lo A 23 307- Foreign countries I' .
I
Table 5 - continuation Example Melting No. R1 R4 US R6 R17 Point t'Cj -COOCH(CH3)2 By OUCH
VII-18 -OUCH H -C~3 -SHEA
OSSIFY
30 V11-21 Of -SHEA H -OOZE -SHEA
By V11-22 -Of H -OUCH -SHEA
lo A 23 307- Foreign countries Table S - continuation Example Melting 10 No. Al R4 R5 R6 R17 point [C]
Of VII-23 -Of H -SHEA -SHEA 136 lo OUCH
VOW -Of H -SHEA -SHEA
VOW -Of H -OOZE -SHEA
SKIFF
By 25 VII-27 -Of H -N(CH3)2 Ho VII-28 -Of H -N~CH3)2 -SHEA
ON
;
~CH2scH3 ; 35 VII-30 -SHEA H -SHEA SHEA
lo A 23 307- Foreign countries US
S Table 5 - continuation I.
Example Melting No. I R4 R5 R6 R17 point I
VlI-31 SHEA H -N(CH3)2 -SHEA
OSSIFY
VII-32 SHEA H -N(CH3)2 -SHEA
SCH(CH3)2 Of Vowel SHEA H -OCHF2 -SHEA
r~-~S02N~CH3)2 Vll-36 -SHEA H -OOZE -C2H5 Ho : VII-37 -SHEA H H -C~3 ~_~OCHF2 V11-33 (/ \ -SHEA H N(CH3)2 SHEA
US
lo 23 307- Foreign countries I
5 table 5 - continuation Example Molting No. R R4 R5 R6 R17 point tCi _ Jo C~25CH3 VII-39 -Of H -OUCH -SHEA
ASIA
OSSIFY
VII-41 -SHEA H -OCHF~ -SHEA
Of Of VOW SHEA- -OH -SHEA H -C~3 150 lo A 23 307- Foreign countries noes of the formula (VIII) _ Example (VIII-1 ) NASH
NC - NH
NASH
A solution, heated to 100C, of 24 9 (û.427 mole of potassium hydroxide in 100 ml of water is added to a mixture of 9.2 9 (Owe mole) of 4,6-dimethoxy-pyrimidin-2-yl-thiourea in 70 ml of water at 100C, with stirring.
The mixture is subsequently stirred at 100C for 2 minutes and a solution, warmed to 100C, of 16.2 9 (0.05 mole) of lead-II acetate in 30 ml of water is then added. The mixture is heated under reflex for a further 5 minutes and then cooled to 0C to 5C, and 30 ml of glacial acetic acid are added to the aqueous solution. The pro-duct thereby precipitated as crystals is isolated by filter-lion with suction.
6.3 9 (81.5% of theory) of cinnamon-dimethoxy-pyrim;dine of melting point 202C are obtained.
Example tVIII-2) N SHEA
NC-NH-( 54 9 of sodium methyl ate (1.0 mole) are added to a suspension of 84 9 (1.0 mole) of dicyanodiamide in 500 ml of methanol, and the mixture is stirred for 15 minutes After 132 9 (1.0 mole) of acetylacetaldehyde dim ethyl acutely have been added, the mixture is stirred under reflex for 3 hours. the clear, dark red reaction solution is evaporated to dryness on vacua, the residue is dissolved lo A 23 307 - Foreign countries .
I
in 1500 ml of titer, and the solution is brought to pi 3 with concentrated hydrochloric acid. The product which is precipitated in crystalline form during this procedure is isolated by filtration with suction.
