DE2444822A1 - 2,1,3-BENZOTHIADIAZIN (4) ON-2,2 DIOXIDE DERIVATIVES - Google Patents

Description

BASF Aktiengesellschaft

Our reference: O „Ζ.30 824 Sws / Wil 6700 Ludwigshafen, 17-9-1974

2,3-Benzothiadiazin (4) one-2,2-dioxide derivatives

The present invention relates to new valuable substituted 2, l _s) > -Benzothiadiazin (4) -one-2,2-dioxides with herbicidal action, herbicides which contain these active ingredients, processes for controlling undesired vegetation with these compounds and processes for their preparation .

It is known that 3-isopropyl-2, l,> - benzothiadiazin (4) one-2,2-dioxide is used as a herbicidal active ingredient (DT-PS 1 542 836). In practice, however, its use leads to damage to the treated crops.

It has now been found that compounds of the general formula

R ₁ -N '

(XXV)

in which R _{1 is} an isopropyl group and R ²

a) a formyl group, a propionyl, n-butyryl, valeryl, Isovaleryl-, sec-valeryl-, capronyl-, l- (oi-methyl-valeryl) -, Oenanthyl radical, an acyl radical with more than 8 carbon atoms, one substituted by halogen, the acetoxy or alkoxy group Acyl radical, an optionally halophenoxy and / or alkylphenoxy-substituted acyl radical, an unsaturated, optionally halogen-substituted acyl radical, a cycloacyl radical, a diacyl radical or

b) an alkoxy or alkylmercapto-carbonyl radical, optionally one phenoxycarbonyl or phenylmercapto-carbonyl radical substituted by alkoxy groups, an optionally halogen-substituted one Benzylmercapto-carbonyl radical or

c) a dialkylcarbamoyl radical optionally substituted by alkoxy groups, a dialkylthiocarbamoyl radical, a

305/74 809815/1253 / 2-

- 2 - O.Z. 30 624

2U4822

N-phenyl-N ', N ^! dialkylformamidinyl radical or

d) an alkylsulfonyl radical or one which is optionally substituted by halogen atoms, nitro groups or alkyl groups Arylsulfonylrest or

e) a mono- or dialkylsulfamoyl radical or

f) an N-alkyl-benzimidyl radical or

g) a 0, 0-dialkyl phosphorothioate or phosphate radical or h) an optionally halogen-substituted alkylsulfenyl radical or

i) denotes a phenyl radical substituted by nitro groups, have a better herbicidal effect than the known Active ingredient,

R ₂ can include mean; Formyl, propionyl, n-butyryl, valeryl, isovaleryl, sec.-valeryl, capronyl, oil- methyl valeryl, önanthyl, pelargonyl, caprinyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, a-, chloroacetoxyacetyl, a-, chloroacetoxyacetyl Chlorpropionyl, α, οί-dichloropropionyl, tf-chlorobutyryl, oi-chlorovaleryl, «-chlorocapronyl, ß-chloropropionyl, / -bromobutyryl, acryloyl, but (2) enoyl-1, pent (3) enoyl-1, methoxyacetyl, ß- Methoxypropionyl, / -Methoxybutyryl, cyclopentanoyl, cyclohexanoyl, benzoyl, ct-naphthoyl, o-, m-, p-bromobenzoyl, o-, m-, p-nitrobenzoyl, phenoxyacetyl, p-chlorophenoxyacetyl, 2,4-dichlorophenoxyacetyl, 2, 4,5-trichlorophenoxyacetyl, 2-methyl-4-chlorophenoxyacetyl, 2,4-dichlorophenoxy-o; -propionyl, oxalyl, malonyl, succinyl, glutaryl, adipoyl, decane (l, 10) dioyl, α-bromobutyryl, methoxycarbonyl, ethoxycarbonyl , Propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, isobutoxycarbonyl, sec “-butoxycarbonyl, n-pentyloxycarbonyl, pentyl (3) oxycarbonyl, cyclope ntyloxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl, Uhdeeyloxycarbonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, tetradecyloxycarbonyl, pentadecyloxycarbonyl, hexadecyloxycarbonyl, o-methoxyphenoxycarbonyl, Methylmercaptocarbonyli, Ä'thylmeroaptocarbonyl, n-PrOpylmeroaptocarbonyl, Isopropyl mercaptocarbonyl, n-butyl mercaptocarbonyl, p-chlorobenzyl mercaptocarbonyl, phenyl mercaptocarbonyl, p-methoxyphenyl mercaptocarbonyl, dimethylcarbamoyl, diethylcarbamoyl, din-propylcarbamoyl, diisopropylcarbamoyl, di-η-butylcarbamoyl,

6ÜSÖ1Ö / 1253 .

- 3 - O.Z. 30 824

Di-sec-butylcarbamoyl, N-methyl-N-propoxymethylcarbamoyl, 1-piperidinoyl-, hexahydro-1'-H-azepin-1 * -oyl, dimethylthiocarbamoyl, Diethylthiocarbamoyl, di-n-propylthiocarbamoyl, diisopropylthiocarbamoyl, N-phenyl-N, N-dimethylformamidinyl, Methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, n-pentylsulfonyl, Benzenesulfonyl, p-toluenesulfonyl, o-, m-, p-bromobenzenesulfonyl, o-, m-, p-nitrobenzenesulfonyl, ß-naphthalenesulfonyl, Dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl, methylaminosulfonyl, Ethylaminosulfonyl, η-propylaminosulfonyl, isopropylaminosulfonyl, n-butylaminosulfonyl, N-methylbenzimidyl, N-ethylbenzimidyl, N-propylbenzimidyl, 0, O-dimethyl-phosphorothioate, 0, O-diethyl phosphorothioate, 0, O-di-n-propyl phosphorothioate, 0,0-dimethyl phosphate, 0,0-diethyl phosphate, perchloromethylthio, 2,4,6-trinitrophenyl.

The preparation of the compounds of the formula XXV, in which Rp is a substituted acyl or aroyl radical, can be carried out, for example, by reacting a 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-1-alkali metal (or alkaline earth metal) or ammonium salt of the formula II with a substituted acyl halide I in a polar solvent in a temperature range from -10 to HO ⁰ C for between half an hour to 12 hours,

0 \ R-C-HaI +> -

-MeHaI

I II

where Me is an equivalent of an alkali metal ion or an alkaline earth metal ion or ammonium ion and Hal denotes a chlorine atom or bromine atom and R-CO- denotes the meanings given above for Rg under a) Has.

For work-up, the precipitated metal or ammonium salt is optionally separated off and concentrated in vacuo. The cleaning

O.Z. 30 624

takes place by recrystallization or by extraction with dilute Alkali and neutral washing from water immiscible solvents. In the latter case, after drying and Concentration of the organic phase isolates the pure compounds IV.

Instead of the starting material II, however, it is also possible to directly use the substance of the formula III which forms it with a substituted acyl halide I react in the presence of a tertiary base under the conditions given above,

0
RC-HaI +

- HHaI

III

IV

where Hai denotes a chlorine atom or a bromine atom and R-CO- denotes the above for Rp has the meanings given under a).

The purification is carried out in the usual way by extracting the water-soluble base hydrochloride and work-up according to the procedure given above.

In the case of the production of the l-formyl - ^ - isopropyl ^ l ^ -benzothiadiazln (4) one-2,2-dioxide VI, the synthesis takes place by reacting the starting material III with the mixed formic acid acetic anhydride V and working up according to the procedure given above,
0 0

Il It

HC-OC-CH ₃ +

III

VI

If 2 equivalents of j5-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-1-sodium salt are used II with one equivalent of oxalyl chloride VII as the simplest representative of lower diacyl halides the above reaction conditions, the compound is obtained

6 Ci i) 8 1 b / 1.2 I = 3

O.Z, 30 824

of formula VIII
0

T.I

0 0

tt!?

