Guanidin derivatives

The invention relates to new guanidine derivatives, several processes for their preparation and their use as herbicides and plant growth regulators.

Various guanidines have become known as potential herbicides from patent specifications (cf., for example, DE-AS 1 089210, DD-PS 71 016 and 84530), but have so far not achieved any great importance as agents for controlling weeds and / or regulating plant growth.

It is also known that certain N'-phenyl-N "-pyridyl-guanidines have fungicidal properties (cf. Agric. Biol. Chem. 42 (4), pp. 803-807 (1978), and that certain N'-phenyl -N "- pyrimidinyl-guanidines have pharmacological effects (cf. CH-A-408 933).

Furthermore, a number of N'-monosubstituted and N ', N "-disubstituted guanidine derivatives are known which can be used as pharmaceuticals (cf. EP-A-30 092, EP-A-59 597 and EP-A-61 318).

New guanidine derivatives of the general formula (I) have been found<chemistry id="chem0001" num="0001"><img file="EP0121082B1_D0001.tif" /></chemistry>in which<ul id="ul0001" list-style="none"><li>R¹ for hydrogen or for the rest -S (O)_m-R⁵ stands in what</li><li>m stands for the numbers zero, 1 or 2 and</li><li>R⁵for the rest<chemistry id="chem0002" num="0002"><img file="EP0121082B1_D0002.tif" /></chemistry>stands in what</li><li>R¹⁶ and R¹⁷ are identical or different and are for hydrogen, halogen [such as in particular fluorine, chlorine and / or bromine], cyano, nitro, C₁-C₆-Alkyl [which may be replaced by fluorine, chlorine, cyano, C₁-C₄Alkoxy-carbonyl, C₁-C₄Alkoxy, C₁-C₄-Alkylthio, C₁-C₄Alkylsulfinyl, C₁-C₄Alkylsulfonyl or phenyl is substituted], for C₂-C₆-Alkenyl [which may be replaced by fluorine, chlorine, cyano or C₁-C_4-Alkoxy-carbonyl is substituted], for C₁-C₄Alkoxy [which may be replaced by fluorine, chlorine, cyano, C₁-C_4-Alkoxy-carbonyl, C₁-C₄-Alkylthio, C₁-C₄-Alkylsulfinyl or C₁-C₄-Alkylsulfonyl is substituted], for the rest -S (O)_p-R¹⁸, where p stands for the numbers zero, 1 or 2 and R¹⁸ for C₁-C₄-Alkyl [which is optionally substituted by fluorine or chlorine], for phenyl or for the radical -CO-R¹⁹ stand, where R¹⁹ for C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₃-C₆-Alkenoxy, C₁-C₄-Alkylthio, C₁-C₄-Alkylamino or di- (C₁-C_4-alkyl) -amino [which are optionally substituted by fluorine and / or chlorine], in which further</li><li>_R⁵ stands for the rest in which<chemistry id="chem0003" num="0003"><img file="EP0121082B1_D0003.tif" /></chemistry></li><li>R²¹ for hydrogen or C₁-C_3-Alkyl stands and</li><li>R22 and R²³ are the same or different and are for hydrogen, fluorine, chlorine, nitro, cyano, C₁-C₄-Alkoxy [which is optionally substituted by fluorine and / or chlorine], C₁-C₄-Alkoxy-carbonyl, C₁-C₄- alkylsulfonyl or di- (C₁-C₄- alkyl) aminosulfonyl; in what further</li><li>R⁵ for the rest<chemistry id="chem0004" num="0004"><img file="EP0121082B1_D0004.tif" /></chemistry>stands in what</li><li>R²⁰ and R²⁷ are the same or different and are for hydrogen, fluorine, chlorine, nitro, cyano, C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine], C₁-C₄-Alkoxy [which is optionally substituted by fluorine and / or chlorine] for C₁-C_4-Alkylthio, C₁-C₄Alkyl sulfinyl or C₁-C₄-Alkylsulfonyl [which are optionally substituted by fluorine and / or chlorine], and for di- (C₁-C₄-alkyl) -aminosulfonyl or C₁-C₄-Alkoxy-carbonyl, in which further</li><li>R⁵ for the rest<chemistry id="chem0005" num="0005"><img file="EP0121082B1_D0005.tif" /></chemistry>stands in what</li><li>R³⁰ and R³¹ are the same or different and are for hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine], C₁-C₄Alkoxy [which is optionally substituted by fluorine and / or chlorine], C₁-C₄Alkylthio, C₁-C_4-Alkylsulfinyl or C₁-C_4-Alkylsulfonyl [which is optionally substituted by fluorine and / or chlorine], di- (C₁-C₄-alkyl) -aminosulfonyl or C₁-C₄-Alkoxy-carbonyl stand, and</li><li>Z stands for sulfur, in which further</li><li>_R² for the rest<chemistry id="chem0006" num="0006"><img file="EP0121082B1_D0006.tif" /></chemistry>stands in what</li><li>R³⁵ and R³⁶ are the same or different and are for hydrogen, fluorine, chlorine, bromine, C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine], C₁-C₄-Alkoxy [which is optionally substituted by fluorine and / or chlorine], C₁-C_4-Alkylamino or di- (C₁-C₄-alkyl) -amino are provided that at least one of the radicals R³⁵ and R³⁶ is different from hydrogen; in which further</li><li>_R² for the rest<chemistry id="chem0007" num="0007"><img file="EP0121082B1_D0007.tif" /></chemistry> stands in what</li><li>R³⁷ for hydrogen, fluorine, chlorine, bromine, C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine] or C₁-C₄Alkoxy [which is optionally substituted by fluorine and / or chlorine],</li><li>R³⁸ for hydrogen, fluorine, chlorine, bromine, C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine], cyano, formyl, C₁-C₄-Alkyl carbonyl or C₁-C₄-Alkoxy-carbonyl and</li><li>R³⁹ for C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine], C₁-C₄-Alkoxy [which is optionally substituted by fluorine and / or chlorine], amino, C₁-C₄-Alkylamino or di- (C₁-C₄-alkyl) -amino, or</li><li>R³⁸ and R³⁹ together for C₃-C₄-Alkandiyl stand in which further</li><li>R² for the rest<chemistry id="chem0008" num="0008"><img file="EP0121082B1_D0008.tif" /></chemistry>stands in what</li><li>R⁴⁰ and R⁴¹ are the same or different and for C₁-C₄-Alkyl [which is optionally substituted by fluorine and / or chlorine] or C₁-C₄-Alkoxy [which is optionally substituted by fluorine and / or chlorine]; in which further</li><li>R³ for hydrogen, C₁-C_4-Alkyl [which may be replaced by fluorine, chlorine, bromine, cyano, hydroxy or C₁-C₂-Alkoxy is substituted], C₃-C₆Cycloalkyl, C₃-C₆Alkenyl, C₃-C₆-Alkynyl, benzyl [which is optionally substituted by fluorine, chlorine or methyl] or for the rest -S (O)_n-R⁶ stands in what</li><li>n stands for the numbers zero, 1 or 2 and</li><li>R⁶ the above for R⁵ has the meaning given, but not in every individual case with R⁵ is identical; in which further</li><li>R³ and R⁴ together for C_4-C.₆-Alkandiyl stand, which is optionally interrupted by an oxygen bridge, in which R 'for the rest -XR⁸ stands in what</li><li>X stands for oxygen and</li><li>R⁸ for C₁-C₆-Alkyl [which may be replaced by fluorine, chlorine, C_l-C._4-Alkoxy, C₁-C₄-Alkylthio, C₁-C₄-Alkylsulfinyl or C₁-C_4-Alkylsulfonyl is substituted], C₃-C₆Alkenyl, C₃-C₆Alkynyl, C₃-C₆-Cycloalkyl, benzyl [which is optionally substituted by fluorine, chlorine or methyl] or phenyl [which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C.₁-C₄-Alkyl, trifluoromethyl, C₁-C₄-Alkoxy, trifluoromethoxy, C₁-C_4-Alkylthio or trifluoromethylthio is substituted]; in which further</li><li>R⁴ for the rest<chemistry id="chem0009" num="0009"><img file="EP0121082B1_D0009.tif" /></chemistry>stands in what</li><li>R⁹ for hydrogen or C₁-C₄-Alkyl stands and</li><li>R¹⁰ for C₁-C-alkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, C₃-C₆-Cycloalkyl [which may be replaced by an -SO₂Bridge is interrupted, benzyl or phenylethyl, phenyl [which may be replaced by fluorine, chlorine, bromine, nitro, cyano, C.₁-C₄ Alkyl, trifluoromethyl, C_l-C._4-Alkoxy, trifluoromethoxy, C_l-C._4-Alkylthio or trifluoromethylthio is substituted], pyrimidyl, C₁-C₄-Alkyl carbonyl, benzoyl, C₁-C_4-Alkoxy-carbonyl, C₁-C₄-Alkylsulfonyl or Phenylsulfonyl [which is optionally substituted by fluorine, chlorine, bromine or methyl], or</li><li>R⁹ and R¹⁰ together for C₄-C₆-Alkanediyl [which may be interrupted by an oxygen bridge; in which further</li><li>_R⁴ for the rest<chemistry id="chem0010" num="0010"><img file="EP0121082B1_D0010.tif" /></chemistry>stands in what</li><li>R¹¹ for hydrogen or C₁-C₄-Alkyl stands and</li><li>R¹² for C₁-C₄-Alkyl, benzyl or phenylethyl or phenyl [which may be replaced by fluorine, chlorine, bromine, C₁-C₄-Alkyl, trifluoromethyl, cyano, nitro, C_l-C._4-Alkoxy or trifluoromethoxy is substituted], stands, or</li><li>R¹¹ and R¹² together for C₄-C₆-Alkanediyl; in which further</li><li>R^{4 -} in the event that R³ is different from hydrogen - for hydrogen or hydroxy or for C₁-C₆-Alkyl [which may be replaced by fluorine, chlorine, cyano, C₁-C₄-Alkoxy-carbonyl, hydroxy or C₁-C₄Alkoxy is substituted], C₃-C₆-Cycloalkyl [which may be replaced by an -SO₂Bridge is broken], C₃-C₆Alkenyl, C₃-C₆-Alkynyl, benzyl [which is optionally substituted by fluorine, chlorine and / or methyl] or phenyl [which is optionally substituted by fluorine, chlorine, cyano, nitro, amino, C₁-C₄-Alkyl, trifluoromethyl, C₁-C₄-Alkoxy, trifluoromethoxy, C_1-C._4-Alkylthio, trifluoromethylthio, aminosulfonyl or C₁-C_4-Alkoxy-carbonyl is substituted] and in which further</li><li>M represents hydrogen, a sodium, potassium, magnesium, calcium or iron equivalent or one optionally substituted by C₁-C₆-Alkyl, C₃-C₆-Alkenyl and / or benzyl substituted ammonium radical.</li></ul>

The invention further relates to 1: 1 adducts of compounds of the formula (I) - as defined above - with hydrohalic acids (such as hydrogen fluoride, chloride, bromide and iodide), with sulfuric acid, phosphoric acid, with or without fluorine, if appropriate Chlorine-substituted alkanesulfonic acids with up to 4 carbon atoms or also benzene or naphthalenesulfonic acids, which are optionally substituted by fluorine, chlorine or methyl.

