DE2402370A1 - SUBSTITUTED BENZOFURANY LESTERS - Google Patents

Description

Our reference: O.Z.30 334 Sws / IG 6700 Ludwigsbafen, January 17, 1974

The present invention relates to new 4-Benzofurany! Esters, the preparation of these compounds, their use as herbicides, and herbicides which these compounds as Contain active ingredients.

It is known that 2,3-dibydro-3,3-diraethyl-2-ethoxybenzofuran-5-yl-methane-sulf to use onate (DT-OS 1 926 139) as a herbicide; however, its effect is limited.

It has been found that benzofuran-5-yl esters of the general formula

CH ,,

in which R is hydrogen or an alkyl (methyl, Ethyl, propyl, isopropyl, butyl), alkenyl (allyl, methallyl) or alkynyl radical (propargyl, butynyl) and R is an alkenyl (allyl, methallyl) or alkynyl radical (propargyl, butynyl), a metallatora (alkali and alkaline earth atom, Sodium, potassium, magnesium, lithium), an alkylsulfonyl residue (Methylsulfonyl), an arainosulfonyl residue or an acyl radical of the general formula

-CR ⁴ ti 0

in which R ⁴ denotes an alkyl, alkenyl or alkynyl radical optionally substituted by halogen (chlorine), alkoxy (methoxy) or alkylthio (thiomethyl), an alkylamino or dialkylamino radical, or one optionally substituted by halogen

■ z

substituted alkoxy radical, and R is hydrogen, an alkyl, alkenyl or alkynyl radical which is optionally substituted by halogen (CHlor) or alkoxy (methoxy)

702/73 5 0 9831/0903 -2-

O.Z. 30th

or an acyl radical of the general formula

-CR ⁵

Il

"means in which R is an optionally halogen (Cblor), Alkoxy (Metboxy) or Alkyltbiο (Tbiomethyl) substituted alkyl, alkenyl or alkynyl radical, a Alkylamino or dialkylaraino radical, or optionally one means alkoxy radical substituted by halogen, Have a good herbicidal effect that is better than that of known herbicides. Also own the new Compounds a better selectivity in tarnish plants, e.g. Gossypium hirsutum, Zea mays, Beta spp. as 2,3-dihydro-3,3-diraetbyl-2-ethoxybenzofuran-5-yl-metban sulfonate.

The compounds according to the invention can be prepared, for example, by the following processes:

a) by acylation of benzofuran-5-yl-aminosulfonates according to the following general equation

CH- + XCR tr H O

13 4-in which the substituents R, R and R are those mentioned above Have meanings and X, for example, a halogen atom (chlorine, bromine) or the remainder

-OCR ⁴

If

means. The benzofuran-5-yl-arainosulfonates to be used as starting materials are described

509831/0903

ο.ζ 30

b) by acylation of 2-Hydro: xybenzofuran-5-yl-aü] inosulfonaten according to the following equation

Ri O

OH,

2 ^

R ² 0

-CSH ₃ + XCR- 8

SO

dd

CH,

OH

OCR '

Il

12 "5

in which R, R and Br have the abovementioned meanings and X is, for example, a halogen atom (chlorine, bromine) or the remainder

-OCR ⁵

Il

means. Those to be used as starting materials Benzofuran derivatives can be made as follows:

D D u +

o = chV; ο

H, C

HO

2) Ίο

H-r.C Q

• OH "

3 + ClS-FHR

ο '\> —ν ο

CH

3 ·

■ 0

N-SO
dd
O

"N-SO
R "8

.CH, H '

dd o

H ₃ C

OH

H ₃ C

H-SO.

S IO

-CH,

R ³ OH / H ©

OH

O ti

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- 4 - O.ζ. 30th

The reaction formulated under 1) is "known from Dutch laid-open specification 6 512 511, from Journal for practical chemistry, 4th series, volume 32, page (1966) and U.S. Patent 3,184,457.

