CA1236837A - Fused phenyl sulfonyl carbamates - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Fused phenyl sulfonyl carbamates of the general formula (VI) , wherein Z is oxygen or sulfur, 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 R is phenyl, C1-C4 alkyl or substituted phenyl together with processes for their preparation are disclosed.
These compounds find use as intermediates in the preparation of herbicidally active compounds of the formula I

Description

1~3683~
DAVY 3.

Fused phenol sulfonylcarbamates -This Application is a divisional from Application 423,425 filed July Thea, 1983. Application 423,425 relates to novel N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'-triazinylureas having herbicidal and growth regulating proper-ties, 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

.\ SKIN-\ (I) . A z R2 \R4 wherein Z is oxygen or sulfur, E is nitrogen or SHEA-, Al is hydrogen, halogen, vitro, Cluck alkyd, Cluck haloalkyl, Cluck alkoxy, Cluck haloalkoxy, Cluck alkoxycarbonyl, Cluck alkyd-trio, Cluck alkylsulfinyl, Cluck alkylsulfonyl or C2-Cs alkoxyal-foxy, R2 is hydrogen, Cluck alkyd or Cluck alkoxy, R3 and R4, each independently of the other, are hydrogen, Cluck alkyd, Cluck alkoxy, Cluck haloalkoxy, C~-C4 haloalkylthio, Cluck alkylthio, halogen, C2-Cs alkoxyalkyl, C2-Cs alkoxyalkoxy or 1236~33'7 -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 sulk fur 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, Amelia-ox or 3-amyloxy,with methoxy, ethics or isopropoxy being preferred.
Alkylthio is e.g. methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio or n-pentylthio, with methylthio and ethylthio being preferred.
Alkylsulfonyl is e.g. methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and n-butylsulfonyl, with methylsulfonyl and ethylsulfonyl being preferred.
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 bromide, with fluorine and chlorine being preferred.
Application 423,425 also describes the salts which the ~2368371 compounds of formula 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, di-methylamine, 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-ammonium cation. I've 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 alkyl-aminocarbonyl, di(Cl-C4)alkylaminocarbonyl, Cluck alkylsulfonyl, C3-Cs alkenyl or C3-Cs alkynyl.

Condense 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, thither, 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, dihydrocoumarin, benzodioxan, phthalide, dihydroisocoumarin, 3-isochromanone, indoline, 2,3-dihydrobenzothiophene, oxide-hydrobenzothiophene, l,l-dioxo- 2,3-dihydrobenzothiophene, 4-chromanone and 3-chromanone.
According to application 423,425 preferred compounds of formula I are those in which either 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, ~X3683~

Cluck alkoxy, di(Cl-C4)alkylamino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
Further preferred subgroups and 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)alkylamino, Cluck haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
Particularly preferred groups of compounds in applique-lion 423,425 comprise those compounds of formula I in which:
- Z is oxygen, Al is hydrogen, halogen or Cluck alkoxycar-bony, Russ hydrogen, each of R3 and R4 independently of the other is Cluck alkyd, Cluck alkoxy, di(Cl-C4)alkylamino, Cluck Hillel-foxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A contains at least one oxygen atom arid is unsubstituted or substituted by halogen or Cluck alkyd, or those in which - Z is oxygen, Al is hydrogen, halogen or Cluck alkoxycar-lZ3683~

bony, R2 is hydrogen, each of R3 and R4 independently of the other is Cluck alkyd, Cluck alkoxy, di(Cl-C4) alkylamino, 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 C1-C4 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)alkylamino, 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 3,4-dihydro-2,2-dioxo-1,2-benzoxathiine system and is unsubstituted or substituted by Cluck alkyd.
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-dimethyl-pyrimidin-2-yl)urea, N-(2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl)No methoxy-6-methylpyrimidin-2-yl)urea.
According to Application 423,425 the process for preparing the compounds of formula I is carried out in an inert organic solvent.
One process for obtaining the compounds of formula I
described in Application 423,425 comprises reacting a fused N-phenylsulfonylcarbamate of the formula VI

~236837 Al _ N / R3 = / 2 11 / -I

(Vim (V) wherein A Al, R2,R3, R4, E and Z are as defined for formula 1 and R is phenol, alkyd or substituted phenol, with an aminopyrimidine or aminotriazine 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 solvents.
Examples of such solvents are: Bunsen, Tulane, zillion or cyclohexane, chlorinated hydrocarbons such as ethylene chloride, 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-di-azabicyclo(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 hydrae 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 aromatic hydrocarbon or a chlorinated hydrocarbon.
This Application is concerned with the fused phenol sulfonyl carbamate intermediates of the formula VI.
Thus in its broadest aspect this invention provides a fused phenylsulfonylcarbamate of the general formula VI

