CA1236835A - Fused phenylsulfonamides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Fused Phenylsulfonamides of the general formula (II), and processes for their preparation, are disclosed:

(II) wherein R1 is hydrogen, halogen, nitro, C1-C4 alkyl, C1-C4 halo-alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkoxycar-bonyl, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl or C2-C5 alkoxyalkoxy and A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms selected from the group consisting of -O-CH2-CH2-, -O-CO-CH2-, -O-CH2-CH2-CH2-, -O-CH2-O-, -CO-O-CH2-, -O-CH2-CH2-O-, -CH2-O-CO-CH2-, -O-CO-CH2-CH2-, -CO-O-CH2-CH2-, -O-CH2-CH2-CO-, -O-CH2-CO-CH2-, -S-CH2-CH2-, -SO-CH2-CH2-, -SO2-CH2-CH2-, -NH-CH2-CH2- -S-CH2-CH2-CO-, -S-CH2-CH2-CH2-, -O-SO2-CH2-CH2- or -NH-CO-CH2-CH2-, wherein the substituents are selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylthiocarbonyl, carbamoyl, C1-C4 alkylaminocar-bonyl, di(C1-C4)alkylaminocarbonlyl, C1-C4 alkylsulfonyl, C3-C5 alkenyl or C3-C5 alkynyl.
These compounds find use as intermediates in the prepa-ration of herbicidally active compounds of the general formula

Description

Fused Phenylsulfonamides This application is a divisional from Application 432,425, filed July Thea, 1983.
Application 423,425 relates to novel N-phenylsulfonyl-N'-pyramid-inylureas and N-phenylsulfonyl-N'-triazinylureas having herbicidal and growth regulating properties, to the production thereof, to compositions containing them, and to the use thereof for controlling weeds, in particular selectively, in crops of useful plants, or for regulating and inhibiting plant growth.
The fused N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'-triazinylureas of Application 423,425, and the salts thereof, have the general formula I

-SUNKEN- (I), wherein Z is oxygen or sulfur, E is nitrogen or SHEA, Al is hydrogen, halogen, vitro, Cluck alkyd, Cluck halo-alkyd, Cluck alkoxy, Cluck haloalkoxy, Cluck alkoxycar-bony, Cluck alkylthio, Cluck alkylsulfinyl, Cluck alkylsulfonyl or C2-Cs alkoxyalkoxy, lZ36835i R2 is hydrogen, cluck alkyd or Cluck alkoxy, R3 and R4, each independently of the other, are hydrogen, Cluck alkyd, Cluck alkoxy, Cluck haloalkoxy, Cluck haloalkylthio, Cluck alkylthio, halogen, C2-Cs alkoxy-alkyd, C2-Cs alkoxyalkoxy or -~RsR6, wherein Us and R6 are hydrogen or Cluck alkyd, and A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms and, together with the linking carbon atom forms a non-aromatic 5- or 6-membered heterocyclic ring system, with the proviso that two oxygen atoms are separated by at least one carbon atom and that oxygen and sulfur atoms are only linked to each other if the sulfur atom takes the form of the -SO- or -SO- group.
In the above definitions, alkyd denotes straight-chain or branched alkyd, e.g. methyl, ethyl, n-propyl, isopropyl, or the four bottle isomers. Alkoxy denotes methoxy, ethics, n propoxy, isopropoxy the four buttocks isomers, n-amyloxy, isoamyloxy,

2-amyloxy or 3-amyloxy, with methoxy, ethics or isopropoxy being 0 preferred.
Alkylthio is e.g. methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio or n-pentylthio, with methylthio and ethylthio being preferred.
Alkylsulfinyl is e.g. methylsulfinyl, ethylsulfinyl, n-propylsulfinyl and n-butylsulfinyl, with methylsulfinyl and ethylsulfinyl being preferred.