103 9 (78X of theory) of 2-cyanoamino-4-methyl-pyrimid;ne of melting point ~03C (decomposition) are obtained.
lo A 23 307 - Foreign countries - 1 oily The compounds of the formula (VIII) listed in the following table 6 can be prepared analogously NC-NH~/ R5 (VOW
N~R6 Table 6 -5 Example Melting point No. I R5 R6 I
Yo-yo -SHEA H -OUCH ~decomp.) VIII-4 SHEA H -OCHF~174 ., V111-5 -Of H -OUCH
10 VIII-6 -Of H OOZE
VIII-7 -Of H -N(CH3), VIII-8 -SHEA H -N~CH3)~
..
lo A 23 307 - Foreign countries aye Table 6 - continuation Example Melting point No. R4 R5 R6 I
20 VOW -OH -COOK H 220 (decomp.) VIII-16 -OH H H > 300 lo A 23 307- Foreign countries Preparation of starting substances of the formula (XIII) Example (XIII-l) ~H30 S
No if I,== NO - C - NH - C O O C 2 H 5 SHEA
A mixture of 15.5 9 (0.1 mole of 2-amino-4,6-dimethoxy-pyrimidine, 13.1 9 (0.1 mole) of e~hoxycarbonyl-isothiocyanate and 200 ml of acetonitrile is stirred at 60C for 2 hours. It is then cooled to 10C and the product obtained as crystals is isolated by filtration ugh suction.
22.5 9 (75X of theory) of 1-(ethoxycarbonyl)-3-(4,6-dimethoxy-pyrimidin-2~yl)-thiourea of melting point 194C (decomposition) are obtained.
lo A 23 307 - Foreign countries ~7~:~5 = 112 -The compounds of the formula (XIII) listed in the following Table 7 can be prepared analogously:
R1~-C-NH-I-NH~/ R5 (XIII) Table 7 5 Example Melting No. R4 R5 I R18 point [-C]
XIII-2 -OUCH H -OUCH lB9 (decomp.) Zoo -SHEA H -OCHF~ 182 XIII-8 -OCHF~ H OCHF~ C2H5 173 lo A 23 307 - Foreign countries I
_ 113 -Table 7 - continuation Example Melting No. R4 R5 R6 R1~ Point [C]
X111-9 -Of H -OUCH OOZE 160-162 XIII-10 -Of H -Of -Osseous 132-136 Xlli-ll -Of H -N(CH3)2C2H5 16~
XIII-14 C2H5 H -OOZE -OC2Hc 159 Xlll-15 -SHEA H -OOZE 156 XIII-16 -Of H -SHEA 144 lo A 23 307- Foreign countries Preparation of starting substances of the formula (XIV) Example tXIV-1) SHEA N I
\~NH-C-NH2 SHEA N
A mixture of 5.0 9 (0~0175 mole) of ethics-carbonyl)-3-(4,6 dimethoxy pyrimidin-2-yl)-thiourea, 4.0 g Tao mole) of sodium hydroxide and 100 ml of water is stirred at 20C for 2 days. Dilute hydrochloric acid is then added drops, with stirring, until the solution has been rendered acid and the evolution of C02 has ended. The product obtained as crystals is isolated by filtration with suction.
3.5 9 (94X of theory) of 4,6-dimethoxy-pyr;midin-2-yl-thiourea of melting point 245-248C (decomposition) are obtained.
lo A 23 3D7 - Foreign countries ....
___ __ __~
~.~Z27~
, ., The compounds of the formula (XIV) listed on the following Table 8 can be prepared analogously:
S No H~N-C-NH~ Or (XIV~
N=-CR6 Table 8 5 Example No. R4 R5 R6 Melting point to 10 XIV-5 -Of H -OUCH 225-227 (decomp.) XIV-6 -Of H -N~CH3)2 XIV-7 -Of H -OOZE
Lea 23 307 - Foreign countries I
Table 8 - continuation _ Example No. R4 R5 R6 Melting point [ DC]
X~V-lo SHEA H -N~CH3)2 Xlv-12 C2H5 H -OOZE 166 X I v - 1 3 - OH 3 H - C l L A 23 307- Foreign countries I
Preparation of starting substances of the formula (XV) Example (XV~1) O2-N=C
SHEA
3 9 (0.2 mole) of sodium hydroxide - dissolved in 15 ml of water - and 6 ml (0.11 mole) of carbon dip sulfide are simultaneously added drops (from differ-en dropping funnels) to a solution of 20 9 (û.1 mole) of 2-chloro-benzenesulphonic acid aside in 8û ml of dip methylformamide at 20C. After the mixture has been stirred for one hour, 13 ml Tao 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 500 ml of utter and is is-fated by filtration with suction.
