DD238190A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The present invention relates to herbicidal compositions containing as active ingredient at least one new sulfonylguanidinopyrimidine derivative of the general formula (I) and 1: 1 adducts of compounds of the formula (I) with strong acids, in addition to extenders and / or surface-active agents. Various guanidine derivatives have become known as potential herbicides from patents (see DE-AS 1 089 210, DD-PS 71 016 and 84 530), but have hitherto not gained much importance as agents for weed control and / or regulation of plant growth. Other guanidine derivatives are the subject of older industrial property rights (EP-OS 121 082). Surprisingly, the new compounds of the formula (I) used according to the invention show considerably better herbicidal activity than previously known guanidines having the same direction of action.

Description

The invention relates to herbicidal compositions which contain as active ingredient at least one sulfonylguanidinopyrimidine derivative of the following general formula (I).

characteristics the known technical solutions

Various guanidine derivatives have become known as potential herbicides from patents (see DE-AS 1 089 210, DD-PS 71 016 and 84 530), but have hitherto received no greater importance as agents for weed control and / or regulation of plant growth.

Other guanidine derivatives are the subject of older industrial property rights (EP-OS 121 082).

Object of the invention

Surprisingly, the compounds of the formula (I) used according to the invention show considerably better herbicidal activity than previously known guanidines of the same mode of action.

Explanation of the essence of the invention

The invention is based on the object, new herbicides

To provide funds.

The invention relates to herbicidal compositions containing as active ingredient at least one novel sulfonylguanidinopyrimidine derivative of the general formula (I)

28.3.85- 278258

in which

M is hydrogen or a metal equivalent,

R is an optionally substituted phenyl radical

stands j in

and R

are the same or different and are hydrogen, halogen C in particular fluorine, chlorine and / or bromine], cyano, nitro, C ^ -C ^ alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, C ^ -C ^ alkoxycarbonyl , C 1 -C 4 -alkylamino-carbonyl, di- (C 1 -C ₄ -alkyl) amino-carbonyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -alkylthio, C 1 -C -alkylsulfinyl or C 1 -C 4 -alkyl sulfonyl], for C 1 -C 4 alkoxy [optionally substituted by fluorine, chlorine, bromine, cyano, C 1 -C ₄ alkoxycarbonyl, C 1 -C ₄ alkoxy , C ₁ -C ₄ alkylthio, C ₁ -C ₄ ~ Alkylsulfiny1

or C ₁ -C ₄ -alkylsulfonyl], for C ₁ -C ₄ -alkylthio _> C ₁ -C ₄ -alkylsulfinyl or C ₁ -C ₄ -alkylsulfonyl [which may be

by fluorine, chlorine, bromine, cyano or

Cj-C ₄ -alkoxy-carbonyl substituted], for C ₁ -C ₄ alkylamino-sulfonyl, di - (C ₁ -C ₄ ~ alky1) -amino-sulfony1, C ₁ -C ₄ -Alkoxyamino-5ulfonyl, benzyloxy aminosulfonyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkyl-aminosulfony1, phenyl or phenoxy, C ₁ -C ₄ -Alkoxysul f ony 1, C 2 ~ C _£) -Alkeny 1 [which is optionally substituted is substituted by fluorine, chlorine, bromine, cyano, C ₁ -C ₄ -alkoxy-CaT-carbonyl, carboxy or phenyl], for C ₂ -C ₆ -alkynyl [which may be substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ -alkoxy-CaTbO-

nyl substituted], for Co-C _A -Al-25 ^{d 6}

kenoxy [which optionally by

Fluorine, chlorine, bromine, cyano or C ₁ -C ₄ - alkoxycarbonyl substituted], for C ^ -C ^ -Alkenylthiο [which optionally by fluorine, chlorine, bromine, 30

Cyano or C ₁ -C ₄ alkoxy-carbonyl1], for C ₁ -Cz-alkoxycarbonyl [which is optionally substituted by fluorine, chlorine, bromine, cyano or C ^ -C ^ - alkoxy], for Cg -C ^ - -Cyc1oalkoxycarbonyl, for Cj-C ^ -Alky1thiocarbony1 [which optionally by fluorine, chlorine, bromine, cyano or

Is Cj-C4 alkoxy-carbonyl substituted], aminocarbonyl, C ^ -C ^ alkylamino-carbonyl, di-CCj-C ^ alkyl) - aminocarbonyl _t C ^ -C ^ alkoxy-aminocarbonyl, Cg C ^ -Alkeny1oxy-amino-car bonyl, Benzyloxyaminocarbony 1, C - ^ - C ^ alkoxy-Cj-C ^ alkyl-amino-carbonyl, Dimethylhydrazinocarbonyl, Dimethylhydraz inosul f onyl _t for C3 ~ C £ _i -A oxy or C 1 -C 4 alkynylthio;

in which further

²⁰ 1 ...

R is an optionally substituted benzyl radical

CH ₂ ^- is, in which

R and R the same or different sand and for

Hydrogen, halogen [in particular fluorine, chlorine or bromine], cyano, nitro, Cj-C ^ alkyl [which is optionally substituted by fluorine and / or chlorine], C ₁ -C ^ alkoxy [which optionally by __ fluorine and / or chlorine substituted

is], C j -C ^ alkoxy-carbonyl, C ^ -C ^ - alkylthio, C ₁ -C ₄ alkylsulfinyl,

or

alky1) -aminosulfony1;

in which further 10

is hydrogen, C ₁ -C ₄ -alkyl or a sulfonyl radical R ¹ ^ -SO-, in which

R for C ₁ -C ₁ O ^- AIkYl [which optionally by

Fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C ₄ -alkyl-carbonyl, di-

C ₁ -C ₄ -alkoxy,

(C ₁ C ₄ B

or

is substituted], for

₁₁ ^ [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkoxycarbonyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio,

or C ₁ -C ₄

is substituted], for C2 ~ C ~ ₁ 2 Alkeny1 [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ ~ Alky1thiο or phenyl], for C2 ~ C ₁ 2-Alene-kenyloxy [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or phenyl], for C ₁ -C 9 -alkylamino, Di - (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ cycloalkylamino or di (C 9 -C ₆ eyeoalkyl) amino [optionally substituted by fluorine, chlorine, bromine, cyano, nitro , Phenyl, phenoxy,

C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkylsulfinyl or C ₁ -C ₄ -alkylsulfonyl are substituted], for C ₂ ^- Cg-alkenyl-amino [which may be substituted by fluorine, chlorine , Bromine, cyano, nitro or phenyl], for phenylamino or benzylamino [which is optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ " Fluoroalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -alkylsulfonyl, cyano, nitro and / or C ₁ -C ₄ -alkoxycarbonyl are substituted], for benzyl [which optionally by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₄ -alkoxycarbonyl, C ₁ -C ₄ -alkoxy or di- (C ₁ -C ₄ -alkyl) -amino-sulfony1 is substituted] or an optionally substituted phenyl radical R ¹² -y! / ~ "\\

where is 25

R and R are the same or different

and the meanings given above for R and R have, but not in each individual case, identical with R ⁷ and R ⁸ s ind;

in which further 35

R ^{3 is} the radical -O-R ¹⁴ , wherein

"*" * - ¹ W ' y - 7 -

R ^{14 is} C ₁ -C ₁₂ ^- AlKyI [which is optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -AlKyI-thio, C ₁ -C ₄ -AlKyISuIfinyl or C ₁ -C _4- alkynylsulfonyl is substituted], for C ₃ -C ₆ -cycloalkyl,

C ₁ -C ₂ -alkyl, C ₃ -C ₆ -alkynyl,

[which is optionally substituted by fluorine, chlorine or bromine], C ₃ -C ₆ -alkynyl, C ₁ -C ₄ -alkyl-carbonyl-C ₁ -C ₂ -alkyl, aminocarbonylmethyl, C ₁ -C ₄ -alkyl-amino carbonyl-methyl, di- (C ₁ -C ₄ -alkyl) amino-carbonyl-1-methyl or phenyl, benzyl, benzhydryl or phenylethyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, C ₁ -C ₄ -alkyl , C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-carbonyl are substituted]

stands; 20

in which further

²⁵ 1 =

R ¹⁵

R is the radical -N, in which

³⁰ ir

R ^{10 is} hydrogen or C ₁ -C ₄ -alkyl and

R ^{16 is} hydrogen, C ₁ -C ₄ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, 35

C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-carbonyl is substituted], for C ₃ -C ₆ -CyClOaIKyI, for

Phenyl, benzyl or phenylethyl [which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-carbonyl], for C C ₁ -C ₄ -alkyl-carbonyl, C ₁ -C ₄ -alkyl-carbonyl, C ₁ -C ₄ -alkyl-sulfonyl or phenylsulfonyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro or methyl] ;

in which further - in the event that R is a sulfonyl radical R ^ -SO ₂ -, wherein R ^{11 has} the meaning given above - R is also hydrogen

in which further

R is hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl

[which is optionally substituted by fluorine and / or chlorine], for C ₁ -C ₄ -AlKoXy [which is optionally substituted by fluorine and / or chlorine _ _n ]] or for C ₁ -C ₄ -AlKylthio [which optionally by fluorine and or chlorine is substituted] stands;

R is hydrogen, fluorine, chlorine, bromine, C 1 -C 4 -alkyl which is optionally substituted by fluorine and / or chlorine, is cyano, formyl, C 1 -C 4 -alkylcarbonyl or C 2 -C 4 -alkoxycarbonyl and

R represents hydrogen, C ^ -C alkyl L which is optionally substituted by fluorine and / chlorine odar ISTJ for C.-C, - ^ alkoxy which is optionally substituted by fluorine and / or chlorine ISTJ, amino, C -C - Alkylamino or di (C -C ^ alkyl) amino

- with MaSgabe is because £ R """and R ° is not methyl simultaneously -

and l: i adducts of compounds of formula (I) with strong acids found,

the following compounds are excluded:

-yl) -! ^ ¹ '-methoxy-N ^1' '- (2-tri-f1uormsthoxy bensolsuIfonyl) -guanidine potassium salt, N ^l -. (4-methoxy-6-methyl-pyrimidin-2-yl) -N '' -dimethyl-amino W ' ' - (2-methylbenzenesulfonyl) guanidine, N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -N''-methoxy-N''' - (2-chloro-benzenesulfonyl) -guanidine and N ^t -. (4-MQthoxy-6-methyl-pyrimidin-2-yl) -N ^l '-dimethyl-amino N "' - (2-chloro-benzenesulfonyl) guanidine .

in addition to stretchers and / or surface-active agents.

The general formula (I), when M is hydrogen, stands for the individual tautomers of the formulas (IA) and (IB)

N ^{d4 10} R 1 SO 4 -Rv, NH-C ^N ) -R ³ (IA)

² "V

NR ² R ³

_D 4

N-

_ (IB)

in which 25

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meanings given above,

as well as mixtures of the tautomers (IA) and (IB),

The mixing ratio (IAW (IB) depends on aggregation-determining factors, such as z, B, temperature,

remedies and concentration »

ο ο ι ν υ

⁵ In the case that in addition to M also R ^ is hydrogen, another tautomeric form (IC) is possible:

R ¹ -SO ₉ -NH NH <'> R ° (IC)

io \ _c /

Il

R ³

The novel sulfonylguanidinopyrimidine-Darivate of the formula (I)

(a) in the case where M is hydrogen, 20

when guanidinopyrimidine derivatives of the formula (II>

25, H I - p4

HN ^ 'N- <J Vr ⁵ (II)

^N C ^XN ^ R ⁶ t N

HR ³

in which

R, R, R and R are as defined above

to have,

with sulfonic acid chlorides of the formula (III)

R ¹ -SO ₂ -C 1 (III) 10

in which R has the meaning given above,

in the presence of acid acceptors and optionally in the presence of diluents;

or

(b) in the case where M is hydrogen and 25

R 1 is hydrogen or C ₁ -C ₄ -alkyl,

if one after the above under (a) specified

__ Process obtainable sulfonylguanidinopyrimidine-30

Derivatives of the formula (ID)

R ¹ -SO ₇ -N. ^V "N- / '^ Vr ⁵ (ID)

\ _c / NI

238 ff

- 13 -

in which

, R ⁴ , R ⁵ , R ^& and R ^{14 have} the meanings given above,

miL amino compounds of the formula (IV)

HN (IV)

in we I rather 20

? is hydrogen or C 1 -C 4 -alkyl and

²⁵ q

R has the above mentioned meaning,

or, miL hydrochlorides of amino compounds of the formula (IV), if appropriate in the presence of acid acceptors and optionally in the presence of diluents]

-Ia-

(c) in the event that M is hydrogen and R ^ is a sulfonyl radical of the formula

stands, wor in 10

R has the meaning given above,

if one takes SuIfony1guanidinopyrimidin derivatives of

Formula (IE)

- -. .., ^X Vr ³ (IE)

in we I rather

R ¹ , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meanings given above,

with sulfonic acid chlorides of the formula (V)

R ¹¹ -SO ₂ -C 1 (V)

in which

R ** has the meaning given above, 10

in the presence of acid acceptors and optionally in the presence of diluents;

or

(d) also in the case where M is hydrogen and

R ^{2 is} a sulfonyl radical of the formula R ¹¹ -S0 ₂ "in which

R has the meaning given above,

when sulfonylguanidinopyrimidine derivatives of the formula (VI)

HN "'NC ^N > R ⁵ (VI)

\ _c / N

35 I

R ³

- 16 -

in which

, R ⁴ , R ⁵ , R ⁶ and R ^{11 have} the meanings given above,

with sulfonic acid chlorides of the formula (III)

¹⁵ ι

R ¹ ^ -SO ₂ -Cl (III)

in which 20

R * has the meaning given above,

_ ,. in the presence of acid acceptors and optionally in the presence of diluents;

or 30

(e) in the event that M is hydrogen and R ^{2 is} hydrogen or C ₁ -C ₄ -alkyl,

when sulfonylisothioureidopyrimidine derivatives of the formula (VII)

R ¹ -SO ₇ -N ^V "N- (Z 1 Vr ⁵ (VII) 10 / V

• R ^c IS

\ d17

in which

R ¹ , E ^, R and R ° are as defined above

have and

R ^{17 is} C ₁ -C ₄ -alkyl or benzyl,

with amino compounds of the formula (IV)

HN (IV)

30 ^R

in which

³⁵

R ^ is hydrogen or C ₁ -C ₄ -alkyl and

-Ιδ-

5ο.

R has the meaning given above,

or

optionally in the presence of diluents;

(f) in the case where M is a metal equivalent, if the compounds of the formula (1) obtainable by the processes indicated above under (a), (b), (c), (d) and (e), in which M is hydrogen and E ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meanings given above,

with metal hydroxides, hydrides or alkoxides or with organometallic compounds, if appropriate in the presence of diluents;

or 30

(g) in the case where 1: 1 adducts of compounds of formula (I) are to be prepared with strong acids,

when compounds of the formula (I) in which

M is hydrogen and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R have the meanings given above,

with strong acids, optionally in the presence of

Diluents reacted.

The exact sulfonylguanidinopyiririidine derivatives of the formula (I) and their adducts with strong acids are distinguished by a strong herbicidal activity.

The invention preferably compounds of formula (I), in which

M is hydrogen or a sodium, potassium or calcium equivalent,

1 R is an optionally substituted phenyl radical

stands in which

7 "3

R and R are the same or different and represent hydrogen, fluorine, chlorine, bromine, cyano, with ro, methyl, which is optionally substituted by fluorine, chlorine,

**? M ί ^ \ ß

Cyano, C ₁ -C ₃ -alkoxy-carbonyl, CJ-C ₃ "alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -alkylsulfinyl or Cj-C ₃ -alkyl-isulfonyl substituted ISt] ₁ for C ₁ ~C ₂ - Alkoxy [which is optionally substituted by fluorine, chlorine, cyano, C ₁ -C ₃ -alkoxy-carbonyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -alkyl-sulfinyl or C ₁ -C ₃ -Alkylsulfonyl], for C ₁ -C 9 -alkylthio, C ₁ -C ₃ -alkylsulfinyl or C ₁ -C ₃ -alkyl-sulfonyl [which are optionally substituted by fluorine, chljsr, cyano or C ₁ -C ₃ -alkoxy-carbonyl ], for di- (C ₁ -C ₃ -alkyl) -amino-sulfonyl, C ₁ -C ₃ -ALK-oxymethyl-amino-sulfonyl, phenyl, phenoxy, for C ₁ -C 4 -alkoxy-carbonyl [optionally substituted by fluorine, Chlorine, bromine, cyano or C ₁ -C ₃ -alkyl), C ₃ -C 4 -cycloalkoxycarbonyl, C ₁ -C 4 -alkynylthio-carbonyl, di- (C ₁ -C ₃ -Blyyl) -amino-carbonyl , C ₁ -C ₃ -alkoxymethylamino-carbonyl, or for C ₂ -C 4 -alkynyl [which is

^ _N bene substituted by fluorine, chlorine, cyano

or C ₁ -C ₃ -alkoxy-carbonyl];

in which further

R is an optionally substituted benzyl radical

stands in which

R ⁹ and R ¹⁰

in which further

are the same or different and are hydrogen, fluorine, chlorine, cyano, nitro, methyl, methoxy or C ₁ -C ₃ alkoxycarbonyl;

R is hydrogen, methyl or a sulfonyl radical R 1 -SO ₂ ", in which

for Cj ^ -Cg-alkyl [which is optionally substituted by fluorine, chlorine or cyano], for C ₁ -Cg -alkoxy [which is optionally substituted by fluorine, chlorine or cyano], for C ₂ -C -alkenyl [which may be substituted by fluorine, chlorine, cyano or phenyl substituted], for C2 ~ Cg-alkenyloxy [which is optionally substituted by fluorine, chlorine, cyano or phenyl], C ₁ -C alkylamino, C ₃ -C _£) -Cycloalky lamino or di - (C ₁ -C 1 -alky) -amino [which are optionally substituted by fluorine, chlorine, cyano, phenyl, phenoxy or C ₁ -C _2], C ₂ -C alkenylamino _fe [which is optionally substituted by Fluorine, chlorine, cyano or phenyl], for phenylamino or benzylamino [which

bene substituted by fluorine, chlorine, bromine, C ^ -C ^ - alkyl, Tr-if trifluoromethyl, C ₁ -C ₃ -alkoxy, Cj-C ₂ "fluoroalkoxy, C ₁ -C ₃ -AlKyILhIo, C ₁ -C ₃ - Alky1sulfinyl, C ₁ -C ₃ alkylsulfonyl, cyano, nitro and / or C ₁ -C ₃ -alkoxycarbonyl are substituted], for benzyl [which is optionally substituted by fluorine, chlorine, cyano, nitro, methyl, methoxy and / or C ₁ -C ₂ -alkoxy-carbonyl1 is substituted] or represents an optionally substituted phenyl radical R ¹² - ^. \\,

wherein

1 r> -to. ,

R and R are the same or different

²⁰ . ..7

and the preceding for R and

Q _t

R preferably have specified meanings, but not in each individual case with R and

R ^{8 are} identical; 25 in which continue

R ^{3 is} the radical -O-R ¹⁴ , wherein

R ^{14 is} C ₁ -Cg-alkyl [which is optionally substituted by fluorine or chlorine], C ₃ -C ₆ -alkenyl [which is optionally substituted by chlorine], for C ₁ -C ₃ -alkoxycarbonyl phenyl, phenylethyl or