The reactions formulated under 2) "to 4) are carried out by the following test descriptions are explained:

Attempt a

2,3-dihydro ~ 3,3-d iraethy1-2-morph olinobenzofuran-5-yl-

meth.ylaminosulfonate

A solution of 48.8 parts (parts by weight) of 2,3-dibydro-3,3-dimethy1-2-morpholino-5-hydroxybenzofuran and 27.3 parts of triethylamine in 130 parts of tetrahydrofuran were stirred at 0 to 5 ^° C 36 parts of methylaminosulfonyl chloride were added. The reaction mixture was filtered off after stirring for one hour at room temperature. The filtrate was concentrated in vacuo and the residue was dissolved in 250 parts of methanol. After adding 100 parts of water and treating the solution with activated charcoal, crystallization was initiated by cooling. The crystal slurry was filtered off with suction, washed with 50 percent (percent by weight) aqueous methanol and dried in a vacuum. The crude product had a melting point of 125-128 ⁰ C. By crystallization of a sample from 80prozentigem methanol was obtained pure 2,3-Dibydro-3, 3-d imethy1-2-raorph olinobenzofuran-5-yl-raethylaminosulfonat. Ep. 129 to 131 ⁰ C

Attempt B

2,3-Dibydro-3..3-dimethyl-2-byro: xybenzofuran-5-yl-methyl- aminosulfonate

A mixture of 133 parts of water and 68 parts of concentrated hydrochloric acid was added at 80 ⁰ C with stirring, 68 parts of 2,3-Dibydro-3,3-dimethyl-2-raorpholinobenzofuran-5-y1-uEfcbylaminosulfonat at once. The mixture obtained was heated rapidly to 90 to 95 ^° C. and kept at this temperature for 2 minutes. The reaction solution was then immediately cooled by adding ice.

509831/0903 "" ⁵ "

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For work-up, the ether solution was extracted with ether was washed twice with water, dried with magnesium sulfate and concentrated in vacuo.

The viscous residue was dissolved in 100 parts of ether and, after addition of 60 parts of η-hexane, was cooled by cooling

aminosulfonate obtained as crystals. 3? P. 111 to 112 ⁰ C

The compound has the following structural formula:

GH-

dd

t H _x CNH-SO.

-> I! 0

3 OH

Attempt C

2,3-dibydro-3,3-d imethyl-2-methoxybenzofuran-5-y1-

methylaminosulfonate

A solution of 22.5 parts 2,3-dihydro-3,3-diraethyl-2-hydroxybenzofuran-5-yl-methylaminosulfonate in 200 parts of methanol was mixed with 4 drops of concentrated sulfuric acid and then refluxed for 30 minutes. For working up, the reaction mixture was neutralized with triethylarain after cooling and then concentrated to dryness in vacuo. Treatment of the viscous residue with ether / n-hexane mixture gave 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-methylaminosulfonate as crystals. Pp. 89 to 91 ⁰ C.

The compound had the following structural formula:

ti CH-

5098 3 1/090 3

OZ 30 334

In the event that in the under a) or t>) "described Method R means an alkylamino radical, is that Acylating agent to be used is an isocyanate as in the following equation for methyl isocyanate as Example is reproduced.

+ OOTCH-

OCNHOIL

c) by reaction of benzofuran-5-yl-aminosulfonaten with an alkylsulphonyl- or araino-sulphony halide, such as it for example in the case of methylsulfonyl chloride is formulated in the following equation

OR-

in which R and R * have the meanings given above.

d) by the action of metal hydroxides, preferably Alkali or alkaline earth hydroxides on benzofuran-5-ylarainοsulfonate as formulated, for example, in the following equation for the pail of sodium hydroxide is:

+ ITaOH

1 5
in which R and R ^ have the meanings given above.

e) by alkylation of benzofuran-5-yl-aroinosulfonaten with Alkenyl or Alkiny! Halides in such a way that one

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for example, the salts prepared according to d) are used as reactants, as is the case for the AlIyL-broraid Pail is shown in the following equation:

R ¹ 0 \ II

^ΌΗ 3 + BrCH ₉ -GH = CH ₉ - »H ₉ C = CH-CH ₉ ^ Ö] Γ) ³ ^ n

1 3
in which R and R have the meanings given above.