+ Cl-C-C-Cl

VII

VIII

For the preparation of substituted 1-alkoxy- or aryloxycarbonyl or alkylraereapto-carbonyl-j5-isopropyl-2,1, j5-benzothiadiazin (4) one ~ 2 _j) 2-dioxides X, the starting salts of the formula II are used with appropriately substituted chloroformic esters IX according to the reaction conditions given above, where Me is an equivalent of an alkali metal ion or alkaline earth metal ion or ammonium ion and -CO-OR or -CO-SR has the meanings given above for R_ under b) »

0 Cl = C-OR

II

-SR

IX

In an analogous manner, reaction of the compounds II with substituted or unsubstituted dialkylcarbamoyl, thiocarbamoyl chlorides is obtained or N-phenyl-N ', N'-dialkylchloroformamidines XI to the compounds XII, where Me is one equivalent of an alkali metal ion or alkaline earth metal ion or ammonium ion means 0 (S) (N-phenyl)

-C-NAIk ₄ .

has interpretations,
0

II

the above for Rp under c)

0 (S); (N-phenyl)

+ Cl-C-NAIk,

XI

(Phenyl-N) j (S) j O = C-NAIk,

XII

6098-15 / 1253

O.Z. 30 824

By reacting optionally substituted alkyl or arylsulfonyl chlorides XIII with the starting compounds II, compounds of the formula XIV are obtained in an analogous manner, where Me is an equivalent of an alkali metal ion or alkaline earth metal ion or ammonium ion and -SO ₀ R has the _{meanings given above for R 2} under d)
0

Cl-SO ₂ R

XIII

II

XIV

If mono- or dialkylsulfamoyl chlorides XV are used, the compounds are obtained in the manner described above XVI, where Me is an equivalent of an alkali metal ion or earth

pp has the meanings given above for Rp under e); NHAlK

II

+ Cl-SO ₂ -NAIk ₂ -NHAIk

XV

XVI

If N-alkyl benzimide chlorides XVII are used in an analogous manner the starting salts II to give 1- (N-alkyl-benzimidyl) -3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide of formula XVIII, where Me is one equivalent of an alkali metal ion or alkaline earth metal ion or ammonium ions and -C = N-AIk denotes

has the meanings given above for R _{2 under f):}

Cl
+ (' VC = N-AIk

Alc

II

XVII
609815/1263

XVIII

O.Z. 30 & 24

2U4822

When using optionally halogenated alkylsulfenyl halides XIX is obtained under the reaction conditions given above, l-alkylthio-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide XX, where Me is an equivalent of an alkali metal ion or alkaline earth metal ion or ammonium ion and -SR is the has the meanings given above for Rp under h);

ClSR

II

XIX

S-R

XX

If the starting salts II are reacted in an analogous manner with a dialkyl phosphoric acid ester halide, 3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide-1- (0, O-dialkylphosphorothioate or _0- phosphate) is obtained ) XXII, where Me is an equivalent of an alkali metal ion or an alkaline earth metal ion or ammonium ion and -P = (OAIk) ₀ those listed above for R ₀ under g)

(0)

Has meanings:

dd

N
Me

II

(0)
S.

HaI-P = (OAIk),

XXI

(O) S = P (OAIk), XXII

Finally, the action of nitrophenyl halides XXIII on the starting salts II stirs in a manner analogous to l- / nitrophenyl7-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxides XXIV, where Me is an equivalent of an alkali metal ion or Alkaline earth metal ions or ammonium ions and Hai is a halogen radical and has the _{meanings given above for R 0} under i):

6 ü i) Ü 1 Ii / 1 2

I!

Me II

+ Hal

XXIII

O. Z. 30 & 24

xxrv

(N0 _o )

The starting materials II or III can be reacted with the desired acid chlorides in stoichiometric amounts or an excess of acid chloride, preferably in a ratio of 1.01 to 1.2 mol of acid chloride per mole of starting material II or III. The preparation of the starting materials II and III is described in UoS ₀ patent specification j5 041 336 and German patent specification 1,542,836.

As a tertiary base for the reactions of the starting materials III are, for example, trimethylamine, triethylamine, pyridine, tf, ß, f-picoline, lutidine, Ν, Ν-dimethylaniline, Ν, Ν-dimethylcyclohexylamine, Quinoline, isoquinoline, quinazoline, tri-n-butylamine, tri-n-propylamine and N-propyl-diisopropylamine »

As polar solvents one can use chlorobenzene, o-, m-, p-dichlorobenzene, Nitrobenzene, anisole, toluene, methylene chloride, chloroform, 1,1- and 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2- and 1,1,1,2-tetrachloroethane, substituted carbonamides such as N-methyl and N, N-dimethylformamide, ketones such as acetone, methyl ethyl ketone, Acetophenone, cyclohexanone, esters such as methyl acetate, isobutyl acetate, ethers such as diethyl ether, di-n-propyl ether, dioxane, tetrahydrofuran and use nitriles such as acetonitrile, isobutyronitrile and benzonitrile.

The reactions are performed in a temperature range of -10 to +70 ⁰ C, preferably from 0 to +40 ⁰ C, generally carried out; however, it may also be necessary in the case of less reactive acid chlorides

O.

to be heated up to 110 C.

- 9 - O.Z. 30 824

example 1

1-Formyl-3-isopropyl-2,1,3-benzothiadiazin (4-) one-2,2-dioxide

32 parts (parts by weight) of a 30% (percent by weight) solution of the mixed formic acid-acetic anhydride (prepared from equimolar amounts of formic acid and acetic anhydride) in a mixture of formic and acetic acid are added at room temperature to a solution of 24 parts of 3-isopropyl-2, l , 3-benzothiadiazin (4) -one-2,2-dioxide fed in 120 parts of acetonitrile. The reaction mixture is ^{stirred for 3 hours at 50 °} C. and then concentrated in vacuo. The residue is taken up in methylene chloride, extracted four times with 0.5 μm sodium hydroxide solution and with water and dried over magnesium sulfate. After concentration in vacuo, 24 parts are obtained (90% of theory) of l-Pormyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide as colorless crystals with Pp. 90 to 99 ⁰ C ()

Example 2

1- (2 ', 4'-dichlorophenoxy - / ^ butyryl) -3-isopropyl-2,1,3-benzothia diazin (4) one-2,2-dioxide

29.5 parts of 2,4-dichlorophenoxy-f-butyryl chloride is allowed within 15 minutes at 15 to 20 ⁰ C to a stirred solution of 26.2 parts of 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2 , 2-dioxide-1-sodium salt in 120 parts of acetonitrile run in. The reaction mixture is ^{stirred for one hour at 20 °} C. and then freed from the solvent in vacuo. The residue is taken up in methylene chloride, extracted four times with 5% sodium carbonate solution, washed with water and dried over magnesium sulfate. After concentration in vacuo, 38 parts (81 % of theory) 1- (2 ', 4'-dichlorophenoxy-Z ^ butyryl) -3-isopropyl-2,1,3-benzothiadiazine) one-2,2-dioxide are obtained as a colorless viscous oil. Colorless crystals with a melting point of 106 ° to 109 ° C. are obtained after trituration in cyclohexane.

The following compounds were obtained in an analogous manner:

.-2,1,3-benzothiadiazine) one-2,2-dioxide,

Mp. 103 to 105 ⁰ C.

6Q9815 / 1253

- 10 - 0.2. 30th

l-butyryl ~ 3-isopropyl-2, l, 3-kenzothiadiazin (4) on-

2,2-dioxide

1-sekoValeryl- "69 bis

1-valeryl- "39 bis

1-iscvaleryl- "

1-capronyl- "67 bis

1- (α-methyl-valeryl) - "42 bis

1-oenanthyl "

1-Pelargonyl- "n ^ ⁵ = 1.5128

1-caprinyl "

1-undecanoyl "

1-dodecanoyl "

1-tridecanoyl "

1-tetradecanoyl "

1-pentadecanoyl "

1-palmitoyl- "65 bis

1-acetoxyacetyl- "69 bis

1-chloroacetyl- "IO6 to IO9

1-dichloroacetyl "

1-a-chloro-propionyl- "83 bis

l- <y, ui-di-chloropropionyl-3- "isopropyl-2,3-ben2othiadiazin (4) one-2,2-dioxide

1-tt-chlorobutyryl- "

1 - ^ - chlorovaleryl "

l-iX-chlorocapronyl- "

1-ß-chloropropionyl- "

1 - / -Bromobutyryl- "

1-acryloyl- ⁿ 71 bis

l-but-2'-enoyl- "

l-pent-3'-enoyl- " ηψ = 1.5334

1-methoxyacetyl "

1-ß-methoxypropionyl-1- / i-methoxybutyryl-

tl

609815/1253

/ 11

- 11 - 0.'Z. 30 824

l-Benzoyl-3-isopropyl-2, l, 3-benzothiadiazin (4) on-

127 to 131 120 to 125

2,2-dioxide Malonyl-bis- dd Ι-α-Nphthoyl- dd Succinyl-bis- dd 1-ο-bromobenzoyl Il Glutaryl-bis- dd 1-p-bromobenzoyl It Adipoyl-bis- It 1 - m-bromobenz oyl- Il 1-p-nitrobenzoyl- It 1-m-nitrobenzoyl- It 1-o-nitrobenzoyl- It 1-phenoxyacetyl- It 1-p-chlorophenoxyacetyl Il 1-2 ', 4'-dichlorophenoxy acetyl It 1-2 ', 4', 5'-trichloro phenoxyacetyl dd l-2'-methyl-4 ^f -chlor- phenoxyacetyl dd 1-2 ', 4'-dichlorophenoxy Ä-propionyl- It 1-cyclopentanoyl It 1-cyclohexanoyl- dd 0xalyl-bis-l - ^ - isopropyl-2, l, 3-be (4) one-2,2-dioxide 7

111 to 116 106 to 111 138 to 143 164 to 170 I6l to I63 105 to 108 94 to 96

223 to 224 dec.