4 U

- 23 -

Benzyl [which is optionally substituted by fluorine, chlorine, nitro, methyl, methoxy or C ₁ -C ₂ -Al

koxycarbonyl is substituted];

in which further R ^{3 is} the radical, R ¹⁵ , wherein

-N 15 N ₁₆

^X R ¹⁶

R ^{15 is} hydrogen or methyl and 20

R is hydrogen, C ₁ -C ₃ -A ^ yI [which is optionally substituted by fluorine, chlorine, cyano, C ₁ -C ₂ alkoxy or C ₁ -C ₂ ~ alkoxycarbonyl], for C ₃ -C _fe -Cycloalkyl, phenyl, benzyl or phenylethyl [which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₂ alkyl, C -Co-alkoxy or C ₁ -Co-alkoxy-carbonyl1], for Acetyl, methoxycarbonyl, benzenesulfonyl or toluenesulfonyl;

in which further

R ^{q is} hydrogen, chlorine, methyl [which is optionally substituted by fluorine and / or chlorine],

- 24 -

C 1 -C 2 -alkoxy [which is optionally substituted by fluorine and / or chlorine] or C 1 -C 4 -alkyl [optionally substituted by fluorine and / or chlorine],

R ^{5 is} hydrogen, fluorine, chlorine, bromine, methyl, acetyl or Cj-C 2 -alkoxy-carbonyl and

15,

R ^{D is} Cj-C3 "alkyl [which is optionally substituted by fluorine and / or chlorine], for Ci-Cq-alkoxy [which is optionally substituted by fluorine and / or chlorine], for amino, C ^ -C ^ alkylamino or di (C ₁ -C ₃ alkyl) amino

with the proviso that R and R are not simultaneously methyl,

The invention further preferably 1: 1 adducts of compounds of formula <I) - as previously defined, wherein M is hydrogen - with hydrochloric acid Ha, such as hydrogen chloride, hydrogen bromide and hydrogen iodide, with sulfuric acid, trifluoroacetic acid, optionally with Fluorine or chlorine substituted alkanesulfonic acids with up to 4 carbon atoms or with benzene or naphthalene sul-. __ -fonic acids, which are optionally substituted by fluorine, chlorine, bromine or methyl,

- 25 -

The invention relates in particular to compounds

of the formula <I>, in which

M is hydrogen or a sodium, potassium or 10

Is calcium equivalent,

R * represents a substituted phenyl radical 15

stands, wor in

R ⁷ represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ -A ^ yI sul f ynyl, C ^ -C ₃ "Alkylsu1fony1, dimethylaminosulphonyl, Di ethyl aminosulfony1, N-methoxy-N-methylamino-sulfonyl, phenyl, Ci-C ^ alkoxy-carbonyl, difluoromethylthio or Trifluormethy1thiο stands and

₃₀ R ^{ö is} hydrogen; in which further

R is hydrogen, methyl or a sulfonyl radical

R ^^ - SO 2 ~, in which

.- '•• a - * w

R ^{11 is} C ₁ -C ₄ -alkyl which is optionally substituted by fluorine or chlorine], C ₁ -C 4 -alkylamino or di- (C ₁ -C ₂ -alkyl) -amino [optionally substituted by fluorine

] or for an optionally substituted

10. _17,.

iert phenyl radical R \\ stands in which

R and R are the same or different 15

and for hydrogen, fluorine,

Chloro, bromo, cyano, nitro, methyl, trifluoromethyl, C ₁ -C ₂ alkoxy [which optionally

by fluorine, chlorine, cyano or

C ₁ carbonyl -CG-alkoxy-substituted], C ₁ -C 3 alkylthio ~, ^c l ^"c ~ 3 alkylsulfinyl or C ₁ -C ₃ -Alkylsulfony1 [which is optionally substituted by fluorine and / or

Chloro substituted], dimethylaminosulfonyl, diethylaminosulfonyl, N-methoxy-N-methyl-aminosulfony1, phenyl or C ₁ -C 4 -alkoxycarbonyl [which is optionally substituted by fluoro, chloro, cyano or C ₁ -Co];

35

in which further

R ^{3 is} the radical -O-R ¹⁴ , wherein

r14 f _{r j Cj-C ^ alkyl [which is optionally substituted by chlorine], for CaC / alkenyl.

[which is optionally substituted by chlorine], for C 1 -C 2 -alkoxy-carbonyl-methyl, phenyl, phenylethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, methyl, methoxy or C 1 -C 4 -alkoxy carbonyl

is substituted] standsj

in which further R ^{3 is} the radical R ¹⁵ , in which

-N

R ^{15 is} hydrogen or methyl and

is hydrogen, C ₁ -C ₃ -alkyl, C ₃ -C ₆ -cycloalkyl, phenyl, acetyl, methoxycarbonylsulfonyl or toluenesulfonyl

kyl, phenyl, acetyl, methoxycarbonyl, benzene ·

in which further

is hydrogen, chlorine or C 1 -C 2 -alkoxy [which is optionally substituted by fluorine and / or chlorine],

R represents hydrogen, methoxycarbonyl, ethoxycarbonyl or acetyl and

R is C2-C2 "alkyl [which is optionally substituted by fluorine and / or chlorine] or C2 ~ C2 ~ A [which is optionally substituted by fluorine and / or chlorine],

and - in the event that M is hydrogen - the l'.l adducts of the previously defined compounds with hydrochloric acid, sulfuric acid, trifluoroacetic acid, Methansulf onsäure, Benzo 1sulfonsäure and Toluolsulfön-

The compounds mentioned individually above are also excluded in the preferred or particularly preferred range.

If, for example, for process variant (a) 2-fluorobenzenesulfonyl chloride id and N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -N'-ethoxy-guanidine are used as

the reaction sequence can be outlined by the following formula scheme!

SO ₂ Cl +

29 -

I H)

^N C ^N -

H 0-C ₂ H ₅

¹⁵ -2 HCl

SO ₂ -N ^

OCH

> 2 OC ₂ H ₅

If one uses, for example, for the process variant <b> N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) -N "-methoxy-N"', N ¹ "-bis (2-trifluoromethyl ] -benzenesulfonyl) -guanidine and phenylhydrazine as starting materials, the reaction sequence can be outlined by the following equation:

'.CF

+ H ₂ NNH

-SO ₂ -NHOCH ₃

OCHF ₂

For example, for process variant (c), use is made of N '- (4 ₎ 6-dimethoxypyrimidin-2-yl) -N'-benzyloxy-N''' - (2-chloro-phenylmethylsulfonyl) -guanidine and trifluoromethane-sulfonic acid chloride as starting materials, the reaction sequence can be outlined by the following equation:

+ CF ₃ -SO ₂ -Cl

-HCl

' ^H I N-r ^OCH 3

-k "m'j

CF ₃ -SO ₂

OCH

Is used for example for the process variant

(d) N '- <4-ethoxy-6-methyl-pyrimidin-2-yl) -N' '- methoxy-N' '- <2-ethoxycarbonyl-benzenesulfonyl) -guanidine and 2-dimethylaminosulfony1-benzo-1-sulfonic acid chloride id Starting material, the reaction sequence can be outlined by the following formula scheme:

' ^H

OCH

^ I

COOCoH

OC ₂ H ₅

SO ₂ -N (CH ₃ ) ₂

W-SO ₂ -Ci

HCl

OCH

'COOC ₂ H ₅

For example, for process variant (e), use is made of N '- (4-methoxy-6-methylpyrimidin-2-yl) -N' '- (2-methylbenzenesulfonyl) -S-methylisothiourea and N, N- Dimethylhydrazine as starting materials, the reaction sequence can be outlined by the following equation:

-λ , KCH ₃ )

^CH 3 » ^H >

HN (CH ₃ ) ₂

If, for example, for process variant (f), N '- (4,6-dimethoxypyrimidin-2-yl) -N''-isopropoxy-N' '' - (2-methoxycarbony1-phenylmethylsulfonyl) -guanidine and potassium ethanolate are used as starting materials , the reaction sequence can be outlined by the following formula scheme:

.COOCH ₃ * H \ _Ν ^ 0CH ₃ + KOC ₂ H ₅

-CH ₇ -SOo-N ", N - // Α ν

C ^{Ν 1} ^ OCHr, I ³

H 0CH (CH ₃ ) ₂

Κ®

COOCH ₃

ff \ - CH ₂ -SO ₂ -N N - </

IN

H OCH (CH ₃ ) ₂

For example, for process variant (g), use is made of N '- (5-acetyl-4-methyl-pyrimidin-2-yl) -N''-methoxy-N' '- (2-chloro-benzenesulfonyl) -N' '' - (2-difluoromethoxy-benzene-sulfonyl) -guanidine and methanesulfonic acid as starting materials, the reaction sequence can be outlined by the following equation:

OCHF ₂ ι H, _N -f ^CH

+ CH ₃ SO ₃ H

OCHr ο ι Η) \ λ ^ . CH - ^ - N ~ 'N- (Z M-COCH-

₃ CH ₃ SO ₃ H

The guanidinopyrimidine derivatives to be used as starting materials for process variant (a) are generally defined by the formula (II). In formula (II), R, R _t R and R preferably or, in particular, have the same meanings as are preferably given above or within the context of the substituent definition of the formula (I) as being particularly preferred.

Q ι y

As starting materials of the formula (II) are, for example

called:

N '- (4-Methyl-pyrimidin-2-yl) -, N ¹ - (4-ethyl-pyrimidin-2-yl) -, N' - (4-methoxy-6-methyl-pyrimidin-2-yl) _t N '- (4-ethoxy-6-methyl-pyrimidin-2-yl), N' - (4-propoxy-6-methyl-2-yl) -, N '- <4-isopropoxy-6- methyl-pyrimidin-2-y1) - N '- (4-chloro-6-methoxy-pyrimidin-2-y 1) -, N' .- (4-Chi or-6-ethoxy-pyrimidin-2-yl ) -, N '- (4-Chipr-6-dimethyl-pyrimidin-2-yl) -, N' - (4-methyl-6-methylthio-pyrimidin-2-yl) - _} N '- (4 , 6-Dimethoxy-pyrimidin-2-yl) -> N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) ->N' - <4-dimethylamino-6-methyl-pyr-imidin-2-yl yl) -N'-methoxy-guanidine , -N'-ethoxy-guanidine, -N'-propoxy-guanidine, -Ν''-isopropoxy-guanidine, -N''-butoxy-guanidine, -N ''-isobutoxy- guanidine, N''- sec-butoxy-guanidine _s -N''pentoxy-guanidine, -N ^1' -isopentoxy-guanidine, N '' - hexyloxy-guanidine, N ¹ ' -octy1-oxy-guanidine, -N ¹ '-allyloxy-guanidine , -N''- (2-chloro-ethoxy) -guanidine, -N''- (2-fluoro-ethoxy) -guanidine, -N''- (2-chloro-propoxy) -guanidine , -N '' - (2-fluoro-propoxy) -guanidine , -N '' - (3-chloro-propoxy) -g uanidine, -N ¹ '- (4-chloro-butoxy) -guanidine, -N ¹ ' -methoxycarbonylmethoxy-guanidine, -N '' - ethoxycarbonyl-methoxy-guanidine _} -N '' - (1-methoxycarbonyl- ethoxy) -guanidine, -N "- (1-ethoxycarbonyl-ethoxy) -guanidine, -N" -dimethylaminocarbonyl-methoxy-guanidine, -N ¹ '- (2-phenyl-ethoxy) -guanidine, -N " -phenoxy-guanidine, -N ¹ '- (4-methyl-benzyloxy) -guanidine, -N''- (4-fluoro-benzyloxy) -guanidine , -N''- (4-chloro-benzyloxy) - guanidine _} -N '' - <4-nitro-benzyloxy) -guanidine _} -N '' - (2J6-dichloro-benzyloxy) -guanidine, -N '' - (4-methoxycarbonyl-benzyl-oxy) -guanidine, and N '' - (4-ethoxy-carbonyl-benzyl-oxy) -guanidine.

The starting materials of the formula (II) are the subject of earlier industrial property rights (see EP-OS 12i 082); However, new compounds of the formula (II), in which

¹⁰ A

(a) R ^{4 is} chlorine,

R is hydrogen and 15

R is C 1 -C 4 -alkoxy [which is optionally substituted by fluorine and / or chlorine], C 1 -C 4 -alkylamino or di- (C 1 -C 4 -alkyl) -amino

stands; or in which 20

(b) R is C 1 -C 4 -alkyl [which is optionally substituted by fluorine and / or chlorine],

R ^{5 is} hydrogen and

R is fluorine-and / or chlorine-substituted Cj-C4-alkoxy, C 1 -C ₄ -alkylamino or di->-amino; or in which

(c) R ⁴ and R ^{5 are} hydrogen and 35

R ⁶ for C _? -Co-alkyl;

wherein each R has the meaning given above.

This gives the guanidinopyrimidine derivatives of the formula (II) - and thus also the previously defined under (a), (b) and (c) new compounds of the formulas (I Ia) j (lib) and (lic) - if cyanaminopyrimidine - Derivatives of the formula (VIII)

15

(^ M ⁵ (VIII)

30

2Q in which

R ₁ R and R have the meanings given above

to have,

with amino compounds of the formula (IX)

HoN-R ^J (IX)

in which

35

R has the meaning given above,

or, with their hydrochlorides,

optionally in the presence of diluents, such as

z _t B, ethanol, isopropanol or butanol, at temperatures 10

between 20 ^° C. and 150 ^° C., preferably between 50 ° C.

and 120 ⁰ C, and if appropriate, the reaction products with acid acceptors such as z, B, ammonia, sodium hydroxide or soda.

The cyanaminopyrimidine derivatives of the formula (VIII) are the subject of earlier industrial property rights (cf., EP-OS 121 082); However, new compounds of the formula (VIII), in weleher

(a) R ^{4 is} chlorine,

25 с

& stands for hydrogen and

R is Cj-C ^ alkoxy [which optionally by

Fluorine and / or chlorine is substituted], for 30

C 1 -C ₄ alkylamino or di (C 1 -C 4 alkyl) amino; or in which

(b) B is C 1 -C 4 -j-alkyl [which may be replaced by

Fluorine and / or chlorine is substituted],

iiiS W VNs * 8 J / W

- 38 R ^ is hydrogen and

R is substituted by fluorine and / or chlorine

, for C ₁ -C 4 -alkylamino or di-

(C ₁ -C 4 alky 1) -snino; or in which

(c) R ⁴ and R ^{5 are} hydrogen and 15

R ^{6 is} C ₂ -C ₃ alkyl.

The compounds of formula (VIII) are obtained - and thus 20

also the novel compounds of the formulas (Villa), (VIIIb) and (VIIIc) previously defined under (a), (b) and (c) - essentially according to the following synthetic routes!

²⁵ '1

(A) By reacting alkali metal or alkaline earth metal salts of cyanamide - such as. As sodium cyanamide or calcium cyanamide - with chloropyrimidines of the formula (X)

30 "

N- < ^R

(Z ^X V ⁵ (X)

in which 35

R ⁴ , R ⁵ and R ^{6 have} the meanings given above

Have ¹

optionally in the presence of inert diluents, such as, for example, ethanol, acetone, acetonitrile or dimethylformamide, at temperatures between 0 ⁰ C and 100 "C, after concentration and dissolution of the residue in water, the cyanaminopyrimidine derivatives of the formula (VIII) Acid, z, B, with hydrochloric acid, precipitated and isolated by suction,

Alternatively, cyanaminopyrimidine derivatives of the formula (VIII) are obtained.

(a ² ) in the case where R ⁴ and / or R ^{6 are} hydroxy, by reacting cyanoguanidine ('dicyanodiamide') with suitable β-dicarbonyl compounds - or derivatives thereof - such as, for example, 1,1- Dimethoxy-3-oxo-butane, methyl acetoacetate or ethyl ester (Comp. J., Prakt. Chem, 77 (1908), 542 and J ₄ Chem, Soc, 1948, 586) or malonic acid dimethyl-

ester or diethyl ester (see, German Patent 158 591).

The esters of acetoacetic acid esters or malonic acid esters

2-cyanamino-4-hydroxy-6-methyl obtained, 35

-4, Fe-dihydroxy-pyrimidines can be prepared in known manner

by reaction with alkylating agents, such as z, B, dimethyl or Diethy1sulfat, 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, 10

such as, B, sodium or Kaiium hydroxide, sodium or Kai ium carbonate, be converted into corresponding 2-cyanamino-4-alkoxy-6-methyl or -4,6-dialkoxy-pyrimidines. To avoid by N-Al.ky 1 i tion is optionally with an acylating agent such. Acylated B, acetic anhydride or acetyl chloride and re-deacylated after alkylation with aqueous acids or bases,

In a further alternative method to obtain cyanamino-pyrimidine derivatives of the formula (VIII), if

(a) Aminopyrimidines of the formula (XI)

(XI)

in which

R, R and R are as defined above

to have,

with carbonyl isothiocyanates of the formula (XII)

, "Il R ^1Ö -CN = C = S (XII)

in which R ^{18 is} ethoxy or phenyl,

if appropriate in the presence of an inert diluent, such as, for example, acetone, acetonitrile or toluene, at temperatures between 0 "C and 100 ⁰ C, the thus formed carbonyl thioureas of the formula (XIII)

0 S _1B II Il R ^lö -C-NH-C-NH- ^{(/ N>} R ^a (XIII)

in which R ⁴ , R ⁵ , R ⁶ and R ¹⁸ are those indicated above

Have meanings

optionally after concentration by suction iso-3 5

liert and with aqueous alkali metal or alkaline earth metal hydroxide solutions, such. B. caustic soda,

optionally in the presence of an organic solvent, such as. B, tetrahydrofuran or dioxane, reacted at temperatures between 0 "C and 120 ° C and after acidification, ζ. B, with hydrochloric acid, crystalline thioureas of the formula

(XIV)

N_ (XIV)

N- / _R 6 15

in our ears

R, R and R are as defined above

to have,

isolated by suction and metal compounds which can bind hydrogen sulfide, such as, for example, with lead (II) acetate, copper (II) acetate, mercury (II) acetate or iron (II) acetate, in the presence of aqueous Alkali metal or Erdalkalimetal1-hydroxide solutions, such as, B, sodium hydroxide, reacted at temperatures between 20 ⁰ C and 100 ⁰ C, filtered after the end of the reaction and the filtrate with an acid such as, B, acetic acid, acidified.