The new guanidine derivatives outlined by the general formula (I) are available as mixtures of tautomers of the formulas (IA) and (IB) if M is hydrogen:<chemistry id="chem0011" num="0011"><img file="EP0121082B1_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP0121082B1_D0012.tif" /></chemistry>

The mixing ratio depends on factors that determine aggregation such as temperature, solvent and concentration.

If, in addition to M, R³ or R⁴ stand for hydrogen, the general formula (I) also stands for other possible tautomers, as outlined in the formulas (IC) and (ID):<chemistry id="chem0013" num="0013"><img file="EP0121082B1_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0121082B1_D0014.tif" /></chemistry>

The new guanidine derivatives of the formula (I) are obtained.<ul id="ul0002" list-style="none"><li>(a) in the event that R¹ represents hydrogen, R³ for the radicals mentioned above - but excluding the radical -S (O)_n-R⁶stands, M stands for hydrogen and the radicals R² and R⁴ have the meanings given above if cyano compounds of the formula (II)<chemistry id="chem0015" num="0015"><img file="EP0121082B1_D0015.tif" /></chemistry>in which<ul id="ul0003" list-style="none"><li>M¹ stands for hydrogen and</li><li>R² has the meaning given above, with amino compounds of the formula (III)<chemistry id="chem0016" num="0016"><img file="EP0121082B1_D0016.tif" /></chemistry>in weicner</li><li>R³ for the radicals mentioned above - but excluding the radical -S (O)_n-R⁶- stands and</li><li>R⁴ has the meaning given above, or with hydrochlorides of amino compounds of the formula (III), if appropriate in the presence of diluents and if appropriate treating the reaction products with acid acceptors; or</li></ul></li><li>(b) in the event that R 'for the remainder -S (O)_m-R⁵ stands in what<ul id="ul0004" list-style="none"><li>m and R⁵ have the meanings given above, and</li><li>M has the meaning given in (a), the radicals R², R³ and R⁴ have the meanings given above, or in the event that R³ for the rest-S (O)_n-R⁶ stands in what</li><li>n and R⁶ have the meanings given above, and</li><li>M has the meaning given in (a), the radicals R¹, R² and R4 have the meanings given above if the guanidine derivatives of the formula (I) obtainable by the preparation process described under (a) above, in which R¹ represents hydrogen, R³ for the above-mentioned residues - but excluding the residue-S (O)_n-R⁶stands, M stands for hydrogen and the radicals R²and R⁴ have the meanings given above, with halogen-sulfur compounds of the formula (IV)<chemistry id="chem0017" num="0017"><img file="EP0121082B1_D0017.tif" /></chemistry>in which</li><li>X¹ represents fluorine, chlorine or bromine and</li><li>m and R⁵ have the meanings given above, and / or with halogen-sulfur compounds of the formula (V)<chemistry id="chem0018" num="0018"><img file="EP0121082B1_D0018.tif" /></chemistry>in which</li><li>X² represents fluorine, chlorine or bromine and</li><li>n and R⁶ have the meanings given above, if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents; or</li></ul></li><li>(c) in the event that R³ for the radicals mentioned above, but excluding the radical S (O)_n-R⁶ - stands and M, R¹, R²and R⁴ have the meanings given above if isothioureas of the formula (VI)<chemistry id="chem0019" num="0019"><img file="EP0121082B1_D0019.tif" /></chemistry>in which<ul id="ul0005" list-style="none"><li>R¹⁵ for C₁-C₄-Alkyl or benzyl and</li><li>M and the residues R¹ and R² have the meanings given above, with amino compounds of the formula (III)<chemistry id="chem0020" num="0020"><img file="EP0121082B1_D0020.tif" /></chemistry>in which</li><li>R³ for the radicals mentioned above - but excluding the radical -S (O)_n-R⁶- stands and</li><li>R⁴ has the meaning given above, or with hydrochlorides of amino compounds of the formula (III), if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents and if appropriate treating the reaction products with acids; or</li></ul></li><li>(d) in the event that R³ for the above-mentioned residues - but excluding the residue-S (O)_n-R⁶ - stands and M, R¹, R² and R⁴ have the meanings given above when guanidine derivatives of the formula (I) in which<ul id="ul0006" list-style="none"><li>R³ for the rest-S (O)_n-R⁶ where n and R⁶ have the meanings given above and M and the radicals R¹, R² and R⁴ have the meanings given above, with amino compounds of the formula (III)<chemistry id="chem0021" num="0021"><img file="EP0121082B1_D0021.tif" /></chemistry>in which</li><li>R³ for the radicals mentioned above - but excluding the radical -S (O)_n-R⁶- stands and</li><li>R⁴ has the meaning given above, or with hydrochlorides of amino compounds of the formula (III), if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents; or</li></ul></li><li>(e) in the event that M stands for a metal equivalent or for an optionally substituted ammonium radical - in each case as defined above - and the radicals R¹, R², R³ and R⁴ have the meanings given above if guanidine derivatives of the formula (I) in which M is hydrogen and the radicals R¹, R², R3 and _R⁴ have the meanings given above, with metal hydroxides, hydrides or alkanolates or with organometallic compounds or with ammonia or corresponding amines, if appropriate in the presence of diluents; or</li><li>(f) in the event that 1: 1 adducts of guanidine derivatives of the formula (I) can be prepared with strong acids if guanidine derivatives of the formula (I) in which M and the radicals R¹, R², R³ and R⁴ have the meanings given above, reacted with strong acids, if appropriate using inert diluents.</li></ul>

The new guanidine derivatives of the formula (I) and their 1: 1 adducts with strong acids are notable for strong herbicidal activity and / or are suitable for regulating the growth of certain plants.

Surprisingly, the new compounds of the formula (I) show substantially better herbicidal and plant growth-regulating activity than previously known guanidines with the same direction of action and good selectivity in cotton and in various types of cereals.

The invention preferably relates to compounds of the formula (I) in which<ul id="ul0007" list-style="none"><li>(A) R 'for the rest -S (O)_m-R⁵ stands in what<ul id="ul0008" list-style="none"><li>m stands for the number 2 and</li><li>R⁵ for the rest<chemistry id="chem0022" num="0022"><img file="EP0121082B1_D0022.tif" /></chemistry>stands in what</li><li>R¹⁶ for fluorine, chlorine, bromine, methyl, trifluoromethyl, C₁-C_2-Alkoxy, difluoromethoxy, trifluoromethoxy, phenyl or C₁-C₂-Alkoxycarbonyl and</li><li>R¹⁷ represents hydrogen; in which further</li><li>R²for the rest<chemistry id="chem0023" num="0023"><img file="EP0121082B1_D0023.tif" /></chemistry>stands in what</li><li>R³⁷ represents hydrogen, methyl or methoxy,</li><li>_R³⁸ represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and</li><li>R³⁹ for C₁-C₄-Alkyl or C₁-C₄-Alkoxy or together with R³⁸ for C₃-C₄-Alkanediyl; in which further</li><li>R³ for hydrogen, methyl or the rest -S (O)_n-R⁶ where n is the number 2 and R⁶ the above for R⁵ has the meaning given as preferred; in which further</li><li>R⁴ for C₁-C₄-Alkoxy, C₃-C₄-Alkenoxy, C₃-C₄-Al- kinoxy, benzyloxy or for the rest<chemistry id="chem0024" num="0024"><img file="EP0121082B1_D0024.tif" /></chemistry>stent, in which</li><li>R⁹ represents hydrogen or methyl and</li><li>R¹⁰ for C₁-C₃Alkyl, phenyl, acetyl, methoxycarbonyl, phenylsulfonyl or p-toluenesulfonyl; in which further</li><li>M represents hydrogen, sodium, potassium, a magnesium or calcium equivalent; and - in the event that M represents hydrogen - the 1: 1 adducts of the previously defined compounds with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid; or in which</li></ul></li><li>(B) R¹ for hydrogen or the rest-S (O)_m-R⁵ stands in what<ul id="ul0009" list-style="none"><li>m stands for the numbers zero, 1 or 2 and</li><li>R⁵ for the rest<chemistry id="chem0025" num="0025"><img file="EP0121082B1_D0025.tif" /></chemistry>stands in what</li><li>R¹⁶ and R¹⁷ stand for hydrogen, or</li><li>R¹⁶ for chlorine, nitro, methyl, trifluoromethyl or for methoxy and</li><li>R¹⁷ for fluorine, chlorine, bromine, methyl. Trifluoromethyl, cyano, nitro or methoxy; in which further</li><li>_R² for the rest<chemistry id="chem0026" num="0026"><img file="EP0121082B1_D0026.tif" /></chemistry>stands in what</li><li>R³⁷ represents hydrogen, methyl or methoxy,</li><li>R³⁸ represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and</li><li>R³⁹ for C₁-C₄-Alkyl or C₁-C₄-Alkoxy or</li><li>_R³⁸ and R³⁹ together for C₃-C₄-Alkandiyl stand in which further</li><li>R³ for hydrogen, methyl or the rest -S (O)_n-R⁶ stands in what</li><li>n stands for the numbers zero, 1 or 2 and</li><li>R⁶ the above for R⁵ has the meaning given as preferred; in which further R⁴ for C₁-C₄-Alkoxy, C₃-C₄-Alkenoxy, C₃-C₄-Al- kinoxy, benzoyloxy or for the rest, wherein<chemistry id="chem0027" num="0027"><img file="EP0121082B1_D0027.tif" /></chemistry>R⁹ represents hydrogen or methyl and</li><li>R¹⁰ for C₁-C₃Alkyl, phenyl, acetyl, methoxycarbonyl, phenylsulfonyl or p-toluenesulfonyl; in which further</li><li>R⁴ stands for hydroxy with the proviso that R³ is different from hydrogen; in which further</li><li>M represents hydrogen, sodium, potassium, a magnesium or calcium equivalent, and - in the event that M represents hydrogen - the 1: 1 adducts of the previously defined compounds with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid; or in which</li></ul></li><li>(C) R¹ for the rest -S (O)_m-R₅ stands in what<ul id="ul0010" list-style="none"><li>m stands for the number 2 and</li><li>R⁵ for the rest<chemistry id="chem0028" num="0028"><img file="EP0121082B1_D0028.tif" /></chemistry>stands in what</li><li>R¹⁶ for fluorine, chlorine, bromine, methyl, trifluoromethyl, C₁-C₂-Alkoxy, difluoromethoxy, trifluoromethoxy or C₁-C₂-Alkoxy-carbonyl and</li><li>B¹⁷ which stands for hydrogen</li><li>R²stands for the rest in which<chemistry id="chem0029" num="0029"><img file="EP0121082B1_D0029.tif" /></chemistry></li><li>R⁴⁰ represents methyl, methoxy or ethoxy and</li><li>R⁴¹ represents methyl, methoxy or ethoxy; in which further</li><li>R³ for hydrogen, methyl or the rest -S (O)_n-R⁶ stands in what</li><li>n stands for the number 2 and</li><li>R⁶ the above for R⁵ has given meaning; in which further</li><li>R⁴ for C₁-C₄-Alkoxy, C_3-C._4-Alkenoxy, C₃-C₄-Al- kinoxy, benzyloxy or for the rest<chemistry id="chem0030" num="0030"><img file="EP0121082B1_D0030.tif" /></chemistry>stands in what</li><li>R⁹ represents hydrogen or methyl and</li><li>R¹⁰ for C₁-C₃Alkyl, phenyl, acetyl, methoxycarbonyl, phenylsulfonyl or p-toluenesulfonyl; in which further</li><li>M represents hydrogen, sodium, potassium, a magnesium or calcium equivalent; and - in the event that M is hydrogen - the 1: 1 adducts of the previously defined compounds with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid; or in which</li></ul></li><li>(D) R¹ for hydrogen or the rest -S (O)_m-R⁵ stands in what<ul id="ul0011" list-style="none"><li>m stands for the numbers zero, 1 or 2 and</li><li>R^S stands for the rest in which<chemistry id="chem0031" num="0031"><img file="EP0121082B1_D0031.tif" /></chemistry></li><li>R¹⁶ and R¹⁷ both stand for hydrogen, or</li><li>R¹⁶ for chlorine, nitro, methyl, trifluoromethyl or methoxy and</li><li>R¹⁷ represents fluorine, chlorine, bromine, methyl, trifluoromethyl, cyano, nitro or methoxy; in which further</li><li>R²for the rest<chemistry id="chem0032" num="0032"><img file="EP0121082B1_D0032.tif" /></chemistry>stands. wherein</li><li>R⁴⁰ represents methyl, methoxy or ethoxy and R⁴¹ represents methyl, methoxy or ethoxy; in which further</li><li>R³ for hydrogen, methyl or the rest -S (O)_n-R⁶ stands in what</li><li>n stands for the numbers zero, 1 or 2 and</li><li>R⁶ the above for R⁵ has the meaning given as preferred; in which further</li><li>R⁴ for C_l-C._4-Alkoxy, C3-C4-alkenoxy, C₃-C₄-Al- kinoxy, benzyloxy or for the rest, wherein<chemistry id="chem0033" num="0033"><img file="EP0121082B1_D0033.tif" /></chemistry></li><li>R⁹ represents hydrogen or methyl and</li><li>R¹⁰ for C₁-C₃Alkyl, phenyl, acetyl, methoxycarbonyl, phenylsulfonyl or p-toluenesulfonyl; in which further</li><li>R⁴stands for hydroxy with the proviso that R³ is different from hydrogen; in which further</li></ul></li></ul>