~236835 Alkylsulfonyl is e.g. methylsulfonyl, ethylsulfonyl or n-propylsulfinyl, with methylsulfonyl and ethylsulfonyl being preferred.
Halogen in the above definitions, as well as moiety of haloalkyl, haloalkoxy and haloalkylthio, is fluorine, chlorine and bromine,with fluorine and chlorine being preferred.
Application 423,425 also describes the salts which the compounds of formula I are able to form with amine, alkali metal bases and alkaline earth metal bases, or with qua ternary ammonium bases.
Preferred salt-forming alkali metal hydroxides and alga-line earth metal hydroxides are the hydroxides of lithium, sodium, potassium, magnesium or calcium, most preferably those of sodium or potassium.
Examples of suitable salt-forming amine are primary, secondary and tertiary aliphatic and aromatic amine such as methyl amine, ethyl amine, propylamine, isopropyl amine, the four butylamine isomers, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropyl-amine, quinuclidine, pardon, quinoline and isoquinoline.
Preferred amine are ethyl amine, propylamine, di-ethylamine or triethylamine, with isopropyl amine and diethanolamine being most preferred.
Examples of qua ternary ammonium bases are, in general, the cations of haloammonium salts, e.g. the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzyl-12368~S

ammonium cation, the tetraethylammonium cation, the trim ethyl-ethylammonium cation, and also the ammonium cation.
Examples of suitable substituents of the bridge A are:
halogen, cyan, Cluck alkyd, Cluck haloalkyl, Cluck alkoxy, Cluck alkylcarbonyl, Cluck alkoxycarbonyl, cluck alkylthiocarbonyl, carbamoyl, Cluck alkylaminocarbonyl, di(Cl-C4)alkylaminocarbonyl, Cluck alkylsulfonyl, C3-Cs alkenyl or C3-Cs alkynyl.
Condensed heterocyclic non-aromatic saturated ring systems, in which the sulfur and carbon atoms contained as chain members may also be present in higher stages of oxidation, are formed by the phenol ring and the fused bridge A. Accordingly, in addition to heterocyclic systems which contain an ether, trio-ether, acutely or amino bridge, these are those heterocyclic systems which contain lactose, lactam, sultan, sultan, sultan or acid android functions or higher oxidation stages of thither functions.
Typical representatives of the basic types of condensed saturated heterocyclic systems which are formed by the sulfonyl-substituted phenol ring and the fused bridge A are: dodder-benzo[b]furan, benzodioxole, 2-(3H)-benzofuranone, Crimean, dip hydrocoumarin, benzodioxan, phthalide, dihydroisocoumarin, issue-chromanone, indoline, 2,3-dihydrobenzothiophene, oxide-hydrobenzothiophene, l,l-dioxo-2,3-dihydrobenzothiophene, Crimea-atone and 3-chromanone.
According to Application 423,425, preferred compounds of formula I are those in which either a) the substituents of a bridge A are halogen or Cluck alkyd, or ~Z36835 b) the bridge A contains at least one oxygen atom, or c) the bridge A contains only one heteroatom, or d) Z is oxygen, or e) Al is hydrogen, halogen or Cluck alXoxycarbonyl, or I) R2 is hydrogen, or g) R3 and R4, independently of each other, are Cluck alkyd, Cluck alkoxy, di(Cl-C4)alkylamino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
Further preferred subgroups of compounds in Application 423,425 comprise those compounds of formula I in which the bridge A contains an oxygen atom as heteroatom and is unsubstituted or substituted by halogen or Cluck alkyd, or - the bridge A contains at least one oxygen atom and is unsubstituted or substituted by halogen or Cluck alkyd, or - the bridge A, together with the phenol nucleus which carries it, forms a 3,4-dihydro-2-dioxo-1,2-benzoxathiine system and is unsubstituted or substituted by Cluck alkyd, or - Z is oxygen, Al is hydrogen, halogen or Cluck alkoxycar~
bony, R2 is hydrogen, and each of R3 and R4 independently of the other is Cluck alkyd, Cluck alkoxy, di(Cl-C4)alkyl-amino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
Particularly preferred groups of compounds in Application 423,425 comprise those compounds in which:
- Z is oxygen, Al is hydrogen, halogen or Cluck alkoxycar-bony, R2 is hydrogen, each of R3 and R4 independently of 123683~