The crystalline products of the formula (VIII) can be isolated by suction.

, -

The starting materials for the production processes for the cyanaminopyrimidine derivatives of the formula (VIII) described above under (a), (a ⁶ ) and (a) are known and / or can be prepared by processes known per se.

These include the chloropyrimidines of the formula (X) (cf., J, Chem, Soc. (C) 1966 , 2031; Chem, Pharm, Bull.

11 (1963), 1382-1388 and Arch. Pharm. 295 (1962), 649-20

- 657), the aminopyrimidines of the formula (XI) (cf., Chem. Pharm, Bull. H (1963), 1382-1388); J. Chem. Soc. 1946 . 81 and US Pat. No. 4,299,960) and the carbonyl isothiocyanates of the formula (XII) (see, J, Heterocycl,

Chem. 5 (1968), 837 and US Pat. No. 4,160,037). 25 ~

The amino compounds of the formula (IX) which are furthermore to be used as starting materials are likewise already

known and / or can according to known methods 30th

Chem. Pharm, Bull, 1_5_ (1967), 345; Bull, Soc., Chim, France 1958 , 664; Synthesis 1976 , 682; J, Chem, Soc., 1930 , 228 and HeIV, Chem, Acta 4J5 (1962), 1387).

The further as starting materials for the process variant

(a) sulfonic acid chlorides to be used are generally defined by the formula (III). In formula (III), R preferably has, in particular the same meaning,

as described above in the context of the substituent definition of the 10th

Formula (I) preferably or, as particularly preferred

is called.

As starting materials of the formula (III) may be mentioned recordable:

2-Chloro, 3-chloro, 4-chloro, 2, 5-dichloro, 2-fluoro, 4-fluoro, 2-bromo, 4-bromo, 2-nitro, 4- Nitro, 2-cyano, 2-methyl, 4-methyl, 2-chloromethyl, 2-trifluoromethyl, 2-methoxy, 2-difluoromethoxy, 2-trifluoromethoxy, 2-methylthio, 2- Methylthiomethyl, 2-methylsulfinylmethyl, 2-methylsulfonylmethyl, 2-dimethylaminosulfonyl, 2-diethylaminosulfonyl, 2-phenyl, 2-methoxycarbonyl, 2-ethoxycarbony1, 2-propoxycarbony1, 2-isopropoxycarbony1, 2 Butoxycarbony1, 2-dimethylaminocarbonyl, 2-diethylaminocarbony1, 2-phenoxy, 2-methyl-5-chloro, 2-chloro-5-trifluoromethyl, 2-methylsulfonyl, 2-ethylsulfonyl, 2-chloro 4-trifluoromethoxy, 3-chloro-4-trifluoromethoxy, 2-trifluoromethoxy-5-chloro , 3,5-dichloro, 2-difluoromethylthio and 2-trifluoromethylthiobenzenesulfonyl chloride, furthermore methane, chloromethane, trifluoromethane Ethane, 2-chloroethane, ethene, propane, butane, perfluorobutane and perfluoro-octane-sulfonic acid chloride; Methyl, ethyl, propyl, isopropyl, cyclohexyl, dimethyl and di-ethyl-sulfamidsäurechlorid and

(2-Chloro-phenyl) -, <2-cyano-phenyl) - and (2-methoxy-carbonyl-phenyl) -methanesulfonyl chloride.

The sulfonic acid chlorides of the formula (III) are known and / or can be prepared by processes known per se (compare J. Qrg, Chem. 3_3 (1968), 2104; J. Org. Chem., 25 (1960), 1824; DE-AS 2 308 262, EP-OS 23 140, 23 141, 23 422, 35 8.93, 48 143/51 466j 64 322, 70 041, 44 808, 44 809, U.S. Patent 2,929,820, 4,282,242 , 4,348,220 and 4,372,778 and Angew, Chem. 93. (1981), 151).

These compounds are obtained essentially according to 20

following two synthetic routes:

(1) by reacting the corresponding sulfonic acids R SO3H or their alkali metal or alkaline earth metal salts with halogenating agents, such as. B, phosphorus (V) chloride (Phosphorpentachlor id), phosphoryl chloride (phosphorus oxychloride), thionyl chloride, phosgene or benzotrichloride, optionally in the presence of catalysts such as z, B, pyridine or dimethylformamide, and optionally using inert diluents, such as. As methylene chloride, chloroform, acetonitrile, chlorobenzene and / or sulfolane at temperatures between -20 ^e C.

__ and +150 "C, preferably between 0" C and 35

+100 "C, after dilution with water, the sulfonyl chlorides - insofar as they are crystalline - can be isolated by suction or by extraction with a water-immiscible solvent, such as, for example, B, methylene chloride, diethyl-10

ether or hexane, washing and drying of the extracts, concentration and recrystallization or distillation; or

(2) in a manner known per se (see J, Org, Chem.

25. (1960), 1824; DE-OS 2 308 262 and EP-OS 59 241)

by reacting entspechender amino compounds

R -NH2 with sodium nitrite and hydrochloric acid, optionally in the presence of acetic acid, at temperatures 20

between -10 "C and +20 ⁰ C, preferably between -5" C and +10 "C, and then (in situ) with sulfur dioxide or a salt of sulfurous acid such. B, sodium sulfite or sodium in Gengenwart a copper compound such as, for example, copper chloride or copper sulfate, as catalyst at temperatures between 0 "C and 80 ° C, preferably between 10" C and 60 ° C,

30.

The work-up can be carried out in a customary manner. On dilution with water, the sulfonyl chlorides are generally crystalline and can be isolated by suction. But you can

also from the aqueous dispersion with a 35th

Water virtually immiscible solvent,

like ζ. As methylene chloride or diethyl ether, extracted, dried and purified by vacuum distillation.

The as starting materials for the process variant (b)

to be used SuIfony1guanidinopyrlmidin Derιvate are generally defined by the formula (ID). In Formula (ID), R ^1, R ^4, R ^, R ⁶ and R ¹⁴ is preferably or in particular have the same meanings as above in

Frame of Substituent Definition of Formula (I) 15

preferably or specified as being particularly preferred

.are.

As examples of the compounds of formula (ID) are 20

called:

N '- (4-chloro-6-methoxy-pyrimidin-2-yl) -N' '- methoxy-

-N ", N ¹ " -bis (2-chloro-benzenesulfonyl) -, 25 -N ¹ ', N ¹ "-bis (2-bromobenzenesulfonyl) -,

-N ¹ ", N"'' - bis- <2-fluoro-benzenesulfonyl) -,

-N '', N '' '- bi s- (2-methyl-benzenesulfonyl) -,

-N '', N '' '- bis- (2-trifluoromethyl-1-benzenesulfony1) -,

-N ", N ¹ " -bi s- <2-methoxy-benzenesulfonyl) -,

-N ¹ ', N ¹ "-bis - (2-phenylbenzenesulfony1) - and

-N '', N '' '-bi s- (2-methoxycarbonyl-benzenesulfonyl) -

-guanid in,

N '- (4-methyl-pyrimidin-2-yl) -N "-methoxy-N'", N '''-bis (2-chloro-benzene-sulfonyl) -, -N'',N''' - bis (2-methoxycarbony1-benzenesulfonyl) -, -N ¹ ', N ¹ ''- bis- (2-difluoromethoxy-benzenesulfonyl) - »

-N '', N "'bis- (2-diethylaminosulfonyl-benzo-1sulfonyl) -,

-N '', N ¹ '' - bis- (2-bromobenzenesulfonyl) -,

N '', N '' '- bis- (2-trifluormethy1thio-benzenesulfonyl) -,

N '', N ¹ '' -bis- (2-phenoxy-benzolsulfony1) - and -N '' ^1, N ¹ '' -bis- (2-methylsulfonyl-benzolsulf onyl) - guanidine,

N '- (4,6-dimethoxy-pyrimidin-2-yl) -N-methoxy ^lt * N'', N ^1' '-bis- (2-chloro-benzenesulfonyl -) - _1-N "', N '''- bis - <2-methoxycarbonyl-benzenesulfony1) -, - N'', N ¹ ''- bis- (2-difluoromethoxy-benzenesulfony1) - , -N'',N''' - bis- (2 -trifluoromethoxy-benzenesulfonyl) -

N '', N '' '- bis- (2-dimethylaminosulfonyl-benzenesulfonyl) -,

-N ¹¹ JN '' - bis (2-methylthio-benzenesulfonyl) -, -N ¹ ', N ¹ ''- bis- (2-ethoxycarbonyl-benzenesulfony1) - _t

N '', N '' '- bis- (2-phenyl-benzenesulfonyl) -,

-N ¹ ', N''' - bis- (2-cyclopropyloxycarbonyl-benzenesulfony1) - , -N '', N '''- bis- (2-trifluoromethylsulfonyl-benzenesulfonyl) -, -N ¹ ', N '''bis- (2-nitro-benzenesulfonyl) - and

-N '' · ^Ν Λ '' bis <2-cyano-benzenesulfonyl-30

guanidine,

N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -N "-methoxy-N ¹ ', N ¹ " -bis (2-chloro-benzenesulfonyl ) -, -N ¹ ' _Λ Ν '''-bi s- (2-methoxycarbonyl-benzenesulfonyl) -,

-N ¹ ', N''' - bis- <2-methylsulfonyl-benzenesulfonyl) -, - N '', N ¹ '' - bis- (2-methylthio-benzenesulfonyl) -, - N '', N ¹ ''- bis (2-trifluoromethoxy-benzenesulfonyl) -, -N ¹ ', N "'- bis- (2-ethoxycarbonyl-benzenesulfonyl) -, -N ¹ ', N '''- bis- (2-trifluoromethyl benzenesulfonyl) -

10 -N '', N '' '- bis- (2-i-sopyoxy-1-thi-benzol sulfonyl) -,

N '', N ¹ '' -bis- (2-N-methoxy-N-methylaminosulfonyl-benzene-

sulfonyl) -

-N ¹ ', N''' - bis- (2-trifluoromethylthio-benzol sulfonyl) -, - N ¹ ', N''' - bis (2,5-dichloro-benzene sulfonyl) -,

15 -N '', N '' '- bis- <2-phenoxy-benzenesulfonyl) - and -N' ', N' '' -Bi s -. (2-phenyl-benzo-sulfonyl) -guanidine,

N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) -N "-methoxy-N"', N '' '- bis- (2-ethoxycarbonyl-benzenesulfonyl) -,

-N ", N '' - bis- (2-bromo-benzenesulfonyl) -,

-N '', N '''- bi s - <2-methylsulfonylmethy1-benzenesulfonyl) -, - N'',N''' bis- <2-trhefluoromethylthio-benzenesulfonyl) -, - N '', N ¹ '' - bis (2-methoxy-benzenesulfonyl) -, -N '', N ¹ '' - bi s - <2-methoxycarbonyl-benzenesulfonyl) - and

-N ¹ ', N''' - bis (2-chlorobenzenesulfonyl) - guanidine,

The compounds of the formula (ID) can be prepared by the process described above under (a).

The amino compounds to be used further as starting materials in process variant (b) are generally defined by the formula (IV). In formula (IV), R and R preferably have, in particular the same meanings as described above in the context of the substituent definition of the formula (I) preferably or, more preferably, have been specified.

As starting materials of the formula (IV), for example, 9 can be ^mentioned:

N, N-dimethylhydrazine, phenylhydrazine, O-methyl-hydroxyamine, O-ethyl-hydroxyamine, O, N-dimethylhydroxylamine, O-propyl, O-isopropyl, O-butyl, O-sec-butyl, O- pen-

γ-tyl, 0-isopentyl, 0-sec-pentyl, O-hexyl, 0-iso

hexyl, O-heptyl, O-isoheptyl, O-octyl, .0-isooctyl, O-allyl, O-crotyl, O- (2-chloroethyl) -, O- (2-fluoro (-ethyl) -, 0- (2-chloro-propyl) - , 0- (3-chloro-propyl) -, 0- (4-chloro-butyl) -, O-methoxycarbonylmethyl-, O-ethoxy-

_ Carbonylmethyl- _0, 0- (1-methoxycarbonyl) ethyl, O- (1-Eth oxycarbonyl) -ethyl -, O-Aminocarbonylmethyl-, O- (2-phenyl-ethyl ') -, O-phenyl , 0- (4-methyl-benzyl) -, 0- (4-fluoro-benzyl) -, 0- (4-chloro-benzyl) -, 0- (4-nitro-benzyl) -, 0- (2 , 6-dichloro-benzyl) - , 0- (4-methoxycarbonyl-benzyl) - and 0- (4-ethoxycarbonyl-benzyl) -hydroxylamine.

Amino compounds of the formula (IV) are known and can be prepared by processes known per se (compare Chem. Pharm. Bull. JJ>., (1967), 345; Bull. Soc. Chim, France 1958 , 664; Synthesis 1976 , 682; J.

Chem, Soc. 1930 , 228 and HeIv, Chim. Acta 45 (1962), 10

1387),

The in process variant (c). In the formula (IE), R ¹ JR ³ , R ⁴ , R ⁵ and R ⁶ preferably have, respectively, in particular the same meanings as described above in the context of the formula (IE) as starting materials to be used SuIfony1guanidinopyrimidin derivatives Substituent definition of the formula (I) preferably or, as particularly preferably indicated ε ind,

As examples of the compounds of the formula (IE) are

called ί 25

N ¹ - (4,6-dimethoxypyrimidin-2-yl) -N''-methoxy-N '''- (2-

chloro-benzenesulfonyl-guanidine,

-N ¹ '' - (3-chloro-benzenesulfonyl ) -, - N ¹ '' - (4-chloro-benzenesulfonyl) -, -N '''- (2-fluoro-benzenesulfonyl) -, -N ¹ '' - (4-fluoro-benzenesulfonyl) -, - N '''- (2-bromo-benzenesulfonyl) - _}

-N '' '- (4-bromo-benzenesulfonyl) -,

-N '''- (2-cyano-benzenesulfonyl) -, -N ¹ ''- (2-nitro-benzenesulfonyl) -,

-N '''-<4-nitro-benzenesulfony1) -, - N''' - (2-methyl-benzenesulfony1) -, -N '''- (4-methyl-benzo-1sulfonyl) -, -N'''- (2-chloromethyl-benzenesulfony1), - N ¹ ''- (2-trifluoromethyl-benzenesulfonyl) -, -N''' - (2-methoxy-benzo-1-sulfo-1-yl) -, -N '''- (4-methoxybenzenesulfony1) -, - N''' - (2-methylthio-benzo1sulfony1) -,. -N '''- (2-difluoromethoxy-benzo-1-sulfonyl) -, - N''' - (2-trifluoromethoxy-benzenesulfonyl) -, -N '''- (2-methylthiomethyl-benzenesulfonyl) -, -N'''- (2-dimethyl-amino-sulfonyl-benzenesulfonyl) - _} - N''' - <2-phenyl-benzenesulfony1) -, - N '''- (2-methoxysulfony1-benzenesulfonyl) -, -N''' - (2-methoxycarbonyl-benzenesulfonyl) -, - N '''-<2-ethoxycarbony1-benzenesulfonyl) -, - N''' - (2-propoxycarbonyl-benzo-1sulfonyl) -, -N '''- (2- methylaminocarbonyl-benzenesulfonyl), - N '''- (2-ethylaminocarbonyl-benzo-1-sulfonyl), - N''' - (2-propylaminocarbony1-benzenesulfony1), - N '''- (2-methoxyaminocarbony1-benzenesulfonyl ) -, - N ¹ '' - <2-ethoxyaminocarbony1-benzenesulfonyl) -, -N '''- (2-propoxyaminocarbony1-benzo 1sulfony1) -, -N ¹ ''- (2-dimethylaminocarbonyl-benzenesulfony1) - and -N '·' - <2 diethylaminocarbony1-benzolsulfony1) guanidine;

further

N '- (4,6-dimethoxy-pyrimidin-2-y1) -N' '- ethoxy-N' ''

benzene-sulfony1-,

-N '''- (2-chloro-benzenesulfonyl) -, -N''' - (3-chloro-benzenesulfony1) -, -N '''- (4-chloro-benzenesulfonyl) -, -N ¹ '' - (2,4-di-chor-1-benzene-sulfonyl) -,

-N ¹ "- (2,5-dichloro-benzenesulfonyl) - , 10

-N '''-(2-difluoromethoxy-benzenesulf-N''' - <2-trifluoromethoxy-benzenesulfonyl) -, -N '''- (2-methylthio-benzenesulfonyl) -, -N''' - (2 -methyl-benzo-1-sulfonyl) -, -N '''-<2-methylthiomethyl-benzenesulfonyl) - _} -N ¹ ''-<2-dimethylaminosulfonyl-benzenesulfonyl) - _} - N''' - (2-methoxysulfonyl-benzenesulfonyl ), -N ¹ "- (2-methoxycarbony1-benzenesulfonyl) -, -N ¹ " - (2-ethoxycarbonyl-benzenesulfonyl) -, -N '''- (2-methylaminocarbonyl-1-benzenesulfonyl) - , --N '''- (2-ethylaminocarbony1-benzenesulfonyl) -,