M stands for hydrogen, sodium, potassium, a magnesium or calcium equivalent, and - if M stands for hydrogen - the 1: 1 adducts of the previously defined compounds with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid.

For example, if you use process variant (a)<ul id="ul0012" list-style="none"><li>O-isopropyl-hydroxylamine hydrochloride and</li><li>2-Cyanamino-4-methoxy-6-methyl-pyrimidine as starting materials, the course of the reaction can be sketched using the following formula:<chemistry id="chem0034" num="0034"><img file="EP0121082B1_D0034.tif" /></chemistry></li></ul>

If, for example, 2-difluoromethoxy-benzenesulfonic acid chloride and N '- (4-methoxy-6-methyl-s-triazin-2-yl) -N "- dimethylamino-guanidine are used as starting materials for process variant (b), the The course of the reaction can be outlined using the following formula:<chemistry id="chem0035" num="0035"><img file="EP0121082B1_D0035.tif" /></chemistry>

If, for example, process variant (c) is used, N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -N "- (2-fluoro-benzosulfonyl) -S-methyl-isothiourea and diethylamine are used as starting materials and treated the ammonium salt initially obtained with hydrochloric acid, the course of the reaction can be sketched using the following formula:<chemistry id="chem0036" num="0036"><img file="EP0121082B1_D0036.tif" /></chemistry>

If, for example, process variant (d) uses N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-chlorobenzenesulfonyl) guanidine and N, N-dimethyl-hydrazine as starting materials, the course of the reaction can be sketched using the following formula:<chemistry id="chem0037" num="0037"><img file="EP0121082B1_D0037.tif" /></chemistry>

For example, N '- (4,6-dimethoxy-pyrimidin-2-yl) -N "-methoxy-N"' - (2-trifluoro-methoxy-benzenesulfonyl) guanidine and potassium ethanolate are used as starting materials for process variant (e) , the course of the reaction can be sketched using the following formula:<chemistry id="chem0038" num="0038"><img file="EP0121082B1_D0038.tif" /></chemistry>

If, for example, process variant (f) uses N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N"' - (2-methoxycarbony! -Benzoisutfonyl) -guanidine and trifluoromethanesulfonic acid as Starting materials, the course of the reaction can be sketched using the following formula:<chemistry id="chem0039" num="0039"><img file="EP0121082B1_D0039.tif" /></chemistry>

Formula (II) provides a general definition of the cyano compounds to be used as starting materials for process variant (a). In this formula M stands¹ for hydrogen, and R² preferably has the same meaning as is preferably given above in the context of the definition of substituents of the formula (I).

The following may be mentioned as starting materials of the formula (II):<ul id="ul0013" list-style="none"><li>2-cyanamino-4,6-dimethyl-pyrimidine,</li><li>2-cyanamino-4-methoxy-6-methyl-pyrimidine,</li><li>2-cyanamino-4,6-dimethoxypyrimidine,</li><li>2-cyanamino-4-ethoxy-6-methyl-pyrimidine,</li><li>2-cyanamino-4-methyl-6-propoxy-pyrimidine,</li><li>2-cyanamino-4-methyl-6-isopropoxy-pyrimidine,</li><li>2-cyanamino-4-methyl-6-butoxypyrimidine,</li><li>2-cyanamino-4-methyl-6-isobutoxypyrimidine,</li><li>2-cyanamino-4,6-dimethyl-s-triazine,</li><li>2-cyanamino-4-methoxy-6-methyl-s-triazine,</li><li>2-cyanamino-4,6-dimethoxy-s-triazine,</li><li>2-cyanamino-4-ethoxy-6-methyl-s-triazine,</li><li>2-cyanamino-5-chloro-4,6-dimethyl-pyrimidine and</li><li>2-cyanamino-4,5,6-trimethyl-pyrimidine.</li></ul>

To the best of our knowledge, only one compound of the cyano compounds of the formula (II) is known, namely 2-cyanamino-4,6-dimethyl-pyrimidine (see J. Chem. Soc. 1953, pp. 1725-1730). The compounds of the formula (II) are obtained essentially by the following two synthetic routes:<ul id="ul0014" list-style="none"><li>(a¹) generally by reacting alkali metal or alkaline earth metal salts of cyanamide - such as. B. sodium cyanamide or calcium cyanamide - with halogen compounds of formula (VII)<ul id="ul0015" list-style="none"><li>Hal¹-R² (VII)</li></ul>in which</li></ul>

R² has the meaning given above and

Hall represents fluorine, chlorine, bromine or iodine, in particular chlorine, optionally in the presence of inert diluents, such as, for example, acetone, acetonitrile or dimethylformamide, at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 100 ° C ; after distilling off the volatile component and dissolving the residue in water, the cyano compounds of the formula (II) can be precipitated by acidification, for example using hydrochloric acid, and isolated by suction; or

(a²) in the event that R² stands for a substituted pyrimidinyl radical, by reacting cyanoguanidine (&lt;dicyandiamide&gt;) with β-dicarbonyl compounds, such as, for example, acetylacetone (see J. Chem. Soc. 1953, 1725-1730), acetoacetic acid esters (see J. Prakt. Chem. 77 , (1908), 542 and J. Chem. Soc. 1948, 586) or malonic esters (cf. DE-PS 158591).

The 2-cyanamino-4-hydroxy-6-methyl- or -4,6-dihydropyrimidines obtained from acetoacetic acid esters or malonic acid esters can be prepared in a known manner by reaction with alkylating agents, such as dimethyl or diethyl sulfate, optionally in the presence of diluents , such as B. water, methanol, ethanol, n- and iso-propanol, acetone, dioxane or dimethylformamide, and in the presence of acid binders, such as Sodium or potassium hydroxide, sodium or potassium carbonate, can be converted into corresponding 2-cyanamino-4-alkoxy-6-methyl- or -4,6-dialk-oxy-pyrimidines. To avoid N-alkylation, acylation is optionally carried out with an acylating agent, such as, for example, acetic anhydride or acetyl chloride, and deacylated again after the alkylation with aqueous acids or bases.

The halogen compounds of the formula (VII) are known (cf. J. Chem. Soc. (C) 1966, 2031; Chem. Pharm. Bull. 11 (1963), 1382-1388; Arch. Pharm. 295 (1962), 649 -657).

The amino compounds of the formula (III) to be used further as starting materials for process variant (a) are largely known or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 15 (1967), 345-349; Bull. Soc. Chem. France 1958, 664; Synthesis 1976, 682).

In formula (III) R⁴ preferably the same meaning as is preferably given above in the context of the substituent definition of the formula (I) and R³ preferably represents hydrogen, C_l-C._4-Alkyl [which may be replaced by fluorine, chlorine, bromine, cyano, hydroxy or C₁-C₄-Alkoxy is substituted], C₃-C₆Cycloalkyl, C₃-C₆Alkenyl, C₃-C₆-Alkynyl or benzyl [which is optionally substituted by fluorine, chlorine or methyl].

Particular preference is given to starting materials of the formula (III) in which R "has the same meaning as is given above as preferred in the context of the substituent definition of the formula (I) and R³ for hydrogen, C optionally substituted by hydroxy₁-C₄-Alkyl, C₅-C₆ Cycloalkyl, C₃-C₄Alkenyl, C₃-C₄-Alkynyl or benzyl.

The following may be mentioned as starting materials of the formula (III):<ul id="ul0016" list-style="none"><li>Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dicyclopentylamine, dicyclohexylamine, diallylamine, dipropargylamine, dibenzylamine, N-methyl-aniline, O-methyl-hydroxylamine, O-ethyl-hydroxylamine, O-propyl-hydroxylamine, O-isopropyl O-butylhydroxylamine, O-isobutyl-hydroxylamine, O-allylhydroxylamine, O-propargyl-hydroxylamine, O-benzyl-hydroxylamine, N, O-dimethyl-hydroxylamine, methylhydrazine, N, N-dimethylhydrazine, N, N'-dimethylhydrazine, ethylhydrazine , n- and iso-propyl hydrazine and the hydrochlorides of these compounds; Phenylhydrazine, acetydrazine, methyl hydrazino formate, benzenesulfonic acid hydrazide and p-toluenesulfonic acid hydrazide.</li></ul>

The guanidine derivatives to be used as starting materials in process (b) are generally defined by the formula (I) and the conditions mentioned under (b) above. In this formula - insofar as it relates to the guanidines to be used as starting materials for process (b) - there are preferably<ul id="ul0017" list-style="none"><li>R¹ for hydrogen,</li><li>R³ for hydrogen, C₁-C₄-Alkyl [which may be replaced by fluorine, chlorine, bromine, cyano, hydroxy or C₁-C₂-Alkoxy is substituted], C₃-C₆Cycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl or benzyl [which is optionally substituted by fluorine, chlorine or methyl],</li><li>M for hydrogen, and</li><li>R² and R⁴ preferably have the same meanings as are preferably given above in the context of the definition of the substituent of the formula (I).</li><li>The starting materials for process variant (b) are in particular the guanidine derivatives of the formula (I), in which</li><li>R¹ represents hydrogen,</li><li>R³ for hydrogen, optionally substituted by hydroxy alkyl, C₅-C₆Cycloalkyl, C₃-C₄-Alkenyl, C3-C4-alkynyl or benzyl, M represents hydrogen and</li><li>R² and R⁴ have the same meanings as given above as preferred within the scope of the definition of the substituent of the formula (I).</li></ul>