Sucker (VI) A' wherein Z is oxygen or sulfur, Al is hydrogen, halogen, vitro, Cluck alkyd, Cluck haloalkyl, lX36837 Of C4 alkoxy~ Cluck haloalkoxy, Cluck alkoxycarbonyl~ 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 l or 2 oxygen, sulfur or nitrogen atoms selected from the group consisting of -0-CH2-CH2-, -O-C0-CH2-, -O-CH2-CH2--CH2-, -SHEA-, -COUCH-, --0-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 SHEA
NH SHEA SHEA -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, cyan, Cluck alkyd, Cluck haloalkyl, Cluck alkylcarbonyl, Cluck aikoxycarbonyl, Cluck alkylthiocar-bony, carbamoyl, Cluck alkylaminocarbonyl, di(Cl-C4)alkylamino-carbonyl, Cluck alkylsulfonyl, C3-Cs alkenyl or C3-Cs alkynyl, and R is phenol, or Cluck alkyd.
Particularly preferred compounds from within this group are:
N-(3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiinn-8-sulfon-yl)-methylcarbamate;
N-(3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiinn-8-sulfon-yl)-ethylcarbamate; and N-(3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiinn-8-sulfon-yl)-phenyl carbamate.
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 12~683~

are described in Japanese patent specification 61 169.
The starting aminopyrimidines and aminotriazines of the formula V, as well as corresponding phenylcarbamates of the formula III, have either long been known or are described in European patent application 70 804, or they can be prepared by known methods from compounds disclosed therein.
It is disclosed in Application 423,425 that the compounds of formula I are stable compounds, and no protective measures 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, properties. The growth of both mounts and divots is inhibited.
Thus, for example, the compounds of Application 423,425 selective-~36~337 lye 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 mechanism 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.
Cat ionic surfactants are preferably qua ternary ammonium salts which contain, as N-substituent, at least 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,methylsulfates or ethylsul-fates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation 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, 19~4.
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, 1 to 99.9 %, of a solid or liquid adjutant, and 0 to 25 I, 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 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 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 drop-wise 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 chloroform, and the mixture is then stirred for a further 15 minutes at 20 -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 broomed-hydro-2-methyl-7-benzo[b]furanylsulfochloride.
c)5-Bromo-2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]fuurn eye crude product obtained in b) is dissolved in 200 ml lZ36837 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-sul-famoylbenzo-[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--dimethylpyrimidin-2-yl)urea 3.9 g (0.025 mole) of 1,S-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-dimethyl-pyrimidin-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 hydrox-ides Yield: 7 g (78 % of theory) of N-(2,3-dihydro-2-methyl-123~837 benzo[b~furan-7-yl-sulfonyl)-N'-(4,6-dimethylpyrimmidin-2-yl)urea with a melting point of 190 - 193C.
Example 2: 1,3-Benzodioxol-4-sulfonamide a) 1,3-senzodioxol-~-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 organ-to phase is separated, dried and concentrated, affording 1,3-benzodioxol-4-sulfonamide.
Example 3:2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyllist-_ Senate)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 ~Z3683~
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-ylsulfonyllouses-Nate 8 g of N-(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 130C, 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 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 substituent in the subsequent Tables of carbamates.
A typical test of a compound of formula I, as disclosed in Application 432,425 is as follows.

~236837 Reemergence herbicidal action Plastic pots are filled with expanded vermiculite (den-sty: 0.135 g/cm3, water-absorbing capacity: 0.565 l/l). After the non-adsorptive vermiculite has been saturated with an aqueous emulsion in deionized water which contains the test compound in a concentration of 70.8 ppm, seeds of the following plants are sown on -the surface: Nasty Tim officinalis, Agrostis tennis, Stellar-it 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 fertilizer (Green-zip I) 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:
l : 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 BY

S02-NH-CO-NH~

OH

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

12368~7 Table 1:
.

So Ho PA
Q

Compounding system _ mop. [C]

1.1 Al I\ I

1.2 2 Jo it 3 1 1 0-193 1.3 3 it 156-158 . OUCH . I

1.6 1 6 176-17 . Q7 I if 1 136-137 , .