22.1 9 (75X of theory) of S',S"-dimethyl No chloro-benzenesulphonyl)-isodithiocarbamate of melting point 112C are obtained.
lo A 23 307 - Foreign countries .
I
I
The compounds of the formula (XV) listed in the fulling Table 9 can be prepared analogously:
/sRl7 (XV) R1 -SO NO \
Sol 7 Table 9 5 Example Melting point No. R1 R17 to rich 3 SHEA
XV-3 (I -SHEA 143 OCHF
XV-4 -OH, 112 OSSIFY
O N(CH3~2 lo A 23 307 - Foreign countries I
5 Tab - continuation Example Melting point No. R1 R17 I
SWISH
Of CH~502CH3 COOK, COOCH(CH3)2 XV-ll -SHEA
F
or lo A I 307- Foreign Countries I
5 Table 9 - continuation Example Melting point No. R1 R17 to 1 0 _ _ SHEA
SCH(CH3)2 25 XV-l9 Of -SHEA I
:30 clue XV-23 SHEA- -CH~CH3)~65-67 lo A 23 307 - Foreign countries S
5 Table 9 - continuation Example Melting point No. Al R17 t D
1.0 Of Of XV-25 SHEA-,- -SHEA 91 ED
lo A 23 307- Foreign countries lo Preparation of starting substances of formula (XVI) SHEA
ONE
50 ml of concentrated aqueous ammonia solution are added drops to a mixture of 60 9 (û.27 mole) of 2-methyl-thiobenzene-sulphonyl chloride and 60 ml of acetone at 20C to 30C, with stirring. The mixture is sub-sequently stirred at 20C for one hour and is then poured into 600 ml of 10 per cent strength sodium hydroxide solution. This solution is filtered and the filtrate is then acidified with concentrated hydrochloric acid. The product thereby obtained as crystals is isolated by filtration with suction.
19 9 (30% of theory) of 2-methylthio-benzene-sulphonic acid aside of melting point 149C are obtained.
lo A 23 307 - Foreign countries _ _ _ _ _ _ _ ox The compounds of the formula (XVI) listed in the following Table 10 can be prepared by the process desk cribbed by way of example in the preceding example:
R1-S02-NH2(XVI) Table 10 _ Example Jo. Al Melting point to S OH ( OH
XVI-2 10~
SKYE
10 XVI-4 2~5 i ye SOWN SHEA ) 2 OSSIFY
XV~-6 lay - 1 lo A I 307 Foreign countries I
5 Table 10 - continuation Example No. R1 Melting print tic]
~;OCHF .
Of 15 XvI-8 SHEA-CH25~2CH3 COOK
COUCH SHEA ) 2 XV I
SHEA-XVI-1~
COUCH
Of XVI-14 SHEA- ~03 lo A I 307- Foreign countries s example A
Reemergence testlgreenhouse Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl po'yglycol 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 Emil-sifter is added and the concentrate is diluted with water to the desired concentration.
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. The concentration of the active compound on the preparation us 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 X damage in comparison to the development of the untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction In this test, for example, the following compounds from the preparation examples exhibited an excellent activity I and ill).
lo A I 3û7 - Foreign countries Example B
Post-emergence test/greenhouse 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 mud ugh the stated amount of solvent, the stated amount of emuls;-lien us added and the concentrate is diluted ugh 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 us so chosen that the particular amounts of active compound desired are applied in 2,000 l of water/ha. After three weeks, the degree of damage to the plants is rated on % damage on comparison to the development of the untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction ; In this test, for example, the following compounds from the preparation examples exhibited an excellent activity: (3), (1û~, (11) and (39~.
lo A 23 307 - Foreign countries Ed
Example tVIII-2) N SHEA
NC-NH-( 54 9 of sodium methyl ate (1.0 mole) are added to a suspension of 84 9 (1.0 mole) of dicyanodiamide in 500 ml of methanol, and the mixture is stirred for 15 minutes After 132 9 (1.0 mole) of acetylacetaldehyde dim ethyl acutely have been added, the mixture is stirred under reflex for 3 hours. the clear, dark red reaction solution is evaporated to dryness on vacua, the residue is dissolved lo A 23 307 - Foreign countries .