Serve to explain the production of the new Terbindungen the following examples:

example 1

To a solution of 30.1 parts by weight of 2,3-Dibydro-3,3-dimethyl-2-ethoxy-benzofuran-5-yl-raethylaiDinosulfonat and 12 parts by weight of triethylamine in 90 parts by weight of ether was added with stirring at 15 to 20 ⁰ C. 9 parts by weight Acetyl chloride added. After one hour, the reaction mixture was extracted three times with water. The ethereal solution, dried with magnesium sulfate, left an oily residue of the compound 2,3-dihydro-3 ₅ 3-dimethyl-2-ethoxybenzofuran-5-yl-N-ynethyl-carbonyl-methylamino-

25th
sulfonate, n ^ 1.5042, which does not occur even when standing for a long time

crystallized.

Analysis, infrared and ITMR spectrum are in good agreement with the following structural formula

H ₅ C

OC ₂ H ₅

The following compounds were made in a similar manner

manufactured:

2,3-Di "hydro-3,3-ethyl- ⁱ -2-i-ethoxyben! Aofuran-5-yl-IT-nie-thyl-

OtZ

carbonyl methyl arainosulfonate, η-η 1.5085

509831 / 09Q3

- 8th -

2Ä0237O

2,3-Dibydro-3,3-dimetbyl-2-metboxybenzofuran-5-yl ~ N -raetbylcarbonyl-ethylarainosulf onat

2,3-Mbydro-3,3-d imetbyl-2-iDetb oxybenzof uran-5-y1-N-ethylcarbonyl-metbylarainosulfonat

2,3-Mbydro-3,3-dimethyl-2-ethboxybenzofuran-5-yl-N-ethylcarbonyl-methylarainosulfonate

2,3-Bibydro-3,3-dimetbyl-2-raetboxybenzofuran-5-yl-N-cblor-

25 methylcarbonyl-methylaminosulfonate, n- ^ 1.5195

2,3-Dibydr 0-3 »3-diniefhyl-2-äfh oxybenzof uran-S-yl-K-

25 methylcarbonyl-methylaniitiosulfonate, n- ^ 1.5140

2,3-Mhydro-3,3-aimethyl - 2-ätT3oxyTDenzof uran-5-yl-H-dichlorine-

25th

raefhylcarTDonyl-metbylaniinosulfonat, ώ- ^ 1.5165

2,3-Dibydro-3,3-dimetbyl-2-tDet · boxy ^^ enzofuran-5-yl-N · -o · chloro-methylcarbonyl-ethylate dinosulf onat

2,3-Dibydro-3,3-dimethyl-2-n] -ethyl-benzofuran-5-yl-N-t-tetl] oxycarbonyl-methylamino-sulfonate

2,3-Di'hyäro-3,3-dimetbyl-2-iDefhoxy'benzofuran-5-yl-N-ethoxycarbonyl-metbylarainosulfonat

2,3-Dibydro-3,3-dimetbyl-2-t-detboxybenzofuran-5-yl-li-isopropoxycarbonyl-metbylaininosulf onat

2,3-Dibydr o-3,3-d imetby l-2-ätb oxybenzof uran-5-y l-lT-metb oxy-

25 carbonyl methylaminosulfonate, n-p 1.5000

2,3-dibydro-3,3-d imetbyl-2-ätb oxybenzofuran-5-y1-U-ätboxy-

25 carbonyl methylaminosulfonate, n-p 1,494-5

2,3-dibydro-3,3-dimetbyl-2-ethoxybenzofuran-5-y1-N-iso-

25 propoxycarbonyl-methylaminosulfonate, n-p 1.4880.