the other is Cluck alkyd, Cluck alkoxy, di(Cl-C4)alkyl-amino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A contains at least one oxygen atom and is unsubstituted or substituted by halogen or Cluck alkyd, or those in which - Z is oxygen, Al is hydrogen, halogen or Cluck alkoxycar-bony, R2 is hydrogen, each of R3 and R4 independently of the other is Cluck alkyd, Cluck alkoxy, di(Cl-C4)alkyl-amino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A contains only one oxygen atom and is unsubstituted or substituted by halogen or Cluck alkyd, or those in which - Z is oxygen, Al is hydrogen, halogen or Cluck alkoxycar-bony, R2 is hydrogen, each of R3 and R4 independently of the other is Cluck alkyd, Cluck alkoxy, di(Cl-C4)alkyl-amino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A, together with the phenol nucleus which carries it, is a dodder-Dixie- 1,2-benæoxathiine system and is unsubstituted or substituted by Cluck alkyd.
Preferred individual compounds are:
N-chroman-~3-ylsulfonyl-N'-(4-methoxy-6-methylpyriimidin-2-yl) urea,N-(2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl)No (4 ,6-dimethylpyramidin-2-yl)urea, N-(2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl))-N'-(4-met-hoxy-6-methylpyrimidin-2-yl)urea.

~Z3~83~
According to application 423,425 the process for proper-in the compounds of formula I is carried out in an inert organic solvent.
One process for the preparation of the compounds of formula I comprises reacting a fused phenylsulfonamide of the formula II Al A ) (II), wherein Al and A are as defined for formula I, with an N-pyrimi-dinylcarbamate or N-triazinylcarbamate of the formula III

Z R2 \ (III), wherein E, R2, R3, R4 and Z are as defined for formula I and R is phenol, alkyd or substituted phenol, in the presence of a base.
If desired, the ureas of formula I can be converted into addition salts with amine, alkali metal hydroxides or alkaline earth metal hydroxides, or with qua ternary ammonium bases. This conversion is carried out e.g. by reacting the compounds of formula I with the equimolar amount of a base and removing the solvent by evaporation.

~Z36835 It is convenient to carry out these reactions for obtaining compounds of formula I in aprotic, inert organic sol-vents.
Examples of such solvents are: Bunsen, Tulane, zillion or cyclohexane, chlorinated hydrocarbons such as ethylene color-ides chloroform, carbon tetrachloride, or chlorobenzene; ethers such as deathly ether, ethylene glycol dim ethyl ether, diethylene glycol dim ethyl ether, tetrahydrofuran or dioxin; nitrites such as acetonitrile or propionitrile; asides such as dimethylformamide, diethylformamide or N-methylpyrrolidinone.
The reaction temperatures are preferably in the range from -20 to +120C. The coupling reactions are normally slightly exothermic and can be carried out at room temperature. To shorten the reaction time or also to initiate the reaction it is expedient to heat the reaction mixture briefly to boiling point. The reaction times can also be shortened by addition of a few drops of a base or isocyanate as catalyst. Preferred bases are tertiary amine such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo(2,2,2)octane, 1,5-diazabicyclo(4,3,0)-non-5-ene or 1,5-diazabicyclo(5,4,0)undec-7-ene. However, the bases employed may also be inorganic bases, e.g. hydrides such as sodium hydrides or calcium hydrides hydroxides such as sodium hydroxide or poles-slum hydroxide, or bicarbonates such as potassium bicarbonate or sodium bicarbonate.
The final products can be isolated by concentrating the reaction mixture and/or removing the solvent by evaporation, and by recrystallization or by triturating the solid residue in a ~.Z368;~5 solvent in which it is poorly soluble, such as an ether, an aromatic hydrocarbon or a chlorinated hydrocarbon.
This application is thus concerned with the compounds of formula II.
Thus, in its broadest aspect, this invention provides a fused phenylsulfonamide of the general formula II