Decan (1,10) -dioyl-bis-1 ' -ß ^x -isopropyl-2 ¹ , 1', 3'-

benzothiadiazine *) one-2 ', 2 * -dioxide / 128 to 135

Example 3

1-a-bromobutyryl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2- dioxide

22.9 parts of tf-bromobutyric acid bromide are left within 10 minutes

6098 1 57 12b3 / 12

- 12 - O. Z, 50 824

2U4822

at 10 ⁰ C with stirring a solution of 24 parts of 3-isopropyl-2, 1,3-benzothiadiazin (4) one-2;, 2-dioxide and 10.1 parts of triethylamine in 130 parts of acetonitrile run. The reaction mixture is stirred for 10 minutes at 2O ⁰ C and then suction filtered. The filtrate is then concentrated in vacuo, taken up in benzene and washed twice each with 5% sodium hydrogen carbonate solution and water. After drying and concentration, 1-a-bromobutyryl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide is obtained as a colorless oil (nfp = 1.5552), which when rubbed in Petroleum ether with pp. 73 to 78 ⁰ C crystallized.

Example 4

3-isopropyl ~ 2, l _J 3-benzothiadiazin (4) one-2,2-dioxide-ln-butyl carbamate

A solution of 15 parts of chloroformic acid is added to a solution of 2β, 2 parts of 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-1-sodium salt in 120 parts of acetonitrile with stirring over the course of 15 minutes -n-butyl run in 15 parts of acetonitrile at 15 to 2O ⁰ C. The reaction mixture is ^{stirred at 20 °} C. for one hour and at 65 ^° C. for 2 hours. After concentration in vacuo, the residue is taken up in methylene chloride, extracted three times with 0.3 η sodium hydroxide solution and with water and dried over magnesium sulfate. Upon concentration of the 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-ln-butyl carbamate as a viscous oil which crystallizes on triturating in petroleum ether with Pp. 48 to 54 ⁰ C.

In the same way the following compounds were obtained:

Fp. ( ⁰ C)

3-isopropyl-2, l, 3-benzothiadiazin (4) -one-2,2-dioxide-

-1-methyl carbamate I03 to 105

"-1-ethyl carbamate 109 to 120

"-1-n-propyl carbamate

"-I-1sopropyl carbamate

"-1-isobutyl carbamate

"-1-sec-butyl carbamate

6 C- υ Ϊ 1 b I 1 2 L. 'J / 13

- 13 - O.Z. 10 824

24U822

3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide-

-1-tert-butyl carbamate

"-1-n-pentyl carbamate

"-l- (3'-pentylcarbaraat)

"-l-cyclopentyl carbamate

"-1-n-hexyl carbamate

"-l-n-cyclohexyl carbamate

"-1-n-heptyl carbamate

"-1-n-octyl carbamate

"-1-n-nonyl carbamate

"-1-n-decyl carbamate

"-1-undecyl carbamate

"-1-dodecyl carbamate

"-1-tridecyl carbamate

"-l-tetradecyl carbamate

"-l-pentadecyl carbamate

"-1-hexadecyl carbamate 66-68

"-1-phenyl carbamate 111-115

"-1-o-methoxyphenyl carbamate 130 to 133

"-1-methyl mercaptocarbamate 117 to 121

"-l-ethyl mercaptocarbamate

"-In-propyl mercaptocarbamate n _D ^ = 1.5553

"-1-isopropyl mercaptocarbamate

"-1-n-butyl mercaptocarbamate

"-1-p-chlorobenzyl mercapto-

carbamate 98 to 100

-1-phenyl mercaptocarbamate

"-1-p-methoxyphenylmercapto-

carbamate

Example 5

l-Dimethylcarbanloyl-3-isopropyl-2,3-benzothiadiazln (4) one-2,2- dioxide

13.9 parts of 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxidkaliumsalz were heated in 15 parts Dimethylcarbaminsäurechlorid 5 hours at 100 to HO ⁰ C. 150 parts of a 1: 2 mixture of benzene and ether were added and the potassium chloride was filtered off with suction (3.6 parts). The filtrate was 100 parts of a

609815/1253

- 14 - O.Z. 30 824

1: 2 mixture of ether and petroleum ether added; then the crystalline product was filtered off with suction and recrystallized from cyclohexane. Were obtained, the l-dimethylcarbamoyl-3-isopropyl-2 l, 3-benzothiadiazin (4) one-2,2-dioxide, Pp. 83 to 85.5 ⁰ C.

In the same way the following compounds were obtained:

Fp. ( ⁰ C)

l-diethylcarbamoyl ~ 3-isopropyl-2, l, 3-benzothia-

diazin (4) one-2,2-dioxide 100 bis l-di-n-propylcarbamoyl- "

l-diisopropylcarbamoyl- "150 bis

1-n-dibutylcarbamoyl- "
l-di-sec-butylcarbamoyl- "

1-N-methyl-Nn-propoxymethyl- _pc -

carbamoyl- "njp = 1.5239

1- / F-piperidinoyl7- "8l to 84

1- / Hexahydro-1'-H-azepine-Γ -

oyl7- "100 to

1-dimethylthiocarbamoyl- "78 to 8l

l-diethylthiocarbamoyl "

l-di-n-propylthiocarbamoyl- "

1-diisopropylthiocarbamoyl- "

l- / N ^f -phenyl-N ", N" -dimethylformamidinyl7-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide

Example 6

l-methylsulfonyl-3-isopropyl-2,3-benzothiadlazine (4) one-2,2- dioxide

To a solution of 26.2 parts of 3-isopropyl-2,1,3-benzothiadiazine (4) one-2,2-dioxid4 sodium salt in 120 parts of acetonitrile is allowed under stirring within 10 minutes at 20 ⁰ C 12.6 Parts of methanesulfonyl chloride run in. The reaction mixture is ^{stirred at 20 °} C. for half an hour and at 60 to 65 ^° C. for 2 hours. Now one sucks off the precipitated table salt and constricts the Pil entered in a vacuum. The residue is rubbed in ether, filtered off with suction and washed neutral with water, the l-methylsulfonyl-3-isopropyl-

609315/1253 ^{/ 15}

- 15 - O, Z. 30 824

24M822

2, l, 3-benzothiadiazin (4) one-2,2-dioxide colorless crystals in Porm Pp is obtained from 156 to 158 ⁰ C.