123~i83~7 Table 1 Continuation ..
owned I . [C¦

, 1.9 Q9 133-135 - ' ~00-701 1.13 Q13 177-17 Jo 1.1 ..

~23683~

Table 1 (Continuation) Compound Ring system ¦ Q ¦ moo. [C]
I _. I
I

OH

1.21 I 1 Clue 33 1.22 Q22 SHEA owe ~C3 1.23 Q23 Table 1 (Continuation) company Ring system ¦ Q ¦ pi [ C]
S\ - I -I

l I
1.28 Q28 Jo I !

l I- SHEA
1.29 Q29 it ~r 20~-206 ~Z~6837 Table 1 (Continuation) .. _ pCoumDd King system _ my it 1.33 Q33 Al 199-200 1.34 Q34 It ,3 119-122 I!, US\
1.35 Q35 I I 211-214 s\ .
1.36 Q36 it IT . 234-236 1.37 Q37 By / \./ 3 174-177 1.38 438 I So 265-269 Lo If ,,02 allele Table 1 Continuation Come Ring system ¦ Q mop. [C]

1.40 Q40 I I 186-188 Ho 1.43 Q43 2 I-/ \-/ \C~2C~3 1.44 Q \/\ 230-233 1 . 45 Q45 Jo \, / \ 129-13 1 ~!~ I 157-158 1 .46 Q46 I "I

lZ36837 Table 4:
Q-so2-NH-co-T

Come Q T mop. LC]
pound .
4.1 Ql4 9 4.2 Q24 9 4.3 Q34 9 4.4 Q4NHCH3 ~>240(decomp.) 4.5 Q5NHCH3 4.6 Q6NHCH3 4.7 Q7NHCH3 4.8 Q8NHCH3 4.9 QgNHCH3 203-204 4.10 Queue NHCH3 4.11 Q11 NilCH3 4.12 Q12 NHCH3 4.13 Q13 NHCH3 4.14 Q14 NHCH3 4.15 Q15 NHCH3 4.16 16 NHC~13 4.17 Q17 NHCH3 4.18 Q18 N~CH3 4.19 Q19 NHCH3 4.20 Q20 4 9 4.21 Q21 NHCH3 4.22 Q22 4 9 4.23 Q23 NHC~13 4.24 Q24 NHCH3 4.25 Q25 NHCH3 4.26Q26 NHCH3 -~23~i837 Table 4: (Continuation) I ._ Coup, Q T my C] Coup. Q T mop. [C]
. _ 4.27 Q27 NHC~I~3 4.55 Q6 C6H5 4.28 Q28 NHCH3 4.56 Q7 C6H5 4.29 Q29 NHCH3 4.57 Q8 C6H5 4.30 Q30 NHCH3 4.58 Qg C6H5 4.31 Q31 NHCH3 4.59 Lo C6H5 4.32 Q32 NASH 4.60 Q11 OOZE
4.33 Q33 NHCH3 4.61 Q12 OOZE
4.34 Q34 NHCH3 4.62 13 C6H5 4.35 Q35 NHCH3 4.63 Q14 OOZE
4.36 Q36 NHCH3 4.64 Q15 C6H5 4.37 Q37 NHCH3 4.65 Q16 C6H5 4.38 Q38 NHCH3 4.66 Q17 C6H5 4.39 Q39 NHCH3 247-249 4.67 Q18 C6H5 4,40 Q39 NH~C4H9~n 4.68 Q19 OOZE
4.41 Q40 NHCH3 ¦ 4.69 Q20 OOZE
4.42 Q40 NH~C4H9~n 4.70 Q21 C6H5 4.43 Q41 NHC113 4.71 Q22 C6H5 4.44 Q42 NHC113 4.72 Q23 C6H5 4.45 Q43 NHCH3 4.73 Q24 clue 4.46 Q43 NIKKO- n 4.74 Q25 OOZE
4.47 Q44 NHCH3 4.75 ~26 OOZE
4.48 Q45 NilCH3 4.76 Q27 C6H5 4.49 Q46 NIKKO- n 4.77 Q28 OOZE
4.50 Q1 clue 4.78Qz9 C6H5 4.51 Q2 C6H5 4.79Q30 C6H5 4.52 Q3 C6H5 4.80Q31 C6H5 4.53 Q4 C6H5 4.81Q32 C6~5 4.54 Q5 OOZE ~4.82 C6H5 ~Z36837 Table 4: (Continuation) Coup Q __ Cowan . Q