-N ¹ '' - (2-methoxyaminocarbonyl-benzenesulfonyl) - and -N ¹ '' - (2-dimethylaminocarbony1-benzenesulfonyl) -guanidine j

further

N '- <4,6-dimethoxy-pyr-imidin-2-yl) -N''-propoxy, -N''-isopropoxy,

-N '' - butoxy

-N''-isobutoxy ,

-N '' - sec-butoxy, -

-N ¹ '-pentyloxy-,

-N''-hexyloxy ,

-N '' -octy1 oxy-,

-N''-Iyloxy,

-N "-crotyl oxy, -N" - <3-chloropropoxy) -, -N "-methyloxycarbony1-methoxy-, -N ¹ '-ethoxycarbony1-methoxy-, -N" - - (1 -methoxy-carbonyl-ethoxy) -, -N "- <1-ethoxycarbony1-ethoxy) -, -N" - (2-phenylethoxy) -, -N "-phenoxy-, -N" - benzyloxy,

-N '' - (4-methyl-benzyloxy) -, 15

-N '' - (4-fluoro-benzyloxy) -, -N '' - (4-chloro-benzyloxy) -, -N '' - (4-nitro-benzyloxy) -, -N '' - (2 , 6-dichloro-benzyloxy) -, -N '' - (4-methoxycarbonyl-benzyloxy) - and U

-N '' - (4-ethoxycarbonyl-benzyl oxy) -, -N '''- (2-chloro-benzenesulfonyl) -guanidine and -N ¹ ''- (2-methoxycarbonyl-benzenesulfonyl) -guanidine;

further

N '- (4-methoxy-6-methylpyrimidin-2-yl) -N''- methoxy- N ¹ "- (2-chloro-benzenesulfonyl) -, -N''' - (2-methyl -benzenesulfonyl), - N '''- (2-methylthio-benzenesulfonyl) -, - N''' - (2-difluoromethoxy-benzenesulfonyl) - and -N '''- (2-trifluoromethoxy-benzenesulfonyl) -guanidine ;

further

N '- (4-ethoxy-6-methylpyr imidin-2-yl) - and

N '- (4-methyl-pyrimidin-2-yl) -N' '- methoxy-N' '' - (2-chloroethyl

benzene sulfonyl) guanidine;

further

N "- <4-chloro-6-methoxy-pyrimidin-2-yl) -N'-methoxy

-N '''- (2-chloro-benzenesulfony1) -, -N''' - (2-methoxycarbonyl-benzenesulfonyl) _-t -N '''- (2-difluoromethylthio-benzenesulfonyl) - and

-N ¹ "- (2-dimethylaminosulfonyl-benzenesulfonyl) -guanidine;

further

N '- (4-chloro-6-ethoxy-pyr-imidin-2-yl) -N ^f ' -ethoxy-N ¹ '' - (2-bromo-benzenesulfonyl) -, -N '''- (2- phenyl-benzenesulfonyl) -,

-N '''- (2-dimethylaminocarbonyl-benzenesulfonyl), - N''' - (2-methylthiomethyl-benzenesulfonyl ), - N '''- (2-phenoxy-benzenesulfonyl) - and ₃ _ -N'"'- (isopropoxybenzenesulfonyl) guanidine;

further

N '- (4-chloro-6-dimethyl-pyrimidin-2-yl) -N'-methoxy

-N ¹ '' - (2-fluoro-benzenesulfonyl) -, - N '''- (2-difluoromethylthio-benzenesulfonyl) -, -N''' - (2-methyl-benzenesulfonyl) -, -N ''' - (2-ethoxycarbony1-benzenesulfonyl) - and -N '''- (2-cyano-benzenesulfonyl) -guanidine;

furthermore 15

N '-' (4-methyl-6-methylthio-pyrimidin-2-yl) -N '' -alkenyloxy

-N '' '- (2-chloro-benzenesulfonyl) -, - N' '' - (2-isopropoxy-benzenesulfonyl) -, -N '' '- (2-phenoxy-benzenesulfonyl) -, 0

-N '' '- (2-methylsulfonyl-benzenesulfonyl) - and

-N '' '- (2-cyclopropyloxycarbonyl-benzenesulfonyl) guanidine;

N '- (4-dimethylamino-6-methylpyrimidin-2-yl) -N''-isopropoxy-N''' - <2-chlorobenzenesulfonyl) -, -N '''- (2-chlorodifluoromethyl -benzenesulfonyl ), -N ¹ "- (2-N-methoxy-N-methyl-aminosulfonylbenzene sulfony1) -,

-N '''- (2-phenyl-benzenesulfonyl) - and -N ¹ ''- (2-isopropylthio-benzene sulfonyl) -guanidine,'

further

N '- (4-Di-fluoromethoxy-6-methylpyrimidin-2-yl) -N' '-methoxycarbonyl-N' '' - (2-methylbenzenesulfonyl), - N '' '- (2-diethylaminosulfonyl -benzenesulfonyl> -, -N '' '- (2-difluoromethoxy-benzenesulfonyl) -,

-N '' '- (2-nitro-benzenesulfonyl) -,

-N '' '- (2-methylthio-benzenesulfonyl) - and

-N ¹ "- (2-ethoxycarbonyl-benzenesulfony1) -guanidine.

The compounds of formula (IE) can be prepared according to the above 15

prepared under (a) and (b)

become,

The in the process variant (c) on as output 20

In the formula (V), in the formula (V), R preferably or in particular has the same meaning as described above in the context of the substituent end derivatives.

nition of the formula (I) preferably or, in particular 25

is preferred,

As examples of the starting materials of the formula (V)

For example, the sulfonyl chlorides listed above as 30

Examples of compounds of the formula (II) mentioned

were,

The sulfonyl chlorides of the formula (V) are known 35

and / or can according to known methods

be prepared (see, literature and synthetic routes

-id

for the compounds of formula (III) - above).

The as starting materials for the process variant (d)

The sulfonylguanidinopyrimidine derivatives to be used are 10

generally defined by the formula (VI). In formula

(VI) R ^3, R ^4, R ^5, R ⁶ and R ¹¹ have preferably or in particular have the same meanings as (I) above in the context of the substituent of the formula or preferably, as particularly preferred, s ind,

Examples of the compounds of the formula (VI) are:

N '-, (4-methyl-pyridin-2-yl) -, N' - (4-methoxy-6-methyl-pyr-imidin-2-yl) -, N '- (4-ethoxy-6-methyl -pyrimidin-2-yl), N '- (4-chloro-6-methoxy-pyrimidin-2-yl) -, N' - (4-chloro-6-ethoxy-pyrimidin-2-yl) - , N'-t4-chloro-6-dimethyl-amino-pyrimidin-2-yl) -, N '- (4-methyl-6-methylthio-pyrimidin-2-yl) -, N' - (4-dimethyl amino-6-methyl-pyrimidin-2-yl), N '- (4,6-dimethoxy-pyr-imidin-2-yl) - and N' - (4-di-fluoromethoxy-6-methyl-pyrimidine-2-yl) yl) --N '' - methoxy,

-N '' - ethoxy,

-N ¹ '-isopropoxy-,

-N '' - propoxy,

-N''-butoxy-,

-N '' - isobutoxy,

-N '' -sec, -butoxy-,

-N '' - pentyloxy,

-N '' -octy1 oxy-,

-N''-Iyloxy,

-N '' - (3-chloro-propoxy) -,

-N '' - methoxycarbonylmethoxy,

-N ¹ '-ethoxycarbonylmethoxy-,

-N '' - (2-phenyl-ethoxy) -,

-N''benzyl oxy-,

-N '' - (4-methyl-benzyloxy) -,

-N '' - (4-fluoro-benzyloxy) -, __-N '' - (4-chloro-benzyloxy) -,

-N '' - (4-nitrobenzyl) oxy) -

-N '' - <4-methoxycarbony1-benzyloxy) - »-N''-benzyolsulfony1-,

-N '' - (2-chloro-benzenesulfonyl) -, _ -N '' - (3-chloro-benzenesulfonyl) -, -N ¹ '- (4-chloro-benzenesulfony1) -, -N ¹ ' - (2 fluoro-benzo1sulfonyl), -N ¹ '- (4-fluoro-benzo1sulfony1) -,

-N '' - (2-bromo-benzenesulfony1) -, __ -N ¹ '- <2-cyano-benzenesulfonyl) -, -N''- (2-nitro-benzenesulfonyl) -, -N''- (4 -nitro-benzenesulfony1) -, - N ¹ '- (2-methyl-benzenesulfonyl> -,

-N '' - (4-methyl-benzenesulfonyl) -, _ _ς -N ¹ '- (2-trifluoromethyl-benzenesulfonyl) -, -N''- (2-methoxybenzoylsulfonyl) -,

-N '' - (4-methoxy-benzenesulfony1) -, -N '' - (2-methylthio-benzenesulfony1) -, -N '' - (2-difluoromethoxybenzenesulfonyl) -, -N '' - (2- trif1uormethoxy-benzo 1su1fony1) -, -N '' - (2-methyl-1 ⁱ th i ome thy 1-benz ο 1 sul f ony 1) - _s N '' - (2-dimethyl aminosulfony1-benzenesulfonyl) -, - N '' - (2-phenyl-benzenesulfony1) -, -N '' - (2-methoxysulfony1-benzenesulfonyl) -, -N '' - (2-methoxycarbanyl-benzenesulfonyl) _-t -N '' - (2-ethoxycarbonyl -benzenesulfonyl), -N "- (2-propoxycarbonyl-benzenesulfonyl) -,

-N '' - (2-methyl-methoxy-amino-carbonyl-benzenesulfonyl) -,

-N '' - (2-dimethylamino-carbonyl-benzenesulfony1) - and

-N '' - (2-diethylamino-carbonyl-benzenesulfonyl) -guanidine.

The sulfonylguanidinopyrimidine derivatives of the formula (VI) are novel and can be prepared analogously to process (a) by reacting guanidinopyrimidine derivatives of the formula (II) with approximately equimolar amounts of sulfonyl chlorides of the formula (V).

The sulphonic acid chlorides which are to be used further as starting materials in process variant (d) are characterized by

the formula (III) is generally defined. In formula (III)

R preferably or, in particular, has the same meaning as mentioned above in the context of the substituent definition of the formula (I) preferably, or is mentioned as being particularly preferred, 35

Examples of the sulfonyl chlorides of the formula (III) and their preparation processes for this have already been mentioned above in connection with the description of the starting materials for process (a).

The sulfonylisothioureidopyrimidine derivatives to be used as starting materials in process variant (e) are generally defined by the formula (VII). In

Formula (VII) preferably have R ¹ , R ⁴ , R ⁵ and R ⁶ or 15

in particular the same meanings as mentioned above in the context of the substituent definition of the formula (I) preferably or as being particularly preferred and R is preferably as well as in particular methyl,

As examples of the compounds of formula (VII) en I called

N '- (4-chloro-6-methylthio-pyrimidin-2-yl) - _} N ¹ - <4-methyl-pyrimidin-2-yl) -, N' - (4-methoxy-6-methyl-pyr imidin-2-yl), N '- (4-ethoxy-6-methylpyr imidin-2-yl), N ¹ - (4-chloro-6-methoxy-pyr-imidin-2-yl) -, N '- (4-chloro-6-ethoxy-pyr-imidin-2-yl) -, N' - (4-chloro-6-dimethyl-amino-pyrimidin-2-yl) -, N '- (4- Methyl 6-methylthio-pyrimidin-2-yl), N '- (4-dimethylamino-6-methyl-pyrimidin-2-yl) -, N' - (4,6-dimethoxy-pyr-imidino-2 -yl) - and

N '- (4-Di-fluoromethoxy-6-methyl-pyrimidin-2-yl), -N''- (2-fluoro-benzenesulfony1) -, -N''- (2-chloro-benzo-1-sulfony1) - ι -N '' - (2-bromo-benzenesulfony1) - ,

-N '' - (2-methyl-benzenesulfonyl) -, 10

-N '' - <2-methoxycarbonyl-benzene-sulfonyl) -, -N '' - (2-ethoxycarbonyl-benzenesulfonyl) -, -N '' - (2-propoxycarbonyl-benzenesulfonyl) - , -N '' - ( 2-i-sopropoxycarbonyl-benzenesulfonyl), -N ¹ '- (2-phenyl-benzenesulfonyl) -,

-N '' - (2-trifluoromethyl-1-sulfonyl) -, -N '' - (2-difluoromethoxy-benzenesulfonyl) - and -N '' - (2-trifluoromethoxy-benzenesulfonyl) -S-methyl-isothioureaf .

The sulfonylisothioureidopyrimidine derivatives of the formula (VII) are known and / or can be prepared by processes known per se (cf., EP-OS 5,986).

The compounds of the formula (VII) are obtained if N-sulfonyl-imino-dithiocarbonic acid ester of the formula (XV)

SR ¹⁷

F 1 -SO ₂ -N = C (XV)

^X SR ¹⁷

in which

R * and R have the meanings given above,

with aminopyrimidines of the formula (XI) ^{10 4}

N-r ^K

N- ( _c

R ⁵ (χι)

in which 15

R, R and R have the meanings given above,

optionally in the presence of bases, such as z, B, sodium hydride or Kai ium tert-butoxide, and optionally in the presence of diluents, such as. As tetrahydrofuran, dioxane or dimethylformamide, at temperatures

between 0 "C and 100 ⁰ C, after the end of reaction with 25

Diluted with water, with a strong acid, such as, for example,

Hydrochloric acid, acidified and isolated the crystalline products of the formula (.VII) by suction.

The N-sulfonyl -iminodithiocarbonic acid esters required herein as starting materials are generally defined by the formula (XV). In formula (XV), R * and R 1 preferably or in particular have the same meanings,

as described above in the context of the definition of substituents for 35

Formula (I) or formula (VII) preferably or, as an

Specifically marked are indicated.

As examples of the compounds of formula (XV) may be

called:

N- (2-fluoro-benzenesulfony1 -. 10

N- (2-chlorobenzenesulfonyl, N- (2-bromo-benzenesulfony1) - ₎ N- (2-methyl-1-benzoylsulfonyl) - , N- (2-methoxycarbonyl-benzenesulfony1) - , N- (2- Ethoxycarbonyl-benzenesulfonyl) -, N- (2-propoxycarbonyl-benzenesulfonyl) - , N- (2-isopropoxycarbonyl-benzenesulfonyl) -, N- (2-phenyl-benzenesulfonyl) - , N- (2-trifluoromethyl-benzenesulfonyl) , N- (2-difluoromethoxy-benzo-1-sulfony1) -, 0

N- (2-trifluoromethoxy-benzenesulfonyl) -, N- (2-trifluoromethylthio-benzenesulfonyl) -, N- (2-di-fluoromethylthio-benzenesulfonyl) -, N - (2-phenoxy-benzenesulfonyl) -, N- (2 -Cyclopropyloxycarbonyl-benzolsulfonyI) - N- (2-methylthio-benzenesulfonyl) - N- (2-1sopropylthio-benzolsulfony1) - N- (2-Tri fluoromethylsulfonyl-benzenesulfonyl) - N- (2-Dimethy aminosulphonyl! benzenesulfonyl) -

N- (2-N-methoxy-N-methylaminosulfony-benzenesulfonyl) -,

N- (2-cyano-benzenesulfonyl), N- (2-nitro-benzenesulfonyl), N- (2-dimethylaminocarbonyl-benzenesulfonyl) - and N- (2-methylsulfony1methyl-benzenesulfonyl) -S, S-dimethyl- iminodi thiocarbonic acid ester «

The N-sulfonyl-imino-dithiocarbonic acid esters of the formula (XV) are known and / or can be prepared by processes known per se (cf. Chem, Ber, 9_9 (1966), 2855 and EP-OS 5 986),

The compounds of the formula (XV) are obtained when sulfonic acid amides of the formula (XVI)

¹⁵ 1

^ (XVI)

in which 20

R has the meanings given above,

with carbon disulfide in the presence of a strong base, such as z, B, sodium hydroxide, and optionally in the presence of diluents, such as. B, water and dimethylformamide, at temperatures between 0 ^d C and 100 "C and then (in situ) with an alkylation

of the formula (XVII) 30

XR ¹⁷ (XVII)

in which

R has the meaning given above and

X is chlorine, bromine or iodine, 10

at temperatures between 0 "C and 100" C.

The crystalline after dilution with water accumulating 15

Products of formula (XV) can be isolated by suction,

The sulfonic acid amides required as starting materials are generally defined by the formula (XVI). In formula (XVI), R * preferably or, in particular, has the same meaning as given above in the context of the substituent definition of the formula (I) preferably or more particularly as preferred.

As examples of the compounds of formula (XVI) may be mentioned!

2-trifluoromethylthio, 2-difluoromethylthio, 2-phenoxy, 2-cyclopropyloxycarbonyl, 2-methylthio, 2-isopropylthio, 2-trifluoromethylsulfony1, 2-dimethylaminocarbonyl, 2-dimethylaminosulfony1, 2-cyano-, 2-fluoro, 2-chloro, 2-bromo, 2-methyl, 2-methoxycarbonyl,

2-ethoxycarbonyl, 2-propoxyxycarbonyl, 2-isopropoxycarbonyl, 2-phenyl, 2-trifluoromethyl, 2-difluoromethoxy, 2-trifluoromethoxy, 2-N-methoxy-N-methylaminosulfonyl, 2 Nitro and 2-methylsulfonylmethylbenzene sulfonamides

The sulfonamides of the formula (XVI) are known and / or can be prepared by processes known per se (cf., for example, EP-OS 23 422, 30 140, 35 893, 44 807, 44 808, 44 809, 51 466, 64 804, 70,041 and 70,802, U.S. Patent 4,372,778 and Zh. Org, Khim, [J, Org. Chem, USSR] 8 (1972), 1023-1026, 1032-1034].

These compounds are obtained in a manner known per se by reacting sulfonyl chlorides of the formula (III) - above - with ammonia, if appropriate in the presence of diluents, such as. B, diethyl ether, tetrahydrofuran or else water, at temperatures between 0 ^° C. and 100 ° C. The products of the formula (XVI) which are obtained in crystalline form can be isolated by suction,

Examples of suitable starting materials of the formula (III) and preparation methods therefor are listed above in the description of the starting materials for process (a),

As examples of the starting materials of the formula (XVII)

be called en:

Methylene chloride, MethyIbromid, methyl, ethyl or chi id, ethyl bromide and ethyl iodide and benzyl or chi id and benzyl bromide ♦

The compounds of the formula (XVII) are known,

Further to be used as starting materials aminopyrimidines are generally defined by the formula (XI).