The following compounds were obtained in an analogous manner;

Fp. ( ⁰ C)

1-ethylsulfonyl-3-isopropyl-2,1,3-benzothiadiazine

(4) on-2,2-dioxide 110 to 112

1-n-propylsulfonyl- "

1-isopropylsulfonyl- "

1-butylsulfonyl- "

1-sec butylsulfonyl- "

1-isobutylsulfonyl- "103 to 110

1-pentylsulfonyl- "

1-Benz oil sulfonyl- "162 to I66

1-p-Toluenesulfonyl- "141 to 143

1-p-bromobenzenesulfonyl- ^1T I63 to I68

1-o-bromobenzenesulfonyl- "

1-m-bromobenzenesulfonyl "

1-p-nitrobenzenesulfonyl- "160 to 175

1-o-nitrobenzenesulfonyl- "

1-m-nitrobenzenesulfonyl- "

1-B-naphthalenesulfonyl- "I06

Example 7

1-dimethylsulfamoyl-3-isopropyl-2,1, 3-benzothiadi azine (4) one-2,2-dioxide

To a solution of 26.2 parts of 3-isopropyl-2, l, 3-benzothiadiazin- (4) one-2,2-dioxide-1-sodium salt in 120 parts of acetonitrile is allowed with stirring at 20 ^° C. within 10 minutes Run 8 parts of dimethylsulfamoylechloride in 15 parts of acetonitrile. The Heaktionsgemiseh is stirred for 4 hours at 65 ⁰ C. After the precipitated common salt has been filtered off with suction, the piltrate is concentrated in vacuo and digested in 50 parts of hot methanol. It now sucks hot from "insoluble matter from the cooled and rubs Piltrat in. After the suction, to be colorless crystals of 1-dimethylsulfamoyl-3-isopropyl-2, l _J 3-benzothiadiazin (4) one-2,2-dioxide with ~ Pp. I35 to 14l ° C obtained.

6 L- d 8 1 6/1 2 L- ^:!

- 16 - O.Z. 30 8ρ4

24U822

The following compounds were obtained in an analogous manner:

Fp. ( ⁰ C)

l-diethylsulfamoyl ^ -isopropyl- ^, 1,3-benzothia-

diazin (4) one-2,2-dioxide 1-di-n-propylsulfamoyl- "

1-methylaminosulfonyl- "151 to 153

l-ethylaminosulfonyl- "
1-n-propylaminosulfonyl- "

1-isopropylaminosulfonyl- "151-153

1-n-butylaminosulfonyl- "

Example 8

1- / N-methyl-benzimidyl. 7-3-isopropyl-2,3-benzothiadiazin (4) one- 2,2-dioxide

A solution of 26.2 parts of 3-isopropyl-2, l, 3-benzothiadiazin (4) -one-2,2-dioxide-l-sodium salt in 120 parts of acetonitrile is allowed at 15 to 2O ⁰ C within 10 minutes while stirring run in to 15.4 parts of N-methylbenzimidyl chloride in 120 parts of acetonitrile. The reaction mixture is stirred for a further hours at 2O ⁰ C and then concentrated in vacuo. The residue is taken up in methylene chloride, extracted four times with 10% sodium carbonate solution, washed with water and dried. After concentration in vacuo, the l- / N-methylbenzimidyl7-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide is isolated as a viscous oil which crystallizes by trituration in petroleum ether; M.p. 85 to 95 ° C. A sample recrystallized from cyclohexane melts at 96 to 103 ° C.

The following compounds were prepared in an analogous manner: l- / N-Ethylbenzimidyl7-3-isopropyl-2, l, 3-benzothladiazin (4) on-

2,2-dioxide
! - / Nn-PropylbenzimidylZ - ^ - isopropyl - ^, 1,3-benzothiadiazin (4) one-2,2-dioxide

Example 9

3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-l- _i / Ö, 0-diethyl-

phosphorothioa_b7

6 0 a ti 1b / 1 2 b 3/17

- 17 - O.Z. 30 & 24

18.9 parts of O ^ O-diethylthiophosphoric acid chloride were added at room temperature to a solution of 2β, 2 parts of 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-1-sodium salt in 120 parts of acetonitrile. The reaction mixture is stirred at reflux for 12 hours. It is then concentrated in vacuo, taken up in benzene and extracted twice each with water, 10 % sodium hydrogen carbonate solution and water. After drying and concentration, the 3-isopropyl-2,1,3-benzothiadiazine) one-2,2-dioxidl- / Ö, 0-diethyl-phosphorothioa_t7 is obtained as a viscous oil with njp = 1.5219.

The following compounds were obtained in an analogous manner: 3-Isopropyl-2, 1,3-benzothiadiazin (4) one-2,2-dioxide-1- / O, O-dimethylphosphorothioate /, n ^ ⁵ = 1.5424
3-Isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide-1- / Ö, 0-di-npropylpho sphoro thi oa_t7

3-Isopropyl-2,1,3-benzothiadiazine) one-2,2-dioxide-1- / O, 0-dimethylphosphate 7

3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-l - ^ / Ö, 0-diethyl-

Example 10

l-Perchloromethylthio-3-isopropyl-2,3-benzothiadiazin (4) one 2,2-dioxide

19.5 parts of perchloromethylsulfenyl chloride are added to a solution of 26.2 parts of 3-isopropyl-2,1,3-benzothiadiazin- (4) one-2,2-dioxide in 52 parts of acetone with stirring at room temperature over the course of 10 minutes. The reaction mixture is ^{stirred for one hour at 20 °} C. and then separated off from the precipitated salt. After concentrating in vacuo, the residue is taken up in methylene chloride, washed three times with 0.3 η sodium hydroxide solution and with water and then dried over magnesium sulfate. After concentration in vacuo, the l-perchloromethylthio-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide is obtained as a viscous oil; by triturating with petroleum ether the substance 77 crystallizes with the Pp. to 80 ⁰ C.

609815/1253 ^{/ l8}

- 18 - C.E. 30th

24U822

Example 11

1- (2 ', 4'j6'-trinitrophenyl) -3-isopropyl-2,1,3-benzothiadiazin- (4) one-2,2-dioxide

27.8 parts of 3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide potassium salt were suspended in 150 parts by volume of acetonitrile at 20 ° C. and a solution of 27.1 parts of picryl chloride in 50 parts by volume of acetoniril was added dropwise. After three hours of refluxing, the potassium chloride was filtered off with suction (6.2 parts) and the filtrate was concentrated. The residue crystallizes on trituration with a mixture of ether and petroleum ether. Yellow-red crystals of 1- (2 ', 4', 6'-trinitrophenyl) -3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide, boiling point 110 to 115 ° C., are obtained after recrystallization from carbon tetrachloride 153 to 157 ⁰ C

The application takes place z. B. in the form of directly sprayable Solutions, powders, suspensions, including high-percentage aqueous, oily or other suspensions, dispersions, emulsions, Oil dispersions, pastes, dusts, grit, granulates by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should have the finest possible distribution ensure the active ingredients according to the invention.

For the production of directly sprayable solutions, emulsions, Pastes and oil dispersions contain mineral oil fractions with a medium to high boiling point, such as kerosene or diesel oil, also coal tar oils etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, z. B. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, e.g. B. Methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc., strongly polar solvents, e.g. B. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration.

Aqueous use forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders), oil dispersions by adding

6Q981 5/1253

- 19 - O.Z. jo 824

2U4822

can be prepared with water »For the production of emulsions, pastes or oil dispersions, the substances can be used as such or dissolved in an oil or solvent, homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. But it can also consist of active substances, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or Oil concentrates can be produced, which are suitable for dilution with water.

The following surface-active substances should be mentioned: alkali, alkaline earth, Ammonium salts of lignosulphonic acid, naphthalenesulphonic acids, Phenolsulfonic acids, alkylarylsulfonates, alkyl sulfates, Alkyl sulfonates, alkali and alkaline earth salts of dibutylnaphthalene sulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid Alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ethers, Condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or »naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated Isooctylphenol, - Octylphenol, - Nonylphenol, Alkylphenolpolyglykoläther, Trlbutylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, Lignin, sulphite waste liquors and methyl cellulose.

Powder, grit and dust can be mixed or mixed together Milling of the active substances with a solid carrier.

Granules, e.g. B. coating, impregnation and homogeneous granules, can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. B. Mineral earths such as Silica gel, silicas, kieael gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, Diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as. B. ammonium sulfate, Ammonium nitrate, ureas and vegetable products such as grain

6Ü9215 / _1253/20

- 20 - UZ 30

24U822

flour, tree bark, wood and nut shell flour, cellulose powder and other solid carriers.

The formulations contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90 percent by weight.