Example 2

To a solution of 28.7 parts by weight of 2,3-dibydro-3,3-diü3etbyl-2-bydroxybenzofuran-5-y 1-dimethylaminosulfonate and 14.1 parts by weight of trietbylamine in 110 parts by weight of ether

508 831/0903 ~ ⁹ ~

2Ä02370

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were 10.3 Gewicbtsteile Acetylcblorld added under Rübren at -8 Ms -12 ⁰ C. The Compound 67 was prepared according to the workup of the Reaktionsmiscbung as described in Example 1, 2 »3 Dibyäro-3,3-diraetbyl-2-n] etbylcarbonyloxybenzofuran-5-onate yldiraetbylaiöinosulf erbalten as crystals, Pp to 68 ⁰ C. she asked the following structural formula:

HC 0

■> \ ti

^ 1TS

The following compounds were made in the same way deployed:

2,3-Dibydro-3J3-diraetbyl-2-ätbylcarbonyloxybenzofuran-5-yldimetbylatDinosuT ± »nat, Pp. 53-54 ⁰ C

2,3 ^ I ^| i'bydro-3,3-dimetbyl-2-cblornjetbylcarbonyloxybenzofuran-5-yl-dimetbylaminosulfonat, 87-88 ⁰ C Pp.

2 »3'-Dibydro-3,3-di ^ letbyl - 2-cblorιDetbylcarbonyloxybenzofuran-5-yl-dietbylatpinosulfonat, n | p 1.5078

2,3-DibydrQ-3,3-ditDetbyl-2-dicblorajetbylcarbonyloxybenzofuran-5-yl-aimetbylarainosulfonat

2,3-Dibydro-3,3-aimetbyl-2-dicblormethylcarbonyloxybenzofuran-5-yl-dietbylaminosulfonate

2,3 "Dibyäro-3,3-diiiietbyl-2 ~ tDetboxyoarbonyloxybenzofuran-5-yldimetbylarainosulfonat, Pp. 101-102 ⁰ C.

2,3-Dibydro-3,3-ditDetbyl-2-ätboxyoarbonylo2? Ybenzofuran-5-yldituetbylaiDinosulfonat, Pp. 84-85 ⁰ C

2,3-Mbydro-3,3-dimethyl-2-isopropoxycarbonyloxybenzofuran-5-yl-dimethylaminosulfonate

2,3-Mbydro-3 '3-d itDetbyl-2-oxy metB carbonyloxybenzof uran-5-y Ια iätbylaminosulfonat, Pp. 95 to 96 ⁰ C.

- 10 509831/0903

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2,3-Diby <3ro-3,3-aimefhyl-2-aatt) oxycarbonyloxybenzofurarL-5-yl diethylaminosulfonate

2,3-Di'hy (3ro-3) 3-aimetbyl-2-isopropoxycarbonyloxy'benzofuran-5-yl dietbylaminosulfonate.

Example 3

To a solution of 28.7 parts by weight of 2,3-Mhyäro-3,3-dirDetbyl-2-hydroxybenzofuran-5-yl-dyne] ethylan3inosulfonate in 90 parts by weight of tetrahydrofuran were after addition of

1 part by weight of triethylamine 6.9 parts by weight of methyl isocyanate

added at room temperature (20 ^° C.). Each one easy

As the temperature increased, the reaction mixture was left to its own devices for 24 hours. The solvent was used for working up removed in vacuo and the residue recrystallized from ether;

Ip. 101 to 103 ⁰ G.

The compound ZjJ-Dibyaro-J ^ -airaetayl ^ -inethylarainocaxbonyloxybenzofuran-5-yl-dimethylaminosulfonate has the following structural formula:

0 '

0-CNHCH,

11 3

The following connections were established in the same way?

2,3-dihydro-3 '3-dimethyl-2-äthylaminocarbonyloxybenzofuran-5-yldimethylarainosulfonat, mp. 112-113 ⁰ C.

2,3-Dihydro-3J3-dimethyl-2-propylaminocarbonyloxybenzofuran-5-yl-dimethylaminosulfonate

Z ^ -dihydro-J ^ -äimethyl-Z-isapropylaminocarbonyloxybenzofuran-5-yl-diraethylaminasulfonat, 107 to 109 ⁰ C Pp.

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Ί1 Ο.Z. 30th

2,3-Bibyäro-3,3-äimetbyl-2-raetbylaminocarbonyloxybenzofuran - 5 - yl diätbylaminosulfonat, Pp 122-123 ⁰ C.