( A ) wherein Al is hydrogen, halogen, vitro, Cluck alkyd, Cluck halo-alkyd, Cluck alkoxy, C1-C4 haloalkoxy, Cluck alkoxycar-bony, Cluck alkylthio, Cluck alkylsulfinyl, Cluck alkylsulfonyl or C2-Cs alkoxyalkoxy and A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms selected from the group consisting of -O-CH2-CH2-, -O-CO-CH2-, -0-CH2-CH2-CH2-, -SHEA-, -CO OUCH-, -O-CH2--CH2--0-, --SHEA -COUCH -, -COUCH -SHEA -, -CO-O-CH2-CH2-, -0-CH2-CH2-CO-, -O-CH2-CO-CH2-, -S-CH2-CH2-, -SO-CH2-CH2-, -S02-CH2-CH2- -NH-CH2-CH2- -S-CH2-CH2 C0-~ -S-CH2-CH2-CH2-~ -O-SO2-CH2-CH2- or -NH-CO SHEA
SHEA-, wherein the substituents are selected from the group consisting of halogen, cyan, Cluck alkyd, Cluck haloalkyl, Cluck alkylcarbonyl, Cluck alkoxycarbonyl, Cluck alkylthiocarbonyl, carbamoyl, Cluck alkylaminocar-12~6835 bony, di(Cl-C4)alkylaminocarbonyl, Cluck alkylsulfonyl, C3-C5 alkenyl or C3-C5 alkynyl.
A particularly preferred compound of this formula is the compound3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8--ylsulfonamide.
The intermediates of the formula II can be prepared by several different methods. For example, the compounds of formula II are obtained by diazotising aniline of formula VII

Al No ) (VII), wherein Al and A are as defined for formula I, and replacing the dyes group with sulfur dioxide, in the presence of a catalyst such as copper chloride, in hydrochloric acid or acetic acid, and reacting the resultant phenylsulfonyl chloride of the formula X

Al Scholl (X), ( A ) 36~33~

wherein A and Al are as defined for formula I, with ammonium hydroxide solution. The corresponding aniline derivatives employed as starting materials are known or they can be prepared by known methods.
Likewise, the compounds of formula II can be obtained by converting a phenylsulfonic acid of the formula VIII

Al \~-- S020H
( ) (VOW

wherein Al and A are as defined for formula I, by treatment with a chlorinating agent such as Pals, PUKE, COOK or SEIKO, to the corresponding phenylsulfonyl chloride of the formula X, and reacting this chloride with ammonium hydroxide solution.
The compounds of formula II can also be obtained by treating a bouncily thither of the formula IX

Al C 2 6 5 (IX), ( A ) wherein Al and A are as defined for formula I, with chlorine, and reacting the resultant phenylsulfonyl chloride of the formula X

~36835 with ammonium hydroxide solution. In specific cases, for example where an activated substitution position is available, a direct sulfochlorination of the phenol nucleus is possible, giving the corresponding phenylsulfonyl chloride by reaction with an excess of chlorosulfuric acid. Correspondingly activated fused Bunsen derivatives are known.
The isothiocyanates of the formula IV are obtained by treating the sulfonamides of formula II with carbon disulfide and potassium hydroxide and by subsequent reaction of the dipotassium salt with phosgene. Such processes are described in Arch. Harm.
299, 174 (1966).
The N-phenylsulfonylcarbamates of the formula VI are obtained by reacting the sulfonamides of the formula II with diphenyl carbonate in the presence of a base. Similar processes are described in Japanese patent specification 61 169.
The fused phenylsulfonylchlorides of the formula X, which are also novel, have likewise been specially developed for the synthesis of the compounds of formula I. Accordingly, they also constitute an object of this invention.
It is disclosed in Application 423,425 that the come pounds of formula I are stable compounds, and no protective mews-uses are required for handling them.
When used in low rates of application, the compounds of Application 423,425 have good selective growth inhibiting and selective herbicidal properties which make them most suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, maize and rice. In some cases damage is also caused to weeds which have only been controlled up to now with total herb-aides.
The mode of action of these compounds is unusual. Many are translocatable, i.e. they are absorbed by the plant and trays-ported to other parts of it where they then exert their action.
Thus, for example, it is possible to damage perennial weeds to the roots by surface treatment. Compared with other herbicides and growth regulators, the novel compounds of Application 423,425 are effective even when used in very low rates of application.
The compounds of Application 423,425 have in addition pronounced growth-regulating, especially growth-inhibiting, prop-reties. The growth of both monocots and divots is inhibited.
Thus, for example, the compounds of Application 423,425 select-lively inhibit the growth of leguminous which are frequently planted as cover crops in tropical regions, so that, while soil erosion between cultivated plants is prevented, the cover crops cannot compete with the cultivated plants.
Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area. A further mocha-noisome of yield increase using growth regulators resides in the fact that nutrients are able increasingly to promote flower formation and fruiting, whilst vegetative growth is inhibited.
At higher rates of application, all tested plants are so severely damaged in their development that they die.
As is disclosed in Application 423,425, the compositions usually contain 0.1 to 95%, preferably 0.1 to 80%, of a compound of the formula I, _ 13 ~Z368~5 1 to 99.9~, of a solid or liquid adjutant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.
Preparatory Examples Example 1:
a) 5-Bromo-2,3-dihydro-2-methylbenzo[b]furan With efficient stirring, 283 g (1.77 moles) of bromide are added drops at 0 - 5C to a mixture of 237 g (1.77 moles) of dodder- 2-methylbenzo[b]furan, 148.7 g (1.77 moles) of sodium bicarbonate, 500 ml of ethylene chloride and 500 ml of water. When the addition of bromide is complete, the mixture is stirred for another 1/2 hour at 20 - 25C. The organic phase is separated, dried over sodium sulfate, concentrated and fraction-axed in vacua. Yield: 242 g (66% of theory) of Brigham-dihydro-2-methylbenzo[b]furan and 77 g (15 of theory) of 5,7-dibromo-2,3-dihydro-2-methylbenzo[b~furan.
b) 5-Bromo-2,3-dihydro-2- ethyl-7-benzo[b]furanylsulfochloride 470 g (4.03 moles) of chlorosulfonic acid are added drops over 20 minutes at -7C to a solution of 106 g (0.5 mole) of 5-bromo-2,3-dihydro-2-methylbenzo[b]furan in 300 ml of sheller-form, and the mixture is then stirred for a further 15 minutes await - 25C. The reaction mixture is taken up in ice/water, the organic phase is separated, and aqueous phase is extracted with two 500 ml portions of chloroform. The combined organic phases are washed with two 250 ml portions of water, dried over sodium sulfate, and concentrated, affording 101 g (65~ of theory) of 5-bromo-2,3-dihydro-2-methyl-7-benzo[b]furanylsulffochloride.