In formula (XI) R, R 'and R preferably have 20

in particular the same meanings as given above in the context of the substituent definition of the formula (I) preferably or particularly preferred

Examples of the compounds of the formula (XI) include:

4-chloro-6-methoxy, 4-chloro-6-ethoxy, 4-chloro-6-dimethylamino, 4-methyl-6-methylthio, 4-dimethylamino-6-methyl, 4-difluoromethoxy 6-methyl, 4,6-dimethoxy, 4-methoxy-6-methyl, 4-ethoxy-6-methyl and 4-methyl-2-amino-pyrimidine,

The aminopyrimidines of formula (XI) are known and / or can be prepared (see, J, Chem, Soc by processes known per se, 1946 _t 81; Chem, Pharm, Bull, υ (1963), 1382 - 1388. U.S. -PS 4 299 960; EP-OS

19,811; AU-OS 8 316 181 and EP-OS 70 804), 10

The amino compounds to be used further as starting materials in process variant (e) are generally defined by the formula (IV). In formula (IV) stands'.

R is preferably hydrogen or methyl, in particular hydrogen, and R preferably has, in particular the same meaning as defined above in the context of the substituent definition for formula (I) preferably

or, is given as being particularly preferred. 2 U

Examples of suitable starting materials of the formula (IV) and references in this regard are listed above in the description of the starting materials for process (b).

The compounds to be used as starting materials in process variant (f) are represented by the formula (I)

- with the proviso that M is hydrogen - general 30

In formula (I) - as far as the compounds to be used as starting materials for process (f) - M is hydrogen and R *, R ^, R, R, R and R are preferably or, in particular

have the same meanings as they did above in frame 35

5 -

the substituent definition for formula (I) preferably

or as being particularly preferred.

The compounds of the formula (I) to be used as starting materials for process (f) can be prepared by the processes described under (a), (b), (c), (d) and (e),

Examples of the metal hydroxides, hydrides, alkanolates or organometallic compounds to be used in process (f) are:

20 ·

Lithium, sodium, potassium, magnesium and calcium

hydroxide, lithium, sodium and calcium hydride, sodium methoxide and ethanolate, potassium methoxide, ethanolate and potassium ium tert-butoxide, and butyl lithium and isopropyl magnesium chloride id,

The compounds to be used as starting materials in process variant (g) are generally defined by the formula (I) - with the proviso that M is hydrogen. In formula (I), insofar as it relates to the compounds to be used as starting materials for process <g), M is hydrogen and R, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ preferably have, in particular the same meanings, as defined above or as being particularly preferred in the context of the substituent definition for formula (I),

The compounds of formula (I) to be used as starting materials for process (g) can be prepared by the processes described under (a), (b), (c), (d) and (e). In process (g) strong acids are used as starting materials. These are preferably hydrogen halide acids, such as hydrogen chloride, hydrogen bromide or hydrogen iodide, further sulfuric acid or optionally fluorine- or chlorine-substituted alkanesulfonic acids having up to 4 carbon atoms, such as, B, methanesulfonic acid, ethanesulfonic acid, chloromethanesulfonic acid, 2-chloroethanesulfonic acid and trifluoromethanesulfonic acid, trifluoroacetic acid Benzenesulfonic acid, p-toluene sulfonic acid, naphthalene-1-sulfonic acid, naphtha-1-n-2-sulfonic acid, naphthalene-1,4-, -1,5-, -1,6-, 2,6- and -2,7- disulfonic.

The process (a) according to the invention for the preparation of the novel compounds of the formula (I) is preferably carried out using diluents. As such are virtually all inert organic, but preferably aprotic polar solvents into consideration, These include optionally substituted hydrocarbons such as, B, Methyleachlor id, chloroform, 1,2-dichloroethane, toluene, xylene and chlorobenzene, nitriles, such as, B , Acetonitrile and propionitrile, ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, and dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, pyridine and 2-methyl-5-ethyl-pyridine.

As acid acceptors in process (a) virtually all commonly used acid binders can be used. These include in particular Alkalimetal1 and alkaline earth metal hydroxides, alkali metal and alkaline earth metal hydrides, organometallic compounds such as Buty11ithium, further aliphatic, aromatic or heterocyclic amines such as trimethylamine, triethylamine, N, N-Dimethylani1 in, N, N-dimethyl-benzylamine, diazabicyclooctane (DABCO) , Diazabieyelonones (DBN), diazabieye 1oundecene (DBU), pyridine, 2-methyl-5-ethyl-1-pyridine and 4-dimethylaminopyridine,

The reaction temperatures can be varied within a relatively wide range in process (a)

generally one works between -80 ° C and +100 "C, preferably zeischen -30" C and +50 ⁰ C, the inventive method (a) is generally carried out at atmospheric pressure.

To carry out process (a), in general between 1 and 5 mol, preferably between 2 and 3 mol, of sulfonyl chloride of the formula (III) are employed per mole of guanidinopyrimidine derivative of the formula (II).

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 workup and isolation of the new compounds is carried out by customary methods: If appropriate, after distilling off volatile components with water and a water-immiscible solvent, such as

_in z, B, methylene chloride, chloroform or toluene, shaken, the organic phase washed with water, dried, filtered and concentrated. The remaining products of the formula (I) are obtained by trituration with organic solvents. such as, B, Di

.,. ethyl ether, ethyl acetate, ethanol or isopropanol crystallized and optionally purified by recrystallization.

The process (b) according to the invention is preferably carried out using diluents. Suitable solvents are virtually all inert organic solvents. These include, in particular, alcohols, such as methanol, ethanol, n- and i-propanol,

₂ c ethers, such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, B, acetonitrile or propionitrile, and also dimethylformamide and water,

Suitable acid acceptors in process (b) can be acid binders which do not appreciably compete in their nucleophilic properties with the amino compounds of the formula (IV). As such, alkali metal and alkaline earth metal carbonates, such as, for example, B, potassium carbonate and calcium carbonate, are tertiary Amines, such as, B, triethylamine, Ν, Ν-Dimethylani1 in and

-7a

N, N-dimethylbenzylamine, as well as nitrogen heterocycles, such as ζ, Β »pyridine, diazabieyelooctane (DABCO) and diazabieye 1oundecene (DBU).

The reaction temperature can in process (b) within

In general, the reaction is carried out between ^0.degree. C. and 150.degree. C., preferably between 10.degree. C. and 100.degree. C. Process (b) is generally carried out under normal pressure

For carrying out the process (b) according to the invention, in general between 1 and 10 mol, preferably between 2 and 20, are employed per mole of compound of the formula (ID)

5 moles of the amino compound of the formula (IV) or its hydro-

chlorine id.

In general, the compound of the formula (ID) with the diluent at 20 ^° C. or with gentle cooling and the amino compound of the formula (IV) or, the hydrochloride thereof and, if appropriate, a suitable acid acceptor are added thereto. The reaction mixture is then generally stirred at room temperature or elevated temperature until the end of the reaction,

The work-up can be carried out by customary methods. As far as the products of formula (I) are crystalline from the reaction mixture, they can be isolated by suction. Otherwise it will - given

if after concentration - diluted with water and with a water-immiscible solvent, such as .z. B, methylene chloride, extracted. By washing the extraction solutions with water, drying, filtering, concentration of the filtrate and recrystallization of the residue, the products of formula (I) can be obtained in pure form,

The process (c) according to the invention is preferably carried out using diluents. As such, virtually all inert oranic, but preferably aprotic, polar solvents are suitable, as mentioned above in connection with the description of the process (a) according to the invention

were,

As acid acceptors in process (c) virtually all commonly used acid binders can be used. These include, in particular, the acid binders mentioned above in connection with the description of process (a) according to the invention,

The reaction temperatures may be varied within a relatively wide range in process (c). In general carried out between -80 ⁰ C and + 100 ⁰ C, preferably between -30 "C and +50" C, Process (c) is in general carried out at normal pressure.

For carrying out process (c) are employed per mole of sulfonyl guanidinopyr imidine-i The vat of formula (IE), in general, 1-2 MoI _1, preferably between 1.1 and 1.5 mol SuIfqnsäurechlor id of the formula (V).

The procedure and workup can be carried out in process (c) analogously to process (a),

The process (d) according to the invention is preferably carried out using diluents. As such, virtually all inert organic, but preferably aprotic, polar solvents come into consideration, as described above in connection with the description of the invention

tion of the process (a) were called,

As acid acceptors in process (d) can be practical

all commonly used acid binders are used. These include, in particular, the acid binders mentioned above in connection with the description of process (a) according to the invention,

The reaction temperatures can be varied within a wider range in process (d). In general carried out between -80 ⁰ C and +100 "C, preferably between -30" C and +50 ° C, Process (d) is in general carried out at normal pressure,

- 77 -

For carrying out process (d), in general between 1 and 2 mol, preferably between 1.1 and 1.5, mol of sulfonyl chloride id of the formula (III) are employed per mole of sulfonylguanidinopyrimidine derivative of the formula (VI),

The procedure and work-up can be carried out in process (d) analogously to process (a),

The process (e) according to the invention is preferably carried out using diluents. As such, virtually all inert organic, but preferably aprotic, polar solvents are suitable. These include in particular tetrahydrofuran, dioxane, 1,2-dimethoxyethane, acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone , Dimethylformamide, dimethylacetamide and dimethyl sulfoxide,

The reaction temperature may be in process (e) within

be varied over a larger area. In general, the reaction is carried out at between 0 ° C. and 150 ° C., preferably between 10 ° C. and 100 ° C. The process (e) is generally carried out under normal pressure or slightly reduced pressure.

To carry out the process (e) according to the invention, use is made per mole of sulfonylisothioureidopyrimidine derivative

of the formula (VII) is generally between 1 and 10 mol, preferably between 1 and 5 mol, of the amino compound of the formula (IV).

In general, the sulfonylisothioureidopyrimidine derivatives of the formula (VII) and the diluent are initially introduced and the amino compound of the formula (IV) is metered in. The reaction mixture is then stirred until the end of the reaction. The products of the formula (I) usually accumulate after cooling and optionally after acidification, for example with hydrochloric acid, in crystalline form and can be isolated by suction,

The process (f) according to the invention is preferably

carried out using diluents. As such, virtually all inert organic solvents come into consideration. These include in particular alcohols, such as. B, ethanol, n- and iso-propanol, ethers, such as z, B, tetrahydrofuran, dioxane and 1, 2-dimethoxyethane, esters, such as. B, ethyl acetate and methyl ester and nitriles, such as. B, acetonitrile,

The reaction temperature can be varied within a relatively wide range in process (f). In general, the reaction is carried out between -20 ° C. and + 50 ° C., preferably between 0 ° C. and 30 ^° C. Method (f) is generally used.

NEN carried out at atmospheric pressure. 3 ο

To carry out the process (f) according to the invention, the formula (I) is generally used per mole of compound between 0.9 and 1.2 mol, preferably between 0.95 and 1.1 mol of metal compound.

In general, the compounds of formula (I) and the diluent are introduced and - optionally with slight external cooling - the metal compound 1 - optionally dissolved in the diluent - dosed, 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,

The process (g) according to the invention is preferably carried out using diluents. 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 and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone,

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

The reaction temperature can be varied within a wide range in process (g). In general, it is carried out between -20 "C and +50 ⁰ C _1, preferably between 0 ⁰ C and 30" C, process (g) is generally carried out at atmospheric pressure.

For carrying out process (g) according to the invention, in general between 1 and 10 mol, preferably 1 and 5 mol, of a strong acid are employed per mole of compound of the formula (I).

In general, the compounds of the formula (I) and the diluent are initially introduced and, if appropriate, U

under slight external cooling - the strong acid added. 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 can be used as defoliants,

Desiccants, haulm killers and especially used as weedkillers. By weeds in the broadest sense are meant all plants which

grow up in places where they are undesirable. Whether the 10th

Substances according to the invention act as total or selective herbicides, depends essentially on the amount used,

The active compounds according to the invention can z, B, in the fol-

plants are used:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Cheno-

Podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, 20

Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,

Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersi con, 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, Eleocharis, Scirpus, Paspalum, Ischaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera,

Monocotyledonous Cultures of the Genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, 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.

The compounds are useful depending on the concentration for total weed control e.g. on industrial and railway tracks and on paths and squares with and without tree cover. Similarly, the compounds for weed control in permanent crops, e.g. Forestry, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, 0

Gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops,

The active compounds according to the invention can be used for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, such as, for example, cotton, rice, cereals and maize.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active substance-impregnated nature and synthetic substances, and also Fe-encapsulations in polymeric substances.

These formulations are prepared in a known manner, z, B, by mixing the. Active substances with extenders, ie liquid solvents and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foaming agents «

In the case of using water as an extender, it is possible to use U

_4, for example, organic solvents are also used as auxiliary solvents. "Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, 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,

Suitable solid carriers are:

"Z, B. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,

Montmorillonite or diatomaceous earth and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules: z, B, fractionated and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic Flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: z, B, nonionic and anionic emulsifiers, such as

oxyethylated fatty acid esters, polyoxyethyl ene fatty alcohol ethers, z, B, alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates, and protein hydrolysates; as a dispersant in question! e.g. Lignin-sulphite liquors and methyl ce IIuI eyelet,

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g.

 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 are used

The formulations generally include 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 used as such or in their formulations also in a mixture with known herbicides for controlling weeds, ready-to-use formulations or tank mixes being possible,

For the mixtures, known herbicides such as e.g.

N- <2-Benzothiazolyl) -N, N ¹ -dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethyl-urea, 3- (4-isopropyl-phenyl) -1,1-dimethyl-urea , 4-Amino-6 - (1,1-dimethylethyl) -3-methylthio-1,2,4-triazine-5- (4H) -one, 4-amino-6 (1, 1-dimethyl-ethyl) - 3-ethylthio-1,2,4-triazine-5- (4H) -one, 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1, 3,5-triazine-2,4- (1H, 3H) -dione, 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5- (4H) -one, 2-chloro-4-ethylamino-6-isopropylamino, -1 3,5-triazine, the P-enantiomers of 2- [4- (3,5-dichloro-U

pyridyl-2-oxy) -phenoxy] -propionic acid (trimethylsilyl) methyl ester, the R-enantiomer of 2- [4- (3,5-dichloropyridyl-2-oxy) -phenoxy] -propionic acid < 2-benzyl oxy) ethyl ester, 2,4-dichlorophenoxyacetic acid, 2- <2,4-dichlorophenoxy) propionic acid, 4-chloro-2-methylphenoxyacetic acid, 2- (2-methyl-4-chlorophenoxy ) Propionic acid, 3,5-diiodo-4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxybenzonitri1 and diphenyl ether and phenylpyridazines, such as Pyridate. Surprisingly, some mixtures also show a synergistic effect. A mixture with other known active ingredients such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers is also possible.

The active ingredient may be used as such, in the form of its formulations or the forms prepared therefrom by further dilution, ready- to- use solutions, suspensions, emulsions, powders, pastes and granules. The application happens in usual VZeiss, ζ. 3. by pouring, spraying, spraying, sprinkling.

The erfindungsgomäßen agents can be applizisrt both before and after dom Auflaufan represent plants.

They can also be incorporated into the ground before sowing.

The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates between O ₁ OOl and 15 kg 'active ingredient per hectare of soil surface, preferably between 0.05 and 10 kg per ha.

embodiments

The preparation and the use of the active compounds according to the invention are evident from the following examples.

Herse te lunqsbe ispi ele

At game 1 10

(Method Ca))

10.1 g (0.048 mol) of 2-chlorobenzenesulfonyl chloride are added at -10 ° C. to a solution of 4.5 g (0.02 mol) of N'- (4,6-dimethoxypyrimidin-2-yl). -N '' -. methoxy-guanidine in 30 ml of pyridine the ReakLionsgemisch is for two days at 20 ⁰ C for "After adding a further 1.5 g of 2-chloro-benzolsulfonsaurechlorid the mixture is stirred for a further 24 hours at 20" C. At a maximum of 40 ^e C is concentrated, the residue taken up in methylene chloride and washed with 5 / iiger hydrochloric acid. The organic phase is dried, filtered and concentrated, 0

The oily residue is crystallized with isopropanol.

2.65 g (23% of theory) of N '- (4,6-dimethoxypyrimidin-2-yl) -N'-methoxy-N'', N ¹ ''-bis (2-chloro -benzenesulfonyl) guanidine of melting point 164-165 "C,

Be i spie 1 2

-SOo-N 10

(Method (b)> 15

A mixture of 5.8 g (0.01 mol) of N '- (4,6-dimethoxypyrimidin-2-yl) -N' '-methoxy-N' ', N' '' - bis- (2- Chloro-benzenesulfonyl) guanidine, 1.5 g (0.025 mol) of N, N-dimethylhydrazine, 20 ml of ethanol and 10 ml of water is refluxed for one hour under reflux. The crystalline product obtained after cooling is isolated by suction filtration and recrystallized from ethyl acetate.

This gives 1.3 g of (31 ', the theory) N' - (4,6-dimethoxy-pyrimidin-2-yl) -N '' -dimethyl-amino-N '' - (2-chloro-benzenesulfonyl) guanidine of melting point 190 ⁰ C,

At game 3

SCH 10

(Method (e)) 15

A mixture of 16.0 g (0.04 mol) of N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -N''- (2-methylthio-benzenesulfony1) -S-methylisothiourea, 4 , 0 g (0.085 mol) of O-methylhydroxylamine and 80 ml of dioxane is 15 hours at 30 ⁰ C.

²⁰ ...

The mixture is subsequently concentrated by evaporation, the residue is crystallized by trituration with ethanol, and the product is isolated by suction filtration.

This gives 8.4 g (53% of theory) of N '- (4-methoxy-6-methylpyrimidin-2-yl) -N''- methoxy-N ¹ ''-<2-methylthio-benzenesulfony1 ) -guanidine of melting point 134 "C,

Be i spi el 4

SO ₂ N (CH ₃ ) ₂ 10

x CH ₃ SO ₃ H

SO ₇ N (CHO) ₇ 15 2 3 2

(Method (g))

A mixture of 5.4 g (0.0075 mol) of N '- (4,6-dimethoxy-pyrimidin-2-yl) -N' '-methoxy-N' ', N' '' - bis- (2 -dimethylaminosulfonyl-benzenesulfonyl) -guanidine, 0.75 g (0.0075 mol) of methanesulfonic acid and 10 ml of acetone are stirred for 24 hours at 20 ° C. The crystalline products are then isolated by suction.