I
in 1500 ml of titer, and the solution is brought to pi 3 with concentrated hydrochloric acid. The product which is precipitated in crystalline form during this procedure is isolated by filtration with suction.
103 9 (78X of theory) of 2-cyanoamino-4-methyl-pyrimid;ne of melting point ~03C (decomposition) are obtained.
lo A 23 307 - Foreign countries - 1 oily The compounds of the formula (VIII) listed in the following table 6 can be prepared analogously NC-NH~/ R5 (VOW
N~R6 Table 6 -5 Example Melting point No. I R5 R6 I
Yo-yo -SHEA H -OUCH ~decomp.) VIII-4 SHEA H -OCHF~174 ., V111-5 -Of H -OUCH
10 VIII-6 -Of H OOZE
VIII-7 -Of H -N(CH3), VIII-8 -SHEA H -N~CH3)~
..
lo A 23 307 - Foreign countries aye Table 6 - continuation Example Melting point No. R4 R5 R6 I
20 VOW -OH -COOK H 220 (decomp.) VIII-16 -OH H H > 300 lo A 23 307- Foreign countries Preparation of starting substances of the formula (XIII) Example (XIII-l) ~H30 S
No if I,== NO - C - NH - C O O C 2 H 5 SHEA
A mixture of 15.5 9 (0.1 mole of 2-amino-4,6-dimethoxy-pyrimidine, 13.1 9 (0.1 mole) of e~hoxycarbonyl-isothiocyanate and 200 ml of acetonitrile is stirred at 60C for 2 hours. It is then cooled to 10C and the product obtained as crystals is isolated by filtration ugh suction.
22.5 9 (75X of theory) of 1-(ethoxycarbonyl)-3-(4,6-dimethoxy-pyrimidin-2~yl)-thiourea of melting point 194C (decomposition) are obtained.
lo A 23 307 - Foreign countries ~7~:~5 = 112 -The compounds of the formula (XIII) listed in the following Table 7 can be prepared analogously:
R1~-C-NH-I-NH~/ R5 (XIII) Table 7 5 Example Melting No. R4 R5 I R18 point [-C]
XIII-2 -OUCH H -OUCH lB9 (decomp.) Zoo -SHEA H -OCHF~ 182 XIII-8 -OCHF~ H OCHF~ C2H5 173 lo A 23 307 - Foreign countries I
_ 113 -Table 7 - continuation Example Melting No. R4 R5 R6 R1~ Point [C]
X111-9 -Of H -OUCH OOZE 160-162 XIII-10 -Of H -Of -Osseous 132-136 Xlli-ll -Of H -N(CH3)2C2H5 16~
XIII-14 C2H5 H -OOZE -OC2Hc 159 Xlll-15 -SHEA H -OOZE 156 XIII-16 -Of H -SHEA 144 lo A 23 307- Foreign countries Preparation of starting substances of the formula (XIV) Example tXIV-1) SHEA N I
\~NH-C-NH2 SHEA N
A mixture of 5.0 9 (0~0175 mole) of ethics-carbonyl)-3-(4,6 dimethoxy pyrimidin-2-yl)-thiourea, 4.0 g Tao mole) of sodium hydroxide and 100 ml of water is stirred at 20C for 2 days. Dilute hydrochloric acid is then added drops, with stirring, until the solution has been rendered acid and the evolution of C02 has ended. The product obtained as crystals is isolated by filtration with suction.
3.5 9 (94X of theory) of 4,6-dimethoxy-pyr;midin-2-yl-thiourea of melting point 245-248C (decomposition) are obtained.
lo A 23 3D7 - Foreign countries ....
