CA1049539A - Substituted benzofuranyl esters - Google Patents
Substituted benzofuranyl estersInfo
- Publication number
- CA1049539A CA1049539A CA218,030A CA218030A CA1049539A CA 1049539 A CA1049539 A CA 1049539A CA 218030 A CA218030 A CA 218030A CA 1049539 A CA1049539 A CA 1049539A
- Authority
- CA
- Canada
- Prior art keywords
- dihydro
- dimethyl
- spp
- substituted
- methylaminosulfonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/80—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Furan Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Subs-tituted benzofuranyl esters of the formula where R1 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, R2 denotes loweralkyl, loweralkenyl, loweralkynyl, a metal atom, loweralkyl-sulfonyl or acyl of the formula , R4 denoting unsubstituted or chloro-, loweralkoxy- or loweralkyl-thio-substituted loweralkyl, loweralkenyl or loweralkynyl, loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-substituted loweralkoxy, and R3 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, or acyl of the formula
Subs-tituted benzofuranyl esters of the formula where R1 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, R2 denotes loweralkyl, loweralkenyl, loweralkynyl, a metal atom, loweralkyl-sulfonyl or acyl of the formula , R4 denoting unsubstituted or chloro-, loweralkoxy- or loweralkyl-thio-substituted loweralkyl, loweralkenyl or loweralkynyl, loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-substituted loweralkoxy, and R3 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, or acyl of the formula
Description
s~ :
The present invention ~elates to new 4-benzofuranyl esters, the preparation of these compounds, their use as herbicides, and herbicides containing these compounds as active ingredients.
It is known (German Laid-Open Application DOS 1,926,139) to use 2,3-dihydro-3,3-dime-thyl-2-ethoxybenzofuran-5-yl methanesulfonate as a herbicide; however, its action is poor.
We have now found that benzofuran-5-yl esters of the formula \ " 3 oR3 where Rl denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, R denotes loweralkyl, loweralkenyl, loweralkynyl, a metal atom, loweralkyl-sulfonyl or acyl of the formula 11 , O
R4 denoting unsubstituted or chloro-, loweralkoxy- or loweralkyl-thio-substituted loweralkyl, loweralkenyl or loweralkynyl, .
loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-substituted loweralkoxy, and R3 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, or acyl of the formula O
R5 denoting unsubstituted or chloro-, loweralkoxy, or loweralkyl-. 30 thio-substituted loweralkyl, loweralkenyl or loweralkynyl, ~.
loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-.` substituted loweralkoxy, have a herbicidal action which is superior .
to that of prior art herbicides. Furthermore, the new compounds - 1 - ' .`,'.' ' , ~. .
9'~39 have better selectivity in crop.s such as Gossypium hirsutum, Zea mays and seta spp. than 2,3-dihydro-3,3-dimethyl-2-ethoxybenzo-furan-5-yl methanesulfonate.
t The compounds of the invention may be prepared for instance by the following methods:
a) Acylation of benzofuran-5-yl aminosulfonates in accordance with the foLIow~ng eq~ation:
" "
'~:
., . ~
, ~.
,, ' ,' ~ ~"
., . ~ .
::' ., .
.... ..
~., i ~. ' -;' . :
i, ..
,: ' ,~ - 2 -A
~04g53g OOZ. 30,334 R1 O R~ O
\~ Nso ~ 0CH3 + XCu ~ R~ CV' o ~ H3 , R1, R3 and R4 having thef above meanings and X denot;ng for instance halogen (chloro, bromo) or the radical -OCR
Tha banzofuran-5-yl aminosulfonates used as starting materials are known.
b) Acylation of 2-hydroxybenzofuran-5-Yl aminosulfonates in accordance with tha following equation: ;
R2 0 ~ ~ CH3 + XCR5 ~ 2/ O ~ 13 OH OCR
O
R1, R2 and R5 having the abova meanings and X denoting for instance halogen (chloro, bromo) or the radical .~ -oCR5 . ,.
.,~, o .
The benzofuran derivatives used as starting materials may ~-, 10 be preparad as follows:
+ / C~CH-N 3 O
:, ~
- 3 ~
.. .
, , :
1~49539 O.Z. 30,334 HO H C O H O H C
The present invention ~elates to new 4-benzofuranyl esters, the preparation of these compounds, their use as herbicides, and herbicides containing these compounds as active ingredients.
It is known (German Laid-Open Application DOS 1,926,139) to use 2,3-dihydro-3,3-dime-thyl-2-ethoxybenzofuran-5-yl methanesulfonate as a herbicide; however, its action is poor.
We have now found that benzofuran-5-yl esters of the formula \ " 3 oR3 where Rl denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, R denotes loweralkyl, loweralkenyl, loweralkynyl, a metal atom, loweralkyl-sulfonyl or acyl of the formula 11 , O
R4 denoting unsubstituted or chloro-, loweralkoxy- or loweralkyl-thio-substituted loweralkyl, loweralkenyl or loweralkynyl, .
loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-substituted loweralkoxy, and R3 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, or acyl of the formula O
R5 denoting unsubstituted or chloro-, loweralkoxy, or loweralkyl-. 30 thio-substituted loweralkyl, loweralkenyl or loweralkynyl, ~.
loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-.` substituted loweralkoxy, have a herbicidal action which is superior .
to that of prior art herbicides. Furthermore, the new compounds - 1 - ' .`,'.' ' , ~. .
9'~39 have better selectivity in crop.s such as Gossypium hirsutum, Zea mays and seta spp. than 2,3-dihydro-3,3-dimethyl-2-ethoxybenzo-furan-5-yl methanesulfonate.
t The compounds of the invention may be prepared for instance by the following methods:
a) Acylation of benzofuran-5-yl aminosulfonates in accordance with the foLIow~ng eq~ation:
" "
'~:
., . ~
, ~.
,, ' ,' ~ ~"
., . ~ .
::' ., .
.... ..
~., i ~. ' -;' . :
i, ..
,: ' ,~ - 2 -A
~04g53g OOZ. 30,334 R1 O R~ O
\~ Nso ~ 0CH3 + XCu ~ R~ CV' o ~ H3 , R1, R3 and R4 having thef above meanings and X denot;ng for instance halogen (chloro, bromo) or the radical -OCR
Tha banzofuran-5-yl aminosulfonates used as starting materials are known.
b) Acylation of 2-hydroxybenzofuran-5-Yl aminosulfonates in accordance with tha following equation: ;
R2 0 ~ ~ CH3 + XCR5 ~ 2/ O ~ 13 OH OCR
O
R1, R2 and R5 having the abova meanings and X denoting for instance halogen (chloro, bromo) or the radical .~ -oCR5 . ,.
.,~, o .
The benzofuran derivatives used as starting materials may ~-, 10 be preparad as follows:
+ / C~CH-N 3 O
:, ~
- 3 ~
.. .
, , :
1~49539 O.Z. 30,334 HO H C O H O H C
2) ~ Cl; ~ ClS~NHR _ ~ / " ~ C~3 N~
:.','`
:.','`
3) / N-SO ~ l~ R1 0 ~ H~
.. .. .
.. .. .
4) / N-SO ~ l~ R30H/H ~ \ N-SO ~ 3 Reaction 1) is known from Dutch PUblish~d Application 6,512,311; ~. Prakt. Chem., 4th series, 32, 144, 1966; and U.S. 3,184,457.
Reactions 2), 3) and 4) are illustrated by the following l~ experiments.
1 ~xperiment A
! 2,3-dihydro-3,3-dimethyl-2-morpholinobenzofuran-5-yl meth~laminosulfonate _ _ _ At Oc to 5~C and while stirring, 36 parts (by weight) of methylaminosulfonyl chloride was added to a solution of 48.8 i parts of 2,3-dihydro-3,3-dimethyl-2-morpholino-5-hydroxybenzo-furan and 27.3 parts of triethylamine in 130 parts of tetra-1 hydrofuran. The reaction mixture was stirred for 1 hour at ¦ room temparature and then filtered. The filtrate was concen-~ ~ 4 ~
, . . . .
!
.. ~
, ~ .
. ~, . .. . . .. ... .. . . . . . .... .. .
1~4'~539 o. z . 30,334 trated in vacuo and the r~sidue di solvad in 250 parts of methanol. Aftex addition of 100 parts of water and treatment of tha solution with activated carbon, crystallization was initiated by cooling. Tha mush Or crystals was suction filtered, washed with 50 wt~ aqueous methanol and driad in vacuo. The crude product melted at 125 to 128C. Pure 293-dihydro-3,3-dimethyl-2-morpholinob~nzofuran-~-yl methylaminosulfonate was obtainad by recrystallizing a sample from ~0% m2thanol.
Melting point: 129 to 131C.
Experiment 8 - 2,3-dihydro-3,3-dimethyl-Z-hydroxybenzofuran-5-yl methyl-aminosulfonate ~ At ~0C ar.d while stirring, 6~ parts of 2,3-dihydro-3,3-; dim~thyl-2-morpholinobenzofuran-5-yl methylaminosulfonata was added all at onca to a mixture of 133 parts of water and ~ parts of concentratad hydrochloric acid~ The resultant mixtura was haat2d rapidly to 90 to 95C and kept at this temperature for 2 minutes, aftar which it was imm~diately cooled by the addition o~ ic?. Tha ~olution was ex~racted with ether, ~, .
and the ather solution was washed twice with ~ater, dried ~lith magnesium sulfata and concentrated in vacuo.
,. . . .
The YiSCoUS residue was dis~olved in 100 parts of ether.
60 parts of n-haxana was addad, and 2,3-dihydro-3,3-dimethyl-2-hydroxybenzofuran-5-yl methylaminosulfonata was obtained in tha form of crystals upon cooling. Melting point: 111 to 112C.
Tha compou-nd has the followlr.g structural formula:
~ H~CNH-S-0 ~ H~
;.` '~ ~; , ` . :, , - , .: :
, ~
': ' , . ' .:
~49539 o~zO 30,334 Experiment C
:
2,3-dihydro-3,3-dimethyl~2-methoxybenzofuran-5-yl ~ethylamino-sulfonate 4 drops of concentrated su~furic acid was added to a solution of 22.5 parts of 2,3-dihydro-3,3-dimethyl-2-hydroxy- -benzofuran-5-yl methylaminosulfonate in 200 parts of methano~.
; The mixtura was subsequantly boiled for 30 minutes under ~;
reflux, and then coolad. The mixture was neutralized with `
triethylamine and concentrated to dryness in vacuo. Treatment of the viscous residue with a mixture of ether and n-hexane gave cystals of 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-
Reactions 2), 3) and 4) are illustrated by the following l~ experiments.
1 ~xperiment A
! 2,3-dihydro-3,3-dimethyl-2-morpholinobenzofuran-5-yl meth~laminosulfonate _ _ _ At Oc to 5~C and while stirring, 36 parts (by weight) of methylaminosulfonyl chloride was added to a solution of 48.8 i parts of 2,3-dihydro-3,3-dimethyl-2-morpholino-5-hydroxybenzo-furan and 27.3 parts of triethylamine in 130 parts of tetra-1 hydrofuran. The reaction mixture was stirred for 1 hour at ¦ room temparature and then filtered. The filtrate was concen-~ ~ 4 ~
, . . . .
!
.. ~
, ~ .
. ~, . .. . . .. ... .. . . . . . .... .. .