~Z368;~S

c)5-sromo-2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]fuurn The crude product obtained in b) is dissolved in 200 ml of ethyl acetate and the solution is added drops at 20~ - 25C
to 250 ml of 25% aqueous ammonia. The reaction mixture is stirred for an hour at the same temperature and the organic phase is then separated, treated with activated carbon, dried over sodium sulk fate, and concentrated. The residue is crystallized, affording 75 g (80% of theory) of 5-bromo-2,3-dihydro-2-methyl-7-sulfamoyl-benzo[b]furan with a melting point of 167 - 169C.
d) 2,3-Dihydro-2-methyl-7-sulfamoylbenzo[b]furan 72.5 g (0.25 mole) of 5-bromo-2,3-dihydro-2-methyl-7-~ulfamoylbenzo[b]furan are hydrogenated in the presence of 22.4 g (0.25 mole) of sodium acetate and 7.5 g of I palladium on carbon catalyst in 750 ml of methanol. The catalyst is removed, the solvent evaporated, and the residue crystallized from a mixture of water/ethanol, affording 42.3 g (79% of theory) of dodder-methyl-7-sulfamoylbenzo[b]furan with a melting point of 174 -177C.
e)N-(2,3-Dihydro-2-methylbenzo[b]furan-7-ylsulfonyl--N'-(4,6-dim ethyl pyrimidin-2-yl)urea

3.9 g (0.025 mole) of 1,5-diazabicyclo(5,4,0)undec-5-ene are added to a solution of 5.2 g (0.025 mole) of dodder-methyl-7-sulfamoylbenzo[b]furan and 6 g (0.025 mole) of N-(4,6-dimethylpyrimidin-2-yl)phenylcarbamate in 50 ml of acetonitrile, and the mixture is stirred for 2 hours at 20 to 25C. When the reaction is complete, the mixture is diluted with water and the product crystallizes out. The precipitate is isolated, washed with water and hexane, and dried in vacua over potassium ~23683S