___ __ __~
~.~Z27~
, ., The compounds of the formula (XIV) listed on the following Table 8 can be prepared analogously:
S No H~N-C-NH~ Or (XIV~
N=-CR6 Table 8 5 Example No. R4 R5 R6 Melting point to 10 XIV-5 -Of H -OUCH 225-227 (decomp.) XIV-6 -Of H -N~CH3)2 XIV-7 -Of H -OOZE
Lea 23 307 - Foreign countries I
Table 8 - continuation _ Example No. R4 R5 R6 Melting point [ DC]
X~V-lo SHEA H -N~CH3)2 Xlv-12 C2H5 H -OOZE 166 X I v - 1 3 - OH 3 H - C l L A 23 307- Foreign countries I
Preparation of starting substances of the formula (XV) Example (XV~1) O2-N=C
SHEA
3 9 (0.2 mole) of sodium hydroxide - dissolved in 15 ml of water - and 6 ml (0.11 mole) of carbon dip sulfide are simultaneously added drops (from differ-en dropping funnels) to a solution of 20 9 (û.1 mole) of 2-chloro-benzenesulphonic acid aside in 8û ml of dip methylformamide at 20C. After the mixture has been stirred for one hour, 13 ml Tao 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 500 ml of utter and is is-fated by filtration with suction.
22.1 9 (75X of theory) of S',S"-dimethyl No chloro-benzenesulphonyl)-isodithiocarbamate of melting point 112C are obtained.
lo A 23 307 - Foreign countries .
I
I
The compounds of the formula (XV) listed in the fulling Table 9 can be prepared analogously:
/sRl7 (XV) R1 -SO NO \
Sol 7 Table 9 5 Example Melting point No. R1 R17 to rich 3 SHEA
XV-3 (I -SHEA 143 OCHF
XV-4 -OH, 112 OSSIFY
O N(CH3~2 lo A 23 307 - Foreign countries I
5 Tab - continuation Example Melting point No. R1 R17 I
SWISH
Of CH~502CH3 COOK, COOCH(CH3)2 XV-ll -SHEA
F
or lo A I 307- Foreign Countries I
5 Table 9 - continuation Example Melting point No. R1 R17 to 1 0 _ _ SHEA
SCH(CH3)2 25 XV-l9 Of -SHEA I
:30 clue XV-23 SHEA- -CH~CH3)~65-67 lo A 23 307 - Foreign countries S
5 Table 9 - continuation Example Melting point No. Al R17 t D
1.0 Of Of XV-25 SHEA-,- -SHEA 91 ED
lo A 23 307- Foreign countries lo Preparation of starting substances of formula (XVI) SHEA
ONE
50 ml of concentrated aqueous ammonia solution are added drops to a mixture of 60 9 (û.27 mole) of 2-methyl-thiobenzene-sulphonyl chloride and 60 ml of acetone at 20C to 30C, with stirring. The mixture is sub-sequently stirred at 20C for one hour and is then poured into 600 ml of 10 per cent strength sodium hydroxide solution. This solution is filtered and the filtrate is then acidified with concentrated hydrochloric acid. The product thereby obtained as crystals is isolated by filtration with suction.
19 9 (30% of theory) of 2-methylthio-benzene-sulphonic acid aside of melting point 149C are obtained.
lo A 23 307 - Foreign countries _ _ _ _ _ _ _ ox The compounds of the formula (XVI) listed in the following Table 10 can be prepared by the process desk cribbed by way of example in the preceding example:
R1-S02-NH2(XVI) Table 10 _ Example Jo. Al Melting point to S OH ( OH
XVI-2 10~
SKYE
10 XVI-4 2~5 i ye SOWN SHEA ) 2 OSSIFY
XV~-6 lay - 1 lo A I 307 Foreign countries I
5 Table 10 - continuation Example No. R1 Melting print tic]
~;OCHF .
Of 15 XvI-8 SHEA-CH25~2CH3 COOK
COUCH SHEA ) 2 XV I
SHEA-XVI-1~
COUCH
Of XVI-14 SHEA- ~03 lo A I 307- Foreign countries s example A
Reemergence testlgreenhouse Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl po'yglycol 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 Emil-sifter is added and the concentrate is diluted with water to the desired concentration.