1~4'~539 o. z . 30,334 trated in vacuo and the r~sidue di solvad in 250 parts of methanol. Aftex addition of 100 parts of water and treatment of tha solution with activated carbon, crystallization was initiated by cooling. Tha mush Or crystals was suction filtered, washed with 50 wt~ aqueous methanol and driad in vacuo. The crude product melted at 125 to 128C. Pure 293-dihydro-3,3-dimethyl-2-morpholinob~nzofuran-~-yl methylaminosulfonate was obtainad by recrystallizing a sample from ~0% m2thanol.
Melting point: 129 to 131C.
Experiment 8 - 2,3-dihydro-3,3-dimethyl-Z-hydroxybenzofuran-5-yl methyl-aminosulfonate ~ At ~0C ar.d while stirring, 6~ parts of 2,3-dihydro-3,3-; dim~thyl-2-morpholinobenzofuran-5-yl methylaminosulfonata was added all at onca to a mixture of 133 parts of water and ~ parts of concentratad hydrochloric acid~ The resultant mixtura was haat2d rapidly to 90 to 95C and kept at this temperature for 2 minutes, aftar which it was imm~diately cooled by the addition o~ ic?. Tha ~olution was ex~racted with ether, ~, .
and the ather solution was washed twice with ~ater, dried ~lith magnesium sulfata and concentrated in vacuo.
,. . . .
The YiSCoUS residue was dis~olved in 100 parts of ether.
60 parts of n-haxana was addad, and 2,3-dihydro-3,3-dimethyl-2-hydroxybenzofuran-5-yl methylaminosulfonata was obtained in tha form of crystals upon cooling. Melting point: 111 to 112C.
Tha compou-nd has the followlr.g structural formula:
~ H~CNH-S-0 ~ H~
;.` '~ ~; , ` . :, , - , .: :
, ~
': ' , . ' .:
~49539 o~zO 30,334 Experiment C
:
2,3-dihydro-3,3-dimethyl~2-methoxybenzofuran-5-yl ~ethylamino-sulfonate 4 drops of concentrated su~furic acid was added to a solution of 22.5 parts of 2,3-dihydro-3,3-dimethyl-2-hydroxy- -benzofuran-5-yl methylaminosulfonate in 200 parts of methano~.
; The mixtura was subsequantly boiled for 30 minutes under ~;
reflux, and then coolad. The mixture was neutralized with `
triethylamine and concentrated to dryness in vacuo. Treatment of the viscous residue with a mixture of ether and n-hexane gave cystals of 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-
5-yl methylaminosulfonate; melting point: ~9 to 91C.
The compound has the following structural formula:
H C-N-S-O ~ -3HH3 If, in methods a) and b), R4 is alkylamino, the acylating ~-l agent is an isocyanake - the following equation exempli~ies this for methyl isocyanate:
, - NS ~ R \ C ~ CH3 O-CNHCH
`i OH o c) Reaction of benzofuran-5-yl aminosulfonates with an alkyl-~, sulfonyl or aminosulfonyl halide - the following equation I demonstrates this for methylsulfonyl chloride:
The compound has the following structural formula:
H C-N-S-O ~ -3HH3 If, in methods a) and b), R4 is alkylamino, the acylating ~-l agent is an isocyanake - the following equation exempli~ies this for methyl isocyanate:
, - NS ~ R \ C ~ CH3 O-CNHCH
`i OH o c) Reaction of benzofuran-5-yl aminosulfonates with an alkyl-~, sulfonyl or aminosulfonyl halide - the following equation I demonstrates this for methylsulfonyl chloride:
- 6 -. ' " .
:`, -.
.
1049S3~
O.Z. 30,334 / NSO ~ CH ~ CH3SCl ~ ~ NSO CH3 H ~ O ~ H C O=S=O O ~ H3 oR3 3 OR
~) Action of metal hydroxides, preferably alkali metal and alkaline earth metal hydroxides, o~ benzofuran-5-yl amino-sulfonates, as is illustrated by the following equation which uses sodium hydroxide by way of example:
:, NSO ~ CcH NSO ~ ~
I H O ~ 3 + NaOH ~ Na O R3 I OR
R1 and R3 having the mea~ings given above.
e) Alkylation of benzofuran-5-yl aminosulfonates with alkenyl or alkynyl halides. There are used as reactants for instance the salts prepared under d), as is demonstrated in the following equation ~or alkyl bromide:
I R1 ~ NO',O H3CCH R1 `i` Na O ~ 33 + BrCH2-CH=CH~ ~ H2C=CH-CH2 Q
R1 and R3 having the meanings given above.
The following examples illustrate the preparation of the ! new compounds.
~t 15 to 20C and while stirring, 9 parts by weight of acetyl chloride was added to a solution of 30.1 parts by weight ` - 7 -,' .
' . ' ::': ,:
.~
.` '' ~049539 o.Z. 3,334 . of 2,3-dihydro-3,3-dimethyl-2-ethoxybanzo~ran-5-yl methyl-aminosulfonate and 12 parts by weight of triethylamine in 90 . parts by weight of ether. After 1 hour the reaction mixture was extracted 3 times with water~ The ethereal solution was ~ dried with magnesium sulfate, and left, upon concentration in ~ vacuo, an oily residue of the compound 2,3-dihydro-3,3-d;methyl-2-ethoxybenzofuran-5-yl-N-methylcarbonyl methylaminosulfonate ~;
; which did not crystallize even after standing for a fairly long period of time.
10 n25: 1.5402 Analysis and infrared and nmr spectra agree well with the . following structural formula: ;
~ j ~
!~ H3C H3C
I - N-S0 ~ ~.
" 0~ OC 2H5 ~i The following compounds were prepared analogously:
'f',~ 2~3-dihydro-3~3-dim~thyl-2-metho~ybenzofuran-5-yl-N-metpy~
``I carbonyl methylaminosulfonate, n25: 1.50~5 ~;
~ 2,3-dihydro-3,3-dimathyl-2-methoxybenzofuran-5-yl-N-methyl-::'. carbonyl ethylaminosulfonate ~-2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-ethyl-I carbonyl methylaminosulfonate `i~ 20 ?, 3-dihydro-3~3-dimethyl-2-athoxybenzofuran-5-yl-N-ethyl-carb~nyl methylaminosulfonate ~;I 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-chloro- -m~thylcarbonyl methylaminosulfonate, n25: 1.5195 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-chloro-methylcarbonyl methylamino~ulfonate, n25: 1.5140 .. . .
;~ . .
;. :
, . , ~ .
~049539 o. z . 30,334 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofura~. 5-yl-N-dichloro-methylcarbonyl methylaminosulfonate, n25: 1.5165 2,3-dihydro-3,3-dimethyl-2 methoxybenzofuran-5-yl-N-chloro-methylcarbonyl ethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methoxy-carbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2 methoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-iso-10 propoxycarbonyl methylaminosulfonate --2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methoxy-carbonyl mathylaminosulfonate, n25: 1.5000 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate, nD5: 1.4945 --2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-isopropoxy-carbonyl methylaminosulfonate, n25: 1.4880.
~, At -~C to -12C and while stirring, 10.3 parts by weight ~-of acetyl chloride was added to a solution of 28.7 part~ by wei~ht of 2,3-dihydro-3,3-dimethyl-2-hydroxybenzofuran-5-yl dimethylaminosulfonate and 14.1 part~ by weight of triethyl-amine in 110 parts by weight of ether. The mixture was worked ~
up as in Example l,the compound 2,3-d;hydro-3,3-dimethyl-2- ;
. . .
methylcarbonyloxybenzofuran-5-yl dimethylaminosulfonate being obtained in the form of crystals; melting point: 67 to 68C. ~;~
The compound has the following struc~ural formula:
:: .
H3C ~ H3C
NS0 ~ H3 9 o , .
` 1~495.~9 O.Z. 30,334 The following compounds were prepared analogously:
2,3-dihydro-3,3-dimethyl-2-ethylcarbonyloxybenzofuran-5-yl dimathylaminosulfonate, m.p. 53 to 54C
2,3-dihydro-3,3-dimethyl-2-chloromethylcarbonyloxybenzofuran-5-yl dimethylaminosulfonate, m.p. 87 to 88C
2,3-dihydro-3,3-dimethyl-2-chloromethylcarbonyloxybenzofuran-5-yl diethylaminosulfonate, n25: 1.5078 - `
2,3-dihydro-3,3-dimethyl-2-dichloromethylcarbonyloxybenzo-furan-5-yl dimethylaminosulfonate : 10 2,3-dihydro-3,3-dimethyl-2-dichloromethylcarbonyloxybenzofuran-5-yl diethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate, m.p. 101 to 102C
2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate, m.p. 84 to 85C
2,3-dihydro-3,3-dimethyl-2-isopropoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl ~ `
di~thylaminosulfonate, m.p. 95 to 96C.
2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzofuran-5-yl diethylaminosulfonate 2~3-dihYdro-3~3-dimethyl-2-isopropoxycarbonyloxybenzofuran s-yl die~hylaminosulfonate, After the addition of 1 part by weight of triethylamine, 6.9 parts by waight of methyl isocyanate was added at room t~mperature (20C) to a solution of 28.7 parts by weight of 2,3-dihydro-3 9 3-dimethyl-2-hydroxybenzofuran-5-yl dimethyl-aminosulfonate in 90 parts by weight of tetrahydrofuran. The .... . . . ....
~4~S39 O.Z. 30,334 t~mp0rature rose slightly,after which the mixture was left for 24 hours. The solvent was then ramoved in vacuo and the residue recrystallized from ether; melting point: 101 to 103C.
The compound, 2,3-dihydro-3,3-dimethyl-2-methylamino~
carbonyloxybenzofuran-5-yl dimethylaminosulfonate, has the following structural formula:
,..... .
H C -" ~ 3 The following compounds were prepared analogously~
2,3-dihydro-3,3-dimethyl-2-ethylaminocarbonyloxybanzofuran- ;~
5-yl dimathylaminosulfonate, m.p. 112 to 113C
2,3-dihydro-3,3-dimethyl-2-propylaminocarbonyloxybenzofuran-5-yl dimethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-isopropylaminocarbonyloxybenzo-furan-5-yl dimethylaminosulfonate, m.p. 107 to 109C
2,3-dihydro-3,3-dimethyl-2-methylaminocarbony~oxybenzofuran-5-yl diethylaminosulfonate, m.p. 122 to 123C
2,3-dihydro-3,3-dimethyl-2-ethylaminocarbonyloxybenzofuran-5-yl diethylaminosulfonate, m.p. 124 to 125C
2,3-dihydro-3,3-dimethyl-2-methylaminocarbonyloxybenzofuran-5-yl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-ethylaminocarbonyloxybenzofuran-5-yl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-propylaminocarbonyloxybenzofuran-5-yl methylaminosulfonate -- 11 -- , ~049539 O.Z. 30,334 2,3-dihydro-3,3-dimethyl-2-isopropylarninocarbonyloxybenzo-furan-5-yl methylaminosulfonate.
~ t 10C and while stirring, 56 parts by weight of acetic anhydride was added to a solution o~ 6~ parts by weight of 2,3-dihydro-3,3-dimathyl-2-hydroxybenzofuran-5-yl methylamino-8ulfonate and 55.5 parts by weight of triethylamine.
After standing overnight, the precipitated reaction pro-duct was suction filtered, washed With cold ether and Water, and dried in vacuo at 60Cj melting point: 103 to 104C.