One obtains 1.6 g (26 'of the theory) of the 1: 1 adduct of N' - (4,6-dimethoxy-pyrimidin-2-yl) -N'-methoxy-N "-N ¹ '' - -bi s- (dimethylaminosulfonyl-benzenesulfonyl) -guanidine and methanesulfonic acid of melting point 145 ° C,

Analogously you get:

Be i spi el 5

S0 ₂ N (CH _3> 2

-OCH

^N ~

OCH

S0 ₂ N (CH _{3) 2}

XH ₂ SO ₄

Melting point: 155 ^° C.

Following the examples described in the preceding examples, the compounds of the formula I listed in Table 1 below can be prepared:

R ¹ -SOo-N

U I D N t-I CD - • J ε X χ: C υ 3 W α

CC

LO

CC

CC

CO

CU Xl Λ

α ♦

OT U

CQ 2

LO LO

CO O

tv

cn

υ O ι

cn

cn a υ ο

cn

cn

a υ ο

cn a α o

X cn Π cn cn cn U a a a a a O U U U U U I I I I i I

a (D cn U a a O α U cn I O O α I I

ro a u ο

a

CO I U ι CO I a CO CO a CO α ο O U O O W co O W O JL JL O L υ U

CM O W

cn a u ο

O U

Table ! -Continuation

Ex, -No. R ^] R ⁴ R ⁵ R ⁶

Melting point C * C]

Cl

-OCH ₃ H -OCH ₃ H 143

OCHF '

OCHF -OCH ₃ -OCH ₃ H -OCH ₃ H 136

OCF

\ VsO ₂ - -OCH ₃ -OCH ₃ H -OCH ₃ H 134

SO ₂ N (CH ₃ ) 2 SO ₂ N (CH ₃ ) ₂

-OCH ₃ -OCH ₃ H -OCH ₃ H 177

SCH,

SCH ₃

\ VsOo-

Cl

-OCH ₃ - H -OCH ₃ H

-CH ₃ H -OCH ₃ H

Table ! -Continuation

Example, no. R ^]

R ⁴ R ⁵ R ⁶

Melting point CC]

COOCH-

-OCH ₃

-OCH ₃ H -OCH ₃ H

OCHF ₂

-OCH ₃

-OCH ₃ H

-OCH ₃ H 135

OCF,

OCH,

OCH ₃ H

H 137

-Cl

-OCH

CH ₃ HH

H 140-141

COOCH ₃

COOCH ₃

\ Vso ₂ -

-OCHR

-CH ₃ HH H 154

SO ₂ N <CH ₃ )

N (CH ₃ ) ₂

-OC ₂ H ₅

-CH ₃ H "OCH ₃ H

Table ! -Continuation

Example - No. R ¹

R ⁵ R ⁶

Melting point CC]

SO ₂ CH ₃

SO ₂ CH ₃ SO, - -OCH ₃ -CH ₃ H -OCH ₃ H

SO ₂ CH ₃

COOC ₂ H ₅

COOC ₂ H ₅ -OC ₄ H ₉ (-η) -CH ₃ H -OCH ₃ H

-OCH ₃ -OCH ₃ H

0OC ₂ H ₅

-OCH ₂ CH = CH ₂ -OCH ₃ H -OCH ₃ H

-OCH (CH ₃ ) ₂ -OCH ₃ H -OCH ₃ H

.COOC ₂ H ₅

29 υ \ y η

-OCH ₃ H -OCH ₃ H

Table ! -Continuation

Example No. R ¹ R ⁵ R ⁶

Melting point CC]

CH-

SCH ₃ SOO - OCH *

-CHo H -OCHo H 178 (Zers.)

COOCH '

-OC ₂ H ₅ -OCH ₃ H -OCH _C

-O-CH ₂ / ^ y-CH ₃ -OCH ₃ H -OCH ₃ H

.cl

-OCH ₂ COOC ₂ H ₅ -CH ₃ HH

.COOCH ₃ 34 O ^N VH

-OC ₃ H ₇ <-n) -CH ₃ HH

Cl

-OC ₄ H ₉ <-n) -CH ₃ H -OCH ₃ H

IN

E υ

3 O.

(M

α ·

U) U

QQ Z

00

η ι

η χ η (D X X U DC X X C. O O O U -JD ο ι O O pl O ι X ¹ ι X I ω CC X X U X π η ι η χ Π U ο X X tf U ι O O U ¹ I Π I , -ν C -1-1 X ι I O 00 σ * O ΙΩ X X X ac U tf X N CO O O U U ο ι O O O CC ο ι ι ι

(M

(VJ

U) I (M ι X (M [Χ. (M CO O X O U W U W 1 O L Z (M O W

CO

X U

<η

CO

tf

Table ! -Continuation

Ex. No. R ^] R ⁵ R ⁶

Melting point CC]

7 \

HpSOoCHq

CH ₂ SO ₂ CH ₃ SO-, - -OCH ₃ -Cl H -OCH ₃ H

SCH

-OC ₃ H ₇ (-i) -Cl H -OCH ₃ -N (CH ₃ ) ₂ -Cl H -OCH ₃

OO

OCHF ₂

OCHF '

-CH ₃ HH

H 163-167

CH,

COO

SO ₂ -

COO

- <J

-Cl H

-OC ₂ H ₅

-CH ₃ H -OCHF ₂ H

Table ! -Continuation

Example No. R ¹ R ⁵ R ⁶

Melting point CC]

COOCHr

CHoSOoCHo

br

00CH ₃

SCF

COOCH ₃

H ₂ SO ₂ CH ₃

SO ₂ -

, Br

SCF, -OCH ₃ -CH ₃ H -OCHF ₂ H -OC ₃ H ₇ (-n) -CH ₃ H -SCH ₃ H -O-C ₄ H ₉ (-n) -CH ₃ H -N (CH ₃ ) ₂ H is -OC ₂ H ₅ -OCH ₃ H -OCH ₃ H -N (CH ₃ > 2 "CH ₃ H -OCHF ₂ H

-CH ₃ H -N (CH ₃ J ₂ H

U I O N O) jj e , γ C U 3 CO α

so

CC

co

α ♦

in L

CQ Z

Ä U W ι

U ι

X U

Il

a: υ

CO X U

in

U)

X U

in X

CO U

U)

(M U O

SC

X O

X co

U O O U

co

X UO

co

ID

X X

U)

a co

ο o

co

U O

(M

U)

U)

U)

co

U)

Table ! -Continuation

Expl

R ⁴ R ⁵ R ⁶

Melting point CC]

-COOCH ₃

COOCH'-OC ₄ H ₉ (-s) -OCH ₃ H -OCH ₃ H 109

Cl

COOCHr

Cl

^N Vso ₂ -

COOCH '

-OC ₄ H ₉ (-i) -OCH ₃ H -OCH ₃ H 164

-OC ₄ H ₉ (-i) -OCH ₃ H -OCH ₃ H 146

br

SO ₂ -

-CH ₃ H -OCH ₃

H 174

OOCH (CHQ)

COOCH (CH ₃ ) ₂

WsO ₂ -

-CH ₃ H -OCH ₃

H η ²⁰ η 1.5391 D

Cl

COOCH,

-OCH ₃ H -OCH ₃

Table! Continuation

Expl R ^] R ⁵ R ⁶

Melting point C ⁰ C]

COOCH ₃

-OCH ₂ COOC ₂ H ₅ -CH ₃ HH

H 91-93

OCH ₃ H

-OCH ₃ H 187

SO ₂ N (CH ₃ ) ₂ 68 // \ VH

.SO ₂ N (CH ₃ ) 69 0 \ VH

-NHCOCH ₃

-OCH ₃ H

-OCH ₃ H 181

-N (CH ₂ ) ₂ -OCH ₃ H -OCH ₃ H 156

Cl

Wso.

OCHF ₂

-OCH ₃ H HH

H 144 -

-N (CH ₃ > 2 -OCH ₃ H -OCH ₃ H 177

Table ! -Continuation

Example No. R ^]

R ⁵ R ⁶

Melting point D C ⁰ C]

-N (CH ₂ ) ₂ -OCH ₃ H -OCH ₃ H 158

COOCH-

-N (CH ₃ ) ₂ -OCH ₃ H -OCH ₃ H 164-167

74 cl

Cl

S0 ₂ -

-OCH ₃ HH -CH ₃ H 148

75 F OCH ₃ HH -CH ₃ H 135

br

Br -OCH ₃ HH -CH ₃ H 163

OCH ₃ HH-CH ₃ H 160

U I β N I-I Q) G £ C U 3 W D

so

LO

a;

cc

JQ ffl H

α ·

(D U

CQ Z

U ι

U ι

LO

cn

U ι

U ι

X CO , Π X X X (M U U X O O U X ι ι (I CO X U X co U χ O U η ι η C) O ι X X υ υ U ο O O ι ι ι

X o

U X U

OO

O (Π X X υ-υ

X X U U O O O O U U 1

CO

co

π ω

Table! Continuation

Ex. No. R ¹ * ⁴ R ⁵ R ⁶

Melting point C ⁰ C]

OCF

OCF-NV ₈ O ₂ -

H H -CH-

H 170

7 \

COOC ₂ H ₅

COOC ₂ H ₅ -OCHo HH -CH-

H H -CH-

H 168

H 107

ι ο

COOC ₂ H ₅

COOC ₂ H ₅

H H

" ^C 2 ^H 5

H 141

COOCH ₃

COOCH ₃ -OC ₂ H ₅ HH -CH ₃ H 135

COOCH ₃

JCOOCH ₃ OCH ₂ - ( ^/ Cl

H H -CH-

Table ! -Continuation

Expl R ^] R ⁵ R ⁶

Melting point D CC]

COOCHr

COOCH. -0C ₄ H ₉ (-n) HH -CH ₃ H

COOCH,

H H -CH-

H 137

COOCH ₃

-OCH ₂ CH ₂ CH ₂ Cl -CH ₃ Cl -CH ₃ H 129

-CH ₃ H -OCH ₃ H 180

V \

COOCH ₃

NO-

-CH ₃ HH

H amoroh

OCF

(^) C ₄ H ₉ -SO ₂ - -OCH ₃ HH -CH ₃ H

Table ! -Continuation

Ex, -No. R ⁴ R ⁵ R ⁶

Melting point D CC]

^C 8 ^F 17 ~ ^S0 2 ~

-OC ₂ H ₅ HH -CH ₃ H

COOCH,

(CH ₃ ) ₂ N-SO ₂ - -OCH ₃ -CH ₃ H -OCH ₃ H

SO ₂ N (CH ₃ ) ₂

CH ₃ -SO ₂ -

-OCH- -OCH ₃ H -OCH ₃ H

br

CF ₃ -SO ₂ -

-CH ₃ H -OCH ₃ H

(CH ₃ ) ₂ CHNHSO ₂ - -OCH ₃ -OCH ₃ H -OCH ₃ H

Table! Continuation

Example No. R ³ R ⁵ R ⁶

Enamel point [

Cl

Cl

-OCH ₂ - ('_ ^X > -CH ₃ H -OCH ₃ H 163

COOCH-

7 \

° 2 ^N "\ - / ^S0 2 ~" ^0CH COOCH-3

7 \

SO ₂ -

2 \ -

-CH-3 H -OCHq H 151

-CH ₃ HH

H 130

COOCH '

COOCH'OCH ₃ Cl H -OCH ₃ H 159

0OC ₂ H ₅

COOC ₂ H ₅

Cl H -OCH ₃ H

I o

E · *

JC C υ W D.

ΙΛ

CC

CC

(M CC

jj L O

ul

QQ

CC

re

u o

υ ο

π ac υ ο

IO

U CO ac π O ac CJ ac ι U O U ο 1 ο ι ι

ac ac cn cn ro υ ο ac SC U ι υ U O

ΙΛ

ac

O O

ac

CM

co

CA

ac υ o

CM

CM

Table ! -Continuation

Example No. R ¹

R ⁵ R ⁶

Melting point CC]

br

\ Vso ₂ -

-OCH

-OCH ₃ H -OCH ₃

H

COOCH,

COQCH ₃

'/ WsO ₂ -

OCH *

H HH

H 144-147

COOC ₂ H ₅

0OC ₂ H ₅ SO ₂ -

-CH ₃ HH

H 150 -

SO ₂ N (C ₂ H ₅ ) ₂ .SO ₂ N (C ₂ H ₅ > ₂

-OCH ₂ K ' _y -CH ₃ HH

H 151 -

COOCHr

.COOCH * SO ₂ -

-C ₂ H ₅ HH

H

Table ! -Continuation

Expl R

R ⁴ R ⁵ R ⁶

Melting point CC]

SO ₂ N (CH ₃ ) 2

^S0 2 ~ -och ₃ -ch ₃ η η

η in - lie

7a) p-toluenesulfonic acid salt of Example 7, amorphous.

8a) p-Toluo1sulfonsäure Sal ζ of Example 8. amorphous, 10

8b) sulfuric acid salt of Example 8, amorphous.

9a) p-toluenesulfonic acid Salζ of Example 9 of

Melting point: 175 "C (Zers.)

9b) of sulfuric acid salt of Example 9.vom melting *> punki: 170 ⁰ C (dec).

22a) p-toluenesulfonic acid salt of Example 22 ^ 01), 25

Preparation of starting materials of the formula (II)

Example (II-1) 10

HN C N- ( \ OCH \ H

15

A mixture of 36.0 g (0.2 mol) of 2-cyanamino-4,6-dimethoxy-pyrimidine, 33.4 g (0.4 mol) of O-methyl-hydroxylamine

Hydrochloride and 200 ml of ethanol is kept under 20 for 6 hours

Reflux heated to boiling. After addition of a further 16.7 g (0.2 mol) of O-methyl-1-hydroxyamine hydrochloride id the mixture is refluxed for a further 6 hours. After cooling, the mixture is filtered through kieselguhr, the filtrate is concentrated and diluted with 200 ml of water. It is brought to pH 7 with dilute sodium hydroxide solution and the product obtained in this process is isolated by filtration with suction.

Recrystallization from isopropanol gives 16.4 g (36 % of theory) of N '- (4,6-dimethoxy-pyrimidin-2-yl) -N'-methoxy-guanidine of melting point 122 ° C.

35

Analogously, the compounds of the formula (II) listed in Table 2 below can be prepared:

table

H ,

HN,

(II)

Ex ♦ -No. R ⁵ R ⁶

SchmelzpunktCC]

I I-2 I I-3 I 1-4 I I-5 I I-6

I 1-8

-OCH ₃

-OCH ₃

-OCH ₂ CH (CH ₃ ) ₂

-OCH ₂ CH = CH ₂

-OCH (CH ₃ ) ₂

-CH-

H H

-CH ₃ H -OCH ₃ -OCH ₃ H -OCH ₃ -OCH ₃ H -OCH ₃ -OCH ₃ H -CH ₃ -OCH ₃ H -OCH ₃ -OCH ₃ H -OCH ₃

152

126

76

I 1-9 -0C ₄ H ₉ (-n) -OCH ₃ H -OCH ₃

Table 2 continuation

Example no.

R ⁵ R ⁶

-sw - * y s

SchmelzpunktCC]

11-10 -OC ₄ H ₉ <-n) -CH ₃ H -OCH ₃

H-II -0C ₈ H ₁₇ (-n)

-OCH ₃ H -CH ₃

11-12 -OCH ₂ CH ₂ CH ₂ Cl -OCH ₃ H -OCH ₃

11-13 -OCH ₂ COOCH ₃ -OCH ₃ H -OCH ₃

11-14 -OCH ₂ COOC ₂ H ₅ -OCH ₃ H -OCH ₃

I 1-15 -OC ₃ H ₇ (-n) -OCH ₃ H -OCH ₃

11-16-OCH

₂ - (/ _ Cl -OCH ₃ H -OCH ₃

II-17 -0

-OCH ₃ H -OCH ₃

I I-18 - ° ^CH 2 "\ ^/ _ ^N / ' ^CH 3

I 1-19

11-20

11 -21 -OCH ₂ -X _

-OCH ₃ H -CH ₃

-OCH ₃ H -OCH ₃

H H

-OCH ₃ H -OCH ₃

Table 2 continuation

Ex-No.

R ⁵ R ⁶

Melting pointC ⁰ C]

11-22 -O- / h \

11-23 -Q-CH ₂ -CH

-OCH ₃ H -OCH ₃ -OCH ₃ H -OCH ₃

I1-24 -O-CH ₂ C0N (CH ₃ > ₂ -OCH ₃ H -OCH ₃

11-25 -OCH ₂ OCH ₃ OCH ₃ H -OCH ₃

11-26 -OCH ₂ SCH ₃ OCH ₃ H -OCH ₃

11-27 - OCH ₂ V_ \ VcOOC ₂ H ₅ -OCH ₃ H -OCH ₃

11-28 -OCH ₂ CF ₃

OCH ₃ H -OCH ₃

11-29 -OCH

2 Λ -OCH ₃ H -OCH ₃

H-30

-CHo H -OCHo n ²⁰ = 1.5645

I 1-31-OCH

11-32

2 Λ -

-OCH ₃ H -OCH ₃ -OCH ₃ H -CH ₃

Table 2 continuation

Ex -

No.

R ⁵ R ⁶

Melting point C ⁰ C]

11-33 '

-OCH ₃ H -OCH ₃

I1-34 -O-CHCH ₂ CH ₃ -OCH ₃ H- -OCH ₃

CH-66

11-35 -OC ₂ H ₅ -CH ₃ H -OC ₂ H ₅

I1-36 -OCH-11-37 -0C ₃ H ₇ (-i) I I-38 -OCH-11-39 -OCH ₃ I1-40 -OCH

2Λ-

-CH-

-CH-

-CH-

H -OCH ₃

HIGH

3 -OC ₂ H ₅

-OCHFo

H -OFF-

11-41 -0C ₃ H ₇ (-n) H-42 -0C ₄ H ₉ (-n)

-CH ₃ H -N (CH ₃ ) ₂

I1-43 -OC ₂ H ₅ -OCH ₃ H -OCH ₃

11-44 -OCH- -OCH ₃ H -N (CH ₃ ) ₂

Table 2 continuation

Ex-No.