hydroxide. Yield: 7 g (78~ of theory) of N-(2,3-dihydro-2-methyl-benzo[b]furan-7-ylsulfonyl)-N'-(4,6-dimethylpyrimiidin-2-yl)urea with a melting point of 190 - 193C.
Example 2:
1,3-Benzodioxol-4-sulfonamide a) 1,3-Benzodioxol-4-sulfonyl chloride 7.5 g of 4-amino-1,3-benzodioxol are suspended in 23 ml of 36~ hydrochloric acid. While cooling with ice, diazotisation is effected with a solution of 4.06 g of sodium nitrite in 8 ml of water. To the solution of the diazonium salt is added drops a mixture of 50 ml of glacial acetic acid, 5 ml of water, 15 g of sulfur dioxide and 2.3 g of copper (II) chloride hydrate. The temperature is kept constant at 40C until the addition to the solution of the diazonium salt is complete. The reaction mixture is then cooled and diluted with 500 ml of ice/water. The crude 1,3-benzodioxol-4-sulfochloride is isolated and dried. Melting point: 121 - 124C.
b) 1,3-Benzodioxol-4-sulfonamide The 1,3-benzodioxol-4-sulfochloride obtained in a) is dissolved in 20 ml of ethyl acetate and the solution is added drops at 20 - 25C to 25 ml of 25% aqueous ammonia. This mixture is stirred for 1 hour at the same temperature. The organic phase is separated, dried and concentrated, affording 1,3-benzodioxol-4-sulfonamide.
Example 3:
2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyllisocyanate a)N-(2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfoonline'-methyl urea 6.54 ml of 1,5-diazabicyclo(5,4,0)undec-5-ene are added to 9.9 g (0.0436 mole) of 2,3:dihydro-2,2-dimethyl-7-sulfamoyl-benzo[b]furan(compound 1.4) in dioxin. While cooling with ice, 2.65 ml of methyl isocyanate are added drops. The reaction mixture is stirred for 2 hours at 20 to 25C, then diluted with water, neutralized with 10 ml of 5 % sodium carbonate solution, and filtered. Acidification of the filtrate yields 11.1 g (89.5 of theory) of N-(2,3-dihydro- 2,2-dimethylbenzo[b]furan-7-yl-sulfonyl)-N'-methylurea.
b)2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyllisocyanate 8 g of~l-(2,3-dihydro-2,2-dimethylbenzo[b]furan-7-ylsul--fonyl)-N'-methylurea are dispersed in 400 ml of absolute sheller-Bunsen and the dispersion is saturated with phosgene at about 130~C, whereupon a clear solution forms. The solvent is then distilled off in vacua, with the exclusion of moisture, to give 2,3-dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyllisocyanate in the form of an oil, which can be used without further purification for obtaining the fused N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'-triazinylureas of the formula I.
The intermediates listed in the following table are obtained in corresponding manner.
The ring system numbers additionally listed in the following table refer only to the fused phenol ring.

~236~335 Table I_ SNOW
PA) Q

Compound¦ Ring system Q mop . [ C]
_ 1.1 Al \ / \ Cal 167-165 Q it C~3 19-193 1.3 Q3 It i 156-158 3 16~-164 6 I Q6 it I 176-177 .7 Q7 __ ' __ 7 . .

12~683S

Table (Continuation) _ _ _ _ . -Compound King system Q mop. [C]
lo 1-12 ¦ 12 200-201 1.13 Q13 I by . 177-179 .
Jo 1.1 1~36835 Table (Continuation) Compound¦ Ring system ¦ Q ¦ my [C]

;': :`

To (Continuation) company King system ¦ Q ¦ pi [ C]

~23683S

Table (Continuation) Come _ mop. lC]
pound King system _ _.

1.33 Q33 to Sot 199-200 I

1.34 Q34 It I 119-122 1.35 Q35 It i' 211-214 1.36 Q36 It I 234-236 1.37 Q37 B / / \ / 3 174-177 1.38 Q38 It Gil/ \S2 265-269 1.39 Q39 Isles 189-191 ~236835 Table (Continuation) Coring system mop. [C]
-I