The compound, 2,3-dihydro-3,3-dimethyl-2-methylcarbonyloxy-benzofuran-5-yl-N-methylcarbonyl methylaminosulfonate, has the following structural formula:
3 " ~ H3 0 ,c,cH3 O
The following compounds wers prepared analogo~sly:
2,3-dihydro-3,3-dimethyl-2-chloromethylcarbonyloxybenzofuran-5-yl-N-chloromethylcarbonyl methylamino9ulfonate 2,3-dihydro-3,3-dimethyl-2-ethylcarbonyloxybenzofuran-5-yl-N-ethylcarbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-mathylcarbonyloxybenzofuran-5-yl-N-methylcarbonyl ethylaminosulfonate.
At -~ to ~12C, a solution of 130~ parts by weight of methylsulfonyl chloride in 30 parts by weight of dichloro-.. .. . ~
~ 49539 oO z . 30,3~4 methane was added to a solution of 2~.7 parts by weighk of 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl methylamino-sulfonate and 13 3 parts by weight of triethylamine in 130 parts by weight of dichloromethanaO 30 minutes after the raaction was over the mixture was extracted three times with water. The organic phase was dried with magnesium sulfate and fraed from solvent in vacuo. The sirupy residue (n25: 1.5150) did not crystallize even upon standing ~or a fairly long period ~ ;~
of time.
~, ,, ~ ~, .v . , , Infrared and nmr spectra and ultimata analysis of the residue agree well with the compound 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methylsulfonyl methylaminosulfonate having the following structural ~ormula: ~;
H C
3 \ ,0, H C
CS/ ~ ~ 3 .
The following compounds were prepared analogously:
2,3-dihydro-3,3 dimethyl-2-ethoxybenzofuran-5-yl-N-methyl-sulfonyl mathylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-ethyl-sulfonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-et~oxyhenzofuran-5-yl ethylsulfonyl methylamino~ul~onate.
After the addition of 0.5 part by weight of triethyl-amine, 5.15 parts by weight of msthyl isocyanate was added to -~
10~9~3~ o o z 30,334 a solution of 20.5 parts by weight of 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylamino~ulfonate in 70 parts by weight of tetrahydro~uran. Subsequently, the mixkure was left for 48 hours. The solution was then concentrated in vacuo and the residue taken up in ether and treated three times with water. The organic phase was dried with magnesium sulfate 9 and concentrated in vacuo after having been treated with activated carbon.
n25: 1.5085 Infrared and nmr spectra and ultimate analysis of the sirupy residue agree well with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methylaminocarbonyl methyl-aminosulfonate having the following structural formula:
H3C \ 0 H C
o ~ .
The following compounds were pr2pared analo~ously:
2~3-dihydro-3~3-dimethyl-2-m~thoxybenzofuran-5-yl-N-meth aminocarbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethylamino-carbonyl methylaminosulfonate 2~3-dihydro-3,3 dimethyl-2-methoxybanzofuran-5-yl-N-ethyl-aminocarbonyl methylaminosulfonate.
A solution of 4 parts by weight of sodium hydroxide in 20 parts by weight of water was added to a suspension of 30.1 parts by weight of 253-dihydro-3,3-dimethyl-2-ethoxybenzofuran-- 1049539 o . z 30,~34 .
5~yl methylaminosulfonate in 55 parts by weight of water. From the solution which formed it was possible to obtain the salt by evaporating the water in va¢uo.
Infrared and nmr ~pectra and ultimate an~al~is of the salt agree wall with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxy- .. -benzofuran-5-yl methylaminosulfonate, sodium salt~ having the :
followi.ng str.uctural formula:
H3C~ ~0, H3C
" ~ 3 :
0 ~ H ; .
2 5 .:
The lithium and potassium salts of the following compounds were prepared analogously:
2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl methylamino- .: .
~ulfonate ~ .
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylamino- ;.
sulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-~-yl ethylamino-sulfonate 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl ethylamino-sulfonate.
EXAMPLE
At 20 to 23C and while stirring, a solution of 8.5 parts by weight of propargyl bromid~ in 20 part~ by weight of acetone was added to 46 parts by weight of a 50 wt% ~queous solution of the ~odium salt of 2,3-dihydro-3,3-dimethyl~2-ethoxybenzo-furan-5-yl methylaminosulfonate (prepared as in Example 7).
- 15 ~
1~9539 o. z . 30,33~
The temperature rose slightly to 29C~ To complete the reaction the mixture was stirred for a further 6 hours at 35C.
Ethyl acetate wa~ then added and extraction was carried out three times with water. ~he organic ph~e was dried with magne~ium sulfate and subsequently concentrated to dryness in vacuo.
n2255: 1.5085 .
Infrared and nmr spectra and ult~mate analysis of the -~
sirupy residue agree well with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-propargylmethylaminosulfonate having the following structural formula:
\ " H C
HC_ C CH
rH
The followin~ compounds were prepared analogously~
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-allyl methylaminosulfonate, b.p. (0.01 mm) 137 to 146C, n25: 1.5065 2,3-dihydro-3~3-dimethyl-2-ethoxybenzofuran-5-yl propargyl-aminosulfonate 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl allylamino-sulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl propargyl-aminosùlfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl~allylamino-sulfonate ~: . . . . . . .
~0~953~ :
0.Z, 30,334 2,3-dihydro-3,3-dimethyl-2-ethoxybenzo~uran~5-yl diallylamino-sulfonate.
The new active ingredients have a strong herbicidal action and may therefore be used as weedkillers or for con-trolling the growth of un~anted plants, Whether they are used as total or selective agents depends in essence on the amount of ingredient used per unit area.
By weeds and unwanted plant growth are meant all mono-cotyledonous and dicotyledonous plants which grow in loci where theY are not desiredO
The agents according to the invention may therefore be used for controlling for instance ~ :
Gramineae, such as Cynodon spp. Dactylis spp.
Digitaria 3pp. Avena spp.
Echinochloa spp. Bromus spp.
Setaria spp. Uniola spp.
Panicum spp. Poa spp. -Alopecurus spp. Leptochloa spp. -~
Lolium 8pp . Brachiaria spp.
Sorghum spp. Eleusine spp.
Agropyron spp. Cenchrus spp.
Phalaris spp. Eragrostis spp.
Apera spp. Phragmites communis etc.;
Cyperaceae, such as Carex spp. Eleocharis spp~
Cyperus spp. Scirpus spp.
etc.; - 17 - ~ .
, ,. . " ,.,,~, , .. . . ~ ,. . .
~049~i39 O.Z. 3,33~ -dicot~ledenous w~eds, such as .
Malvaceaa, e.g., Abutilon theoprasti Hibiscus spp.
Sida spp. Malva spp.
~tc.;
Compositae, such as .
Ambrosia spp. Centaurea spp.
Lactuca spp. Tussilago spp.
Senecio spp. Lapsana communis Sonchus spp. Tagetes spp.
Xanthium spp. Erigeron spp.
Iva spp. Anthamis spp.
Galinsoga spp. Matricaria spp, Tara~acum spp. Artemisia spp.
Chrysanthamum spp. Bid2ns spp.
Cirsium spp. etc.;
Convolvulacea~, such as Convolvulus spp. Cu8 cuta spp.
Ipomea spp. Jaquemontia tamnifolia etc.;
Cruci~erae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp. Descurainia spp.
Capsella spp. Draba spp.
Sisymbrium spp. Coronopus didymus Thlaspi spp. Lapidium spp.
Sinapis arvansis Raphanus spp.
etc.;
~ ~ .
1~49539 o z 30,334 Geraniaceae, such as Erodium spp. Geranium spp.
etc.;
Portulacaceae, such as -Portulaca spp. etc.;
Primulaceae, such as Anagallis arvensis Lysimachia spp.
etc.
Rubiaceae, such as Richardia spp. Diodia spp.
Galium spp. etc., Scr ~hulariaceaa, such as Linaria spp. Digitalis spp.
Veronica spp. etc.;
Solanaceae, such as Physali~ spp. Nicandra spp.
Solanum spp. Datura spp. ~
etc.; ~ ~ `
Urticacea~, such as Urtica spp.
Violaceae, such as Viola spp. etc.;
Zygophyllacea~, such as Tribulus terrestris etc.;
Euphorbiaceae, such as Mercurialis annua Euphorbia spp.
Umbelliferae, such as Daucus carota Ammi majus .
4~539 o.z. 30,33 Aethusa cynapium etc.;
CDmmelinaceae, such as Commelina spp. etc.;
Labiatae, such as Lamium spp. Galeopsis spp.
etc.;
Leguminosae, such as Madicago spp. Sesbania exaltata Trifolium spp. Cassia spp.
Vicia spp. Lathyrus spp.
etc.;
Plantaginaceae, uch as Plantago spp. etc.;
Polygonaceae, such as `~
Polygonum spp. Fagopyrum spp.
Rumex spp. etc.;
Aizoaceaey such as Mollugo verticillata ~tc.;
Amaranthaceae, such as Amaranthus spp. etc., 80raginacea~, such as Amsinckia spp. Anchu~a spp.
Myostis spp. Lithospermum spp.
etc.j Caryophyllaceae, such as Stellaria spp. Silane spp.
Spergula spp. Cerastium spp.
Saponaria spp. Agrostemma githago Scleranthus annuus etc.;
" 1~49539 O.Z. 30,334 ChPnopodiaceae, such as Chenopodium spp. Atriplex spp.
.. ... .
Kochia 8pp. Monolepsis nuttalliana Salsola Kali etc.;
Lythraceae, such as Cuphea spp. etc.j -Oxalidaceae, such as Oxalis spp.
Ranunculaceae, such as Ranunculus 8pp. Adonis spp.
Delphinium spp. etc.;
Papaveraceae, ~uch as Papaver 8pp. Fumaria officinalis~ `
etc.;
Onagraceae, such as Jussiaea spp. etc.; ~ -Rosaceaa, such as Alchemillia spp. Potentilla spp.
~tc.;
Potamogetonaceae, such as Potamogeton spp. etc.; ' :
Na j adaceae, such as Najas spp. etc.;
Eq~isetaceae Equisbtum spp. etc.;
Marsileaceae, such as ;
Marsilea quadrifolia etc.;
Polypodiaceae, Pteridium quilinum ~049S3~ -z~ 30~334 Alismataceae, such as Alisma 8pp. Sagittaria sagittifolia etc.
The amount used of the agents according ~o the invention may vary and depends in essence on the type of effec~ ~o~be achieved; it is generally from O.1 to 15 (and more), prefer-ably from 0.2 to 6, kg per hectare of active ingredient.
The herbicides according to the invention may he used in cereals such as Avena spp. Sorghum Triticum spp Zea mays Hordeum spp. Panicum miliaceum Secale spp- Oryza 5pp. "
Saccharum officinarum ;
and in dicotyledon crops such as Cruciferae, e.g.
Bras~ica spp. Raphanus spp.
Sinapis spp. Lepidium spp. ~ -Compositae, e.g.
Lactuca spp. Carthamus spp.
Helianthus spp. Scorzonera spp.
Malvaceae, e.~.
Gossypium hirsutum Leguminosae, e.g.
Medicago spp. Phaseolus spp.
Tri~oliu~ spp. Arachis spp.
Pisum spp. Glycine max.
'. ;'.:' , :
': , 104~S39 o . z . 30, 334 - :
Chenopodiaceae, e.g.
Beta vulgaris Spinacia spp.
Solanaceae, e.g.
Solanum Bpp. Capsicum annuum Nicotiania spp. ~ -Linaceae, e.~g.
Linum spp.
Umbelliferae, e.g.
Petroselinum spp. Apium graveolens Daucus carota Rosaceae, e.g. Fragaria -Cucurbitaceae, e.g.
