CA1236838A - Fused phenylsulfonylchlorides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Fused phenylsulfonylchlorides of the formula (X) (X) wherein R1 is hydrogen, halogen, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkoxycarbonyl, 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 alkylaminocarbonyl, di(C1-C4)alkylaminocarbonyl, C1-C4 alkylsulfonyl, C3-C5 alkenyl or C3-C5 alkynyl, and process for their preparation are disclosed. These compounds find use as intermediates in the preparation of herbicidally active compounds of the general formula I

Description

Fused Phenylsulfonylchlorides This Application is a divisional from Application 432,425, filed July Thea, 1983.
Application 423,425 relates to novel N-phenylsulfonyl-N'-pyramidinylureas 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

Al R3 -S02-NH-C-N - (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, R2 is hydrogen, Cluck alkyd or Cluck alkoxy, R3 and R4, each independently of the other, are hydrogen, Cluck alXyl, Cluck alkoxy, Cluck haloalkoxy, Cluck haloalkylthio, Cluck alkylthio, halogen, C2-Cs alkoxy-alkyd, C2-cs alkoxyalkoxy or -NRsR6, 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 -S02- 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.

~:~36838 Alkylsulfonyl is e.g. methylsulfonyl, ethylsulfonyl or n-propylsulfonyl, 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 salts which the come pounds 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-~23~i8~3 ammonium cation, the tetraethylammonium cation, the trin,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-C5 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, there 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 ~236838 a) the substituents of the bridge A are halogen or Cluck alkyd, or 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 alkoxycarbonyl, or f) 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.

:123Çi838 Particularly preferred groups of compounds in Application 423,425 comprise those compounds of formula I 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 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-benzoxathiine system and is unsubstituted or substituted by Cluck alkyd.

123~83t3 Preferred individual compounds of Application 423,425 are:
N-chroman-8-ylsulfonyl-N'-(4-methoxy-6-methylpyrimmedianly) urea, N-~2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl))-N'-(4,6-dimethylpyrimidin-2-yl)urea, N-(2,3-dihydro-2-methylbenzo [b]furan-7-ylsulfonyl)-N'-(4-methoxy-6-methylpyrimidin-2-yl)urea.
According to Application 423,425 the process for pro-paring the compounds of formula I is carried out in an inert organic solvent.
A first process according to Application 423,425 for the preparation of the compounds of formula I comprises reacting a fused phenylsulfonamide of the formula II

SO -NH

/ (II), wherein Al and A are as defined for formula I, with an N-pyrimi-dinylcarbamate or N-triazinylcarbamate of the formula III

N
R-O-C-N - \ (III), 1~3683~

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.
A second process for obtaining the compounds of for-mute I comprises reacting a fused phenylsulfonylisocyanate or phenylsulfonylisothiocyanate of the formula IV

Al Jo SNAKES
(IV), wherein A, Al and Z are as defined for formula I, with an amino-pardon or aminotriazine of the formula V

N

No< ( V ), wherein E, R2, R3 and R4 are as defined for formula I, optionally in the presence of a base.
Finally, the compounds of formula I may also be obtained by reacting a fused N-phenylsulfonylcarbamate of the formula VI

R

SNICKER
(VI), A

1;~36?338 wherein A, Al and Z are as defined for formula I and R is phenol, alkyd or substituted phenol, with an aminopyrimidine or aminotria-zinc of the formula V above.
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.
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 short ten the reaction time or also to initiate the reaction it is expel dint to heat the reaction mixture briefly to boiling point. I've 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-g _ ~236~3~3 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 solvent in which it is poorly soluble, such as an ether, an art-matte hydrocarbon or a chlorinated hydrocarbon.
The intermediates of the formula II can be prepared by different methods. For example, the compounds of formula II are obtained by diazotizing aniline of formula VII

Al ( ) (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

12:~6~338 I S02 -Of ( X ), ( A ) 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 (VIII), 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 SCHICK (IX), A

lX36838 wherein Al and A are as defined for formula I, with chlorine, and reacting the resultant phenylsulfonyl chloride of the formula X
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 phenylsulfonylisocyanates of the formula IV, can be obtained by reacting the sulfonamides of the formula II with pros-gene, in the presence of butylisocyanate, in a chlorinated hydra-carbon as solvent, at reflex temperature. Similar reactions are described in "Newer Methods of Preparative Organic Chemistry", Vol. VI, 223 - 241, Academic Press, New York and London.
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 dip phenol carbonate in the presence of a base. Similar processes are described in Japanese patent specification 61 169.
It is thus apparent that the fused phenol sulfonyl chlorides of formula (X) comprise a link between all of these processes providing, finally, compounds of formula I.