R ⁵ R ⁶

Melting point C ⁰ C]

I1-45 -OCH ₂ -CH = CH ₂ oH -SCH ₃

I1-46

-CH-

H H

I I-47 -OCH ₂ -COOC ₂ H ₅ -CH ₃ HH

95

11-48 -OCH

/ V

2Λ _ -CH-

H H

150

I 1-49 - ° ^CH 2 "(O

H is -OC ₂ H ₅

11-50 -0C ₃ H ₇ (-n>

H is -N (CH ₃ ) ₂

I 1-51 -OCH-

H-SCH,

11-52 -OCH ₂ CF ₃ -CH ₃ H -SCH ₃

11-53 -OCHo-CH = CHo H -OCHFo

³⁰ I 1-54 -OCH ₂ - (^) - COOC ₂ H ₅ -CH ₃ H -OC ₂ H ₅

11-55 -0

II-56 -0

H-SCH,

-CH ₃ H -N (CH ₃ ) ₂

Table 2 continuation

At sp 4 No. R ⁵ R ⁶

Melting point [ ⁰ C]

11-57 -OCH ₂ CH ₂ CH ₂ Cl -Cl H -OCH _:

I 1-58

-CH ₃ H. -OC ₂ H ₅

11-59 -OCH ₂ - (Z \;

he

H -CH ₃ 140

I 1-60 -OCH

H -CH ₃ 205

11-61 -OCH-

~ ^C 2 ^H 5

98

11-62 -OCH ₂ CH ₂ CH ₂ Cl

H -CH.

102

I I -63 -OCH-

-C ₂ H ₅ HH

112

11-64 -OCH ₂ -C (CH ₃ ) ₃

H -CH-

11-65 -OCH ₂ CH ₂ -OCH ₃

H -CH-

242

11-66 -OCH ₂ CH ₂ -OC ₂ H ₅

H -CH-

11-67 -OCH ₂ CH ₂ -SCH ₃

H "* CH '

Table 2 continuation

, Be i sp.-no. R ⁵ R ⁶

Melting pointC ⁰ C]

11-68 -OCHoCH ₇ -SC ₇ Hc

H -CH-

I I -69

-OCH ₂ -CONH ₂

H -CH-

I 1-70

-OCH ₂ -CH = CHCl

11-71 -OCH

7 v

- / y

H -CH-

165

11-72 -OC

- / 3

H -CH-

11-73 -OCH-

H H

107-109

11-74 -OCH-OC ₂ H ₅ H -OC ₂ H ₅

11-75 -OCH ₇ -CH = CH ₇

83

I1-76 -OCH ₂ -CH = CH ₂ -CH ₃ -COOC ₂ H ₅ H 143

Preparation of starting materials of the formula (III)

Example <II 1-1) 10

295 ml Phosphory1 chi or id ('Phosphoroxychlor id') 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, an-U

After cooling with petroleum ether, washing the extraction solution with water, drying, filtration and concentration, the product remaining in the residue is purified by vacuum distillation.

This gives 117 g (70% of theory) of 2-chloro-benzenesulfonyl chloride of boiling point 110 "C / 1.1 mbar,

Example (I I 1-2)

COOCH ₃

(/ V 10

75.5 g (0.5 mol) of 2-aminobenzoic acid methyl ester are dissolved in 176 ml of concentrated hydrochloric acid and 100 ml of acetic acid. For this purpose, a solution of 34.4 g of sodium nitrite in 70 ml of water is added dropwise at 0 ⁰ C, After 15 minutes of stirring, the reaction mixture is slowly added to a cooled to 0 ⁰ C saturated solution of sulfur dioxide in 450 ml of acetic acid, After removal of the cooling bath is stirred until the end of gas evolution, where -0

at 10 g of copper (I I) - chloro added in portions

After dilution with ice-water, extraction with methylene chloride, washing the extraction solution with water, drying, filtration and concentration, the product remaining in the residue is removed by vacuum distillation

cleans,

45 g (38 V, theory) of 2-methoxycarbonyl

benzenesulfonyl chloride id of boiling point 150 "C / 1.3330 F>

rabar,

Analogously, the compounds of the formula <I I I> listed in Table 3 below can be prepared!

R ¹ -SO, -C1

(III)

table

Ex-No.

Boiling point / pressure

III-3

I I 1-4 III-5 III-6

OCH

7 \

(Oil, decomposition on distillation)

[Melting point: 100 ^p C3 (01)

142 * C / 4 mbar

III-7

106 ° C / 4 mbar

Table 3 continuation

Example, no.

R ^J boiling point / pressure

I I 1-8 I I 1-9

.-OCF

CHF '[melting point: 32 ° C]

(oil, decomposition at Dest i hat ion)

IH-IO IH-H

SO ₂ N (CH ₃ ) ₂

SCH [melting point: 103 "C]

(Oil, decomposition on distillation)

I I-12

SCH (CH ₃₎ 90 "C / 1.33 mbar

I I-13 III-14 I I -15

7 \

COOC ₂ H ₅

CH ₂ SOCH ₃ [melting point: 12O ^e C3 155 "C / 5.32 mbar

Table 3 continuation

With sp.no.

Boiling point / pressure

II 1-16

SO ₂ CH ₃ [melting point: 128 "C]

11 1-17

CH ₂ Cl

111 -18

OOCH (CH ₃ ) ₂

I I 1-19

^f / \

COOC ₃ H ₇ <-n)

III-20 III-21 III-22

COOC ₄ H ₉ (n)

CON (CHg) ₂

COO

III-23

0 ₂ N (C ₂ H ₅ ) [m.p .: 73 "C]

⁵ Table 3 continuation

Example no.

10

Boiling point / pressure

III-24

15

I I1-25

SCF '

SO ₂ N

CH-

OCH

[Melting point: 41-43 ⁰ C3

20

I I-26

III-27

7 \

-SO ₂ CF ₃

25

III-28

30

III-29

7 \

III-30

35

7 \

Table 3 continuation

Ex ♦ -No.

10 boiling point / pressure

I I1-31

I I 1-32

III-33

20

25

30

COOCH ₃

CN NVCH ₂ -

Cl

[Melting point: 84 ^° C.] waxartia

35

Preparation of starting materials of the formula (VI)

Example (VI-I) 10

'COOCH ₃

OCH ₃

A solution of 2.8 g (0.012 mol) of 2-methoxycarbonyl-benzenesulfonyl chloride id in 10 ml of tetrahydrofuran is added at -5 ° C with stirring to a mixture of 2.3 g (0.01 mol) of N '- (4, 6-Dimethoxy-pyrimidin-2-yl) -N'-methoxy-guanidine and 30 ml of tetrahydrofuran. Then, a solution of 1.3 g (0.012 mol) of diazabieye 1ooctane in 10 ml of tetrahydrofuran is added dropwise thereto at -5 ° C and the mixture is stirred at 20 ° C for 2 hours. After addition of another 0.5 g of 2-methoxycarbonyl-benzenesulfonyl chloride and 0.25 g of diazabieye 1ooctan is added

Stirred for 2 hours at 20 ° C. After filtration, the mixture is turned on

The residue is concentrated with toluene for crystallization

brought and isolated by suction.

This gives 2.25 g (57% of theory) of N '- (4,6-dimethoxy-pyrimidin-2-yl) -N'-methoxy-N' '- (2-methoxycarbonyl) benzene sulfonyl) guanidine of melting point 142-143 "C,

Analogously, the compounds of the formula (VI) listed in Table 4 below can be prepared:

10 _c

R ¹¹ -SO ₂ R ³

Table 4 continuation

At sp ♦ No.

R ⁴ R ⁵ R ⁶ melting point [ ³ C]

VI-2 -OCH ₃

-OCH ₃ H -OCH ₃

Cl

(glass type ig)

VI-3 -OCH ₃

-CH ₃ H -OCH ₃

Cl

VI-4 -OCH-VI-5 -OCH ₃

7 \

-OCH ₃ H -OCH ₃

COOCH ₃

OCF,

(Qlasartiq)

VI-6 -OCH-

-OCH ₃ H -OCH ₃

OCHF ₂

(glass type ig)

Table 4 continuation

Ex-No.

R ⁵ R ⁶

11

Melting point C "C"

VI-7 -OCH ₂ CH (CH ₃ ) ₂ -OCH ₃ H -OCH ₃

SO ₂ N (CH ₃ J ₂

VI-8 -OCH ₃

-OCH ₃ H -OCH ₃

S0 ₂ N (CH _{3> 2}

VI-9 -OCH ₃

-OCH ₃ H -OCH ₃

VI-IO-OCH,

-CH ₃ HH

Cl

7A

124

VI-Il

OCHCH ₂ CH ₃

CHO

-OCH ₃ H -OCH ₃

Cl

124

Table 4 continuation Ex.

R ⁴ R ⁵ R ⁶

11 Melting point C ⁰ C]

VI-12 -OCH-

-CH ₃ H -OCH ₃ (t \

VI-13 -OCH ₃

-CH ₃ H -OCH ₃ ( ^f

VI-14 -OCH-

CH ₃ HH

VI-15

-OC ₂ H ₅

-CH ₃ H "OC ₂ H ₅

VI-16 -OCH-

-Cl H -OCH ₃

Table 4- progress

Example no.

R ⁵ R ⁶

11

Melting point C ⁰ C]

VI-17

OC ₃ H ₇

-OCH ₃ H -OCH ₃

VI-18-OCH

-Cl H -OCH ₃

VI-19 -OCH ^

CH ₃ HH

Br

VI-20

-CH ₃ H -OCH ₃

Cl

VI-21-OCH

-CHo H -OFF '

COOCH '

Table 4 continuation

Example no.

R ⁴ R ⁵ R ⁶

Melting point CC]

VI-22 -OCH ₂ CH = CH ₂ -CH ₃ HH

VI-23 -OC ₄ H ₉ C-η) -CH ₃ HH ° 2 ^U ~ \ -}

VI-24-OCHr

-CH ₃ H -OCH ₃ Cn-OC ₄ H ₉ -

VI-25 -OCH-

-OCH ₃ H -OCH ₃ CCH ₃ ) ₂ N-

VI-26 -OCH ₃

-CH ₃ HH Cn-) C ₈ F ₁₇ ·

C co co 3 »Η t-l O. N ι I 0) ΙΛ co ε co co sz , -I υ

• 43

I /)

σ · η π cn C CC 3 U U N O O β) ι ι m jj U O Cl.

U)

•H

CQ

co co

Preparation of starting materials of the formula (VII)

Example (VII-1)

Cl

SCH ₃

^ A suspension of 8.4 g (0.35 mol) of sodium hydride (in oil) is 2-amino-4-methoxy-6-methyl-pyrimidine was added with stirring to a mixture of 28.0 g (0.2 mol) and the mixture is stirred for 15 hours at 20 ^° C. Then 60 g (0.2 mol) of N- (2-chlorobenzenesulfonyl) -S ', S' * -

"Dimethyl-iminodithiokohlensäureester added portionwise to the reaction mixture, that the reaction temperature does not rise above 40 ⁰ C. After five hours of stirring at 20 ° C, 1 1 of ice water is added and filtered." The filtrate is acidified with concentrated hydrochloric acid

3 ^ and the case crystalline product is isolated by suction.

This gives 67 g (87 V * of theory N '- (4-methoxy-6-methyl-pyrimidin-2-yl) -N''-<2-chloro-benzenesulfonyl) -S- methyl-isothiourea of melting point 148th "C.

Analoq may have the properties shown in Table 5 below.

ι ^:

led compounds of formula <VII) are produced!

R ¹ SO-]

17

(VII)

table

Expl R ^]

_? 4 ρ5 _R 6

Schmel z R ¹⁷ point [° C]

VI I-2 0 ^ VII-3 VII-4 VII-5

_VII _ ₆ // \

CH-

SCH

Cl

Cl

OCHF '

-CH ₃ H -OCH ₃ -CH ₃ 163

-CH ₃ H -OCH ₃ -CH ₃ 163

-OCH, H -OCHo -CH-, 168

-CH ₃ HH -CH ₃ 152-153

-OCH ₃ H -OCH ₃ -CH ₃

Table 5 continuation

Example »- No. R ^]

R ⁵ R ⁶

Enamel R ¹⁷ point C'C]

VII-7

-OCH ₃ H -OCH ₃ -CH ₃

VII-8

-CH ₃ HH

-CH-

VII-9

OCF ^ -OCH ₃ H -OCH ₃

-CH-

VII-10

OCHF ₂ -CH ₃ HH

-CH-

VII-Il

SO ₂ CH ₃ -CH ₃ H -OCH ₃

-CH-

VII-12

SCH- OOCH ₃ H -OCH ₃

-CH-

VII-13

SO ₂ N (CH ₃ ) ₂

-OCH ₃ H -OCH ₃

-CH-

VII-14 U

COOC ₂ H ₅ -OCH ₃ H -CH ₃

CH,

Table 5 continuation

Example no.

R ⁴ R ⁵ R ⁶

¹⁷

Melting point C ⁰ C]

VII-15

COOCH (CH ₃ ) ₂

-OCH ₃ H -OCH ₃ -CH-

VII-16

-OCH ₃ H -OCH ₃ -CH ₃

VII-17 VII-18

br

OCH

-OCH ₃ H -OCH ₃ -CH ₃ -OCH ₃ H -OCH ₃ -CH ₃

VII-19 VII-20

CF

OCF 1 -OCH ₃ H -OCH ₃ -CH ₃ -CH ₃ H "OC ₂ H ₅ -CH ₃

Cl -CH ₃ H "OC ₂ H ₅ -CH _:

VII-22

Br -Cl H -OCHo -CH-

Table 5 -Fortsetzun.q

Expl

4 _R 5 _R 6

Schmelz-R ¹⁷ punktC "C]

VI1-23

Cl -Cl H -SCH ₃ -CH ₃

VII-24

OCH- Cl H -SCH ₃ -CH ₃

VII-25

OCHF '

7 \ -Cl H -OC ₂ H ₅ -CH ₃

VII-26

SCF ^ -OCH ₃ H -OCH ₃ -CH ₃

VII-27

br

VII-28

-Cl H -N <CH ₃ > ₂ -CH ₃ -Cl H -N (CH ₃ > 2 "CH ₃

VII-29

CN-CH ₃ H -SCH ₃ -CH ₃

VII-30

o H SCHo

Table 5 Continuation

Example no. R ³ R ⁵ R ⁶

Enamel R ¹⁷ DunkC'C]

VII-31

-CH ₃ H -N (CH ₃ ) ₂

VII-32

OCF

7 \ -CH ₃ H -N (CH ₃ ) ₂ -CH ₃

VI1-33

SCH (CH ₃ ) ₂ -CH ₃ H -OCHF ₂ "CH ₃

VII-34

Cl -CH ₃ H -OCHF ₂ -CH _:

VI1-35

SO ₂ N (CH ₃ ) ₂ -CH ₃ H -OCHF ₂ -CH ₃

VI 1-36 (/ \

-CH ₃ H -OC ₂ H ₅ -C ₂ H ₅

VII-37

CH- CH ₃ HH

VII-38

OCHF- CH ₃ H -N (CH ₃ ) ₂ -CH ₃

⁵ Table 5 continuation

Expl R "R ⁵ R ⁶

17

Melting point [ ⁰ C]

10

VII-39

VII-40

CH ₂ SCH ₃

.-CH

-Cl H -OCHo -CH- -OCH ₃ H -OCH ₃ -CH ₃

OCF

VII-41

.CI VII-42 (f \

VII-43

25

Cl H -OCHFo -CH-

-CH ₃ -CH ₃ H -CH ₃ "CHq" CHn

-CH ₃

30

35

Preparation of starting materials of the formula (VIII)

Example (VIII-I) 10

_N OCH ₃

NC ~ ^w "3

NC-NH- ^ V>

^N = ^ OCH ₃

A heated to 100 ⁰ C solution of 24 g (0.427 mol) Kai iurnhydrox id in 100 ml of water at 100 ° C under result in a mixture of 9.2 g (0.043 mol) of 4,6-dimethoxy-pyrimidin-2- yl-thiourea in 70 ml of water

given. The mixture is stirred for 2 minutes at 100 ° C and then a heated to 100 "C solution of 16.2 g (0.05 mol) of lead (II) acetate in 30 ml of water was added, Man heated for 5 minutes under reflux , then cooled to 0 "C to 5" C and the aqueous solution is mixed with 30 ml of glacial acetic acid, the case precipitating crystalline product is isolated by suction,

This gives 6.3 g (81.5 V. of theory) of 2-cyanamino-4,6-

dimethoxy-pyrimidine of melting point 202 ⁰ C,

⁵ Example (VIII-2)

N 10

To a slurry of 84 g (1.0 mol) of dicyandiamide in 500 ml of methanol are added 54 g of sodium methoxide (1.0 mol) and stirred for 15 minutes. After addition of 132 g <l, 0 mol) Äcetylacetaldehyddimethylacetal is stirred under reflux for hours. The clear, dark red reaction solution is concentrated in vacuo to dryness, the residue is dissolved in 1500 ml of water and adjusted to pH 3 with concentrated hydrochloric acid with stirring. The crystalline precipitating product is isolated by suction.

This gives 103 g (78 % of theory) of 2-cyanamino-4-methyl-pyrimidine of melting point 203 ^C C (Zers,),

Analogously, the compounds of the formula (VIII) listed in Table 6 below can be prepared:

N- ^{κ κ} NC-NH - ^ / \ - R ⁵ (VIII)

table

At sp, no melting point C ⁰ C]

VII1-3 -CH ₃ H -OCH-

258 (Zers.)

VIII-4 is -CH ₃ H

VIII-5-Cl

--OCHF. -OCH

174

200

VIII-6-Cl

Ohn

VIII-7-Cl

VIII-8 -CH ₃ H -N (CHo) -,

w ut

-N (CH ₃ ) o

VIII-9 -CH ₃

-OC ₂ H ₅

VIII-IO-CH ₃ -COOC ₂ H ₅ H 126

Table 6 continuation

Example, - melting point

No. R ⁴ R ⁵ R ⁶ C ⁰ C]

VIII-III-CH ₃ -COCH ₃ H

VIII-12 "C ₂ H ₅ HH

VIII-13 HH H

VI I 1-14 -OCoHc H -OCoHc 235 -

²⁰ VIII-15-OH -COOCoHc H 220 (Zers.)