Cucumis spp. Cucurbita spp. -~
Liliaceae, e.g. ~;
Allium 8pp. ~ .
Vi~aceae, e.g.
Vitis vinifera Bromeliaceae, e.g.
Ananas sati~us.
Applications may be effected for instance in the form o~
directly sprayable solution~, powders, suspen8ion~, di~per-sions~ emulsions, oil dispersions, pastes, dusts, broadcast-ing agents, or granules by spraying, atomizing, dusting, bPQad-casting or wataring. The forms of application depend entirely on the purpose for which tha agents are being used; in ~ny case they should ensure a fine distribution of the active ingredient.
O.Z. 30,334 For the preparakion of solutions, emu'sions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oilR of veg~table or animal origin, aliphatic, cyclic and aroma~ic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphtalene, alkyl~ted naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform~ carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc.
and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion ~on~
centrates, paste~, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil Idispersions the ingredients as such or dissolved in an oil or solvent may be homogeni7ed in water by mean~ of wetting or dispersing agents, adherents or emulsifiers. Concantrates which are suit-able for dilution with water may be prepared from active ingredient, wetting agant, adherent, emul~ifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are; alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulf~nates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty a~ohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethar, condensation products of ~ 0 ~9 539 O.Z. 30,334 sulfonat~d naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphtha-lenesulfonic acids with phenol and formaldehyde, polyox~et~ylene octylphenol ethars, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol~olyglycol ethers, tributylphenyl poly~lycol ethers, alkylaryl polyether alc~hols, isotridecyl alcohol, fatty alcohol ethylene oxide :
condensates, e~hoxylated castor oil 9 polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal~ sorbitol esters, lignin, sulfite waste llquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared ~y .
mixing or ~rinding the active ingredients with a solid carrier.
Granules, a.g., coated, impregnated or homogeneous gra-nules, n;ay be prepared by bonding the active ingredients to solid carriers. ~xample~ of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, limestone, lime, chal]c, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate,. and ureas, and ve~etable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc. ~.
The formulations contain from 0.1 to 95, and preferably 0.5 to gO~0 by weight of active ingredient.
There may be added to the compositions or individual activ~ ingredierlt~ (if desired, immediately before use (tank- :
mix) ) oils of various types, herbicides, fungicides, nernato-cidas, insecticides, bactericides, trace element~, fertilizer3, 25 - .
, ~, ,.. .
. , ; , . ... : ~ , ~ , . .
10~953~
O.Z. 30,334 antifoams (e.g., silicones), growth regulators, antidotes and othar herb~cidally effective compounds such as substituted anilines substitutad aryloxycarboxylic acids and salts, esters and amides thereof, substituted ethers substituted arsonic acids and their salts, esters and amides substituted benzimidazoles substituted benzisothiazoles ;
substitu~ed benzothiadiazinone dioxides substituted benzoxazines substibuted benzoxadinones æubstituted benzothiadiazoleæ
substituted biurets substituted quinolines substituted carbamates ;:
substituted aliphatic carboxylic acids and their salts, esters and amides substit~ted aromatic carboxylic acids and their salts, esters and amides su~stituted carbamoyla~kylthlol- or dit~iophosphates : ~
substituted quinazolines ;. .
~ubstituted cycloalkylamidocarbothiolic acids and their saltæ, esters and amides substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and their salts, esters and ~- :
amides substituted dihydrobenzofuranyl sulfonates - 2~ - ` ~-.
-,' , 1~49539 O.Z. 30,33substituted disul~ides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters and amides substituted ureas substituted hexahydro~ carbothioates substituted hydantoins substituted hydrazi~as .
substituted hydrazonium salts substituted isoxazol~ pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones substi~uted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxad~iazinones. .
substituted oxadiazolidone diones substituted oxadiazine diones substituted phenols and their salts and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkyl glycines :
substituted phosphites substituted phosphoric acids and their salts, esters and amides - 27 -. . . .
. . : , . - , . ~: . . ~ , ~49S39 o.z, 30,334 substituted piperidines substituted pyrazoles substituted pyrazole alkylcarboxylic acids and their salts, esters and amides substituted pyrazolium salks substituted pyrazolium alkyl sulfates substituted pyridazines subskituted pyridazones substituted pyridine carboxylic acids and their salts, es~ers and amides substituted pyridinas subStituted pyridine carboxylates substituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidone carboxylic acid and its salts, esters ~ :
and amidas substituted pyrro~idine~
substituted pyrrolidones : .
substitiuted arylsulfonic acids and their salts, esters and amides ~:
subskituted styrenas substituted tetrahydrooxadiazine diones :
substituted tetrahydroxadiazole diones substituked tetrahydromethanoindenes substituted tetrahydroxadiazole thiones substituted ~ietrahydrothiadiazine ~hiones ~:
substituted tetrahydrothiadiazole diones . - 2 .... - . . , .. : : .
~4~53~ o . z . ~0,S34 substituted aromatic thiocarbonylamides substituted thiocarboxylic ac~ds and their salts, esters and amides substituted thiol carbamates substituted thioureas substituted thiophosphoric acids and their salts, esters and amides substituted triazines substituted triazoles substituted uracils, and substituted uretidine diones.
The last-mentioned herbicidal compounds may also be ap--- lied before or after the activa ingredient~ or compositions thereof according to the invention.
These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.
The herbicide according to the invention may ba used one or more times before or after planting, be~ore sowing, pre-emergence, po~temergence or during emergence of tha crop or unwanted plants.
In the greenhouse, loamy sandy soil was filled into pots and sown with the seeds of various plants. The soil was im-mediately treatad with 2 kg per hectare of each of the following active ingredients, each being dispersed, emulsi~ied i, .
or dissolvèd`in 500 liters of watar per hectare;
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylamino-sulfate, ~odium salt ~I) -... . . . . .
- ~.
-.
; . . .
~04~39 o. z . 30,334 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methyl-carbonyl methylaminosulfonate (II) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-chloro-methylcarbonyl methylaminosulfonate (III) 2,3-dihydro-3,3-dim~thyl-2-methoxyb2nzofuran-5-yl-N-methyl-carbonyl methylaminosulfonake (IV) 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-chloro-methylcarbonyl methylaminosulfonate (V) 2,3-dihydro-3,3-dimethyl-2-methylcarbonyloxybenzofuran-5-yl-N-10 methylcarbonyl methylaminosulfonate (VI) :~
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methoxy- : :
carbonyl methylaminosulfonate (VII) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate (VIII) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-isopropoxy-carbonyl methylaminosulfonate (IX) 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate (X) ~ ~:
2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzo~uran-5-yl ;
dime~hylaminosulfQnate (XI) 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl diethylaminosulfonate (XII) and, for comparison, 2-ethoxy-2,.3 dihydro-3,3-dimethyl-5-benzofuranyl methane-sulfonate (XIII) 2~3-dihydro-3,3-dimethyl-2-isopropoxybenzofuran-5-yl ethyl- :
aminosulfonate (XIV).
109~9~39 O.Z. 30,334 After 4 to 5 weeks it was ascertained-that active ingredients I to XII had a better herbicidal action than com-pounds XIII and XIV, combined with the same crop plant compatibility.
The results are given below:
. - 31 -: , , `' . , ,: ' : - ~ ' ' 104953g 0 . Z . 30, 334 ~H ~U O O O O Ll~ C~
O O o o L~ o L~ ir\ o o ' ~' '' '.
H ~ a~ O cr~ 0~o ~C) X
X ~ O o o o o o o o o O O O O O ~ ', X :, H ~J O O O O O O 1~ L~ IS~O
~ 3 :
H O O O O 15~ L~ L~
H a~ 0~C~ J
~? . '',, ~
H ~`J O O O O lS~ O L~ O O O
P ' a~ o ~ o o H (~J O O O O O O O O O O . . ~
~ c~ 3 : :
. ' ' ~ ' .',~', .
p t\l O O O O Lr\ g Lr~ O g O
H ~ O O OO lr~ O `~D O O O
~ O C~ O O
H
H (~l O O OO ~ O 15~ O ~ Ll~
1_1 C~ O ~ O C~Lr~ , -"''':.
H ~1 O 15~ O O O OL~ O O 15~
H O O O~ O O~D :
': :
H ~\1 O O OO O O O O O O .:
~ O O 0 ~0 ~0~ Co ,"~,, ~
' g '~''''' rl ' Ul rl r~
r rl U~ h I :J
a~ ~ 0~~3 o r rl CO ~0 ~ ~ O ~!j r-l C'~ ~0 :1 r~ S ~ O ~ S~
a~ ~ 0 E~ rl ~a ~ H ~ U H
bO ~ ~ m ~ ~ ~ o r~
~ ~ 1 ~ ::tr~
rl ~d p, ~ ~ cd ~ O O
~1 p, Or~ O ~ ~S O ,C~ O
a~ ~ ~ rl O~ ~ C> O ~ 5:`, rl ~d u~ l S ~
P ~ rl ~ ~ rl rl O ~ ~d ~ r l ~ ~ O ~ O O
o bD ~1 ~ ~ : -r-l O:~1 0rl O
~: ~ c~ m m P~ x P ~
- 32 - .
~'"' ''' ., ,, , , , ~ , - , , - - - - , .
~049~3~ -z., 30,334 ;
' ~ O O O O O O O O U~ O . ':
X : . .
H ~U O Lr~ O OL~ O O If~ O
X ~1 .1 ~a~ ) N
~.' ~ ' W ." ~ :
~I h rl oq o ~: h ~ h ~1 ~ . .-~d ~ Gq 0~:~ O
5:: ~ O h h t~~> ~1 ~: ~ ~ ~
rl t~ ~ ~ ~ ~ h,s~ 5 o O
~1p~C) r I ~a) ~
G~ Qu~ O ~ ~ C~ O ~ 5: rl ~ Oqa) ~d rl S ~ ~ rla1 S~
O ~ ~ ~ a) o ~ ~ o o c~ bD ha) h S a)~: ~ O O ~1 O
¢ ~: ~ m a~ ¢ ¢ ~ ~
' ' ' '''' '''" '"
; .
- 33 - ~
. .
" '' , - . , -: . :: .
-1~4953~ ~:
O.Z. 30,334 : :
In the greenhousa, various plants were treated at a growth -height of from 2 to 15 cm with 2 kg per hectare of each of - .
active ingrediants I to XIV (as defined in Example 9), aach being emul~ified, dispersed or dissolved in 500 litars of water per hectare. ~: :
After 2 to 3 weaks it was ascartained that active :~
ingradients I ~o XII had a better herbicidal action than com- -pounds XIII and XIV, combined with the same crop plant compati~ :
bility.
Tha results ara given below~
. , , .
- 34 - ~:
104~539 " ~ Z . 30, 3311 H r~l O-Ir~ IS`\ O O 1~
~C x) a\ o~
.'-,, H N OO 0 15~ O
X o~ a~ o~ o ~ ,, X ~ OO Lr~ O O O
~ ra~ O -X N OO O Lr~ O L~
H O~ O~ ~
H ~ '.
H N OO ~D ~0 ~ ~ .
P O~ 0~
H ~U O O L~
P O~ O~
: ' -H N OO O Lr~ O 1~
O~ X~ O~
. r~
P N OO L
O~ ~ C~ ' '' ~ N O O L~
H ~ r J~
H O L~ O O
H N OO C~
' '' H N OO O ~ In H O~ O~
H N OO O O O I
o a~ o CJ~ ' g ~ ,;
H ~ h ~ r~ ~ "
5~ ~
~rl ~ ~ h O bO a c~ ~ Cd a) .. p, ~d ~q ~ ~
b~ ~ 5: R ~ O ~Q ~ Q.