123~838 Thus in its broadest aspect this invention provides a fused phenylsulfonyl chloride of the general formula X

Al Scholl (X), A ) wherein 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 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-, -0-CH2-0--,-CO-O-CH2-, -O-CH2-CH2-0-, -CH2-0-CO-CH2-, -0-CO-CH2-CH2-, -CO-O-CH2--CH2-, --0-CH2--CH2-CO-, -O-CH2-CO-CH2-, -S--CH2-CH2-, -SO-CH2-CH2-, -S02-CH2-CH2- -N~-CH2-CH2- SHEA SHEA
CO-, -S-CH2-CH2-CH2-, -O-SO2-CH2-CH2- or -NH-CO-CH2-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-bony, di(Cl-C4)alkylaminocarbonyl, Cluck alkylsulfonyl, C3-Cs alkenyl or C3-Cs alkynyl.

lZ3683~

A particularly preferred compound is dodder-dioxo-3-methyl-1,2-benzoxathiine-8-sulfonyl chloride.
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 123~838 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 mechanism of yield increase using growth regulators resides in the fact that nutrients are able increase tingly 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.
Cat ionic surfactants are preferably qua ternary ammonium salts which contain, as N-substituent, at lease one Cg-C22alkyl radical and, as further substituents, lower unsubstituted or halo-jointed alkyd, bouncily or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethylsul-fates, e.g. stearyltrimethyl ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of form-elation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MY Publishing Corp. Rouged, New Jersey, 1979, and Sibley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1964.
As 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, 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 lZ36838 are added drops at 0 - 5C to a mixture of 237 g (1.77 moles) of 2,3-dihydro-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 broomed-hydro-2-methylbenzo[b]furan and 77 g (15% of theory) of Dow-bromo-2,3-dihydro-2-methylbenzo[b]furan.
b)5-Bromo-2,3-dihydro-2-methyl-7-benzo[b]furanylsulffochloride 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 at 20 - 25C. 'rho 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 S-bromo-2,3-dihydro-2-methyl-7- benzo[b]furanylsulfochloride.
c)5-Bromo-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 lZ36~338 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-sulfamoylbenzo[b]furan are hydrogenated in the presence of 22.4 g (0.25 mole) of sodium acetate and 7.5 g of 5% 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-di-methylpyrimidin-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 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-~enzodioxol-4-sulfonyl chloride 7.5 g of 4-amino-1,3-benzodioxol are suspended in 23 ml ~236838 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 l,3-benzodioxol-4-sulfonamide.
Example 3:2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyllist-Senate 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-ylsul-fonyl)-N'-methylurea.
b)2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyllisocyanate 8 g of N-(2,3-dihydro-2,2-dimethylbenzo[b]furan-7-yl-sulfonyl)-N'- methyl urea are dispersed in 400 ml of absolute chlorobenzene and the dispersion is saturated with phosgene at about 130C, whereupon a clear solution forms. The solvent is then distilled off in vacua, with the exclusion of moisture, to give dodder- dimethylbenzo[b]furan-7-ylsulfonylisocyanate in the form of an oil, which can be used without further purify-cation for obtaining the fused N-phenylsulfonyl-N'-pyrimidinyl-ureas and N-phenylsulfonyl-N'- triazinylureas of -the formula I.
The intermediates listed in the following tables are obtained in corresponding manner.
The ring system numbers additionally listed in Table 1 refer only to the fused phenol ring and are employed for the same substituents in the subsequent Table concerned with the compounds of this invention.

~LZ36838 Table 1 I
So NH

PA) Q

Compounding system mop. [C]
. .. ._ 1.1 Al I)\ I 167-16S

2 1 '\ I

1.3 Q3 . \ I SHEA 156-158 1.4 Q4 I SHEA 162-164 lZ3683~3 Table 1 (Continuation) I

1.12 Q12 ] _.~ 200-201 1.13 Q13 1~;/;\0/ . 177-179 1.1 . . .

~2368~8 Table 1 (Continuation) Compound Ring system Q mop. [C]
I-' b' `'~

SCHICK ~!~ Jo\ SHEA
1.22 Q22 Jo 1.23 Q23 / \ /

I _ _ Table 1 (Continuation) company Ring system Q ¦ mop. [C]
25 Q~5 3,!
I

Table 1 (Continuation) Come m-p- C]
pound King system I Jo i 199-200 -I I]

I; / \ /. SHEA

1.38 Q38 B / / \ / 265-269 \ /\30 ~Z36~3~3 Table 1 (Continuation) Come Ring system mop. [C]
pound 1.40 Q40 I'/ \'/ SHEA 186-188 .41 Q41 / \ /

1.42 Q42 Isle owe 1.44 Q44 230-233 1.45 Q45 j 129-131 I!, owe 157-158 1.46 Bra I./- I

Table 2 Q - Scholl comma d¦ Q my C] pound ¦ Q mop. [C]

2.1 Al 2.27 Q27 2.2 Q2 2.28 Q28 2.3 Q3 2.29 Q29 2.4 Q4 84-86 2.30 Q30 2.5 Q5 2'32 Q31 2.6 Q6 .3 32 2.7 Q7 121-124 ~2.33Q33 108-lll 2.8 Q8 2.34 Q34 oil 2.9 Qg oil 2.35 Q35 clue 2.36 Q36 2.13Q13 oil 2.39 Q39 22 clue 2 441Q41 2.16Q16 2.42 Q42 2.1918 2.45 Q45 130 (decomp.) 2.20Q20 12.46_ Q46 2.21Q21 2.22Q22 2.23Q23 2.24 Q~4 2.25Q25 2.~6 Q26 ~2368~

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 I. 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 (Greenest 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).

Claims (4)

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

1. A fused phenylsulfonyl chloride of the formula X

(X), 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--sulfonyl chloride.

4. A process for the preparation of a phenyl sulphonyl chloride of the formula (X) 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 sulfurdioxide 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 phenyl sulphonyl 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).