,C113 Q Jo 129-131 I!, Jo\ 157-158 1.46 or/ I-/ _ ~Z3683~

A typical test of a compound of formula I, as disclosed in Application 432,425 is as follows.
Reemergence herbicidal action Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm3, water-absorbing capacity: 0.565 1/1).
After the non-adsorptive vermiculite has been saturated with an aqueous emulsion in deionized water which contains the test come pound in a concentration of 70.8 ppm, seeds of the following plants are sown on the surface: Nasturtium officinalis, Agrostis tennis, Styler media and Digit aria sanguinalis. The pots are then kept in a climatic chamber at 20C, an illumination of about 20 lug and a relative humidity of 70 %. During the germinating phase of 4 to 5 days, the pots are covered with light permeable material and watered with deionized water to increase the local humidity. After the Thea day, 0.5 % of a commercial liquid fermi-liver (Grunt) is added to the water. The test is evaluated 12 days after sowing and the action on the plants is assessed according to the following rating:
1 : plants have not emerged or are totally withered 2-3 : very pronounced action

4-6 : medium action 7-8 : weak action 9 : no action (as untreated controls).

The compound OH
BY , 3 ~=~S02-NH-CO-NH-~ \

OH
SHEA

showed a "1" rating in this test, at a concentration of 70.8 ppm in the test compound emulsion.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fused phenylsulfonamide of the general formula II

(II) wherein R1 is hydrogen, halogen, nitro, C1-C4 alkyl, C1-C4 halo-alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkoxycar-bonyl, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl or C2-C5 alkoxyalkoxy and A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms selected from the group consisting of -O-CH2-CH2-, -O-CO-CH2-, -O-CH2-CH2-CH2-, -O-CH2-O-, -CO-O-CH2-, -O-CH2-CH2-O-, -CH2-O-CO-CH2-, -O-CO-CH2-CH2-, -CO-O-CH2-CH2-, -O-CH2-CH2-CO-, -O-CH2-CO-CH2-, -S-CH2-CH2-, -SO-CH2-CH2-, -SO2-CH2-CH2-, -NH-CH2-CH2-, -S-CH2-CH2-CO-, -S-CH2-CH2-CH2-, -O-SO2-CH2-CH2- or -NH-CO-CH2-CH2-, wherein the substituents are selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylthiocarbonyl, carbamoyl, C1-C4 alkylaminocar-bonyl, di(C1-C4)alkylaminocarbonyl, C1-C4 alkylsulfonyl, C3-C5 alkenyl or C3-C5 alkynyl.

2. A compound according to claim 1 wherein A is an unsubstituted or substituted bridge of 3 or 4 atoms selected from the group consisting of -O-CH2-CH2-; -O-CO-CH2-;
-O-CH2-CH2-CH2-; -O-CH2-O-; -CH2-CH2-O-; -CO-O-CH2-; -CH2-O-CO-;
-O-CH2-CH2-O-; -CH2-CO-O-; -CH2-CO-O-CH2-; -O-CO-CH2-CH2-;
-CO-O-CH2-CH2-; -CH2-CH2-CO-O-; -O-CH2-CH2-CO-; -O-CH2-CO-CH2-;
-S-CH2-CH2-; -SO-CH2-CH2-; -SO2-CH2-CH2-; -NH-CH2-CH2-;
-S-CH2-CH2-CO-; -S-CH2-CH2-CH2-; -SO2-CH2-CH2-CO-; -SO2-CH2-CH2-;
-O-SO2-CH2-CH2-; -CH2-CH2-CO-NH-; and -CH2-CH2-CH2-NH-, with the proviso that where the specified bridge is unsymmetrical, then it is given in sequence beginning with the atom linked to the phenyl ring in the ortho position relative to the sulphonyl group, and wherein the substituents are as defined in claim 1.

3. 3,4-Dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-ylsulfonamide.

4. A process for the preparation of a compound of formula II as defined in claim 1 which comprises (a) diazotising an aniline of the formula VII

in which R1 and A are as defined in claim 1, and replacing the diazo group with sulfur dioxide in the presence of a catalyst to provide a phenylsulfonyl chloride of the formula (X); or (b) reacting a phenylsulfonic acid of formula (VIII) in which R1 and A are as defined in claim 1 with a chlorinating agent to provide a phenylsulphonyl chloride of the formula (X);
or (c) treating a benzyl thioether of formula (IX) wherein R1 and A are as defined in claim 1 to provide a phenyl sulphonyl chloride of formula (X); and (d) reacting the thus obtained compound of formula (X) with ammonium hydroxide to provide the desired sulphonamide.