2,3-Dibydro-3,3-äiraetbyl-2-ätbylaminocarbonyloxybenzof uran-5-yl-diäthylarainosulfonat, 124-125 ⁰ C Pp.

2,3-I) ibydro-3,3-diraethyl-2-metbylaminocarbonyloxybenzofuran - 5'-yl-methylaminosulfonate

2,3-Mhydro-3,3-aimetbyl-2-ethylau] inocarbonyloxybenzofuran-5-yl-methylaminosulfonate

2,3-Dibydro-3j3-aimetbyl-2-propylan) inocarbonyloxybenzofuran-5-yl-methylaminosulfonate

2,3-I> ibyäro-3,3-diraetbyl-2-isopropylaminocarbyniyloxybenzof uran-5-yl-tetbylaminosulfonate.

Example 4

To a solution of 68 G-ewiobtsteilen 2,3-Dibyclro-3,3-clin] etbyl-2-bydroxybenzofuran-5-yl-raetbylaiDinosulfonat and 55 »5 Gewicbts-.teilen Triätbylamin were incubated at 1O ⁰ C 56 Gewicbtsteile Acetanbydri'd added with stirring.

NACB Steben about ITacbt the precipitated reaction product was suction filtered, then gewascben with cold ether and water and dried in Yakuum at 6O ⁰ C. Pp. 103 to 104 ⁰ C.

The compound 2,3-dibydro-3,3-diraetbyl-2-methylcarbonyloxybenzofuran-5-yl-IT-t-tetbylcarbonyl-methylamino-sulfonate bat the following structural formula

- 12 50 98 3 1 /0.9 0 3

- 12 - O.Z. 30th

The following statements were made accordingly deployed:

2,3-Dibydro-3,3-dimethyl-2-chloro-defylcarl) onyloxytenzofuran-5-yl-IT-chloro-ethylcarbonyl-methylaminosulf onat

2,3-Dihydro-3,3-dimethyl-2-ethylcarbonyloxybenzofuran-5-yl-M-ethylcarbonyl-methylaminosulfonate

2,3-Dibydro-3,3-dimetbyl-2-methcarbonylo: Kybenzofuran-5-yl-IT-methylcarbonyl-ethylaminosulf onat.

Example 5

To a solution of 28.7 parts by weight of 2,3-dihydro-3,3-dimethyl-2-metho2: ybenzofuran-5-yl methylarainosulfonate and 13.3 parts by weight of triethylamine in 130 parts by weight of dicblormetban was added at -8 to -12 ⁰ G a solution of 13.8 parts by weight of methylsulfonyl chloride in 30 parts by weight of dicblorraetban was added. Thirty minutes after the end of the reaction, the mixture was extracted three times with water. The organic phase was dried with magnesium sulfate and the solvent removed in vacuo. The syrupy residue (η · τ) 1.5150) did not crystallize, even on prolonged standing.

IR and KMR spectra as well as the elemental analysis of the residue are in good agreement with the compound 2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-N-methylsulfonyl-methylaminosulfonate the following structural formula

In a corresponding ^T .iege the following compounds were prepared:

2,3-Dibydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-IT-methyl-

sulfonyl methyl arainosulfonate

- 13 5098 3 1/0903

2,3-Mbydro-3,3-d imetbyl-2-metb oxybenzof uran-5-yl-N-ethylsulfonyl-metbylarainosulfonate

2,3-Eibydro-3,3-d imetbyl-2-ätb oxybenzof uran-5-yl-ethylsulfonyl-aetbylarainosulfonate.

Example 6

To a solution of 20.5 parts by weight of 2,3-dibydro-3,3-ainethyl-2-ethboxy-benzofuran-5-yl-i-methylaminosulfonate in 70 parts by weight of letrabydrofuran was added after 0.5 parts by weight of trietbyl arain 5.15 parts by weight of methyl isocyanate added and the mixture then left to sieve for 48 hours. The solution was used for working up concentrated in vacuo, the residue taken up with ether and taped three times with water. The organic base was dried with magnesium sulphate and after treatment with activated coble

25 constricted in Yakuura, n-p 1.5085.