S~ ~ . ~ ~1 ~ ~d ~ ~ -d ~ O O
H ~C) Q) ~ r~
07rl ~ O ,~, C) a ~ ~ i~(d ~ 11 11 ~rl rC ~ ~ S~
O ~ ~ ~:~V ,5~ l O O O ' ., C) bl~ ~ID S~ ~ ~ C) O vl O
~: ~ t~ ~ m ~ ~
- 3~ -,. . - . , ~ ~ . i ~L~4953~ o . z . 30, 334 o o o ~ o H ~I o~ ~ x) x~
X ,' ' ' ' .:- ~
~ ,' O O L~ O O o H ~I
' 5: '' .
O '.': ' o t~
~0 0 ~-J~ I h ~ ..
5:: ' ~ '' :,:
u~
~rl 0 J~ h O ~o a~ -~ ~ ~> ~ ~ ~ .
~d ~ ~
~o .~~: ~ ::f o s:: s::~ ~ ~ ~ o o '' ~ ~ o 9) ~ o ~ ~ ~ o a~ Q ~q rl ~ O
, 5 ~ u~ ~ ~ ~ ~ a) " ,.
,1 .C t2 ~ d O ~ ~ a) 5:: ~d O O O
o ~0 h ~ h ~ :~ o O ~ O
~: ~ ~m ~q ~
..
'. ".. . ....
, .':
" ' ' ' ~.
~ ~ ~9 53 9 O.Z. 30,334 The action of the following compounds-corre~ponds to that of the compounds according ko the invention in tha foregoing examples:
2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methyl-sulfonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl diathylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-mathoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonata 2,3-dihydro-3,3-dimethyl-2-ethoxycarbonylbanzofuran-5-yl dimethylaminosulfonate In the greenhouse, loamy sandy ~oil was ~illed into pots and sown with the saeds of various plants. The soiI was then immediately treated with 3 kg per hectare of each of the following active ingredients, each baing dispersed or emulsified in 500 liters of water per hectare~
2,3-dihydro-3,3-dimethyl-2-ethoxybsnzofuran-5-yl-N-methyl-carbonyl methylaminosulfonate (II) ~,3-dihydro 3,3-dimethyl-2-athoxybanzofuran-5-yl-N-chloromethyl-carbonyl methylaminosulfonate (III)2,3-dihydro-3,3-dimethyl-2-sthoxybenzofuran-5-yl-N-methoxy-carbonyl ~,ethylaminosulfonate (VII) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate (VIII) and, for comparison, 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methane-sulfona~a (XIII).
1049539 o z 30,33~
During the experimant the plants were watered well.
After 3 to 4 week6 it was ascertained that active ingredients II, III, VII and VIII had better crop plant com-patibility than compound XIII, combined with the same herbididal ~
action. :
Tha results are given below~
Activ ingredient II III VII VIII XIII
kg/ha 3 3 3 3 3 .
~.. . .
Cro~ ~lants:
' Gossypium hirsutum 5 0 5 10 40 Zea mays 20 5 10 15 60 ~
Beta spp. 10 0 5 5 3 .
Unwanted plants: ~
.
-~chinochloa crus-galli100100100 100 100 : -Setaria faberii 100100100 100 100 :~
Alopecurus myosuroide~ 100 100 100 100 100 Avena fatua 100100100 100 100 Galium aparine 100100100 100 100 ,; . . .
0 - no damaga 100 ~ complete de~truction .
' ~
, .:-- 38 ~
:`, -.
.
1049S3~
O.Z. 30,334 / NSO ~ CH ~ CH3SCl ~ ~ NSO CH3 H ~ O ~ H C O=S=O O ~ H3 oR3 3 OR
~) Action of metal hydroxides, preferably alkali metal and alkaline earth metal hydroxides, o~ benzofuran-5-yl amino-sulfonates, as is illustrated by the following equation which uses sodium hydroxide by way of example:
:, NSO ~ CcH NSO ~ ~
I H O ~ 3 + NaOH ~ Na O R3 I OR
R1 and R3 having the mea~ings given above.
e) Alkylation of benzofuran-5-yl aminosulfonates with alkenyl or alkynyl halides. There are used as reactants for instance the salts prepared under d), as is demonstrated in the following equation ~or alkyl bromide:
I R1 ~ NO',O H3CCH R1 `i` Na O ~ 33 + BrCH2-CH=CH~ ~ H2C=CH-CH2 Q
R1 and R3 having the meanings given above.
The following examples illustrate the preparation of the ! new compounds.
~t 15 to 20C and while stirring, 9 parts by weight of acetyl chloride was added to a solution of 30.1 parts by weight ` - 7 -,' .
' . ' ::': ,:
.~
.` '' ~049539 o.Z. 3,334 . of 2,3-dihydro-3,3-dimethyl-2-ethoxybanzo~ran-5-yl methyl-aminosulfonate and 12 parts by weight of triethylamine in 90 . parts by weight of ether. After 1 hour the reaction mixture was extracted 3 times with water~ The ethereal solution was ~ dried with magnesium sulfate, and left, upon concentration in ~ vacuo, an oily residue of the compound 2,3-dihydro-3,3-d;methyl-2-ethoxybenzofuran-5-yl-N-methylcarbonyl methylaminosulfonate ~;
; which did not crystallize even after standing for a fairly long period of time.
10 n25: 1.5402 Analysis and infrared and nmr spectra agree well with the . following structural formula: ;
~ j ~
!~ H3C H3C
I - N-S0 ~ ~.
" 0~ OC 2H5 ~i The following compounds were prepared analogously:
'f',~ 2~3-dihydro-3~3-dim~thyl-2-metho~ybenzofuran-5-yl-N-metpy~
``I carbonyl methylaminosulfonate, n25: 1.50~5 ~;
~ 2,3-dihydro-3,3-dimathyl-2-methoxybenzofuran-5-yl-N-methyl-::'. carbonyl ethylaminosulfonate ~-2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-ethyl-I carbonyl methylaminosulfonate `i~ 20 ?, 3-dihydro-3~3-dimethyl-2-athoxybenzofuran-5-yl-N-ethyl-carb~nyl methylaminosulfonate ~;I 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-chloro- -m~thylcarbonyl methylaminosulfonate, n25: 1.5195 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-chloro-methylcarbonyl methylamino~ulfonate, n25: 1.5140 .. . .
;~ . .
;. :
, . , ~ .
~049539 o. z . 30,334 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofura~. 5-yl-N-dichloro-methylcarbonyl methylaminosulfonate, n25: 1.5165 2,3-dihydro-3,3-dimethyl-2 methoxybenzofuran-5-yl-N-chloro-methylcarbonyl ethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methoxy-carbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2 methoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-iso-10 propoxycarbonyl methylaminosulfonate --2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methoxy-carbonyl mathylaminosulfonate, n25: 1.5000 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate, nD5: 1.4945 --2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-isopropoxy-carbonyl methylaminosulfonate, n25: 1.4880.
~, At -~C to -12C and while stirring, 10.3 parts by weight ~-of acetyl chloride was added to a solution of 28.7 part~ by wei~ht of 2,3-dihydro-3,3-dimethyl-2-hydroxybenzofuran-5-yl dimethylaminosulfonate and 14.1 part~ by weight of triethyl-amine in 110 parts by weight of ether. The mixture was worked ~
up as in Example l,the compound 2,3-d;hydro-3,3-dimethyl-2- ;
. . .
methylcarbonyloxybenzofuran-5-yl dimethylaminosulfonate being obtained in the form of crystals; melting point: 67 to 68C. ~;~
The compound has the following struc~ural formula:
:: .
H3C ~ H3C
NS0 ~ H3 9 o , .
` 1~495.~9 O.Z. 30,334 The following compounds were prepared analogously:
2,3-dihydro-3,3-dimethyl-2-ethylcarbonyloxybenzofuran-5-yl dimathylaminosulfonate, m.p. 53 to 54C
2,3-dihydro-3,3-dimethyl-2-chloromethylcarbonyloxybenzofuran-5-yl dimethylaminosulfonate, m.p. 87 to 88C
2,3-dihydro-3,3-dimethyl-2-chloromethylcarbonyloxybenzofuran-5-yl diethylaminosulfonate, n25: 1.5078 - `
2,3-dihydro-3,3-dimethyl-2-dichloromethylcarbonyloxybenzo-furan-5-yl dimethylaminosulfonate : 10 2,3-dihydro-3,3-dimethyl-2-dichloromethylcarbonyloxybenzofuran-5-yl diethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate, m.p. 101 to 102C
2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate, m.p. 84 to 85C
2,3-dihydro-3,3-dimethyl-2-isopropoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl ~ `
di~thylaminosulfonate, m.p. 95 to 96C.
2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzofuran-5-yl diethylaminosulfonate 2~3-dihYdro-3~3-dimethyl-2-isopropoxycarbonyloxybenzofuran s-yl die~hylaminosulfonate, After the addition of 1 part by weight of triethylamine, 6.9 parts by waight of methyl isocyanate was added at room t~mperature (20C) to a solution of 28.7 parts by weight of 2,3-dihydro-3 9 3-dimethyl-2-hydroxybenzofuran-5-yl dimethyl-aminosulfonate in 90 parts by weight of tetrahydrofuran. The .... . . . ....
~4~S39 O.Z. 30,334 t~mp0rature rose slightly,after which the mixture was left for 24 hours. The solvent was then ramoved in vacuo and the residue recrystallized from ether; melting point: 101 to 103C.
The compound, 2,3-dihydro-3,3-dimethyl-2-methylamino~
carbonyloxybenzofuran-5-yl dimethylaminosulfonate, has the following structural formula:
,..... .
H C -" ~ 3 The following compounds were prepared analogously~
2,3-dihydro-3,3-dimethyl-2-ethylaminocarbonyloxybanzofuran- ;~
5-yl dimathylaminosulfonate, m.p. 112 to 113C
2,3-dihydro-3,3-dimethyl-2-propylaminocarbonyloxybenzofuran-5-yl dimethylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-isopropylaminocarbonyloxybenzo-furan-5-yl dimethylaminosulfonate, m.p. 107 to 109C
2,3-dihydro-3,3-dimethyl-2-methylaminocarbony~oxybenzofuran-5-yl diethylaminosulfonate, m.p. 122 to 123C
2,3-dihydro-3,3-dimethyl-2-ethylaminocarbonyloxybenzofuran-5-yl diethylaminosulfonate, m.p. 124 to 125C
2,3-dihydro-3,3-dimethyl-2-methylaminocarbonyloxybenzofuran-5-yl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-ethylaminocarbonyloxybenzofuran-5-yl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-propylaminocarbonyloxybenzofuran-5-yl methylaminosulfonate -- 11 -- , ~049539 O.Z. 30,334 2,3-dihydro-3,3-dimethyl-2-isopropylarninocarbonyloxybenzo-furan-5-yl methylaminosulfonate.
~ t 10C and while stirring, 56 parts by weight of acetic anhydride was added to a solution o~ 6~ parts by weight of 2,3-dihydro-3,3-dimathyl-2-hydroxybenzofuran-5-yl methylamino-8ulfonate and 55.5 parts by weight of triethylamine.
After standing overnight, the precipitated reaction pro-duct was suction filtered, washed With cold ether and Water, and dried in vacuo at 60Cj melting point: 103 to 104C.