Examples of guanidine derivatives of the formula (I) which are to be used as starting materials in production process (b) are:<ul id="ul0018" list-style="none"><li>N '- (4,6-dimethyl-pyrimidin-2-yl) -,</li><li>N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-ethoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-propoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-isopropoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-butoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-isobutoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4,6-dimethoxypyrimidin-2-yl) -,</li><li>N '- (4,6-dimethyl-s-triazin-2-yl) -,</li><li>N '- (4-methoxy-6-methyl-s-triazin-2-yl) -,</li><li>N '- (4-ethoxy-6-methyl-s-triazin-2-yl) -,</li><li>N '- (4,6-dimethoxy-s-triazin-2-yl) -,</li><li>N '- (4,5,6-trimethyl-pyrimidin-2-yl) and</li><li>N '- (5-chloro-4,6-dimethyl-pyrimidin-2-yl) guanidine,<ul id="ul0019" list-style="none"><li>-N "-methyl guanidine,</li><li>-N "-ethyl guanidine,</li><li>-N "-propyl guanidine,</li><li>-N "-isopropyl guanidine,</li><li>-N "-butyl guanidine,</li><li>-N "-isobutyl-guanidine,</li><li>-N "-sec.-butyl-guanidine,</li><li>-N "-tert.-butyl-guanidine,</li><li>-N "-cyclopentyl-guanidine,</li><li>-N "-cyclohexyl-guanidine,</li><li>-N "-allyl-guanidine,</li><li>-N "-propargyl-guanidine,</li><li>-N "-benzyl-guanidine,</li><li>-N "-phenyl guanidine,</li><li>-N "- (2-fluorophenyl) -,</li><li>- (3-fluorophenyl) - and</li><li>- (4-fluorophenyl) guanidine,</li><li>-N "- (2-chlorophenyl) -,</li><li>- (3-chlorophenyl) - and</li><li>- (4-chlorophenyl) guanidine,</li><li>-N "- (2-bromo-phenyl) -,</li><li>- (3-bromo-phenyl) - and</li><li>- (4-bromo-phenyl) guanidine,</li><li>-N "- (2-nitro-phenyl) -,</li><li>- (3-nitro-pheny!) - and</li><li>- (4-nitro-phenyl) guanidine,</li><li>-N "- (2-aminophenyl) -,</li><li>- (3-aminophenyl) - and</li><li>- (4-aminophenyl) guanidine,</li><li>-N "- (2-cyano-phenyl),</li><li>- (3-cyano-phenyl) - and</li><li>- (4-cyano-phenyl) guanidine,</li><li>-N "- (4-aminosulfonylphenyl) guanidine,</li><li>-N "- (2-hydroxy-phenyl) -,</li><li>- (3-hydroxy-phenyl) - and</li><li>- (4-hydroxy-phenyl) guanidine,</li><li>-N "- (2-methylphenyl) -,</li><li>- (3-methyl-phenyl) - and</li><li>- (4-methylphenyl) guanidine,</li><li>-N "- (2-trifluoromethyl-phenyl) -,</li><li>- (3-trifluoromethyl-phenyl) - and</li><li>- (4-trifluoromethyl-phenyl) guanidine,</li><li>-N "- (2-methoxy-phenyl) -,</li><li>- (3-methoxy-phenyl) - and</li><li>- (4-methoxy-phenyl) guanidine,</li><li>-N "- (2-trifluoromethoxy-phenyl) - and</li><li>- (4-trifluoromethoxy-phenyl) guanidine,</li><li>-N "- (4-trifluoromethylthio-phenyl) guanidine,</li><li>-N "- (2-methoxycarbonyl-phenyl) - and</li><li>- (4-methoxycarbonyl-phenyl) guanidine,</li><li>-N ", N" -dimethyl-guanidine,</li><li>-N ", N" -diethyl-guanidine,</li><li>-N ", N" -dipropyl-guanidine,</li><li>-N ", N" -diisopropyl-guanidine,</li><li>-N ", N" -dibutyl-guanidine,</li><li>-N ", N" -diisobutyl-guanidine,</li><li>-N ", N" -dicyclopentyl-guanidine,</li><li>-N ", N" -dicyclohexyl-guanidine,</li><li>-N ", N" -diallyl-guanidine,</li><li>-N ", N" -dipropargyl-guanidine,</li><li>-N ", N" -dibenzyl-guanidine,</li><li>-N "-methyl-N" -phenyl-guanidine,</li><li>-N "-methoxy-guanidine,</li><li>-N "-ethoxy-guanidine,</li><li>-N "-propoxy-guanidine,</li><li>-N "-isopropoxy-guanidine,</li><li>-N "-butoxy-guanidine,</li><li>-N "-isobutoxy-guanidine,</li><li>-N "-allyloxy-guanidine,</li><li>-N "-propargyloxy-guanidine,</li><li>-N "-benzyloxy-guanidine,</li><li>-N "-methyl-N" -methoxy-guanidine,</li><li>-N "-methylamino-guanidine,</li><li>-N "-dimethylamino-guanidine,</li><li>-N "-methyl-N" -methylamino-guanidine,</li><li>-N "-ethylamino-guanidine,</li><li>-N "-propylamino-guanidine,</li><li>-N "-isopropylamino-guanidine,</li><li>-N "-morpholino-guanidine,</li><li>-N "-acetamino-guanidine,</li><li>-N "-methoxycarbonylamino-guanidine,</li><li>-N "-benzenesulfonylamino-guanidine and</li><li>-N "-p-toluenesulfonamino-guanidine.</li></ul></li></ul>

The guanidine derivatives of the formula (I) to be used as starting materials for process (b) have largely not yet been described in the literature and can be prepared by process (a) according to the invention.

The formulas (IV) and (V) generally define the halogen-sulfur compounds to be used as starting materials in process (b). In these formulas, m, n, R have⁵ and R⁶ preferably the same meanings as are preferably given above in the context of the substituent definition of the formula (I) and X¹ and X² preferably represent chlorine.

The following may be mentioned as starting materials of the formulas (IV) and (V):<ul id="ul0020" list-style="none"><li>2-chloro, 2-fluoro, 2-bromo, 2-nitro, 2-methyl, 2-methoxycarbonyl, 2-ethoxycarbonyl, 2-methoxy, 2-ethoxy, 2-phenyl, 2-trifluoromethyl, 2-difluoromethoxy, 2-trifluoromethoxy, 2-methyl-5-chloro, 2,5-dichloro and 2-chloro-5-trifluoromethyl-benzenesulfonic acid chloride as well as the corresponding sulfonic acid and sulfinic acid chloride.</li></ul>

Some of the halogen-sulfur compounds of the formulas (IV) and (V) are known (cf. Chemistry Lett. 1978, 951; EP-PA 23 422, 35 893, 42 731, 44 808, 44 809, 51 466, 64804 and 70041; U.S. Patents 2,929,820, 4,282,242 and 4,372,778; J. Org. Chem. 33 (1968), 2104).

The compounds of the formulas (IV) and (V) in which m and n represent the number 2 are obtained essentially by the following two synthesis methods:<ul id="ul0021" list-style="none"><li>(b¹) by reacting the corresponding sulfonic acids R⁵-SO₃H or R⁶-SO₃H or their alkali metal or alkaline earth metal salts with halogenating agents, such as. B. phosphorus (V) chloride (phosphorus pentachloride), phosphoryl chloride (phosphorus oxychloride), thionyl chloride, phosgene or benzotrichloride, optionally in the presence of catalysts, such as pyridine or dimethylformamic acid, and optionally using inert diluents, such as Methylene chloride, chloroform, acetonitrile, chlorobenzene and / or sulfolane at temperatures between -20 ° C and +150 ° C, preferably between 0 ° C and + 100 ° C; after dilution with water, the sulfonic acid chlorides - insofar as they are crystalline - can be isolated by suction or by extraction with a water-immiscible solvent, such as. As methylene chloride, diethyl ether or hexane, washing and drying the extracts. Concentration and recrystallization or Distilling to be cleaned; or</li><li>(b²) in the event that X 'and X² stand for chlorine and R⁵ or R⁶ stand for an aromatic radical, in a manner known per se (cf. J. Org. Chem. 25 (1960). 1824; DE-OS 2 308 262 and EP-PA 59 241) by reacting corresponding amino compounds R⁵-NH₂ or R⁶-NH₂ with sodium nitrite and hydrochloric acid, optionally in the presence of acetic acid, at temperatures between -10 ° C and + 20 ° C, preferably between -5 ° C and + 10 ° C, and then (in situ) with sulfur dioxide or a salt of the sulfurous acid , such as B. sodium sulfite or sodium bisulfite in the presence of a copper compound, such as. As copper chloride or copper sulfate, as a catalyst at temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 60 ° C.</li></ul>

Working up can be carried out in the usual way: when diluted with water, the sulfonyl chlorides are generally crystalline and can be isolated by suction. However, they can also be extracted from the aqueous dispersion using a solvent which is virtually immiscible with water, such as methylene chloride or diethyl ether, dried and purified by vacuum distillation.

Formula (VI) defines the isothioureas to be used as starting materials in process (c). In this formula, R stands¹⁵ preferably for C₁-C₄-Alkyl or benzyl, especially for methyl, and R¹, R² and M preferably have the same meanings as are preferably given above in the context of the substituent definition of the formula (I).

The following may be mentioned as examples of the starting materials of the formula (VI):<ul id="ul0022" list-style="none"><li>N '- (4,6-dimethoxy-s-triazin-2-yl) -,</li><li>N '- (4,6-dimethyl-pyrimidin-2-yl) -,</li><li>N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-ethoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-propoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-isopropoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-butoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4-isobutoxy-6-methyl-pyrimidin-2-yl) -,</li><li>N '- (4,6-dimethoxypyrimidin-2-yl) -,</li><li>N '- (4,6-dimethyl-s-triazin-2-yl) -,</li><li>N '- (4-methoxy-6-methyl-s-triazin-2-yl) -,</li><li>N '- (4-ethoxy-6-methyl-s-triazin-2-yl) -,</li><li>N '- (4,5,6-trimethyl-pyrimidin-2-yl) - and</li><li>N '- (5-chloro-4,6-dimethyl-pyrimidin-2-yl) -,</li><li>-N "- (2-fluoro-benzenesulfonyl) -,</li><li>-N "- (2-chloro-benzenesulfonyl) -,</li><li>-N "- (2-bromo-benzenesulfonyl) -,</li><li>-N "- (2-nitro-benzenesulfonyl) -,</li><li>-N "- (2-methyl-benzenesulfonyl) -,</li><li>-N "- (2-methoxycarbonyl-benzenesulfonyl) -,</li><li>-N "- (2-ethoxycarbonyl-benzenesulfonyl) -,</li><li>-N "- (2-methoxy-benzenesulfonyl) -,</li><li>-N "- (2-ethoxy-benzenesulfonyl) -,</li><li>-N "- (2-phenyl-benzenesulfonyl) -,</li><li>-N "- (2-trifluoromethyl-benzenesulfonyl) -,</li><li>-N "- (2-difluoromethoxy-benzenesulfonyl) -,</li><li>-N "- (2-trifluoromethoxy-benzenesulfonyl) -,</li><li>-N "- (2-methyl-5-chlorobenzenesulfonyl) -,</li><li>-N "- (2,5-dichlorobenzenesulfonyl) - and</li><li>-N "- (2-chloro-5-trifluoromethyl-benzenesulfonyl) -S-methyl-isothiourea.</li></ul>

Some of the isothioureas of the formula (VI) are known (cf. EP-PA 5 986). These compounds are obtained in a manner known per se by reacting corresponding isodithiocarbamic acid derivatives of the formula (VIII)<chemistry id="chem0040" num="0040"><img file="EP0121082B1_D0040.tif" /></chemistry>in which R¹ and R¹⁵ have the meanings given above, with amino-hetarenes of the formula (IX)<chemistry id="chem0041" num="0041"><img file="EP0121082B1_D0041.tif" /></chemistry>in which M and R² have the meanings given above, optionally in the presence of a strong but weakly nucleophilic base. such as sodium hydride, and optionally in the presence of a diluent such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, dimethylformamide or dimethyl sulfoxide, at temperatures between -20 ° C and 100 ° C, preferably between 0 ° C and + 80 ° C. Working up can be carried out by customary methods, for example by dilution with water and acidification, for example with hydrochloric acid, after which the crystalline products of the formula (VI) can be isolated by suction.