IR and MR spectra as well as the elemental analysis of the syrupy residue are in good agreement with the compound 2,3-dibydro-3 , 3-dimethyl-2-ethboxybenzofuran-5-yl-N-acetylaminocarbonyl-acetylaminosulfonate with the following structural formula

In a similar manner the following compounds deployed:

2,3 ~ Dibydro-3,3 - diraetbyl-2-metboxybenzofuran-5-yl-II-metbyl ~ aminocarbonyl methylaminosulfonate

_{2/3-Dibydro-3,3} ~ dimetbyl-2-ätboxybenzofuran-5 ~ yl-N-ätbylarainocarbonyl-metbylaminosulfonat

2,3-Dibydro-3,3-aimetbyl-2-raetboxybenzofuran-5-yl-1) 3 "-ethyl-aminocarbonyl-methylaminosulfonate.

- 14 509831/0903

- 14 - ο.ζ,

example

To a suspension of 30.1 parts by weight of 2,3-Mhydro-3,3-dimethyl-2-ätboxybenzofuran-5-yl-methylaminosulfonate in 55 parts by weight of water became a solution of 4 parts by weight Sodium hydroxide added in 20 parts by weight v / water. A solution arose. The salt could be obtained from this solution by evaporating the water in vacuo. IR and KMR spectra as well as the elemental analysis of the salt are in good agreement with the compound 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-y1-methylarainosulfonate sodium salt the following structural formula

N / A

OG ₂ H ₅

In a corresponding way, the lithium or sodium or. Potassium salts made of the following compounds:

2,3-Dihydro-3 ₅ 3-di-ethy1-2-methoxybenzofuran-5-yl-roethy1-arainosulfonate

2,3-Dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-y1-methylaminosulfonate

2,3-Dihydro-3,3-dimethyl-2-methoxybenzofuran-5-y1-ethby1-amine ο sulf onate

2,3-Dihydro-3,3-dimethyl-2-ethboxybenzofuran-5-y1-ethy1-amine ο sulf onate.

Example 8

To 46 parts by weight of a 50 percent (percent by weight) aqueous solution of 2,3-dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-ylmethylaminosulfonate sodium salt (prepared as described in the previous example) was added at 20 to 23 ^° C. Solution of 8.5 parts by weight of propargyl bromide in 20 parts by weight of acetone was added with stirring. It was

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a slight increase in temperature to 29 ° C was observed. To complete the reaction, 6 hours "at 35 ° C touched. The reaction mixture was worked up with Acetic acid ethyl ester is added and the mixture is then extracted three times with water. The organic phase was made with magnesium sulfate dried and then concentrated to dryness in vacuo, njp 1.5085.

IR and HMR spectra as well as the elemental analysis of the syrupy Residue are in good accordance with the compound 2,3-Dihydro-3,3-dimethy 1-2-ethoxybenzofuran-5-yl-N-propargylraethylaminosulfonate the following structural formula

= O-CH, Ö IO

C J

The following compounds were made in a similar manner manufactured:

2,3-X> ihydro-3,3-d imethy 1-2-eth oxybenzof uran-5-yl-N-allylmethylaminosulphonate, bp _{0 Q1 mXÜ} 137 to 146 ⁰ O, n ^ ⁵ 1.5065.

2,3-Dibydro-3,3-d iraethy1-2-ethoxybenzofuran-5-yl-propargylaminosulfonate

2,3-Dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-allylaminosulfonate

2,3-Dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-propargylaminosulfonate

2,3-dihydro-3,3-dimethyl-2-methoxybenzofuran-5-yl-allylaminosulfonate

2,3-Dihydro-3 »3-dimethyl-2-ethoxybenzofuran-5-yl-diallylaminosulfonate.

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ο «ζ. 3C 3

Vir ^ ßrofie have a strong herbicide effect and can therefore be used as a weed killer "or, for Combat unwanted vegetation can be used. Whether the agents act as total or selective agents depends mainly on the amount of active ingredient per unit area from ο

All are under weeds or ο undesirable plant growth Monocotyledonous and dicotyledonous plants that grow in places where they are undesirable.