The mixtures or individual active ingredients can include oils of various types, wetting agents or adhesives, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g. silicones), growth regulators, antidotes or other herbicidally active compounds, such as. B. substituted anilines
substituted aryloxycarboxylic acids and their salts, esters and amides

substituted ethers

substituted arsonic acids and their salts, esters and amides substituted benzimidazoles
substituted benzisothiazoles
substituted benzthiadiazinone oxides
substituted benzoxazines
substituted benzoxazinones
substituted benzothiadiazoles
substituted biurets
substituted quinolines
substituted carbamates
substituted aliphatic ^ carboxylic acids and their salts, esters

and amides
substituted aromatic carboxylic acids and their salts, esters and amides

substituted carbamoylalkyl thiol or dithiophosphates substituted quinazolines
substituted Cycloalkylamidocarbonthiolsäuren and their salts, esters and amides

substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and salts, esters and amides substituted dihydrobenzofuranylsulfonates substituted disulfides
substituted dipyridylium salts
substituted dithiocarbamates

609-3 15/1253 / ₂₁

- 21 - O, line 30 έ: · 24

2,4,822

substituted dithiophosphoric acids and their salts, esters and Amides

substituted ureas substituted hexahydro-1-H-carbothioate substituted hydantoins substituted hydrazides substituted hydrazonium salts substituted isooxazole pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones, substituted naphth ο quinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidinediones substituted oxadiazinediones substituted phenols and their salts and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkylglyzines substituted phosphites substituted phosphoric acids and their salts, esters and amides substituted piperidines substituted pyrazoles substituted pyrazole alkyl carboxylic acids and their salts, esters and amides

substituted pyrazolium salts substituted pyrazolium alkyl sulfates substituted pyridazines substituted pyridazones substituted pyridinecarboxylic acids and their salts, esters and Amides

substituted pyridines substituted pyridine carboxylates substituted pyridinones substituted pyrimidines substituted pyrimidones

609815/1253 / ²²

- 22 - 0, Z. "50

substituted pyrrolidinecarboxylic acid and its salts, esters and Amides

substituted pyrrolidines
substituted pyrrolidones

substituted arylsulfonic acids and their salts, esters and amides substituted styrenes

substituted tetrahydro-oxadiazinediones
substituted tetrahydro-oxadiazole diones
substituted tetrahydromethanoindenes
substituted tetrahydro-diazol-thiones
substituted tetrahydro-thiadiazine-thiones substituted tetrahydro-thiadiazole-diones substituted aromatic thiocarboxamides substituted thiocarboxylic acids and their salts, esters and amides substituted thiocarbamates
substituted thioureas
substituted thiophosphoric acids and their salts, esters and amides

substituted triazines
substituted triazoles
substituted uracils
substituted uretidinediones

possibly also immediately before use (tank mix) can be added. The herbicidal compounds mentioned last can also be used before or after the individual active ingredients according to the invention or mixtures are used "

The admixture of these agents to the herbicides according to the invention can be done in a weight ratio of 1:10 to 10 s 1. The same applies to oils, wetting agents or adhesives, fungicides, nematocides, Insecticides, bactericides, antidotes and growth regulators.

The agents according to the invention can, inter alia, in the preplanting process, Post-planting procedures, pre-sowing procedures, pre-emergence procedures, Post-emergence method or during emergence of the crop plants or the undesired plants one or more times be applied,

609815/1253

O.Z. 30th

The agents according to the invention can vary in the amount used. The amount used depends mainly on the species the desired effect.

The application rate is generally between 0.1 and 15 or more, preferably 0.2 and β kg of active ingredient per hectare.

The new funds can be used in cereal crops such as

Avena spp ₀ Triticum spp, Hordeum spp «Seeale spp ₀ Sorghum
Zea mays

Panicum miliaceum Oryza spp »

and in cultures of dicotyledons such as Cruciferae, e.g. B ₀ Brassica spp.

Sinapis spp. Compositae, Z ₀ B ₀ Lactuea spp.

Helianthus spp "Malvaceae, ζ", B ₀

Gossypium hirsutum Leguminosae, e.g. "B.

Medicago spp "Trifolium spp.

Pisum spp. Chenopodiaceae, for example ₀ Beta spp.

Spinacia Solanaceae, e.g. “B ₀ Solanum sppο

Nicotiania spp ₀ Linaceae e.g. B.

Linum spp. Umbelliferae, e.g. B ₀ Petroselinum spp.

Daucus car-ota Rosaceae, e.g. B.

Pragaria Raphanus spp. Lepidium spp.

Carthamus spp " Scorzonera spp,

Phaseolus spp. Arachis spp. Glycine max.

Capsicum annuum

Apium graveolens

9815/12 / 24

UZ J>

Cucurbitaceae, e.g. B.

Cucumis spp "Liliaceae, e.g. B ₀

Allium spp. Vitaceae, e.g. B.

Vitis vinifera Bromeliaceae, Z ₀ B ₄ ,

Pineapple sativus

can be applied.

2U4822

Cucurblta spp.

The new agents have a strong herbicidal effect and can therefore be used as weed killers or for control unwanted vegetation can be used. Whether the new remedies act as total or selective remedies depends mainly on the amount of active ingredient per unit area.

Among weeds and unwanted vegetation, all are monocotyledons and dicotyledonous plants that grow in places where they are not wanted.

For example, Gramineae, such as

Cynodon spp ₀

Digitaria spp "

Echinochloa spp »

Setaria spp "

Panicum spp »

Alopecurus spp.

LoIium spp »

Sorghum spp.

Agropyron spp.

Phalaris spp.

Apera spp.

Cyperaceae, like

Carex spp. Cyperus spp. and other

Dactylis spp. Avena spp. Bromus spp. Uniöla spp. Poa spp.
Leptochloa spp. Brachiaria spp. Eleusine spp. Cenchrus spp. Eragrostis spp. and other

Eleocharis spp. Scirpus spp.

15/1253

dicot weeds such as Malvaceae e.g. B.

Abutilon theoprasti

Sida spp.

and other compositae, such as

Ambrosia spp.

Lactuca spp.

Senecio spp "

Sonchus spp.

Xanthium spp.

Iva spp.

Galinsoga spp ".

Taraxacum spp.

Chrysanthemum spp.

Cirisum spp. Convolvulaceae, like

Convolvulus spp.

Ipomoea spp "

and other Cruciferae, such as

Barbarea vulgaris

Brassica spp.

Capsella spp,

Sisymbrium spp,

Thlaspi spp.

Sinapis arvensis

and other Geraniaceae, such as

Erodium spp.

and other Portulacaceae, such as

Portulaca spp. Primulaceae, like

Anagallis arvensis

and other Rubiaceae, such as

Richardia spp.

Galium spp.

609815 /

O, Z. 10 b24

2U4822

Hibiscus spp. Malva spp.

Centaurea spp. Tussilago spp. Lapsana communis Tagetes spp. Erigeron spp. Anthemis spp. Matricaria spp. Artemisia spp. Bidens spp. and other

Cuscuta spp. Jaquemontia tamnifolia

Arabidopsis thaliana Descurainia spp. Draba spp. Coronopus didymus Lepidium spp. Raphanus spp.

Geranium spp.

and other Lysimachia spp.

Diodia spp. and other

1253

- 2β -

CZ. 30 ö24

Scrophulariaceae, such as

Linaria spp "

Veronica spp, Solanaceae ^ like

Physalis spp "

Solanum spp ₀

and other Urticaceae, such as

Urtica spp »Violaceae, like

Viola spp, Zygophyllaceae such as

Tribulus terrestis Euphorbiaceae, such as

Mercurial! S annua Umbelliferae, like

Daucus carota

Aethusa cynapium Commelinaceae, like

Commelina spp _o Labiatae, such as

Lamium spp <,

and other Leguminosae, such as

Medicago sppο

Trifolium spp.

Vicia sppο

and other Plantaginaceae, such as

Plantago spp ₀ Polygonaceae how

Polygonum spp.

Rumex spp. Aizoaceae, like

Mollugo verticillata, like Amaranthaceae

Amaranthus spp.

Digitalis spp. and other

Nicandra spp. Datura spp.

and other and other Euphorbia spp.

Amtni majus and other and other Galeopsis spp.

Sesbania exaltata Cassia spp. Lathyrus spp.

and other

Pagopyrum spp. and others and others and others

6 0 9815/1253

CZ. 50 l2h

2U4822

Boraginaceae, like

Amsinckia spp.

Myostis sppο

and other Caryophyllaceae such as

Stellaria spp,

Spergula spp.

Saponaria spp.

ScIeranthus annuus Chenopodiaceae, such as

Chenopodium spp "

Kochia spp.