The compound, 2,3-dihydro-3,3-dimethyl-2-methylcarbonyloxy-benzofuran-5-yl-N-methylcarbonyl methylaminosulfonate, has the following structural formula:
3 " ~ H3 0 ,c,cH3 O
The following compounds wers prepared analogo~sly:
2,3-dihydro-3,3-dimethyl-2-chloromethylcarbonyloxybenzofuran-5-yl-N-chloromethylcarbonyl methylamino9ulfonate 2,3-dihydro-3,3-dimethyl-2-ethylcarbonyloxybenzofuran-5-yl-N-ethylcarbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-mathylcarbonyloxybenzofuran-5-yl-N-methylcarbonyl ethylaminosulfonate.
At -~ to ~12C, a solution of 130~ parts by weight of methylsulfonyl chloride in 30 parts by weight of dichloro-.. .. . ~
~ 49539 oO z . 30,3~4 methane was added to a solution of 2~.7 parts by weighk of 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl methylamino-sulfonate and 13 3 parts by weight of triethylamine in 130 parts by weight of dichloromethanaO 30 minutes after the raaction was over the mixture was extracted three times with water. The organic phase was dried with magnesium sulfate and fraed from solvent in vacuo. The sirupy residue (n25: 1.5150) did not crystallize even upon standing ~or a fairly long period ~ ;~
of time.
~, ,, ~ ~, .v . , , Infrared and nmr spectra and ultimata analysis of the residue agree well with the compound 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methylsulfonyl methylaminosulfonate having the following structural ~ormula: ~;
H C
3 \ ,0, H C
CS/ ~ ~ 3 .
The following compounds were prepared analogously:
2,3-dihydro-3,3 dimethyl-2-ethoxybenzofuran-5-yl-N-methyl-sulfonyl mathylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-ethyl-sulfonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-et~oxyhenzofuran-5-yl ethylsulfonyl methylamino~ul~onate.
After the addition of 0.5 part by weight of triethyl-amine, 5.15 parts by weight of msthyl isocyanate was added to -~
10~9~3~ o o z 30,334 a solution of 20.5 parts by weight of 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylamino~ulfonate in 70 parts by weight of tetrahydro~uran. Subsequently, the mixkure was left for 48 hours. The solution was then concentrated in vacuo and the residue taken up in ether and treated three times with water. The organic phase was dried with magnesium sulfate 9 and concentrated in vacuo after having been treated with activated carbon.
n25: 1.5085 Infrared and nmr spectra and ultimate analysis of the sirupy residue agree well with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methylaminocarbonyl methyl-aminosulfonate having the following structural formula:
H3C \ 0 H C
o ~ .
The following compounds were pr2pared analo~ously:
2~3-dihydro-3~3-dimethyl-2-m~thoxybenzofuran-5-yl-N-meth aminocarbonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethylamino-carbonyl methylaminosulfonate 2~3-dihydro-3,3 dimethyl-2-methoxybanzofuran-5-yl-N-ethyl-aminocarbonyl methylaminosulfonate.
A solution of 4 parts by weight of sodium hydroxide in 20 parts by weight of water was added to a suspension of 30.1 parts by weight of 253-dihydro-3,3-dimethyl-2-ethoxybenzofuran-- 1049539 o . z 30,~34 .
5~yl methylaminosulfonate in 55 parts by weight of water. From the solution which formed it was possible to obtain the salt by evaporating the water in va¢uo.
Infrared and nmr ~pectra and ultimate an~al~is of the salt agree wall with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxy- .. -benzofuran-5-yl methylaminosulfonate, sodium salt~ having the :
followi.ng str.uctural formula:
H3C~ ~0, H3C
" ~ 3 :
0 ~ H ; .
2 5 .:
The lithium and potassium salts of the following compounds were prepared analogously:
2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl methylamino- .: .
~ulfonate ~ .
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylamino- ;.
sulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-~-yl ethylamino-sulfonate 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl ethylamino-sulfonate.
EXAMPLE
At 20 to 23C and while stirring, a solution of 8.5 parts by weight of propargyl bromid~ in 20 part~ by weight of acetone was added to 46 parts by weight of a 50 wt% ~queous solution of the ~odium salt of 2,3-dihydro-3,3-dimethyl~2-ethoxybenzo-furan-5-yl methylaminosulfonate (prepared as in Example 7).
- 15 ~
1~9539 o. z . 30,33~
The temperature rose slightly to 29C~ To complete the reaction the mixture was stirred for a further 6 hours at 35C.
Ethyl acetate wa~ then added and extraction was carried out three times with water. ~he organic ph~e was dried with magne~ium sulfate and subsequently concentrated to dryness in vacuo.
n2255: 1.5085 .
Infrared and nmr spectra and ult~mate analysis of the -~
sirupy residue agree well with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-propargylmethylaminosulfonate having the following structural formula:
\ " H C
HC_ C CH
rH
The followin~ compounds were prepared analogously~
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-allyl methylaminosulfonate, b.p. (0.01 mm) 137 to 146C, n25: 1.5065 2,3-dihydro-3~3-dimethyl-2-ethoxybenzofuran-5-yl propargyl-aminosulfonate 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl allylamino-sulfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl propargyl-aminosùlfonate 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl~allylamino-sulfonate ~: . . . . . . .
~0~953~ :
0.Z, 30,334 2,3-dihydro-3,3-dimethyl-2-ethoxybenzo~uran~5-yl diallylamino-sulfonate.
The new active ingredients have a strong herbicidal action and may therefore be used as weedkillers or for con-trolling the growth of un~anted plants, Whether they are used as total or selective agents depends in essence on the amount of ingredient used per unit area.
By weeds and unwanted plant growth are meant all mono-cotyledonous and dicotyledonous plants which grow in loci where theY are not desiredO
The agents according to the invention may therefore be used for controlling for instance ~ :
Gramineae, such as Cynodon spp. Dactylis spp.
Digitaria 3pp. Avena spp.
Echinochloa spp. Bromus spp.
Setaria spp. Uniola spp.
Panicum spp. Poa spp. -Alopecurus spp. Leptochloa spp. -~
Lolium 8pp . Brachiaria spp.
Sorghum spp. Eleusine spp.
Agropyron spp. Cenchrus spp.
Phalaris spp. Eragrostis spp.
Apera spp. Phragmites communis etc.;
Cyperaceae, such as Carex spp. Eleocharis spp~
Cyperus spp. Scirpus spp.
etc.; - 17 - ~ .
, ,. . " ,.,,~, , .. . . ~ ,. . .
~049~i39 O.Z. 3,33~ -dicot~ledenous w~eds, such as .
Malvaceaa, e.g., Abutilon theoprasti Hibiscus spp.
Sida spp. Malva spp.
~tc.;
Compositae, such as .
Ambrosia spp. Centaurea spp.
Lactuca spp. Tussilago spp.
Senecio spp. Lapsana communis Sonchus spp. Tagetes spp.
Xanthium spp. Erigeron spp.
Iva spp. Anthamis spp.
Galinsoga spp. Matricaria spp, Tara~acum spp. Artemisia spp.
Chrysanthamum spp. Bid2ns spp.
Cirsium spp. etc.;
Convolvulacea~, such as Convolvulus spp. Cu8 cuta spp.
Ipomea spp. Jaquemontia tamnifolia etc.;
Cruci~erae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp. Descurainia spp.
Capsella spp. Draba spp.
Sisymbrium spp. Coronopus didymus Thlaspi spp. Lapidium spp.
Sinapis arvansis Raphanus spp.
etc.;
~ ~ .
1~49539 o z 30,334 Geraniaceae, such as Erodium spp. Geranium spp.
etc.;
Portulacaceae, such as -Portulaca spp. etc.;
Primulaceae, such as Anagallis arvensis Lysimachia spp.
etc.
Rubiaceae, such as Richardia spp. Diodia spp.
Galium spp. etc., Scr ~hulariaceaa, such as Linaria spp. Digitalis spp.
Veronica spp. etc.;
Solanaceae, such as Physali~ spp. Nicandra spp.
Solanum spp. Datura spp. ~
etc.; ~ ~ `
Urticacea~, such as Urtica spp.
Violaceae, such as Viola spp. etc.;
Zygophyllacea~, such as Tribulus terrestris etc.;
Euphorbiaceae, such as Mercurialis annua Euphorbia spp.
Umbelliferae, such as Daucus carota Ammi majus .
4~539 o.z. 30,33 Aethusa cynapium etc.;
CDmmelinaceae, such as Commelina spp. etc.;
Labiatae, such as Lamium spp. Galeopsis spp.
etc.;
Leguminosae, such as Madicago spp. Sesbania exaltata Trifolium spp. Cassia spp.
Vicia spp. Lathyrus spp.
etc.;
Plantaginaceae, uch as Plantago spp. etc.;
Polygonaceae, such as `~
Polygonum spp. Fagopyrum spp.
Rumex spp. etc.;
Aizoaceaey such as Mollugo verticillata ~tc.;
Amaranthaceae, such as Amaranthus spp. etc., 80raginacea~, such as Amsinckia spp. Anchu~a spp.
Myostis spp. Lithospermum spp.
etc.j Caryophyllaceae, such as Stellaria spp. Silane spp.
Spergula spp. Cerastium spp.
Saponaria spp. Agrostemma githago Scleranthus annuus etc.;
" 1~49539 O.Z. 30,334 ChPnopodiaceae, such as Chenopodium spp. Atriplex spp.
.. ... .
Kochia 8pp. Monolepsis nuttalliana Salsola Kali etc.;
Lythraceae, such as Cuphea spp. etc.j -Oxalidaceae, such as Oxalis spp.
Ranunculaceae, such as Ranunculus 8pp. Adonis spp.
Delphinium spp. etc.;
Papaveraceae, ~uch as Papaver 8pp. Fumaria officinalis~ `
etc.;
Onagraceae, such as Jussiaea spp. etc.; ~ -Rosaceaa, such as Alchemillia spp. Potentilla spp.
~tc.;
Potamogetonaceae, such as Potamogeton spp. etc.; ' :
Na j adaceae, such as Najas spp. etc.;
Eq~isetaceae Equisbtum spp. etc.;
Marsileaceae, such as ;
Marsilea quadrifolia etc.;
Polypodiaceae, Pteridium quilinum ~049S3~ -z~ 30~334 Alismataceae, such as Alisma 8pp. Sagittaria sagittifolia etc.
The amount used of the agents according ~o the invention may vary and depends in essence on the type of effec~ ~o~be achieved; it is generally from O.1 to 15 (and more), prefer-ably from 0.2 to 6, kg per hectare of active ingredient.
The herbicides according to the invention may he used in cereals such as Avena spp. Sorghum Triticum spp Zea mays Hordeum spp. Panicum miliaceum Secale spp- Oryza 5pp. "
Saccharum officinarum ;
and in dicotyledon crops such as Cruciferae, e.g.
Bras~ica spp. Raphanus spp.
Sinapis spp. Lepidium spp. ~ -Compositae, e.g.
Lactuca spp. Carthamus spp.
Helianthus spp. Scorzonera spp.
Malvaceae, e.~.
Gossypium hirsutum Leguminosae, e.g.
Medicago spp. Phaseolus spp.
Tri~oliu~ spp. Arachis spp.
Pisum spp. Glycine max.
'. ;'.:' , :
': , 104~S39 o . z . 30, 334 - :
Chenopodiaceae, e.g.
Beta vulgaris Spinacia spp.
Solanaceae, e.g.
Solanum Bpp. Capsicum annuum Nicotiania spp. ~ -Linaceae, e.~g.
Linum spp.
Umbelliferae, e.g.