For example, with the agents according to the invention Gramineae, how

uynodon spp. Digitaria spp. -Ec'binochloa Setaria spp. PanicutD spp. Alopecurus spp LoIium spp. Sorghum spp. Agropyron spp. Phalaris spp. Apera spp.

Dactylis spp. Avena spp. Bromus spp, Uniοla spp. «Poa spp. leptochlca spp. Practaiaria spp. Eleusine spp. Cenchrus spp. Eragrostis spp. Phragmites communis and others

Oyperaoeae, like Carex spp. Cyperus spp. Scirpus spp.

dicot weeds, like

Malvaceae, e.g.

Abutilon theoprasti Sida spp. MaIva spp "

Eleocharis spp. and other

Hibiscus spp. and other

5098 3 1/0903

Compostiae, like Ambrosia spp. Lactuca spp. Senecio spp. Sonebus spp. Xantbium spp. Iva spp. G-alinsoga spp. Taraxacum spp. Chrysanthemum spp, Bid ens spp. Cirsiura spp »ο.ζ.

Gentaurea spp. Tu.ssilago spp. Lapsana comraunis Tagetes spp. Erigeron spp * Antbemis spp » Hatricaria spp »Artemisia spp. and other

Oonvolvulaceae such as Convolvulus spp. Ipomoea spp = Jaquemontia tamnifolia Guscuta spp. and other

Cruciferae such as Barbarea vulgaris Brassica spp. Capsella spp. Sisymbrium spp. T "b laspi spp. Sinapis arvensis Raphanus spp.

A: c ab i d ο ρ s i s tb al i ans Descurainia spp. Draba spp. Coronopus didyraus Lepidium spp »and other ere

Geraniaceae, such as Erodium spp »G-eranium spp, and other

Portulacaceae such as Portulaca spp.

and other

Primulaceae such as Anagallis arvensis Lysiraacbia spp.

and other

509831/0903

RuMaceae such as Richardia spp. Galiura spp.

Diodia spp.

Soropbulariaceae such as Linaria spp. Veronica spp.

Digitalis spp. and other

Solanaceae such as Pbysalis spp. Solanum spp. Datura sppα Mcandra spp. and other

Urticaceae, such as Urtica spp »

Yiolaceae such as Viola spp.

and other

Zygopbyllaceae such as Tribulus terrestis and other

Eupborbiaceae, such as Mercurialis annua Euphorbia spp.

Fmbelliferae such as Daucus carota Aetbusa cynapiura raajus and others

CotDtnelinaeae Gommelina spp.

and aid ere

Labiatae such as Lamium spp. G aleopsis spp.

and other

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2AQ237Q

Le. {J.v.j) inosae, like Meäicago spp. Trifolium spp. Yicia spp. Latnyrus spp.

Plantaginaceae, such as Plantation »spp. Sesbania exaltata Cassia spp. and other

and other

Pol ^ gonaceae, such as Polygonura spp. Rumex spp. Iagopyrum spp, and other

Aizoaceae, such as Mollugo verticillata and other

Amaranthaceae, like Araaranfhus spp. and others

BoraginaGeae, such as Amsinclcia spp ο fly ο st is spp c Lifh ο apermum spp. Anchusa spp. and other

Garyopljyllaceae> v / i e Stellaria spp. Spergula spp. Saponaria spp. Sclerantnus annuur oilene spp. Cerastium spp «A ^ r ο st e atna £ i th ago

Ghenopodiaceae, such as Chenopodium spp. Eocbia spp. Salsola potash Atripleχ spp, rionolepsiβ nut talliana and other

Lyfhraceae, like Gapnea spp. and other

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5 0 9 8 3 1/0903

O.Z. 30/5? 4

Oxalidaceae, such as Oxalls spp.

Ranunculaceae such as Ranunculus spp. Delphinium spp.