Salsola Kali Lythraceae, such as

Cuphea spp »Oxalidaeeae, like

Oxalis spp. Ranunculaceae, like

Ranunculus spp.

Delphinium spp "Papaveraceae, such as

Papaver spp "

and other Onagraceae, such as

Jussiaea spp. Rosaceae, like

Alchemillia spp.

and other Potamogetonaceae, such as

Potamogeton spp. Najadaceae, like

Najas spp. Marsileaceae, like

Marsilea quadrifolia

be fought.

Anchusa spp. Lithospermum spp.

Silene spp. Cerastium spp. Agrostemma pallida and others

Atriplex spp. Monolepsis nuttalliana and others

and other

Adonis spp. and other

Fumaria officinalis

and other Potentilla spp.

and others and others and others

6 0 9 S 1 5/1 2 5 3

- 28 - 0, Z. "30 Ü24

2U4822

Example 12

In the greenhouse, cotton (Gossypium hirsutum) grew strong was weeded with field mustard (Sinapis arvensis), treated with the following active ingredients at a height of 2 to 10 cm:

I 3-Isopropyl ~ 2,3-benzothiadiazin (4) one-2,2-dioxide-1-ethyl carbamate

II l-Isobutylsulfonyl-O-isopropyl- ^, 1,3-benzothiadiazine4) one 2,2-dioxide

III l-ethylsulfonyl-; 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide

IV l-Di &: ethylcarbamoyl-3-isopropyl-2,3-benzothiadiazin (4) -one-2,2-dioxide

The application rate was 1 kg / ha of active substance in each case. The active ingredients were each dispersed in 500 liters of water per hectare or emulsifiedo After 2 to 3 weeks it was found that the Compounds I to IV showed a better tolerance to the culture plant than

XIV 3-Isopropyl ~ 2 _J) 1,3-benzothiadiazin (4) one-2,2-dioxide. The following table shows the test result:

Active ingredient I II III IV XIV

Useful plants:

Gossypium hirsutum 0 0 0 10 30

unwanted plants:

Sinapis arvensis 100 100 100 100 100

0 = without damage
100 = total damage

Example 13

Various test plants were placed in the greenhouse at one height from 2 to 25 cm treated with the following active ingredients:

6 0 9 * 15/1253

- 29 - O.ζ. 30th

2U4822

I 3-Isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide-1-ethyl carbamate

II l-Isobutylsulfonyl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide

III l-ethylsulfonyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide

IV 1-Diethylcarbamoyl-3-isopropyl-2, 1, 3-benzothiadiazin (4) one-2,2-dioxide

V l-Dimethylearbamoyl - ^ - isopropyl ^, 1,3-benzothiadiazin (4) -one-2,2-dioxide

VI 1-N-methyl-N-n-propoxymethylcarbamoyl-3-isopropyl-2,1,3-benzothiadiazine. (4) one-2,2-dioxide

VII 1-Dimethylthiocarbamoyl-3-isopropyl-2,1,3-benzothiadiazin- (4) one-2,2-dioxide

VIII 1-β-Nphthalinsulfonyl-3-isopropyl-2,1,3-benzothiadiazin- (4) one-2,2-dioxide

IX 1-Isopropylaminosulfonyl-3-isopropyl-2,3-benzothiadiazin- (4) one-2,2-dioxide

X 1-methylaminosulfonyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide

XI 1- (2 ', 4', 6'-trinitrophenyl) -3-isopropyl-2, 1,3-benzothiadiazin (4) one-2,2-dioxide

XII 3-Isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide-1-methylcarbamate

XIII 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-l-phenylcarbamate "

The application rate was 4 kg / ha of active substance. The active ingredients were dispersed or emulsified in 500 l of water / ha.

After 2 to 3 weeks it was found that the active ingredients a showed very good tolerance to the useful plants and a good herbicidal action.

The test results can be seen from the following table.

6 0 9 815/1253

I. - 30 - IV V VI o, z. ^ o 824 2 444 822 Active ingredient 0 II III 0 0 0 VII VIII Useful plants: 0 0 0 0 Oryza sativa 0 0 0 0 0 0 0 0 Glycine max. 0 0 0 0 0 0 0 0 Sorghum bicolor 0 0 0 0 0 0 0 0 Zea mays 0 0 0 0 0 0 0 0 Triticum aestivum 0 0 0 0 10 0 0 0 Hordeum vulgar 0 0 0 0 0 0 0 0 Seeale cereale •
* 0 0 0 0 Solanum tuberοsum 0 0 0 0 unwanted plants

Sinapis arvensis 100 100 100 100 100 100 100 100 Cyperus esculentus 80 75 75 90 100 85 90 95

Active ingredient

IX X

XI XII XIII

Crops; Oryza sativa Glycine max. Sorghum bicolor Zea mays Triticum aestivum Hordeum vulgar Seeale eereale Solanum tuberosum

unwanted plants; Sinapis arvensis Cyperus esculentus

0 = no damage 100 = total damage

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

100 100 100 100 90 75 100 70

609815/1253

- 31 - ο.ζ. 30 824

Example 14

In the greenhouse, test vessels were filled with loamy sandy soil and sown with the seeds of rice (Oryza sativa), wheat (Triticum aestivum) and field mustard (Sinapis arvensis). Direct this was followed by treatment with the active ingredients

IV l-diethylcarbamoyl - ^ - isopropyl-S, l, 3-benzothiadiazin (4) on-

2,2-dioxide and
XII 3-Isopropyl-2,1,3-benzothiadiazine) one 2,2-dioxide-1-methylcarbamate.

The application rate was 3 kg / ha of active substance in each case. The active ingredients were each dispersed in 500 liters of water per hectare or emulsified.

After 4 to 5 weeks it was found that the active ingredients IV and XII is very well tolerated by the crop plants and showed a good herbicidal effect.

The test result can be seen from the following table:

Active ingredient IV XII

Useful plants:

Oryza sativa 0 0

Triticum aestivum 0 0

unwanted plants:

Sinapis arvensis 90 90

0 = without damage
100 = total damage.

The following compounds showed a corresponding biological effectiveness as the active ingredients mentioned in Examples 12 to 14:
1- (N'-Phenyl-N ", N" -dimethylformamidinyl) -3-isopropyl-2,1,3-benzo- ■ thiadiazin (4) one-2,2-dioxide (XV)

3-Isopropyl-2, l, 3-t> enzothiadiazin (4) one-2,2-dioxide-1-p-chlorobenzyl mercaptocarbamate (XVl)

- 32 - CZ. ^ O

2U4822

3-Isopropyl-2,3-benaothiadiazin (4) one-2,2-dioxide-1-methyl mercaptocarbamate (XVII).

Example 15

90 parts by weight of the compound from Example 1 are mixed with 10 parts by weight of N-methyl - * - pyrrolidone and a Solution that is suitable for use in the form of tiny drops.

Example 16

20 parts by weight of the compound from Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide with 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 Mol of ethylene oxide consists of 1 mol of castor oil. The mixture contains 20 % active ingredient. A spray mixture is obtained by pouring the solution into water and finely distributing it.

Example 17

20 parts by weight of the compound from Example 3 are in a Dissolved mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 Parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil consists.

Example 18

20 parts by weight of the compound from Example 4 are in a Dissolved mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight a mineral oil fraction with a boiling point of 210 to 28o ° C and 10 parts by weight of the adduct of 40 mol Ethylene oxide consists of 1 mole of castor oil.

/ 33

WIJ ν 13 / I α * ww ¹

- 33 - 0%. 30 824

Example I9

20 parts by weight of the active ingredient from Example 5 are mixed with 3 Parts by weight of the sodium salt of diisobutylnaphthalene-asulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a SuIfit waste liquor and 60 parts by weight of powdered Silica gel mixed well and ground in a hammer mill.

Example 20

3 parts by weight of the compound from Example 6 are 97 parts by weight finely divided kaolin intimately mixed. In this way, a dust containing 3 percent by weight of the active ingredient is obtained contains.

Example 21

30 parts by weight of the compound from Example 7 are powdered with a mixture of 92 parts by weight! Silica gel and 8 weight of steep paraffin oil which has been sprayed onto the surface of this silica gel, intimately mixed. One receives on this way a preparation of the active ingredient with good adhesion.