VI I 1-16 -OH HH>

VIII-17-Cl H -CH ₃ 25

Preparation of the starting materials of the formula (XIII)

Example (XIII-I) 10

^ NH-C-NH-COOC ₂ H ₅ ^: N

CH ₃ O

A mixture of 15.5 g (0.1 mol) of 2-amino-4,6-dimethoxy-pyrimidine, 13.1 g (0.1 mol) of ethoxycarbonyl isothiocyanate and 200 ml of acetonitrile is stirred at 60 ⁰ C for 2 hours. It is then cooled to 10 ⁰ C and the resulting crystalline product by suction isolated »

22.5 g is obtained (75% of theory) of 1- (ethoxycarbonyl) -3- (4,6-dimethoxy-2-y1-pyrimidίη) thiourea melting point of 194 ⁰ C (ZersJ,

Analogously, the compounds of the formula (XIII) listed in Table 7 below can be prepared:

O S

R ¹⁸ -C-NH-C-NH

(XI I I)

table

Example - no.

R ⁵ R ⁶ »18

SchmeIz-DunktC ⁰ C]

XI I 1-2 -OCH ₃ H -OCH ₃

XIII-3

XIII-4

XIII-5 XIII-6

XIII-7

XII1-8

-CH ₃

-CH ₃ -CH ₃ -CH ₃ -CH ₃ -OCHF ₂

H H

-OCH ₃ -OCH ₃ -OCHF-

H -OFF

-OCHF ₂

-OC ₂ H ₅

-OC ₂ H ₅

189

198-199 (Zers.

217

190

182

184-185

173

Table 7-continuation

At sp ♦ -Nr.

Melting Dunki ⁰ C]

XI.I 1-9

-Cl

H is -OCH- -OC ₂ H ₅

160-162

XIII-10-Cl

H -Cl-0C, Hc

XIII-H-Cl H -N <CH ₃ ) ₂ XIII-12H

XIII-15 -CH-

XIII-16-Cl

H H

XII1-13 "OC ₂ H ₅ H XII1-14 -OC ₂ H ₅ H

H is -OC ₂ H ₅ H -CHo

-OC ₂ H ₅

132-136

168

173

179

159

156

144

Preparation of the starting materials of the formula (XIV)

Example (XIV-I) 10

CH ₃ O> - ^N 15

A mixture of 5.0 g (0.0175 mol) of 1- (ethoxycarbony1) -3- (4,6-d-imethoxy-pyr-imidin-2-yl) -thiourea, of 4.0 g (0.1 mol) Sodium hydroxide and 100 ml of water

is stirred for 2 days at 20 ° C. Then with stirring 20

dilute dilute hydrochloric acid until the solution is acidic and the evolution of C0 _{2 has} ceased. The crystalline product is isolated by suction,

This gives 3.5 g (94 '/ of theory.) 4,6-Dimethoxy-pyr imidine-2-yl-thiourea, melting point 245 - (dec.) 248 ⁰ C,

Analogously, the compounds of the formula (XIV) listed in Table 8 below can be prepared

become:

N-

-R "

H ₂ NC-NH- { ^/ N (XIV)

Table 8

With sp.no.

R ⁵ R ⁶ melting point C ⁰ C]

XIV-2 -CH-

H H 264-265

XIV-3 XIV-4

-CH-

CH,

H -OCH ₃

H-OCHF-205-207 192-194

XIV-5-Cl

H-OCH-225-227 (ZersJ

XIV-6-Cl XIV-7-Cl

-N (CH ₃ > ₂

H -OCoHc

XIV-8 -CH ₃ -CH XIV-9,

-OCoHc -SCH,

Table 8 continuation

Be i sp, -

Nr, R ⁴ R ⁵ R ⁶ melting point [ ⁰ C]

XIV-IO _-CH3 H -N _(CH3> 2

XIV-U H HH

XIV-12 "OC ₂ H ₅ H" OC ₂ H ₅

XIV-13 -CH ₃ H -Cl

Preparation of starting materials of the formula (XV)

Example (XV-I) 10

σ "1 SCH ₃  SO ₂ -N = C ^

SCH ₃

To a solution of 20 g (O ₁ l mol) of 2-chlorobenzenesulfonamide in 80 ml of dimethylformamide at 20 ^e C at the same time (from different dribbling) 8 g (0.2 mol) NaLriumhydroxid - dissolved in 15 ml of water - and 6 ml (O ₁ Il mole) SchwefelkohlensLoff added dropwise, After stirring 13 ml (0.22 mol) of methyl iodide are added dropwise and the reaction mixture is stirred for another hour at 20 ⁰ C. By adding

500 ml of water, the product is precipitated and by 25

Vacuuming isolated,

This gives 22.1 g (75 '/ of theory.) N- (2-chloro-benzene sulfonyl) -S' _J S '"- dimethyl-isodithi ocarbamidsäureester of melting point 112 ⁰ C,

^ ₃ %, < sj j

Analogously, the compounds of the formula (XV) listed in Table 9 below can be prepared:

R ¹ -SO -> - N = (

, SR

SR

17

17

(XV)

table

At sp, -Nr.

^RJ

> 17

Melting point C ⁰ C]

XV-2 XV-3 XV-4 XV-5 XV-6

JCH

SCH

O ₂ N (CH ₃ ) ₂

-CH-

-CH-

-chō

-CH-

-CH-

103

143

112

88

Table 9-Continued

At sp. No.

10

17

Melting point C ⁰ C]

XV-7 XV-8

XV-9

20

25

XV-IO

XV-Il

XV-12 XV-13

XV-14

O ₂ CH ₃

Cl

CH ₂ SO ₂ CH ₃

V \

COOCH (CH ₃ )

--CF--

-CH-

-CH-

-CH-

-CH-

-CH-

-CH-

-CH-

96

35

Table 9-Continued

No.

^RJ

Melting point C ^e C]

XV-15

XV-16

OCH

7 \

-CH-

-CH-

SCH (CH ₃ ) ₂

XV-17 (/ _ \ V \ '

-CH-

XV-18

-CH-

100

XV-19 Cl

7 \

-CH-

XV-20

-CH-

107

XV-21

-CH-.

170

XV-22

64-66

XV-23

65-67

Table 9 continuation

At sp. No.

Lard point C ⁰ C]

XV-24

Cl

-CH-.

84

XV-25

91

Preparation of starting materials of the formula (X VI)

Example (XVI-I) 10

SO ₂ -NH ₂ 15

50 ml of concentrated aqueous ammonia solution are added dropwise with stirring at 20 ° C to 30 ⁰ C to a mixture of 60 g (0.27 mol) of 2-methyl thiobenzolsulfonsaurechlorid and 60 ml of acetone, stirred for one hour at 20 "C and poured the The reaction mixture is then poured into 600 ml of 10% sodium hydroxide solution, which is filtered and then acidified with concentrated hydrochloric acid, and the product which has crystallized is isolated by suction.

This gives 19 g (30% of theory) of 2-methylthio-benzenesulfonamide of melting point 149 ^° C.,

- 159 -

The compounds of the formula <XVI) listed in Table 10 below can be prepared by the process described by way of example in the preceding example:

R ¹ -SO ₂ -NH ₂

(XVI)

Table 10

Example no.

Melting point C ⁰ C]

XVI-2 XVI-3 XVI-4 XVI-5 XVI-6

SCH (CH ₃ ) ₂

SO ₂ CH ₃

S0 ₂ N (CH _{3) 2}

156

235

186 - 189

Table IQ continuation

Ex-No.

Melting point [ ⁰ C]

XVI-7

OCHF 134

XVI -

Cl

7 \

CH ₂ "

X VI -

XVI-10

CH ₂ SO ₂ CH ₃

00C ₂ H ₅ 175

78

XVI-11

COOCH (CH ₃ )

XVI-12

XVI-13

COOCH ₃

XVI-14

Ϊ03

At game A pre-emergence test / greenhouse

Solvent: 5 parts by weight of acetone 10

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated 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 after 24 hours with the preparation of active compound beqosa a

sen. While keeping the amount of water per unit area appropriately constant, the active ingredient concentration in the preparation is of no RoIIe ₁ only decisive factor is the amount of active compound per unit area, after three weeks of Schädigungsqrad of the plants.

scores in% damage compared to development

the untreated control, it means:

0 % - no effect (like untreated control) 100 '/. = total annihilation

In this test, for example, the following compounds of Preparation Examples showed excellent activity (3) and (11).

Example B

PosL emergence test / greenhouse

Solvent: 5 parts by weight of acetone 10

.. Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To prepare 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,

With the preparation of active compound injected test plants, which have a height of 5-15 cm so that the thus desired amounts of active ingredient per unit area are applied, the concentration of the spray mixture is chosen so that in 2000 1 water / ha, the respective desired amounts of active ingredient are applied. After three weeks, the degree of damage of the plants is rated in % damage compared to the development of the untreated control, which means:

0% = no effect (as untreated control) 30

100 V. = total annihilation

In this test, z. B, the following compounds of Preparation Examples have excellent activity: (3), (10), (11) and (39)

Claims (1)

R ⁷ and R ⁸ are the same or different and are hydrogen, halogen, in particular fluorine, chlorine and / or BronT), cyano, nitro, C.sub.1 -C.sub.4 -alkyl, which is optionally substituted by fluorine, chlorine, bromine, cyano, C.C. ^ alkoxy "carbonyl" C. -C, -Alkylair.ino-earbonyl, di (C.-C ^ -alkylJ-amino-carbonyl, C ₁ -C. alkoxy, C ₁ 'C ₄ alkylthio, C -C ^ ₁ alkyl - 153a ! sulfinyl or C.-C ^ -Alky sulfonyl substituted ^ i ^ -alkoxy is C ₁ -C £ which gegebonanfalls by fluorine, chlorine, bromine, cyano, C ₁ -C -AlUoxy-carbonyl, CC ^, - Alkoxy, C ^ -C ^ alkylthio, C ₁ -C -Alley 1-3ulfinvl or C ₁ -C ₄ -alkylsulfony1], for C ₁ -C ₄ -alkylthio _, C ₁ -C ₄ -alkyl-sulfinyl or C ₁ -C ₄ -alkylsulfonyl [which is optionally substituted by fluorine, chlorine, ._ Bromine, cyano or C ₁ -C ₄ -alkoxycarbonyl substituted], for C ₁ -C ₄ -AlKyI-amino-sulfonyl, di- (C ₁ -C ₄ -alkyl) -amino -sulfonyl, C ^ -C ₄ -alkoxyamino-sulfony1, benzyloxy-aminosulfony1, C ₁ -C ₄ -alkoxy "E" -C ₁ -C ₄ alkyl-aminosulfony1, for phenyl or, ~ phenoxy C ₁ -C ₄ -Alkoxysulfony1 for C2 C _£) alkenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, C ₁ -C ₄ -alkoxy-carbonyl, carboxy or 2Q phenyl is substituted], for ^ 2 ~ ^ 6 ~ Alkynyl [which is optionally substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ - alkoxy-carbonyl], for C 9 -C 12 alkenoxy [which may be substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ -alkoxy-carbonyl is substituted], for C 9 -C 12 -alkenylthio [which is optionally substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ -alkoxycarbonyl 3Q is substituted], for C ₁ -C ^ -alkoxy carbonyl [which is optionally substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ -alkoxy], for C 9 -C 12 -cycloalkoxycarbonyl, for C ₁ -C 12 -alkylthiocarbony1 [which may be by fluorine, chlorine, bromine, cyano or C ₁ -C 4 alkoxycarbonyl is substituted], for aminocarbonyl, C ₁ -C 4 alkylamino carbonyl, di (C ₁ -C 4 alkyl) amino carbonyl, C ₁ -C 4 alkoxyaminocarbonyl, Co ^- C ^ -Alkenyloxy-amino-carbonyl ^ Benzyloxyaminocarbony1, C ^ -C ^ - alkoxy-Cj-C ^ -alky1-amino-carbonyl , Dimethylhydrazinocarbonyl, Dimethylhydra z inosulfonyl, for Cg-C ^ -Alkinyloxy or Cg-C ^ Alkynylthio). in which further R is an optionally substituted benzyl radical stands in which R ⁹ and R ¹⁰ are identical or different and are hydrogen, halogen [in particular fluorine, chlorine or bromine], cyano, nitro, C 1 -C 4 -alkyl [which is optionally substituted by fluorine and / or chlorine], C 1 -C 4 -alkoxy [ which is optionally substituted by fluorine and / or chlorine], C ₁ -C 4 -alkoxy-carbonyl, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl or di (C ₁ -C ₄ alkyl) aminosulfony1; in which further 10 R ^{2 is} hydrogen, C ₁ -C ₄ -alkyl or a sulfonyl radical R - ^ - SO ₂ -, wherein R ^{11 is} C ₁ -C ₁₂ -AlRyI [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro ,. C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylamino-carbonyl, di- (C ₁ -C ₄ alkyl) -amino-carbonyl, C ₁ -C ₄ alkoxy, C ₁ -C _4- alkylthio, C ₁ -C ₄ -AlRyIsUlfinyl or C ₁ -C ₄ ~ alkylsulfonyl substituted], for C ₁ -C ₁₂ -Akoxy [which optionally by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -Alkoxy-carbonyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -aryl-sulfinyl or C ₁ -C ₄ -alkyl-5-cykenyl], for C ₂ -C ₁₂ -alkenyl [optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -Al- koxy, C ₁ -C ₄ ~ alkylthio or phenyl subsets U is substituted], for C ₂ -C ₁₂ -alkenyloxy [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl or phenyl], for C ₁ -Cg- alkylamino, di - (C ₁ -C ₄ -alkyl) -amino, C ^ C ^ - -Cycloalkyl-ami.no or di - (C3 ~ C _£) -eye loalkyl) -amino [which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, phenyl, phenoxy, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -A ₁₄ sulfinyl or C ₁ -C ₄ ~ Alky1sulfonyl are substituted], for C ^ ^- Cg-alkenylamines [which is optionally substituted by fluorine, chlorine, Bromine, cyano, nitro or phenyl substituted is], for phenylamino or benzylamino [which is optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -fluoroalkoxy, C ₁ -C ₄ - Alky1thio, C ₁ -C ₄ - _. Alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, cyano, Nitro and / or C 1 -C ₄ -alkoxy-carbonyls], for benzyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ - C ₄ - __-Alkoxy-carbonyl1 ,. C ₁ -C ₄ alkoxy or di- (C ₁ - -C ₄ alkyl] -sulfonyl-substituted] or an optionally substituted th phenyl radical R and R are the same or different and the meanings given above for R and R. but not in everyone Individual case with R ⁷ and R ⁸ ident is ch ind; in which further R ^{3 is} the radical -QR ¹⁴ in which R ¹⁴ for C ₁ -C ₁₂ " ^Alk y! [Which optionally by fluorine, chlorine, bromine, C ₁ -C ₄ -alkoxy, C ₁ - substituted -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ ~ -C -Alky1sulfony1 is], for C ₃ -C ₆ - Cycloalkyl, C ₃ -C ₆ -cycloalkyl-C 1 -C ₄ -alkyl, C ₁ -C 4 -alkenyl 1, [which is optionally substituted by fluorine, chlorine or bromine], C ₃ -C ₆ -alkynyl, C ₁ -C ₄ -alkyl alkoxy-carbonyl C ι ~ -C2 alky 1, amino-car bony lme thy 1, C ₁ -C ₄ -alkylamino-carbonyl-methyl, di- (C ₁ -C ₄ alkyl) - amino-carbonyl methyl or phenyl, benzyl, benzhydryl or phenylethyl [which may be substituted by fluorine, chlorine, nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl substituted] stands; in which further ²⁵ ir R ¹⁵ R ^{3 is} the radical -N, in which ³⁰ ις R ^{iD is} hydrogen or C ₁ -C ₄ -A ^ yI and R ^{16 is} hydrogen, C ₁ -C ₄ -AhCyI [which is optionally substituted by fluorine, chlorine, bromine, cyano, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl], for C ₃ -C ^ -Cyc1oalky1, for Phenyl, benzyl or phenylethyl [which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Cj-C ^ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-carbonyl], for C ₁ -C ₄ alkyl - carbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylsulfony1 or phenylsulfonyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro or methyl]; in which further - in the event that R is a sulfonyl radical R-SOo ", where R has the meaning given above - R is also hydrogen; in which further R ^{4 is} hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -A [which is optionally substituted by fluorine and / or chlorine], for C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine and / or chlorine] or for C ₁ -C 1 -alkylthio [wel ches optionally substituted by fluorine and / or chlorine is substituted] stands; R is hydrogen, fluorine, chlorine, bromine, C.sub.1 -C.sub.4 -alkyl, and the radical is optionally substituted by fluorine and / or chlorine !, for cyano, formyl, C.sub.1 -C.sub.12, -alkylcarbonyl, c.sub.ds, C. -C ^ alkoxycarbonyl and R ^{3 is} hydrogen, for C -C, alkyl fluoride given J. F when substituted by fluorine and / or chlorine, j, for C ₁ -C ₇ -alkoxy, optionally substituted by fluorine, and / or chlorine ', JJ, for amino, C ₁ -C -alkylamino or di- (C ₁ -C -alkyl) -amino stands • 4 5 - with the proviso that R and R are not simultaneous stand for methyl - ' and l: 'l adducts of compounds of formal (I) with strong acids, the following compounds are exempted: N ^t - (4,5-dimethoxy-pyris-midin-2-yl) -N ^f '-mothoxy-W ¹ "- (2-t-rifluoromethoxy-benzenesulfonyl) -guanidine dinium salt, N' - (4-methoxy-6 -methyl-pyrimidin-2-yl) -N "-dimethylamino-N '''- (2-methyl-benzenesulfonyl) -guanidine, N' - (4-mothoxy-6-methyl-pyrimidin-2-yl ) -N '' - msthoxy-N '''- (2-chloro-benzenesulfonyl) -guanidine and N' - (4-methoxy-6-methyl-pyrimidin-2-yl) -M '' - dimothylamino-N '''- (2-chlorobenzenesulfonyl) guanidine, in addition to extenders and / or surface-active agents. Use of sulfonylguanic-jinopyrimidine-darivaton of the general formula (I) according to item 1, characterized in that it is used to combat unerviceable _β process z ^ r l-brotellung of 'horbizidsn means, characterized in that nan Sulfonylguanidincpyrinidin ™ derivative dsr allgoniainsn formal (I) are mixed according to item i with Streckniittaln and / or surface active agents _β