Petroselinum spp. Apium graveolens Daucus carota Rosaceae, e.g. Fragaria -Cucurbitaceae, e.g.
Cucumis spp. Cucurbita spp. -~
Liliaceae, e.g. ~;
Allium 8pp. ~ .
Vi~aceae, e.g.
Vitis vinifera Bromeliaceae, e.g.
Ananas sati~us.
Applications may be effected for instance in the form o~
directly sprayable solution~, powders, suspen8ion~, di~per-sions~ emulsions, oil dispersions, pastes, dusts, broadcast-ing agents, or granules by spraying, atomizing, dusting, bPQad-casting or wataring. The forms of application depend entirely on the purpose for which tha agents are being used; in ~ny case they should ensure a fine distribution of the active ingredient.
O.Z. 30,334 For the preparakion of solutions, emu'sions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oilR of veg~table or animal origin, aliphatic, cyclic and aroma~ic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphtalene, alkyl~ted naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform~ carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc.
and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion ~on~
centrates, paste~, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil Idispersions the ingredients as such or dissolved in an oil or solvent may be homogeni7ed in water by mean~ of wetting or dispersing agents, adherents or emulsifiers. Concantrates which are suit-able for dilution with water may be prepared from active ingredient, wetting agant, adherent, emul~ifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are; alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulf~nates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty a~ohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethar, condensation products of ~ 0 ~9 539 O.Z. 30,334 sulfonat~d naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphtha-lenesulfonic acids with phenol and formaldehyde, polyox~et~ylene octylphenol ethars, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol~olyglycol ethers, tributylphenyl poly~lycol ethers, alkylaryl polyether alc~hols, isotridecyl alcohol, fatty alcohol ethylene oxide :
condensates, e~hoxylated castor oil 9 polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal~ sorbitol esters, lignin, sulfite waste llquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared ~y .
mixing or ~rinding the active ingredients with a solid carrier.
Granules, a.g., coated, impregnated or homogeneous gra-nules, n;ay be prepared by bonding the active ingredients to solid carriers. ~xample~ of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, limestone, lime, chal]c, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate,. and ureas, and ve~etable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc. ~.
The formulations contain from 0.1 to 95, and preferably 0.5 to gO~0 by weight of active ingredient.
There may be added to the compositions or individual activ~ ingredierlt~ (if desired, immediately before use (tank- :
mix) ) oils of various types, herbicides, fungicides, nernato-cidas, insecticides, bactericides, trace element~, fertilizer3, 25 - .
, ~, ,.. .
. , ; , . ... : ~ , ~ , . .
10~953~
O.Z. 30,334 antifoams (e.g., silicones), growth regulators, antidotes and othar herb~cidally effective compounds such as substituted anilines substitutad aryloxycarboxylic acids and salts, esters and amides thereof, substituted ethers substituted arsonic acids and their salts, esters and amides substituted benzimidazoles substituted benzisothiazoles ;
substitu~ed benzothiadiazinone dioxides substituted benzoxazines substibuted benzoxadinones æubstituted benzothiadiazoleæ
substituted biurets substituted quinolines substituted carbamates ;:
substituted aliphatic carboxylic acids and their salts, esters and amides substit~ted aromatic carboxylic acids and their salts, esters and amides su~stituted carbamoyla~kylthlol- or dit~iophosphates : ~
substituted quinazolines ;. .
~ubstituted cycloalkylamidocarbothiolic acids and their saltæ, esters and amides substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and their salts, esters and ~- :
amides substituted dihydrobenzofuranyl sulfonates - 2~ - ` ~-.
-,' , 1~49539 O.Z. 30,33substituted disul~ides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters and amides substituted ureas substituted hexahydro~ carbothioates substituted hydantoins substituted hydrazi~as .
substituted hydrazonium salts substituted isoxazol~ pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones substi~uted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxad~iazinones. .
substituted oxadiazolidone diones substituted oxadiazine diones substituted phenols and their salts and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkyl glycines :
substituted phosphites substituted phosphoric acids and their salts, esters and amides - 27 -. . . .
. . : , . - , . ~: . . ~ , ~49S39 o.z, 30,334 substituted piperidines substituted pyrazoles substituted pyrazole alkylcarboxylic acids and their salts, esters and amides substituted pyrazolium salks substituted pyrazolium alkyl sulfates substituted pyridazines subskituted pyridazones substituted pyridine carboxylic acids and their salts, es~ers and amides substituted pyridinas subStituted pyridine carboxylates substituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidone carboxylic acid and its salts, esters ~ :
and amidas substituted pyrro~idine~
substituted pyrrolidones : .
substitiuted arylsulfonic acids and their salts, esters and amides ~:
subskituted styrenas substituted tetrahydrooxadiazine diones :
substituted tetrahydroxadiazole diones substituked tetrahydromethanoindenes substituted tetrahydroxadiazole thiones substituted ~ietrahydrothiadiazine ~hiones ~:
substituted tetrahydrothiadiazole diones . - 2 .... - . . , .. : : .
~4~53~ o . z . ~0,S34 substituted aromatic thiocarbonylamides substituted thiocarboxylic ac~ds and their salts, esters and amides substituted thiol carbamates substituted thioureas substituted thiophosphoric acids and their salts, esters and amides substituted triazines substituted triazoles substituted uracils, and substituted uretidine diones.
The last-mentioned herbicidal compounds may also be ap--- lied before or after the activa ingredient~ or compositions thereof according to the invention.
These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.
The herbicide according to the invention may ba used one or more times before or after planting, be~ore sowing, pre-emergence, po~temergence or during emergence of tha crop or unwanted plants.
In the greenhouse, loamy sandy soil was filled into pots and sown with the seeds of various plants. The soil was im-mediately treatad with 2 kg per hectare of each of the following active ingredients, each being dispersed, emulsi~ied i, .
or dissolvèd`in 500 liters of watar per hectare;
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylamino-sulfate, ~odium salt ~I) -... . . . . .
- ~.
-.
; . . .
~04~39 o. z . 30,334 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methyl-carbonyl methylaminosulfonate (II) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-chloro-methylcarbonyl methylaminosulfonate (III) 2,3-dihydro-3,3-dim~thyl-2-methoxyb2nzofuran-5-yl-N-methyl-carbonyl methylaminosulfonake (IV) 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-chloro-methylcarbonyl methylaminosulfonate (V) 2,3-dihydro-3,3-dimethyl-2-methylcarbonyloxybenzofuran-5-yl-N-10 methylcarbonyl methylaminosulfonate (VI) :~
2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methoxy- : :
carbonyl methylaminosulfonate (VII) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate (VIII) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-isopropoxy-carbonyl methylaminosulfonate (IX) 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonate (X) ~ ~:
2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzo~uran-5-yl ;
dime~hylaminosulfQnate (XI) 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl diethylaminosulfonate (XII) and, for comparison, 2-ethoxy-2,.3 dihydro-3,3-dimethyl-5-benzofuranyl methane-sulfonate (XIII) 2~3-dihydro-3,3-dimethyl-2-isopropoxybenzofuran-5-yl ethyl- :
aminosulfonate (XIV).
109~9~39 O.Z. 30,334 After 4 to 5 weeks it was ascertained-that active ingredients I to XII had a better herbicidal action than com-pounds XIII and XIV, combined with the same crop plant compatibility.
The results are given below:
. - 31 -: , , `' . , ,: ' : - ~ ' ' 104953g 0 . Z . 30, 334 ~H ~U O O O O Ll~ C~
O O o o L~ o L~ ir\ o o ' ~' '' '.
H ~ a~ O cr~ 0~o ~C) X
X ~ O o o o o o o o o O O O O O ~ ', X :, H ~J O O O O O O 1~ L~ IS~O
~ 3 :
H O O O O 15~ L~ L~
H a~ 0~C~ J
~? . '',, ~
H ~`J O O O O lS~ O L~ O O O
P ' a~ o ~ o o H (~J O O O O O O O O O O . . ~
~ c~ 3 : :
. ' ' ~ ' .',~', .
p t\l O O O O Lr\ g Lr~ O g O
H ~ O O OO lr~ O `~D O O O
~ O C~ O O
H
H (~l O O OO ~ O 15~ O ~ Ll~
1_1 C~ O ~ O C~Lr~ , -"''':.
H ~1 O 15~ O O O OL~ O O 15~
H O O O~ O O~D :
': :
H ~\1 O O OO O O O O O O .:
~ O O 0 ~0 ~0~ Co ,"~,, ~
' g '~''''' rl ' Ul rl r~
r rl U~ h I :J
a~ ~ 0~~3 o r rl CO ~0 ~ ~ O ~!j r-l C'~ ~0 :1 r~ S ~ O ~ S~
a~ ~ 0 E~ rl ~a ~ H ~ U H
bO ~ ~ m ~ ~ ~ o r~
~ ~ 1 ~ ::tr~
rl ~d p, ~ ~ cd ~ O O
~1 p, Or~ O ~ ~S O ,C~ O
a~ ~ ~ rl O~ ~ C> O ~ 5:`, rl ~d u~ l S ~
P ~ rl ~ ~ rl rl O ~ ~d ~ r l ~ ~ O ~ O O
o bD ~1 ~ ~ : -r-l O:~1 0rl O
~: ~ c~ m m P~ x P ~
- 32 - .
~'"' ''' ., ,, , , , ~ , - , , - - - - , .
~049~3~ -z., 30,334 ;
' ~ O O O O O O O O U~ O . ':
X : . .
H ~U O Lr~ O OL~ O O If~ O
X ~1 .1 ~a~ ) N
~.' ~ ' W ." ~ :
~I h rl oq o ~: h ~ h ~1 ~ . .-~d ~ Gq 0~:~ O
5:: ~ O h h t~~> ~1 ~: ~ ~ ~
rl t~ ~ ~ ~ ~ h,s~ 5 o O
~1p~C) r I ~a) ~
G~ Qu~ O ~ ~ C~ O ~ 5: rl ~ Oqa) ~d rl S ~ ~ rla1 S~
O ~ ~ ~ a) o ~ ~ o o c~ bD ha) h S a)~: ~ O O ~1 O
¢ ~: ~ m a~ ¢ ¢ ~ ~
' ' ' '''' '''" '"
; .
- 33 - ~
. .
" '' , - . , -: . :: .
-1~4953~ ~:
O.Z. 30,334 : :
In the greenhousa, various plants were treated at a growth -height of from 2 to 15 cm with 2 kg per hectare of each of - .
active ingrediants I to XIV (as defined in Example 9), aach being emul~ified, dispersed or dissolved in 500 litars of water per hectare. ~: :
After 2 to 3 weaks it was ascartained that active :~
ingradients I ~o XII had a better herbicidal action than com- -pounds XIII and XIV, combined with the same crop plant compati~ :
bility.
Tha results ara given below~
. , , .
- 34 - ~:
104~539 " ~ Z . 30, 3311 H r~l O-Ir~ IS`\ O O 1~
~C x) a\ o~
.'-,, H N OO 0 15~ O
X o~ a~ o~ o ~ ,, X ~ OO Lr~ O O O
~ ra~ O -X N OO O Lr~ O L~
H O~ O~ ~
H ~ '.
H N OO ~D ~0 ~ ~ .
P O~ 0~
H ~U O O L~
P O~ O~
: ' -H N OO O Lr~ O 1~
O~ X~ O~
. r~
P N OO L
O~ ~ C~ ' '' ~ N O O L~
H ~ r J~
H O L~ O O
H N OO C~
' '' H N OO O ~ In H O~ O~
H N OO O O O I
o a~ o CJ~ ' g ~ ,;
H ~ h ~ r~ ~ "
5~ ~
~rl ~ ~ h O bO a c~ ~ Cd a) .. p, ~d ~q ~ ~
b~ ~ 5: R ~ O ~Q ~ Q.