Example 22

Various plants were grown in the greenhouse at a height of 2 to 18 cm with the following active ingredients

I l-Phenoxyacetyl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide

II 1-p-Chlorophenoxyacetyl-3-isopropyl-2,1,3-benzothiadiazin- (4) one-2,2-dioxide

III 1-2 ^1, 4'-O-isopropyl ^ dichlorophenoxyacetate, 1,3-benzothiadiazine (4) one-2,2-dioxide

V 1-2 ', 4' -Dichlorophenoxy-oi; -propionyl-3-isopropyl-2,1,3-

benzothiadiazin (4) one 2,2-dioxide

/ 34 609815/1253

- ~ $ K - 0.7 ,, 30 824

VII 1-chloroacetyl-jJ-isopropyl ^, 1 , 3-benzothiadiazin (4) one-2,2-dioxide

VIII l-acetoxyacetyl-3-isopropyl-2, l, 5-benzothiadiazin (4) one-2,2-dioxide

IX l-propionyl-3-isopropyl-2, l, 3-benzothlacllazine (4) one-2.2 «- dioxide

X la-chloropropionyl-3-isopropyl-2, l _i 3-benzothiadiazin (4) one-2,2-dioxide

XI l-ft'-bromobutyryl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide

XII 1-sec-valeryl-3-isopropyl-2, 1, 3-benzothiadiazin (4) one-2, 2- dioxide

XIII 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-l- (0,0-dimethylphosphorothioate)

XIV> Isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dloxid-l- (0,0-diethyl phosphorothioate)

XV 0xalyl ~ bis-l- / 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-

dioxide /

XVI l-palmitoyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-

XVII l-pormyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide

each dispersed or emulsified in 500 liters of water per hectare, treated. The application rate was 2 kg / ha of active substance,

After 2 to 3 weeks it was found that the active ingredients have a good herbicidal action with very good tolerance to the Crops showed.

The test result can be seen from the following table:

609815/1253

I. 95 95 - 35 mm V VII VIII 0.2. 30 82 * X XVII 2 XI 2 2 2 2444822 2 2 Active ingredient 2 II III IX 0 kg / ha 0 0 2 2 0 0 0 2 0 0 Useful plants: 0 0 0 0 0 0 0 Triticum aestivum 0 0 0 0 0 0 0 0 0 0 Hordeum vulgar 0 0 0 0 0 0 0 0 0 0 Secale cereale 0 0 0 0 0 0 0 0 0 Oryza sativa unwanted plants: unwanted plants: 0 0 0 90 Glycine max. Sinapis arvensis Sinapis arvensis 0 0 95 100 100 0 95 Active ingredient XIV XV XVI kg / ha 100 90 2 2 2 90 Triticum aestivum XII XIII 0 0 0 Hordeum vulgar 2 2 0 0 0 Secale cereale 0 0 0 0 0 Oryza sativa 0 0 0 0 0 Glycine max 0 0 0 0 0 0 0 0 0 95 90 90 100 100

0 = without damage
100 = total damage

Example 23

In the greenhouse, test pots were made with loamy; Sandy bottom filled and sown with various seeds. Immediately thereafter, the treatment with the active ingredients took place

II 1-p-Chlorophenoxyacetyl-3-isopropyl-2,1,3-benzothiadiazin- (4) one-2,2-dioxide

III l-2 ^f , 4'-dichlorophenoxyacetyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide

IV 1-2'-methyl-4'-chlorophenoxyacetyl-O-isopropyl ^,! ^ - benzothiadiazine) on-2, 2-dioxide

- 36 - G.Z. 30 824

2U4822

V 1-2 ', 4 ^f -Dichlorophenoxy-Ä-propionyl-3-isopropyl-2, 1,3-benzothiadiazin (4) one-2,2-dioxide

VIII l-aceto; cyacetyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide

IX 1-Propionyl-3-isopropyl-2, 1, 3-benzothiadiazin (4) -one-2, 2- dioxide

X 1-a.-Chlorpropionyl-3-isopropyl-2,3-benzothiadiazin (4) -one-2,2-dioxide

XIII 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-l- (0,0-dimethylphosphorothioate)

XIV 3-isopropyl-2, l _i 3-benzothiadiazin (4) one-2,2-dioxide-l- (0,0-diethyl phosphorothioate)

each dispersed or emulsified in 500 liters of water per hectare. The application rate was 3 kg / ha of active substance in each case.

After 4 to 5 weeks it was found that the active ingredients a showed good herbicidal action with very good tolerance on the crop plants.

The test result can be seen from the following table.

Active ingredient II 100 III IV V VIII IX X XIII XIV kg / ha a. S. 3 3 3 3 3 3 3 3 3 Useful plants: Zea mays 0 0 0 0 0 0 0 0 0 Triticum aestivum 0 0 0 0 0 0 0 0 0 Oryza sativa 0 0 0 0 0 0 0 0 0 Glycine max. 0 0 0 0 0 0 0 0 0 Gossypium hirsutum 0 0 0 0 0 0 0 0 0 unwanted plants: Sinapis arvensis 95 95 100 80 90 80 8o 100

0 = without damage
100 = total damage

- YY - CZ. yo &2'4

Example 24

Various plants were grown in the greenhouse at a height of 2 to 10 cm with the following active ingredients

VII 1-Chloroacetyl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide

VIII 1-acetoxyacetyl-3-isopropyl-2,1,> benzothiadiazine) one-2,2-dioxide

X l-o (^ chloro-propionyl-3-isopropyl-2, l, 3-benzothiadiazine (4) -

on-2,2-dioxide
XIII 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide-l- (0,0-dimethylphosphorothioate)

compared to the active ingredient

XIX 3-Isopropyl-2,3-benzo-thiadiazinon- (4) -2,2-dioxide

each dispersed or emulsified in 500 liters of water per hectare,
treated.

The application rate for the crop was 1 kg / ha a. S. and for the undesired plants 0.8 kg / ha a. S.

After 2 to 3 weeks it was found that the active ingredients VII, VIII, X and XIII at 1 kg / ha a. S. a better tolerance to the crop and with 0.8 kg / ha a. S. showed the same herbicidal effect on the unwanted plants as the
Active ingredient XIX.

The test result can be seen from the following table.

Active substance VII VIII X XIII XIX

kg / ha 0.8 1 0.8 1 0.8 1 0.8 1 0.8 1

Crops;

Gossypium hirsutum - 0-10- 0- 0 0

unwanted plants;

Sinapis arvensis 100 - 95 - 95 - 100 - 95 Matricaria chamomilla 100 - 96 - 95 - 100 - 95 -

0 = no damage, 100 = total damage

609815/1253 / 38

- 38 - O.Z, 30 824

24U822

Correspondingly biologically active as the compounds in the examples 22 to 24 are:

l-Pelargonyl-3-isopropyl-2, l, 3-benzothiadiazine4) one-2,2-dioxide and

1-pent-3'-enoyl-3-isopropyl-2, 1, 3-benzothladiazin (4) one-2,2-dioxide.

609815/1253

Claims (63)