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. The concentration of the active compound on the preparation us 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 X damage in comparison to the development of the untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction In this test, for example, the following compounds from the preparation examples exhibited an excellent activity I and ill).
lo A I 3û7 - Foreign countries Example B
Post-emergence test/greenhouse 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 mud ugh the stated amount of solvent, the stated amount of emuls;-lien us added and the concentrate is diluted ugh 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 us so chosen that the particular amounts of active compound desired are applied in 2,000 l of water/ha. After three weeks, the degree of damage to the plants is rated on % damage on comparison to the development of the untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction ; In this test, for example, the following compounds from the preparation examples exhibited an excellent activity: (3), (1û~, (11) and (39~.
lo A 23 307 - Foreign countries Ed
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A sulphonylisothioureidopyrimidine derivative of the general formula (VII A) (VII A) in which R1 represents a substituted phenyl radical wherein R7 represents C1-C4-alkylthio, C1-C4-alkyl-sulphinyl or C1-C4- alkylsulphonyl, or C1-C4-fluoroalkoxy, R4 represents hydrogen, fluorine, chlorine, bromine or C1-C4-alkyl [which is optionally substituted 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], R5 represents hydrogen, fluorine, chlorine, bromine or C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents cyano, formyl, C1-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl, R6 represents hydrogen, or represents C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represents amino, C1-C4-alkylamino or di-(C1-C4-alkyl)-amino - with the proviso that R4 and R6 do not simultaneously represent methyl - and R17 represents C1-C4-alkyl or benzyl.
2. The compound of claim 1 wherein R7 represents methylthio, isopropylthio, difluoromethoxy, trifluoromethoxy, methylsulphonyl, R4 represents methyl, methoxy, ethoxy, hydrogen, chlorine or methylthio, R5 represents hydrogen or chlorine and R6 represents methyl, ethyl, methoxy, ethoxy, difluoromethoxy, dimethylamino or hydrogen.
3. The compound of claim 1 wherein R7 represents methylthio, R4 represents methyl or methoxy, R5 represents hydrogen, R6 represents methyl or methoxy and R17 represents methyl.
4. The compound of claim 1 wherein R7 represents methylthio, R4 represents methyl, R5 represents hydrogen, R6 represents methoxy and R17 represents methyl.
5. N'-(4-methyl-6-methoxypyrimidin-2-yl)-N"-(2-methylthio-benzenesulphonyl)-S-methyl-isothiourea of the formula .
6. A process for the preparation of a sulphonylisothio-ureidopyrimidine derivative of the formula (VII A) as defined in claim 1, which process comprises reacting an N-sulphonyl-imino-dithiocarbonic acid ester of the formula (XV A) (XV A) in which R1 and R17 have the meanings given in claim 1, with an aminopyrimidine of the formula (XI) (XI) in which R4, R5 and R6 have the meanings given in claim 1, if required, in the presence of a base and, if required, in the presence of a diluent, and, when the reaction has ended, diluting the mixture with water and acidifying with a strong acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000513443A CA1227205A (en) | 1984-08-30 | 1986-07-09 | Sulphonylisothioureidopyrimidine derivative |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3431924 | 1984-08-30 | ||
DEP3431924.7 | 1984-08-30 | ||
DE19853517842 DE3517842A1 (en) | 1984-08-30 | 1985-05-17 | SULFONYLGUANIDINOPYRIMIDINE DERIVATIVES |
DEP3517842.6 | 1985-05-17 | ||
CA000489594A CA1221699A (en) | 1984-08-30 | 1985-08-28 | N'-(4,5,6-trisubstituted-pyrimidin-2-yl)-n''(di) substituted-n''-(di)substituted-n'''-(substituted- benzenesulphonyl)-guanidines |
CA000513443A CA1227205A (en) | 1984-08-30 | 1986-07-09 | Sulphonylisothioureidopyrimidine derivative |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000489594A Division CA1221699A (en) | 1984-08-30 | 1985-08-28 | N'-(4,5,6-trisubstituted-pyrimidin-2-yl)-n''(di) substituted-n''-(di)substituted-n'''-(substituted- benzenesulphonyl)-guanidines |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1227205A true CA1227205A (en) | 1987-09-22 |
Family
ID=27167543
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000513443A Expired CA1227205A (en) | 1984-08-30 | 1986-07-09 | Sulphonylisothioureidopyrimidine derivative |
Country Status (1)
Country | Link |
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CA (1) | CA1227205A (en) |
-
1986
- 1986-07-09 CA CA000513443A patent/CA1227205A/en not_active Expired
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