Formula (VIII) defines the isodithiocarboxylic acid derivatives required as intermediates. In this formula, R¹ and R¹⁵ preferably the same meanings as used above in the context of the substituent definitions for formula (I) or (V1). are preferably specified.

The following may be mentioned as examples of the compounds of the formula (VIII):<ul id="ul0023" list-style="none"><li>N- (2-fluoro-benzenesulfonyl) -,</li><li>N- (2-chloro-benzenesulfonyl) -,</li><li>N- (2-bromo-benzenesulfonyl) -,</li><li>N- (2-nitro-benzenesulfonyl) -,</li><li>N- (2-methyl-benzenesulfonyl) -,</li><li>N- (2-methoxycarbonyl-benzenesulfonyl) -,</li><li>N- (2-ethoxycarbonyl-benzenesulfonyl) -,</li><li>N- (2-methoxy-benzenesu (fonyl) -,</li><li>N- (2-ethoxy-benzenesulfonyl) -,</li><li>N- (2-phenyl-benzenesuffonyl) -,</li><li>N- (2-difluoromethoxy-benzoisulfonyl) -,</li><li>N- (2-trifluoromethoxy-benzenesulfonyl) -,</li><li>N- (2-methyl-5-chlorobenzenesulfonyl) -,</li><li>N- (2,5-dichlorobenzenesulfonyl) - and</li><li>N- (2-chloro-5-trifluoromethyl-benzenesulfonyl) -S ', ​​S "-dimethyl-isodithiocarbamic acid ester.</li></ul>

The isodithiocarbamic acid derivatives of the formula (VIII) have largely not yet been described in the literature. These compounds are obtained in a manner known per se (cf. Chem. Ber. 99 (1966), 2885) by reacting amino compounds of the formula (X)<chemistry id="chem0042" num="0042"><img file="EP0121082B1_D0042.tif" /></chemistry>in which<ul id="ul0024" list-style="none"><li>R¹ has the meaning given above, with carbon disulfide in the presence of a strong base, such as sodium hydroxide, and optionally in the presence of diluents, such as water and dimethylformamide, at temperatures between ―20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C, and subsequent reaction (in situ) with an alkylating agent of formula (XI)<chemistry id="chem0043" num="0043"><img file="EP0121082B1_D0043.tif" /></chemistry>in which</li><li>R¹⁵ has the meaning given above and</li><li>Hal¹² represents chlorine, bromine or iodine, at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.</li></ul>

The products of the formula (VIII) obtained in crystalline form after dilution with water can be isolated by suction.

In formula (X) R¹ preferably the same meaning as given above in the context of the definition of substituents for formula (I).

Examples of the compounds of the formula (X) are: 2-fluoro, 2-chloro, 2-bromo, 2-nitro, 2-methyl, 2-methoxycarbonyl, 2-ethoxycarbonyl, 2- Methoxy, 2-ethoxy, 2-phenyl, 2-difluoromethoxy, 2-trifluoromethoxy, 2-methyl-5-chloro, 2,5-dichloro and 2-chloro-5-trifluoromethyl-benzenesulfonic acid amide.

The amino compounds of the formula (X) are known in some cases (cf. EP-PA 23422, 30140, 35 893, 44 807, 44 808, 44 809, 51466, 64 804, 70 041 and 70 802; US Pat. No. 4,372,778 ).

These compounds are obtained in a manner known per se by reacting appropriate chlorine compounds R.¹-Cl with ammonia, optionally using inert diluents, such as. As diethyl ether or tetrahydrofuran, at temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C. The products of the formula (X) obtained in crystalline form can be isolated by suction.

Examples of suitable precursors of the formula R.¹-Cl and production methods for this are listed above in the description of the starting materials for process (b).

In formula (XI), R is¹⁵ preferably for C₁-C₄-Alkyl or benzyl, especially for methyl, and Hal² for chlorine, bromine or iodine.

The following may be mentioned as examples of the compounds of the formula (XI): methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide and ethyl iodide as well as benzyl chloride and benzyl bromide.

The compounds of formula (XI) are known.

The aminohetarenes to be used further as intermediates are defined by the formula (IX). In this formula, R is preferably² represents the same radicals as are preferably specified in the context of the definition of substituents for formula (I) and M preferably represents hydrogen, sodium, potassium, a magnesium or calcium equivalent, in particular hydrogen.

The following may be mentioned as examples of the compounds of the formula (IX):<ul id="ul0025" list-style="none"><li>4,6-dimethyl, 4,5,6-trimethyl,</li><li>5-chloro-4,6-dimethyl-, 4-methoxy-6-methyl-,</li><li>4-ethoxy-6-methyl-, 4-propoxy-6-methyl-,</li><li>4-isopropoxy-6-methyl-, 4-butoxy-6-methyl-,</li><li>4-isobutoxy-6-methyl and</li><li>4,6-dimethoxy-2-aminopyrimidine</li><li>and 4,6-dimethyl-, 4-methoxy-6-methyl-, 4-ethoxy-6-methyl- and 4,6-dimethoxy-2-amino-s-triazine.</li></ul>

The compounds of the formula (IX) are known and / or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 11 (1963), 1382-1388; US Pat. No. 4,299,960).

The amino compounds to be used further as starting materials in process (c) according to the invention are defined by the formula (III). The preferred meanings of the formula (III) are listed above in the context of the description of the starting materials for process (a).

The guanidine derivatives to be used as starting materials in process (d) are generally defined by the formula (I) and the conditions mentioned under (d) above.

In formula (1) - insofar as it relates to the guanidine derivatives to be used as starting materials for process (d) - R¹ or R³ preferably for the residues -S (O)_m-R⁵ or -S (O)_n-R⁶, in which mouth. n and R⁵ and R⁶ preferably have the same meanings as are preferably given above in the context of the definition of substituents for formula (I); furthermore R², R⁴ and M preferably has the same meanings as are preferably given above in the context of the definition of substituents for formula (I).

Examples of the compounds of the formula (I) to be used as starting materials in process (d) are:<ul id="ul0026" list-style="none"><li>N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-</li><li>N ", N" '- bis- (2-chlorobenzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-bromo-benzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-fluoro-benzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-methoxy-benzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-methyl-benzenesulfonyl) - and</li><li>-N ", N" '- bis- (2-methoxycarbonyl-benzene-sulfonyl) guanidine.</li></ul>

The guanidine derivatives of the formula (I) to be used as starting materials for process (d) have not yet been described in the literature. They can be obtained by the manufacturing process described in (b) above.

The amino compounds to be used further as starting materials in process (c) according to the invention are defined by the formula (III). The preferred meanings of R³ and R⁴ and examples of compounds of formula (III) are listed above in the description of the starting materials for process (a).

The guanidine derivatives to be used as starting materials in process (e) are defined by the formula (I) and the conditions mentioned under (c) above. In formula (I) - insofar as it relates to the guanidine derivatives to be used as starting materials for process (e) - M represents hydrogen and the radicals R¹, R², R³ and R⁴ preferably have the same meanings as are preferably given above in the context of the definition of substituents for formula (I).

Examples of the compounds of the formula (I) to be used as starting materials in process (e) are: N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' -bis- (2-fluoro-benzenesulfonyl) -,<ul id="ul0027" list-style="none"><li>-N ", N" '- bis- (2-chlorobenzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-bromo-benzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-methoxy-benzenesulfonyl) -,</li><li>-N ", N" '- bis- (2-methyl-benzenesulfonyl) - and</li><li>-N ", N '" - bis- (2-methoxycarbony) -benzenesulfonyl) -guaniain and</li><li>N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N"' - (2-fluoro-benzenesulfonyl) -</li><li>-N "'- (2-chloro-benzenesulfonyl) -,</li><li>-N "'- (2-bromo-benzenesulfonyl) -,</li><li>-N "'- (2-methyl-benzenesulfonyl) -,</li><li>-N "'- (2-methoxy-benzenesulfonyl) - and</li><li>-N "'- (2-methoxycarbonyl-benzenesulfonyl) guanidine.</li></ul>

The guanidine derivatives of the formula (I) to be used as starting materials for process (e) have not yet been described in the literature. They can be obtained by the production processes described in (a), (b), (c) and (d) above.

Examples of the metal hydroxides, hydrides, alkanolates or organometallic compounds to be used in process (e) are: sodium, potassium, magnesium and calcium hydroxide, sodium and calcium hydride, sodium methanolate and ethanolate, potassium methanolate, ethanolate and potassium tert-butoxide and isopropyl magnesium chloride.

Examples of the amines to be used in process (e) are: isopropylamine, diisopropylamine, isobutylamine, sec-butylamine, tert-butylamine, diisobutylamine, trimethylamine, triethylamine, dibenzylamine and ethyl-diisopropylamine.

Formula (I) defines the guanidine derivatives to be used as starting materials in process (f). In formula (I), R¹, R², R³, R⁴ and M preferably has the same meanings as are preferably given above in the context of the definition of substituents for formula (I). Examples of compounds of the formula (I) which can also be used as starting materials in process (f) are listed above in the context of the description of the starting materials for process (e).

In process (f) strong acids are used as starting materials. These are preferably hydrogen halide acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, further sulfuric acid and phosphoric acid or optionally alkanesulfonic acids having up to 4 carbon atoms substituted by fluorine or chlorine, such as, for example, methanesulfonic acid, ethanesulfonic acid, chloromethanesulfonic acid. 2-chloroethanesulfonic acid and trifluoromethanesulfonic acid, also benzenesulfonic acid, p-toluenesulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, naphthalene-1,4-, -1,5-. -1,6-, -2,6- and -2,7-disulfonic acid. Hydrochloric acid (hydrogen chloride), sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid are particularly preferred.

Process (a) is preferably carried out using diluents. Practically all inert organic solvents can be considered as such. Alcohols, such as methanol, ethanol, n- and iso-propanol, n-, iso-, sec- and tert-butanol, are particularly suitable. Ethanol is particularly preferred as the solvent.

Practically all customary acid binders can be used as acid acceptors. These include, in particular, alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, (optionally aqueous) ammonia, furthermore aliphatic, aromatic or heterocyclic amines, such as triethylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, diazabicycloo Diazabicycloundecene (DBU).