4 . 83 Q34 C6H5 4 .111 Q16 ooze 4 . 84 Q35 C6H5 4 .112 Q17 OUCH
4 . 85 Q36 C6H5 4 .113 Q18 ooze 4 . 86 Q37 C6H5 4 .114 Q19 Ooze 4 . 8 7 Q38 C6H5 4 . 115 Q20 OUCH
4 . 88 Q39 C6H5 4 .116 Q21 OOZE
4 . 89 Q40 C6HS 4 .117 Q22 OUCH
4 . 90 Q41 C6H5 4 .113 Q23 OUCH
4 . 91 Q42 C6H5 4 .119 Q24 Ouzel 4 . 92 Q43 C6H5 4 .120 Q2s OOZE
4 . 93 Q44 C6H5 4 .121 Q26 Ouzel 4 . 94 Q45 osseous 4 . 122 Q27 OOZE
4 . 95 Q46 C6H5 4 .123 Q28 OUCH
4 . 96 Al OUCH 4 .124 Q29 OOZE
4 . 97 Q2 OUCH 4 .125 Q30 ouzel 4 . 98 Q3 OUCH 4 .126 Q3 1 OOZE
4 . 99 Q4 OUCH 4 .127 Q32 OOZE
4 .100 Q5 OUCH 4 .128 Q33 OOZE
4 .101 Q6 OUCH 4 .129 Q34 OOZE
4 .102 Q7 OUCH 4 .130 Q35 OOZE
4 .103 Q8 OUCH 4 .13 1 Q3 6 OOZE
4 .104 Qg OUCH 4 .13 2 Q3 7 OOZE
4 .105 Queue OUCH 4 .133 Q38 OOZE
4 .106 Al 1 OUCH 4 .134 Q39 OOZE
4 .107 Q12 OUCH 4 .135 Q40 ooze 4 .108 Q13 OUCH 4 .136 Q41 OOZE
4 .109 Q14 OUCH 4 .13 7 Q42 OUCH
4. 110 Qls OUCH__ 4.138 Q43 QCH3 ~236837 Table 4: (Continuation) Coup. ¦ Q T pi [C] Compaq T m.p.~oc]
I _ .139 Q44 OUCH Q27 clue .14C Q45 OUCH Q28 clue .141 Q46 OUCH Q29 C2H5 .142 I C2H5 4.171Q30 OOZE
.143 Q2 C2H5 4.172Q31 C2H5 .144 Q3 C2H5 4.173Q32 C2H5 .145 Q4 C2H5 4.174Q33 C2H5 .146 Q5 C2H5 4.175Q34 OOZE
4.147 Q6 C2H5 4.176Q35 clue .148 Q7 C2H5 4.177Q36 C2H5 4.149 Q8 C2H5 4.178Q37 clue .150 Qg C2H5 4.179Q38 C2H5 .151 QlC C2H54.180 Q39 C21!5 .152 Ill C2H54.181 Q40 C2H5 .153 Q12 C2H54.182 Q41 clue 4.154 Q13 C2H54.183 Q42 OOZE
4.155 Q14 C2H54.184 Q43 C2H5 4.156 Q15 C2H54.185 Q44 OOZE
4.157 Q16 Ouzel 4.186 Q45 Ouzel 4.158 Q17 C2H54.187 46 C2 4.159 Q18 OOZE
4.160 Ql9 C2H5 4.161 Q20 OOZE
4.162 Q21 OOZE
4.163 Q22 OOZE
4.164 Q23 OOZE
4.165 Q24 Ouzel 4.166 Q25 OOZE
4.167 Q26 OC2P5

Claims (5)

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

1. A fused phenylsulfonylcarbamate of the general formula VI

(VI) , wherein Z is oxygen or sulfur, 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 alkylthiocar-bonyl, carbamoyl, C1-C4 alkylaminocarbonyl, di(C1-C4)alkylamino-carbonyl, C1-C4 alkylsulfonyl, C3-C5 alkenyl or C3-C5 alkynyl, and R is phenyl, or C1-C4 alkyl.

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-CH -;
-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. N-(3,4-Dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-ylsulfonyl)-methyl-carbamate.

4. N-(3,4-Dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-ylsulfonyl)-ethyl-carbamate.

5. N-(3,4-Dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-ylsulfonyl)-phenyl-carbamate.