- 39 - O.ζ. 30 b2 ': - 2U4822 claims 1. Substituted 2, l, 3-Benzothiadiazin (4) one-2,2-dioxides of formula XXV in which R, an isopropyl group and R " a) a formyl group, a propionyl, n-butyryl, valeryl, Isovaleryl-, sec-valeryl-, capronyl-, l- (ai-methylvaleryl) -, Oenanthyl radical, an acyl radical with more than 8 carbon atoms, one with halogen atoms, acetoxy or alkoxy groups substituted acyl radical, an optionally halogen- and / or alkylphenoxy-substituted acyl radical, an unsaturated, optionally halogen-substituted acyl radical, a cycloacyl radical and a diacyl radical or b) an alkoxy or alkylmercapto-carbonyl radical, optionally one phenoxycarbonyl or phenylmercapto-carbonyl radical substituted by alkoxy groups, one optionally halogen-substituted benzyl mercapto-carbonyl radical or c) a dialkylcarbamoyl radical optionally substituted by alkoxy groups, a dialkylthiocarbamoyl radical, an N-phenyl-N ^f , N'-dialkylformamidinyl radical or d) an alkylsulfonyl radical or an optionally through Substituted halogen atoms, nitro groups or alkyl groups 'Arylsulfonylrest or e) a mono- or dialkylsulfamoyl radical or f) an N-alkyl-benzimidyl radical or g) a 0,0-dialkyl phosphorothioate or phosphate radical or h) an optionally halogen-substituted alkylsulfenyl radical or i) denotes a phenyl radical substituted by nitro groups. - 40 - GZ 30 824 2. Herbicide containing a solid or liquid carrier and a substituted 2, l, j5-benzothiadiazine (4) one-2,2-dioxide according to claim I ₀ 3 “Use of a compound according to claim 1 as a herbicide. 4. A process for the preparation of compounds according to claim 1, characterized in that a compound of the formula II in the R-, has the aforementioned meaning and the radical Me denotes an alkali or alkaline earth metal or an ammonium ion, with an acid halide of the formula R ₂ Hal, in which Rp has the aforementioned meaning and the remainder Hal denotes a chlorine or bromine atom, rt + HaIR, II XXV Reacts in a polar solvent in a temperature range from -10 to HO ⁰ C for half a hour to 12 hours, 5. The method according to claim 4, characterized in that a compound of formula III + HaIR ₂ III XXV in the R, which has the aforementioned meaning, with an acid halide of the formula RgHaI, in the Rg and Hai the aforementioned Have meaning, reacts in the presence of a tertiary organic base. 6. A process for the preparation of the l-formyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide, characterized in that 6C '; i $ 1 5/1 2 £ J - 41 - CZ. 3C that the 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide with a solution of the mixed formic acid-acetic anhydride according to claim 4. 7. l-Formyl-3-isopropyl-2, I ₃ 3-benzothiadiazin (4) one-2,2-dioxide. 8. 1-PropionylO-isopropyl - ^, 1,3-benzothiadiazin (4) one-2,2-dioxide. 9. l-sec. Valeryl-3-isopropyl-2 _i 1,3-benzothiadiazin (4) one-2,2-dioxide. 10. l-Valeryl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide. 11. l-capronyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide, 12. 1- (ct ~ methyl-valeryl) -3-isopropyl-2, 1,3-benzothiadiazin (4) one-2,2-dioxide. 13. l-Pelargonyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide. 14. 1-Palmitoyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide. 15. l-acetoxy-acetyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide. 16. l-Chloroacetyl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide. 17 · l-06-chloropropionyl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide. 18. l-Acryloyl-3-isopropyl-2,3-benzothiadiazin (4) -one-2,2-dioxido 19. l-pent-3 ^t -enoyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide. 60931 5/1253 - 42 - CZ. 30 scik 2U4822 20 »l-benzoyl-3-isopropyl ~ 2 _i, l ,, 3 '" benzothiadiazin (4) one-2 _J 2-dioxide. 21. l-ot-Naphthoyl-3-isopropyl-2, lj, 3-benzothiadiazin (4) one-2,2-dioxide. 22. 1-Phenoxyacetyl-3-isopropyl-2, 1, 3-benzothiadiazin (4) one-2,2-dioxide. 23 »l-p-Chlorophenoxyacetyl-3-isopropyl-2,3-benzothiadiazine (4) -one-2,2-dioxide. 24. l-2 _'i 4'-dichlorophenoxyacetate 3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide. 25 »1-2 ', 4 *, 5'-Trichlorophenoxyacetyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide. 26. 1-2'-Methyl-4 ^f -ehlorphenoxyacetyl - ^ - isopropyl ^, 1,3-benzotthiadiazin (4) one-2,2-dioxide. 27. 1-2 ' _i 4'-dichlorophenoxy-ß-propionyl-3-isopropyl-2, l, 3- "benzothiadiazin (4) one-2,2-dioxide, 28. Oxalyl-bis-1- / 3 ~ isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide /. 29. Decane (l ', 10') - dioyl-bis-l- / 5-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide 7. 30. l-α-Bromobutyryl-3-isopropyl-2 _ί 1,3-benzothiadiazin (4) one-2,2-dioxido 31. 3-isopropyl-2, l _j, 3-benzothiadiazin (4) one-2,2-dioxide 1-methylcarbamate. 32. 3-isopropyl-2 l, _i 3-benzothiadiazin (4) one-2,2-dioxide-l-äthylcarbamat. 609815/1253 - 43 - O.Z. 30th 33. 3-Isopropyl-2,3-benzothiadiazin (4) one 2,2-dioxide-1-n-butyl carbamate. 34. 3-Isopropyl-2,3-benzothiadiazin (4) one 2,2-dioxide-1-hexadecyl carbamate. 35. 3-Isopropyl-2, I ^ -benzothiadiazine4) one-2,2-dioxide-1-phenylcarbamate. 36. 3-Isopropyl-2 _i l, 3-benzothiadiazin (4) one-2,2-dioxide-l-ome thoxyphenyl carbamate. 37 · 3-Isopropyl-2, 1,3-benzothiadiazin (4) one-2,2-dioxide-1-methylmercaptocarbamate 38. 3-Isopropyl-2, l _J 3-benzothiadiazin (4) one-2,2-dioxide-in-propyl mercaptocarbamate » 39. 3-Isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide-1-p-chlorobenzyl mercaptocarbamate » 40. 1-Dimethylcarbamoyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide. 41. 1-Diethylcarbamoyl-3-isopropyl-2 _i 1,3-benzothiadiazin (4) one-2,2-dioxide. 42. l-Di ~ n-propylcarbamoyl-3 ~ isopropyl-2,3-benzothiadiazin (4) -one-2,2-dioxide. 43i 1-N-Methyl-N-n -propoxymethylcarbamoyl-3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide. 44. 1- (1'-piperidinoyl) -3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxide. 45. 1- (Hexahydro-l'-H-azepine-l'-oyl) -3-isopropyl-2,3-benzothiadiazine (4) one-2,2-dioxide. / 44 6Ü9815 / Ί 2bü. - 44 - c.Z. ^ c 2U4822 46 ", l-dimethylthiocarbamoyl-3-isopropyl-2 _i 1,3-benzothiadiazine 47. 1- (N'-Phenyl ~ N ", N" -dimethylformamidinyl) -> isopropyl-2, l,> benzothiadiazin (4) one-2,2-dioxido 48. l-Methylsulfonyl-3-isopropyl-2, l,> - benzoth ± adiazin (4) one-2,2 ~ dioxide. 49ο l-ethylsulfonyl-3-isopropyl-2, l, 3-benzothiadiazin (4) one-2,2-dioxide _{or similar} 50. l-Isobutylsulfonyl-O-isopropyl - ^, l _i 3-benzothiadiazin (4) one-2,2-dioxido 51. l-benzenesulfonyl-3-isopropyl-2 _ί IJ3 ~ benzothiadiazin (4) one-2,2-dioxido 52. l-p-Toluenesulfonyl ~ 3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide. 53 »l-p-bromobenzenesulfonyl-3-isopropyl-2, l, 3-benzothiadiazine (4) on-2,2-dioxide. 54o lp ~ nitrobenzenesulfonyl-3-isopropyl-2, l, 3-benzothiadiazin- (4) one-2 _i 2-dioxide, 55. l-ß-naphthalenesulfonyl-3-isopropyl ~ 2, l, 3-benzothiadiazine (4) on-2,2-dioxide. 56. l-Dimethylsulfamoyl-3-isopropyl-2,3-benzothiadiazin (4) one-2,2-dioxide. 57. 1-Methylaminosulfonyl-3-isopropyl-2,3-benzothiadiazin (4) -one-2,2-dioxide. 58. l-Isopropylaminosulfonyl-3-isopropyl-2,3-benzothiadiazin- (4) one-2,2-dioxld. 0 9 8 15/1253 - 45 - CZ, 30 59. 1- (N-Methyl ~ benzimidyl) -3-isopropyl-2,3-benzothiadiazin- (4) one-2,2-dioxide. 60. 3-isopropyl-2 _J l, 3-benzothiadiazin (4) one-2,2-dioxide-l- (0 _i 0-diethyl-phosphorothioate). 61. 3-Isopropyl-2, 1,3-benzothiadiazin (4) one-2,2-dioxide-1- (0,0-dimethyl-phosphorothioate). 62. l-Perchloromethylthio-3-isopropyl-2,3-'ben2othiadiazin (4) -one-2,2-dioxide. 63. 1- (2 ', 4', 6 ^f -trinitrophenyl) -3-isopropyl-2,1,3-benzothiadiazin (4) one-2,2-dioxidec BASF Aktiengesellschaft 609815/1253