The reaction temperature can be varied within a substantial range in process (a). Generally one works between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C. Process (a) is generally carried out under normal pressure.

To carry out process (a) according to the invention, generally between 0.5 and 5 mol, preferably between 1 and 3 mol, of amino compound of formula (III) or its hydrochloride is used per mole of cyano compound of the formula (II).

The starting materials of the formulas (11) and (III) and, if appropriate, the diluents are generally combined at room temperature or with slight external cooling and the reaction mixture is stirred, if appropriate at elevated temperature, until the end of the reaction.

The new compounds of the formula (I) are worked up and isolated by customary methods: the mixture is diluted — if appropriate after cooling and if appropriate after filtration. Solution with water or concentrated in vacuo and the residue is dissolved in water and, if appropriate after filtration, is adjusted to a weakly alkaline pH by adding one of the acid acceptors mentioned above. The products of the formula (I) are obtained in crystalline form and can be isolated by suction.

Process (b) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents.

Practically all inert organic solvents, but preferably aprotic polar solvents, are suitable as such. These may include halogenated hydrocarbons such as methylene chloride, chloroform, toluene and chlorobenzene, nitriles such as acetonitrile and propiononitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric acid triamide, 1,2-dimethoxyethane, pyridine and 2-methyl-5-ethyl- pyridine.

Practically all commonly used acid binders can be used as acid acceptors in process (b). These include, in particular, alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal hydrides, organometallic compounds, such as butyllithium, and also aliphatic, aromatic or heterocyclic amines, such as trimethylamine, triethylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, diazabicycl , Diazabicycloundecene (DBU), pyridine and 2-methyl-5-ethyl-pyridine.

The reaction temperatures can be varied within a substantial range in process (b). Generally one works between - 80 ° C and + 100 ° C, preferably between -30 ° C and + 50 ° C. Process (b) according to the invention is generally carried out at normal pressure.

To carry out process (b) according to the invention, in general between 0.5 and 5 mol, preferably between 1 and 3 mol, of halogen-sulfur compound of the formula (IV) or (V) are used per mole of guanidine intermediate of the formula (I) ) a.

The reaction components are usually combined at room temperature or with external cooling and the reaction mixture is stirred until the end of the reaction.

The new compounds are worked up and isolated by customary methods: if necessary after volatile components have been distilled off, the mixture is shaken with water and a water-immiscible solvent, such as methylene chloride, chloroform or toluene, and the organic phase is washed with water, dried, filtered and concentrated . The products of formula (I) remaining in the residue are digested with organic solvents, such as. B. Diethyl ether, ethyl acetate, ethanol or isopropanol brought to crystallization and, if necessary, purified by recrystallization.

Process (c) according to the invention for the preparation of compounds of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents can be considered as such. These include in particular optionally chlorinated hydrocarbons, such as chloroform, carbon tetrachloride, toluene, xylene, chlorobenzene and 1,2-dichlorobenzene, ethers, such as Diisopropyl and dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane and diglycol dimethyl ether (diglyme), nitriles, such as acetonitrile and propiononitrile, and also dimethylformamide, dimethylacetamide, dimethyl sulfoxide and sulfolane.

In process (c), acid binders can be used as acid acceptors which, in their nucleophilic properties, do not significantly compete with the amino compounds of the formula (III). As such, alkali metal and alkaline earth metal carbonates, such as. B. potassium carbonate and potassium carbonate, tertiary amines, such as triethylamine, N, N-dimethylaniline and N, N-dimethylbenzylamine, and nitrogen heterocycles, such as Pyridine, Diazabicyclooctan (DABCO) and Diazabicycloundecen (DBU) called.

The reaction temperature can be varied within a substantial range in process (c). Generally one works between 0 ° C and 200 ° C, preferably between 20 ° C and 120 ° C. Process (c) is generally carried out under normal pressure.

To carry out process (c) according to the invention, generally between 1 and 5 mol, preferably between 1 and 3 mol, of amino compound of formula (III) or its hydrochloride is used per mole of isothiourea of ​​the formula (VI).

In general, the isothioureas of the formula (VI) and the diluent are initially introduced at room temperature and the amino compounds of the formula (III) or their hydrochlorides and suitable acid acceptors are metered in. The reaction mixture is then generally stirred at elevated temperature until the end of the reaction. The products of formula (I) are usually obtained in crystalline form on cooling and can be isolated by suction. Insofar as the products of the formula (I) are obtained as ammonium salts, the corresponding acids (M = H) can be prepared therefrom after being dissolved in water by acidification, for example using hydrochloric acid or sulfuric acid.

Process (d) according to the invention is preferably carried out using diluents. Practically all inert organic solvents and, if appropriate, also water are suitable as such. These include in particular alcohols, such as methanol, ethanol, n- and iso-propanol, ethers, such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters, such as methyl acetate and ethyl acetate, nitrites, such as, for. B. Acetonitrile or propiononitrile, as well as dimethylformamide and water.

In process (d), acid binders can be used as acid acceptors whose nucleophilic properties do not significantly compete with the amino compounds of the formula (111).

As such, alkali metal and alkaline earth metal carbonates, such as. As potassium carbonate and calcium carbonate, tertiary amines, such as triethylamine, N, N-dimethylaniline and N, N-dimethylbenzylamine, and nitrogen heterocycles, such as. B. pyridine, diazabicyclooctane (DABCO) and diazabicycloundecene (DBU).

The reaction temperature can be varied within a substantial range in process (d). Generally one works between 0 ° C and 150 ° C, preferably between 10 ° C and 100 ° C. Process (d) is generally carried out at normal pressure.

For carrying out process (d) according to the invention, generally between 1 and 10 mol, preferably between 2 and 5 mol, of amino compound of formula (III) or its hydrochloride is used per mole of guanidine intermediate of formula (I).

In general, the guanidine derivatives of the formula (I) and the diluent are introduced at room temperature or with gentle cooling, and the amino compound of the formula (III) or its hydrochloride and suitable acid acceptors are metered in. The reaction mixture is then generally stirred at room temperature or elevated temperature until the end of the reaction.

Working up can be carried out according to customary methods. If the products of the formula (I) are obtained in crystalline form from the reaction mixture, they can be isolated by suction. Otherwise - if necessary after concentration - diluted with water and with a water-immiscible solvent, such as. B. methylene chloride extracted. 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 recrystallizing the residue.

Process (e) according to the invention is preferably carried out using diluents. Practically all inert organic solvents are suitable as such. These include in particular alcohols, such as. As ethanol, n- and iso-propanol, ethers such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters such as. B. methyl acetate and ethyl ester and nitriles, such as. B. acetonitrile ..

The reaction temperature can be varied within a substantial range in process (e). Generally one works between -20 ° C and + 50 ° C, preferably between 0 ° C and 30 ° C. Process (e) is generally carried out at normal pressure.

To carry out process (e) according to the invention, generally between 0.9 and 1.2 mol, preferably between 0.95 and 1.1 mol, of metal compound or amine are used per mole of guanidine derivative of the formula (I).

In general, the guanidine derivatives of the formula (I) and the diluent are initially introduced and, if appropriate with slight external cooling, the metal compound or the amine, if appropriate dissolved in the diluent, is metered in. The reaction mixture is stirred until the end of the reaction. The salt-like products of the formula (I) are generally crystalline and can be isolated by suction.

Process (f) according to the invention is preferably carried out using diluents. Practically all inert organic solvents can be considered as such. These include in particular alcohols, such as methanol, ethanol, n- and iso-propanol, ethers, such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, and also esters, such as methyl acetate and ethyl acetate.

If the acids used as starting materials are used in aqueous solution, acetic anhydride can advantageously also be used as a diluent.

The reaction temperature can be varied within a substantial range in process (f). Generally one works between -20 ° C and + 50 ° C, preferably between 0 ° C and 30 ° C. Process (f) is generally carried out at normal pressure.

To carry out process (f) according to the invention, generally between 1 and 10 mol, preferably between 1.5 and 5 mol, of a strong acid are used per mole of guanidine derivative of the formula (I).

In general, the guanidine derivatives of the formula (I) and the diluent are initially introduced and the strong acid is metered in, if appropriate with slight external cooling. The reaction mixture is stirred until the end of the reaction. The 1: 1 adducts are generally crystalline and can be isolated by suction.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers and in particular as weed killers, but also as plant growth regulators. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides or as plant growth regulators essentially depends on the amount used.

The active compounds according to the invention can be used, for example, in the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, lpomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, .Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumum, Scarumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. B. forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops become.

The active compounds according to the invention also interfere with the metabolism of the plants and can therefore, as already stated, be used as growth regulators under certain conditions.

Experience has shown that the mode of action of plant growth regulators applies. that an active ingredient can also have several different effects on plants. The effects of the substances essentially depend on the point in time of use, based on the stage of development of the plant, on the amounts of active compound applied to the plants or their environment and on the type of application. In any case, growth regulators should influence the crop plants in a certain desired manner.

Plant growth regulating substances can be used, for example, to inhibit the vegetative growth of the plants. Such inhibition of growth is of economic interest, among other things, for grasses, since it can reduce the frequency of grass cuts in ornamental gardens, parks or sports facilities, on the side of the road, at airports or in orchards. It is also important to inhibit the growth of herbaceous and woody plants on the side of the road and near pipelines or overland lines or in general in areas in which a strong growth of the plants is undesirable.

It is also important to use growth regulators to inhibit the longitudinal growth of cereals. This reduces or completely eliminates the risk of the plants bending over before harvesting. In addition, growth regulators in cereals can cause stalk reinforcement, which also counteracts storage. The use of growth regulators for stalk shortening and stalk reinforcement makes it possible to apply higher amounts of fertilizer in order to increase the yield without the risk of the grain being stored.

An inhibition of vegetative growth enables denser planting in many crops, so that additional yields can be achieved based on the soil area. Another advantage of the smaller plants obtained in this way is that the crop can be processed and harvested more easily.

An inhibition of the vegetative growth of the plants can also lead to increased yields in that the nutrients and assimilates benefit the bloom and fruit formation to a greater extent than the vegetative parts of the plants.

Growth regulators can often also be used to promote vegetative growth. This is of great benefit when the vegetative parts of the plant are harvested. A promotion of vegetative growth can also lead to a promotion of generative growth at the same time, in that more assimilates are formed, so that more or larger fruits are produced.

In some cases, increases in yield can be achieved by intervening in plant metabolism without any changes in vegetative growth being noticeable. Furthermore, growth regulators can be used to change the composition of the plants, which in turn can lead to an improvement in the quality of the harvested products. For example, it is possible to increase the sugar content in sugar beets, sugar cane, pineapple and citrus fruits, or to increase the protein content in soybeans or cereals. It is also possible, for example, to inhibit the breakdown of desired ingredients, such as sugar in sugar beets or sugar cane, with growth regulators before or after the harvest. In addition, the production or outflow of secondary plant constituents can be positively influenced. One example is the stimulation of the latex flow in rubber trees.

Parthenocarpic fruits can develop under the influence of growth regulators. The gender of the flowers can also be influenced. Sterility of the pollen can also be generated, which is of great importance in the breeding and production of hybrid seeds.