S~ ~ . ~ ~1 ~ ~d ~ ~ -d ~ O O
H ~C) Q) ~ r~
07rl ~ O ,~, C) a ~ ~ i~(d ~ 11 11 ~rl rC ~ ~ S~
O ~ ~ ~:~V ,5~ l O O O ' ., C) bl~ ~ID S~ ~ ~ C) O vl O
~: ~ t~ ~ m ~ ~
- 3~ -,. . - . , ~ ~ . i ~L~4953~ o . z . 30, 334 o o o ~ o H ~I o~ ~ x) x~
X ,' ' ' ' .:- ~
~ ,' O O L~ O O o H ~I
' 5: '' .
O '.': ' o t~
~0 0 ~-J~ I h ~ ..
5:: ' ~ '' :,:
u~
~rl 0 J~ h O ~o a~ -~ ~ ~> ~ ~ ~ .
~d ~ ~
~o .~~: ~ ::f o s:: s::~ ~ ~ ~ o o '' ~ ~ o 9) ~ o ~ ~ ~ o a~ Q ~q rl ~ O
, 5 ~ u~ ~ ~ ~ ~ a) " ,.
,1 .C t2 ~ d O ~ ~ a) 5:: ~d O O O
o ~0 h ~ h ~ :~ o O ~ O
~: ~ ~m ~q ~
..
'. ".. . ....
, .':
" ' ' ' ~.
~ ~ ~9 53 9 O.Z. 30,334 The action of the following compounds-corre~ponds to that of the compounds according ko the invention in tha foregoing examples:
2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methyl-sulfonyl methylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl diathylaminosulfonate 2,3-dihydro-3,3-dimethyl-2-mathoxycarbonyloxybenzofuran-5-yl dimethylaminosulfonata 2,3-dihydro-3,3-dimethyl-2-ethoxycarbonylbanzofuran-5-yl dimethylaminosulfonate In the greenhouse, loamy sandy ~oil was ~illed into pots and sown with the saeds of various plants. The soiI was then immediately treated with 3 kg per hectare of each of the following active ingredients, each baing dispersed or emulsified in 500 liters of water per hectare~
2,3-dihydro-3,3-dimethyl-2-ethoxybsnzofuran-5-yl-N-methyl-carbonyl methylaminosulfonate (II) ~,3-dihydro 3,3-dimethyl-2-athoxybanzofuran-5-yl-N-chloromethyl-carbonyl methylaminosulfonate (III)2,3-dihydro-3,3-dimethyl-2-sthoxybenzofuran-5-yl-N-methoxy-carbonyl ~,ethylaminosulfonate (VII) 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxy-carbonyl methylaminosulfonate (VIII) and, for comparison, 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methane-sulfona~a (XIII).
1049539 o z 30,33~
During the experimant the plants were watered well.
After 3 to 4 week6 it was ascertained that active ingredients II, III, VII and VIII had better crop plant com-patibility than compound XIII, combined with the same herbididal ~
action. :
Tha results are given below~
Activ ingredient II III VII VIII XIII
kg/ha 3 3 3 3 3 .
~.. . .
Cro~ ~lants:
' Gossypium hirsutum 5 0 5 10 40 Zea mays 20 5 10 15 60 ~
Beta spp. 10 0 5 5 3 .
Unwanted plants: ~
.
-~chinochloa crus-galli100100100 100 100 : -Setaria faberii 100100100 100 100 :~
Alopecurus myosuroide~ 100 100 100 100 100 Avena fatua 100100100 100 100 Galium aparine 100100100 100 100 ,; . . .
0 - no damaga 100 ~ complete de~truction .
' ~
, .:-- 38 ~
Claims (15)
1. A substituted benzofuranyl ester of the formula , where R1 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, R2 denotes loweralkyl, loweralkenyl, loweralkynyl, a metal atom, loweralkyl-sulfonyl or acyl of the formula , R4 denoting unsubstituted or chloro-, loweralkoxy- or loweralkyl-thio-substituted loweralkyl, loweralkenyl or loweralkynyl, loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-substituted loweralkoxy, and R3 denotes hydrogen, unsubstituted or chloro- or loweralkoxy-substituted loweralkyl, loweralkenyl or loweralkynyl, or acyl of the formula , R5 denoting unsubstituted or chloro-, loweralkoxy- or loweralkyl-thio-substituted loweralkyl, loweralkenyl or loweralkynyl, loweralkylamino, di-loweralkylamino, or unsubstituted or chloro-substituted loweralkoxy.
2. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methylaminosulfonate, sodium salt.
3. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl methyl-aminosulfonate, potassium salt.
4. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methylcarbonyl methylaminosulfonate.
5. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-chloromethylcarbonyl methylaminosulfonate.
6. A compound according to claim 15 characterized in that it is 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methylcarbonyl methylaminosulfonate.
7. A compound according to claim 19 characterized in that it is 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-chloromethylcarbonyl methylaminosulfonate.
8. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-methylcarbonyloxybenzofuran-5-yl-N-methylcarbonyl methylaminosulfonate.
9. A compound according to claim 1, characteriæed in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-methoxycarbonyl methylaminosulfonate.
10. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-ethoxycarbonyl methylaminosulfonate.
11. A compound according to claim 1, characterized in -that it is 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-isopropoxycarbonyl methylaminosulfonate.
12. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3 dimethyl-2-methoxybenzofuran-5-yl-N-methylsulfonyl methylaminosulfonate.
13. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofu-ran-5-yl diethylaminosulfonate.
14. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofu-ran-5-yl dimethylaminosulfonate.
15. A compound according to claim 1, characterized in that it is 2,3-dihydro-3,3-dimethyl-2-ethoxycarbonyloxybenzofu-ran-5-yl dimethylaminosulfonate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2402370A DE2402370A1 (en) | 1974-01-18 | 1974-01-18 | SUBSTITUTED BENZOFURANY LESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049539A true CA1049539A (en) | 1979-02-27 |
Family
ID=5905110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA218,030A Expired CA1049539A (en) | 1974-01-18 | 1975-01-16 | Substituted benzofuranyl esters |
Country Status (24)
| Country | Link |
|---|---|
| JP (1) | JPS50101533A (en) |
| AT (1) | AT339659B (en) |
| BE (1) | BE823879A (en) |
| BG (1) | BG25979A3 (en) |
| BR (1) | BR7500273A (en) |
| CA (1) | CA1049539A (en) |
| CH (1) | CH595754A5 (en) |
| CS (1) | CS181286B2 (en) |
| DD (1) | DD115561A5 (en) |
| DE (1) | DE2402370A1 (en) |
| DK (1) | DK632474A (en) |
| ES (1) | ES433918A1 (en) |
| FR (1) | FR2258385B1 (en) |
| GB (1) | GB1488575A (en) |
| HU (1) | HU171224B (en) |
| IL (1) | IL46287A (en) |
| IT (1) | IT1050270B (en) |
| LU (1) | LU71663A1 (en) |
| NL (1) | NL7500326A (en) |
| NO (1) | NO750140L (en) |
| PL (1) | PL91954B1 (en) |
| SE (1) | SE7500519L (en) |
| SU (1) | SU519108A3 (en) |
| ZA (1) | ZA75335B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6476011B1 (en) | 1991-08-28 | 2002-11-05 | Sterix Limited | Methods for introducing an estrogenic compound |
| US6011024A (en) | 1991-08-28 | 2000-01-04 | Imperial College Of Science Technology & Medicine | Steroid sulphatase inhibitors |
| US6903084B2 (en) | 1991-08-29 | 2005-06-07 | Sterix Limited | Steroid sulphatase inhibitors |
| GB2331988B (en) * | 1997-12-04 | 2003-04-16 | Imperial College | Polycyclic sulphamate inhibitors or oestrone sulphatase |
| US7335650B2 (en) | 2000-01-14 | 2008-02-26 | Sterix Limited | Composition |
-
1974
- 1974-01-18 DE DE2402370A patent/DE2402370A1/en not_active Withdrawn
- 1974-12-05 DK DK632474A patent/DK632474A/da unknown
- 1974-12-19 IL IL46287A patent/IL46287A/en unknown
- 1974-12-20 FR FR7442348A patent/FR2258385B1/fr not_active Expired
- 1974-12-23 JP JP49146898A patent/JPS50101533A/ja active Pending
- 1974-12-27 BE BE151944A patent/BE823879A/en unknown
-
1975
- 1975-01-10 NL NL7500326A patent/NL7500326A/en not_active Application Discontinuation
- 1975-01-15 CH CH44275A patent/CH595754A5/xx not_active IP Right Cessation
- 1975-01-15 IT IT47690/75A patent/IT1050270B/en active
- 1975-01-15 BG BG7528725A patent/BG25979A3/xx unknown
- 1975-01-15 BR BR273/75A patent/BR7500273A/en unknown
- 1975-01-16 CA CA218,030A patent/CA1049539A/en not_active Expired
- 1975-01-16 PL PL1975177378A patent/PL91954B1/pl unknown
- 1975-01-16 DD DD183665A patent/DD115561A5/xx unknown
- 1975-01-16 SU SU2097790A patent/SU519108A3/en active
- 1975-01-16 LU LU71663A patent/LU71663A1/xx unknown
- 1975-01-16 HU HU75BA00003190A patent/HU171224B/en unknown
- 1975-01-17 ES ES433918A patent/ES433918A1/en not_active Expired
- 1975-01-17 GB GB2067/75A patent/GB1488575A/en not_active Expired
- 1975-01-17 CS CS7500000357A patent/CS181286B2/en unknown
- 1975-01-17 NO NO750140A patent/NO750140L/no unknown
- 1975-01-17 AT AT33675A patent/AT339659B/en not_active IP Right Cessation
- 1975-01-17 ZA ZA00750335A patent/ZA75335B/en unknown
- 1975-01-17 SE SE7500519A patent/SE7500519L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SE7500519L (en) | 1975-07-21 |
| ATA33675A (en) | 1977-02-15 |
| SU519108A3 (en) | 1976-06-25 |
| IL46287A (en) | 1978-03-10 |
| PL91954B1 (en) | 1977-03-31 |
| DK632474A (en) | 1975-10-13 |
| FR2258385A1 (en) | 1975-08-18 |
| NL7500326A (en) | 1975-07-22 |
| FR2258385B1 (en) | 1978-11-03 |
| ES433918A1 (en) | 1976-11-16 |
| AU7660074A (en) | 1976-06-24 |
| CH595754A5 (en) | 1978-02-28 |
| CS181286B2 (en) | 1978-03-31 |
| HU171224B (en) | 1977-12-28 |
| IL46287A0 (en) | 1975-03-13 |
| DE2402370A1 (en) | 1975-07-31 |
| BR7500273A (en) | 1975-11-04 |
| GB1488575A (en) | 1977-10-12 |
| ZA75335B (en) | 1976-01-28 |
| IT1050270B (en) | 1981-03-10 |
| LU71663A1 (en) | 1975-06-24 |
| BE823879A (en) | 1975-06-27 |
| DD115561A5 (en) | 1975-10-12 |
| JPS50101533A (en) | 1975-08-12 |
| AT339659B (en) | 1977-11-10 |
| NO750140L (en) | 1975-08-11 |
| BG25979A3 (en) | 1979-01-12 |
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