The branching of the plants can be controlled by using growth regulators. On the one hand, the development of side shoots can be promoted by breaking the apical dominance, which can be very desirable, especially in ornamental plant growing, in connection with growth inhibition. On the other hand, it is also possible to inhibit the growth of the side shoots. For this effect z. B. great interest in tobacco growing or in the planting of tomatoes.

Under the influence of growth regulators, the number of leaves in the plants can be controlled in such a way that defoliation of the plants is achieved at a desired time. Such defoliation plays a major role in the mechanical harvesting of cotton, but is also in other crops such as. B. in viticulture to facilitate the harvest of interest. Defoliation of the plants can also be carried out in order to reduce the transpiration of the plants before transplanting.

The crop fall can also be controlled with growth regulators. On the one hand, premature fruit fall can be prevented. On the other hand, the fall of fruit or even the falling of the flowers can be promoted to the desired extent («thinning») in order to break the alternation. Alternance is understood to mean the peculiarity of some types of fruit that bring endogenously very different yields from year to year. Finally, it is possible to use growth regulators at the time of harvest to reduce the forces required to detach the fruit in order to enable mechanical harvesting or to facilitate maritime harvesting.

With growth regulators it is also possible to accelerate or delay the ripening of the crop before or after the harvest. This is of particular advantage because it can be optimally adapted to the needs of the market. Furthermore, growth regulators can improve fruit coloration in some cases. In addition, a temporal concentration of maturity can also be achieved with growth regulators. This creates the conditions for z. B. with tobacco, tomatoes or coffee a complete mechanical or manual harvesting can be carried out in one operation.

By using growth regulators, the seed or bud rest of the plants can also be influenced, so that the plants, such as. For example, pineapples or ornamental plants in nurseries germinate, sprout or bloom at a time when they are normally not ready to do so. A delay in leaving. Especially from buds or the germination of seeds with the help of growth regulators may be desirable in frost-prone areas in order to avoid damage from late frosts.

Finally, growth regulators can induce plant resistance to frost, drought or high salinity in the soil. This makes it possible to cultivate plants in areas that are normally unsuitable for this.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, liquefied gases and / or solid carriers under pressure, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, z. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. B. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifying and / or foam-generating agents are: B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and other growth regulators.

Known herbicides such as z. B.<ul id="ul0028" list-style="none"><li>1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione or</li><li>N- (2-benzothiazolyi) -N, N'-dimethylurea for weed control in cereals;</li><li>4-Amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one for weed control in sugar beets and</li><li>4-Amino-6- (1,1-dimethylethyl) -3-methylthio-1,2,4-triazin-5 (4H) -one for weed control in soybeans, in question. Surprisingly, some mixtures also show a synergistic effect.</li></ul>

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is done in the usual way, e.g. B. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. The seeds of the plants can also be treated.

The active compounds according to the invention can be applied both before and after emergence of the plants. It is preferably used before the plants emerge, that is to say in the pre-emergence process. They can also be worked into the soil before sowing.

The amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect desired. In general, the application rates are between 0.001 and 10 kg of active ingredient per ha, preferably between 0.01 and 5 kg / ha.

For the time of use, the growth regulators are used in a preferred period, the exact delimitation of which depends on the climatic and vegetative conditions.

The following examples serve to explain the invention further.

Manufacturing examples:

Example 1:

<chemistry id="chem0044" num="0044"><img file="EP0121082B1_D0044.tif" /></chemistry>

(Method a)

A mixture of 109 g (0.67 mol) of O-methylhydroxylamine hydrochloride, 99 g (0.67 mol) of 2-cyanoamino-4,6-dimethyl-pyrimidine and 600 ml of ethanol is heated to boiling under reflux for 7 hours . The alcohol is then distilled off in a water jet vacuum, the residue is dissolved in hot water and this solution is added to 100 ml of concentrated ammonia. The product which has crystallized out is filtered off with suction and recrystallized from ethanol.

71.8 g (55% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-guanidine of melting point 134 ° C. to 136 ° C. are obtained.

Example 2:

<chemistry id="chem0045" num="0045"><img file="EP0121082B1_D0045.tif" /></chemistry>

(Method b)

A mixture of 29.4 g (0.15 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-guanidine, 63.6 g (0.3 mol) of 2-chlorine -benzenesulfonic acid chloride and 150 ml of pyridine are stirred for 2 days at 20 ° C. After the pyridine has been largely distilled off in a water jet vacuum, 200 ml of water are added to the residue and the mixture is extracted with 200 ml of methylene chloride, the organic phase is separated off, dried and concentrated brought to crystallization by digesting with ethanol.

41.2 g (51% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-chlorobenzene- sulfonyl) guanidine with a melting point of 164 ° C to 166 ° C.

The structural formula above applies to the crystalline state and is proven by X-ray structure analysis. Further spectroscopic data (IR,¹Dog ¹³C-NMR) and elemental analysis are in agreement with this structure assignment.

Example 3:

<chemistry id="chem0046" num="0046"><img file="EP0121082B1_D0046.tif" /></chemistry>

(Method b)

113 g (0.48 mol) of 2-methoxycarbonyl-benzenesulfonic acid chloride become a mixture of 35.1 g (0.18 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) cooled to -10 ° C. ) -N "-methoxy-guanidine and 160 ml of pyridine are added and the reaction mixture is stirred for two days at 20 ° C. After the pyridine has been largely distilled off in a water jet vacuum, the residue is mixed with 200 ml of water and extracted with 200 ml of methylene chloride. The organic phase is separated off, dried with sodium sulfate, filtered and concentrated. The residue is crystallized by digesting with isopropanol.

59 g (55% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-methoxycarbonyl-benzenesulfonyl) guanidine are obtained melting point 165 ° C.

The above structural formula applies to the crystalline state and has been proven by X-ray structure analysis. Further spectroscopic data (IR,¹Dog ¹³C-NMR) and elemental analysis are consistent with this structure assignment.

Example 4:

<chemistry id="chem0047" num="0047"><img file="EP0121082B1_D0047.tif" /></chemistry>(Method b)

21.2 g (0.1 mol) of 2-chloro-benzenesulfonic acid chloride are converted at 20 ° C. to a mixture of 12.1 g (0.05 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenyl-guanidine, 10.5 g (0.1 mol) of triethylamine and 100 ml of chloroform are added dropwise and the reaction mixture is stirred for 15 hours at 20 ° C. The reaction mixture is then shaken with water, the organic phase is separated off and constricted. The residue is suspended in ethanol, the suspension is filtered, the filtrate is concentrated and the residue is crystallized by digesting with ethyl acetate.

6.6 g (22% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenyl-N", N "' - bis- (2-chlorobenzenesulfonyl) are obtained. -guanidine with a melting point of 120 ° C.

Example 5:

<chemistry id="chem0048" num="0048"><img file="EP0121082B1_D0048.tif" /></chemistry>(Method b)

12.2 g (0.05 mol) of 2,5-dichlorobenzenesulfonic acid chloride are converted into a mixture of 12.1 g (0.05 mol) of N '- (4,6-dimethyl- pyrimidin-2-yl) -N "-pheny guanidine, 5.1 g (0.05 mol) of triethylamine and 150 ml of chloroform are added, and the reaction mixture is stirred for 15 hours at 20 ° C. Then the reaction mixture is mixed with 100 ml of 5 % hydrochloric acid washed, concentrated, the residue digested with ethanol and suction filtered.

3.5 g (16% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenyl-N"' - (2,5-dichlorobenzenesulfonyl) guanidine are obtained Melting point 188 ° C.

The product which gradually crystallized out of the mother liquor was isolated by suction after a few days. 1.8 g (8% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenyl-N" - (2,5-dichlorobenzenesulfonyl) guanidine (5 ) melting point 153 ° C.

Example 6: x

<chemistry id="chem0049" num="0049"><img file="EP0121082B1_D0049.tif" /></chemistry>

(Method b)

5.3 g (0.025 mol) of 2-chloro-benzenesulfonic acid chloride are converted at 20 ° C. to a mixture of 7.3 g (0.025 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N ", N "'- dibutyl guanidine and 5.3 g (0.05 mol) of triethylamine were added dropwise. The reaction mixture is stirred for 15 hours at 20 ° C., then washed with 100 ml of 5% hydrochloric acid and concentrated. The residue is crystallized by digesting with ethanol.

1.8 g (16% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N ", N"' - dibutyl-N "'- (2-chlorobenzenesulfonyl) - guanidine melting point 150 ° C.

Example 7a

<chemistry id="chem0050" num="0050"><img file="EP0121082B1_D0050.tif" /></chemistry>and

Example 7b

<chemistry id="chem0051" num="0051"><img file="EP0121082B1_D0051.tif" /></chemistry>

(Method c)

4.5 g (0.1 mol) of dimethylamine are at 25 ° C to 35 ° C in a mixture of 15 g (0.037 mol) of N '- (4,6-dimethoxy-s-triazin-2-yl) -N "- (2-chlorobenzenesulfonyl) -S-methyl-isothiourea and 100 ml of dioxane are introduced. The reaction mixture is then stirred for one hour at 80 ° C. After cooling, the crystalline product was isolated by suction.

12.1 g (73% of theory) of N '- (4,6-dimethoxy-s-triazin-2-yl) -N ", N"' - dimethyl-N "'- (2-chlorobenzenesulfonyl ) -guanidine-dimethyl-ammonium salt (7a) with a melting point of 162 ° C.

The ammonium salt (7a) is dissolved in 20 ml of water and acidified with concentrated hydrochloric acid. The product obtained in crystalline form is isolated by suction.

4 g (28% of theory) of N '- (4,6-dimethoxy-s-triazin-2-yl) -N ", N"' - dimethyl-N "'- (2-chlorobenzenesulfonyl) - guanidine (7b) melting at 185 ° C.

Example 8:

<chemistry id="chem0052" num="0052"><img file="EP0121082B1_D0052.tif" /></chemistry>

(Method d)

A mixture of 5.5 g (0.01 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-chloro-benzenesulfonyl ) -guanidine (2), 1.5 g (0.025 mol) of N, N-dimethylhydrazine, 20 ml of ethanol and 10 ml of water are refluxed for 15 minutes and after cooling, the crystalline product is isolated by suction.

2.5 g (65% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-dimethyl-amino-N"' - (2-chlorobenzenesulfonyl) guanidine are obtained Melting point 176 ° C.

Example 9:

<chemistry id="chem0053" num="0053"><img file="EP0121082B1_D0053.tif" /></chemistry>

(Method f)

5 ml of concentrated hydrochloric acid (0.05 mol) are converted at 20 ° C. to a mixture of 5.5 g (0.01 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy- N ", N" '- bis- (2-chlorobenzenesulfonyl) guanidine and 25 ml of acetic anhydride are added (exothermic reaction!) And the reaction mixture is stirred for 2 hours. The crystalline product is isolated by suction.

4.3 g (74% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-chlorobenzenesulfonyl) are obtained. -guanidine hydrochloride melting at 142 ° C.

The compounds of the formula (I) listed in the table below could be prepared by the processes described by way of example in the preceding examples.<chemistry id="chem0054" num="0054"><img file="EP0121082B1_D0054.tif" /></chemistry><tables id="tabl0001" num="0001"><img file="EP0121082B1_D0055.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0121082B1_D0056.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0121082B1_D0057.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0121082B1_D0058.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0121082B1_D0059.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0121082B1_D0060.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0121082B1_D0061.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0121082B1_D0062.tif" /></tables>

The preparation of some further compounds by process (b) according to the invention is described by way of example below: Preparation of the compound listed above as example (65)<chemistry id="chem0055" num="0055"><img file="EP0121082B1_D0063.tif" /></chemistry>

10.6 g (0.05 mol) of 2-chloro-benzenesulfonic acid chloride become a mixture of 4.9 g (0.025 mol) of N '- (4,6-dimethyl-pyrimidine-2-) cooled to -7 ° C. yl) -N "-methoxy-guanidine and 50 ml of pyridine are added dropwise.

After stirring for 10 minutes at -7 ° C., 400 ml of water are added to the reaction mixture. The crystalline product is isolated by suction.

5.2 g (56% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "- (2-chlorobenzenesulfonyl) -N" -methoxy-guanidine of melting point 90 ° are obtained C.

Preparation of the compound listed above as example (4)<chemistry id="chem0056" num="0056"><img file="EP0121082B1_D0064.tif" /></chemistry>

10.6 g (0.05 mol) of 2-chloro-benzenesulfonic acid chloride are converted at 30 ° C. to a mixture of 9.3 g (0.05 mol) of tributylamine, 6.1 g (0.025 mol) of N '- ( 4,6-Dimethyl-pyrimidin-2-yl) -N "-phenyl-guanidine and 60 ml of cyclohexane are added dropwise. After stirring for 15 hours at 25 ° C., the residue is concentrated and the residue is triturated with 50 ml of ethanol. The product obtained in crystalline form is isolated by suction.

1.4 g (13% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenyl-N"' - (2-chloro-benzenesulfonyl) guanidine of melting point 196 are obtained ° C.

400 ml of water and 10 ml of concentrated hydrochloric acid are added to the mother liquor. The crystalline product formed is isolated by suction.

5.0 g (34% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenyl-N", N "' - bis- (2-chlorobenzenesulfonyl) are obtained. -guanidine (4) with a melting point of 120 ° C.

The following acid adducts of compounds of the formula (I) were also obtained analogously to Example 9:<ul id="ul0029" list-style="none"><li>(3a) 1: 1 adduct of the compound of Example (3) with sulfuric acid;</li><li>(2a) 1: 1 adduct of the compound of Example (2) with p-toluenesulfonic acid;</li><li>(43a) 1: 1 adduct of the compound from Example (43) with sulfuric acid. Examples for the preparation of the starting materials of formula (II)</li></ul><chemistry id="chem0057" num="0057"><img file="EP0121082B1_D0065.tif" /></chemistry>

(Method (a '))

52.7 g (0.3 mol) of 2-chloro-4,6-dimethoxy-s-triazine are added to a solution of 30 g (0.3 mol) of cyanamide disodium salt in 600 ml of acetone, and the reaction mixture is 6 Heated to reflux for hours. After the solvent has been distilled off, the crystalline residue is dissolved in 250 ml of water and the solution is acidified with concentrated hydrochloric acid. The crystalline product is isolated by suction.

33 g (61% of theory) of 2-cyanamino-4,6-dimethyl-s-triazine with a melting point above 300 ° C. are obtained.<chemistry id="chem0058" num="0058"><img file="EP0121082B1_D0066.tif" /></chemistry>

(Procedure (a2))

A mixture of 42 g (0.5 mol) of cyanoguanidine (“dicyandiamide”) and 50 g (0.5 mol) of 2,4-pentanedione (“acetylacetone”) is heated to 120 ° C. for 15 hours. Then, after cooling, the reaction mixture is mixed with 500 ml of water and the solution is acidified at 0 ° C. to 10 ° C. with hydrochloric acid. The product obtained in crystalline form is isolated by suction. 51.8 g (70% of theory) of 2-cyanamino-4,6-dimethyl-pyrimidine with a melting point of 205 ° C. are obtained.

Examples for the preparation of starting materials of the formulas (IV) and (V):

<chemistry id="chem0059" num="0059"><img file="EP0121082B1_D0067.tif" /></chemistry>

(Procedure (b

1

))

295 ml of phosphoryl chloride ("phosphorus oxychloride") are added dropwise at 20 ° C to 30 ° C to a mixture of 172 g (0.8 mol) of 2-chloro-benzenesulfonic acid sodium salt, 300 ml of acetonitrile and 300 ml of sulfolane. The reaction mixture is stirred for 4 hours at 70 ° C., then cooled to 5 ° C. and diluted with ice water. After extracting with petroleum ether, washing the extraction solution with water, drying, filtering and concentrating, the product remaining in the residue is purified by vacuum distillation.

117 g (70% of theory) of 2-chlorobenzenesulfonic acid chloride with a boiling point of 110 ° C./0.8 Torr are obtained.

The compounds of the formula (IV) listed below could be prepared in the same way:<chemistry id="chem0060" num="0060"><img file="EP0121082B1_D0068.tif" /></chemistry><chemistry id="chem0061" num="0061"><img file="EP0121082B1_D0069.tif" /></chemistry><chemistry id="chem0062" num="0062"><img file="EP0121082B1_D0070.tif" /></chemistry>

(Procedure (b

2

))

75.5 g (0.5 mol) of methyl 2-aminobenzoate are dissolved in 176 ml of concentrated hydrochloric acid and 100 ml of acetic acid. A solution of 34.4 g of sodium nitrite in 70 ml of water is added dropwise at 0 ° C. After stirring for 15 minutes, the reaction mixture is slowly added to a saturated solution of sulfur dioxide in 450 ml of acetic acid cooled to 0 ° C. After the cooling bath has been removed, the mixture is stirred until the evolution of gas has ended, 10 g of copper (II) chloride being introduced in portions. After dilution with ice water, extraction with methylene chloride, washing the extraction solution with water, drying, filtering and concentration, the product remaining in the residue is purified by vacuum distillation.

45 g (38% of theory) of 2-methoxy-carbonyl-benzenesulfonic acid chloride with a boiling point of 150 ° C./1 torr are obtained.

The compounds of the formula (IV) listed below could be prepared in the same way:<chemistry id="chem0063" num="0063"><img file="EP0121082B1_D0071.tif" /></chemistry>(Oil, decomposition during distillation)<chemistry id="chem0064" num="0064"><img file="EP0121082B1_D0072.tif" /></chemistry>Mp 100 ° C<chemistry id="chem0065" num="0065"><img file="EP0121082B1_D0073.tif" /></chemistry>oil<chemistry id="chem0066" num="0066"><img file="EP0121082B1_D0074.tif" /></chemistry>Bp. 142 ° C / 3 torr<chemistry id="chem0067" num="0067"><img file="EP0121082B1_D0075.tif" /></chemistry>Kp. 106 ° C / 3 Torr examples for the preparation of starting materials of formula (VI)<chemistry id="chem0068" num="0068"><img file="EP0121082B1_D0076.tif" /></chemistry>

11 g (0.4 mol) of sodium hydride (80%) are added in portions at 20 ° C. to a suspension of 31.2 g (0.2 mol) of 2-amino-4,6-dimethyl-s-triazine in 200 ml of tetrahydrofuran given. After stirring for 12 hours, 60 g (0.2 mol) of N- (2-chlorobenzenesulfonyl-S ', ​​S "-dimethyl-isodithiocarbamic acid ester are added, the reaction temperature rising to 60 ° C. The reaction mixture is 5 hours at 20 ° C. stirred, diluted with 800 ml of water and filtered. After acidification with concentrated hydrochloric acid, the product crystallizes and is isolated by suction.

42 g (48% of theory) of N '- (4,6-dimethoxy-s-triazin-2-yl) -N "- (2-chloro-benzenesulfonyl) -S-methyl-isothiourea of ​​melting point 176 ° C. are obtained .

The compounds of the formula (VI) listed below could be prepared in the same way:<chemistry id="chem0069" num="0069"><img file="EP0121082B1_D0077.tif" /></chemistry><chemistry id="chem0070" num="0070"><img file="EP0121082B1_D0078.tif" /></chemistry><chemistry id="chem0071" num="0071"><img file="EP0121082B1_D0079.tif" /></chemistry><chemistry id="chem0072" num="0072"><img file="EP0121082B1_D0080.tif" /></chemistry><chemistry id="chem0073" num="0073"><img file="EP0121082B1_D0081.tif" /></chemistry>Examples for the preparation of starting materials of the formula (VIII):<chemistry id="chem0074" num="0074"><img file="EP0121082B1_D0082.tif" /></chemistry>

8 g (0.2 mol) of sodium hydroxide dissolved in 15 ml of water and 6. Of a solution of 20 g (0.1 mol) of 2-chlorobenzenesulfonic acid amide in 80 ml of dimethylformamide are simultaneously at 20 ° C. (from different dropping funnels) ml (0.11 mol) of carbon disulfide added dropwise. After stirring for one hour, 13 ml (0.22 mol) of methyl iodide are added dropwise, and the reaction mixture is stirred at 20 ° C. for a further hour. The product is precipitated by adding 500 ml of water and isolated by suction.

22.1 g (75% of theory) of N- (2-chloro-benzenesulfonyl) -S ', ​​S "-dimethyl-isodithiocarbamic acid ester of melting point 112 ° C. are obtained.

The following compound of formula (VIII) could be prepared in the same way:<chemistry id="chem0075" num="0075"><img file="EP0121082B1_D0083.tif" /></chemistry>

Examples of use

Example A

Pre-emergence test

<ul id="ul0030" list-style="none"><li>Solvent: 5 parts by weight of acetone</li><li>Emulsifier: 1 part by weight of alkylaryl polyglycol ether</li></ul>

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered with the preparation of active compound after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:<ul id="ul0031" list-style="none"><li>0% = no effect (like untreated control)</li><li>100% = total annihilation</li></ul>

In this test, e.g. B. the following compound of the preparation examples excellent activity: (2).

Example B

Inhibition of growth in soybeans

<ul id="ul0032" list-style="none"><li>Solvent: 30 parts by weight of dimethylformamide</li><li>Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate</li></ul>

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Soybean plants are grown in the greenhouse until the first subsequent leaf is fully developed. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 3 weeks, the growth of all plants is measured and the growth inhibition is calculated as a percentage of the growth of the control plants. 100% growth inhibition means that growth has stopped and 0% means growth corresponding to that of the control plants.

In this test, for example, the following compound according to the preparation examples shows excellent activity: (2).

Example C

Inhibition of growth in barley

<ul id="ul0033" list-style="none"><li>Solvent: 30 parts by weight of dimethylformamide</li><li>Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate</li></ul>

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Barley plants are grown in the greenhouse to the 2-leaf stage. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 3 weeks, the growth of all plants is measured and the growth inhibition is calculated as a percentage of the growth of the control plants. 100% growth inhibition means that growth has stopped and 0% growth corresponding to that of the control plants.

In this test, for example, the following compounds according to the preparation examples show excellent activity: (2), (10), (22), (23), (24), (25), (27), (28), (29) and (30).

Example D

Inhibition of growth in cotton

<ul id="ul0034" list-style="none"><li>Solvent: 30 parts by weight of dimethylformamide</li><li>Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate</li></ul>

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Cotton plants are grown in the greenhouse until the 5th following leaf is fully developed. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 3 weeks, the growth of the plants is measured and the growth inhibition is calculated as a percentage of the growth of the control plants. 100% growth inhibition means that growth has stopped and 0% means growth corresponding to that of the control plants.

In this test, for example, the following compound according to the preparation examples shows excellent activity: (2).