Adonis spp. and other

Papaveraceae, such as Papaver sppο Pumaria officinalis and and ere

Onagraceae, such as Jussiaea spp, and others

Rosaceae, like

Alchemillia spp. Potentilla spp.

and other

Potamogetonaceae such as Potamogeton spp.

and other

Majadaceae, like ITa j as spp.

and other

Marsileaceae, like

Marsilea quadrifolia and other ere

Polypodiaceae, such as

Pteridium aguilinum

Alismataceae, such as Alisma spp. Sagittaria sagittifolia and other ere

Equisetaceae, such as

Equisetaceae spp.

and other

to be fought,

5 09831/0903 -

ο.ζ.

The herbicides according to the invention can be applied in their Amount fluctuate. The amount used mainly depends on the type of effect desired.

The application rate is generally between 0.1 and 15 or more, preferably 0.2 and 6 kg of active ingredient per hectare.

The herbicides according to the invention can be used in "cereal crops,

how

Avena spp "Sorghum

Triticum spp. Zea mays

Hordeura spp. Panicum railiaceura

Seeale spp _o "~ Oryza spp. Saccharum officinarum

un in cultures of dicotyledons such as oruciferae, Z ₀ B.

Brassioa spp. Raphanus spp.

Sinapis spp _o Lepidium spp.

Gomposistae, for example Iactuea spp ₀ Helianthus spp.

Malvaceae, e.g.

Gossypiura hirsutum

Leguminosae, e.g. Medicago spp. Trifolium spp. Pisum spp.

Chenopodiacea, e.g. Beta vulgaris Spinacia spp.

Solanaceae, e.g. Solanura spp. Ficotiania spp.

Carthamus spp. Scorzonera spp.

Phaseolus spp. Arachis spp.
Glyane Max

Capsicum annuum

509 8 31/0903

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Linaceae, ζ "Β. Linura spp.

Umbelliferae, e.g.

Petroselinum spp. Apium graveolens

Daucus carota

Rosaceae, e.g. Fragaria

Cueurbitaceae, e.g.

Cucumis spp. Cucurbita spp.

Liliaceae, e.g. AlliutD spp.

Yitaceae e.g.

Titis vinifera

Bromeliaceae, e.g. _o Ananas sativus

can be applied.

The herbicides are used, for example, in the form of direct sprayable solutions, powders, suspensions or dispersions, Emulsions, oil dispersions, pastes, dusts, Spreading agents, granules by spraying, misting, dusting, Scatter or pour. Align the application forms depending on the intended use; in each case they should have the finest possible distribution of the substances according to the invention Ensure active ingredients.

For the production of directly sprayable solutions, emulsions, Pastes and oil dispersions come from mineral oil fractions medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils etc., as well as oils of vegetable or of animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, Tetrahydronaphthalene, alkylated naphthalenes or their

509831/0903

O.Z.

30th

O ¹ Z _ ^ KJ · ίι · ^ v.

Derivatives z. B. methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents such as ZcB. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration.

Aqueous application forms can be made from emulsion concentrates, Pastes or wettable powders (wettable powders), oil dispersions by adding water "can be prepared. For the production of The substances can be emulsions, pastes or oil dispersions as such or dissolved in an oil or solvent, by means of hardening agents, adhesives, dispersants or emulsifiers in Water to be homogenized. But it can also be made more effective Concentrates consisting of substances, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil prepared that are suitable for dilution with water,

The following surface-active substances should be mentioned: alkali, alkaline earth, ammonium salts of lignin sulfonic acid, Naphthalenesulfonic acids, phenolsulfonic acids, alkylarylsulfonates, Alkyl sulfates, alkyl sulfonates, alkali and alkaline earth salts of Dibutylnaphthalene sulfonic acid, lauryl ether sulfate, petalcohol sulfate, fatty acid alkali and alkaline earth salts, salts of sulfated hexadecanols, heptaecanoic, octadecanols, Salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of Naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octyl benzene ether, ethboxylated Isooctylphenol, -Octylphenol, -Nonylphenol, Alkylphenolpolyglykoläther, Tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, Isotridecy alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, Sorbitol esters, lignin, sulphite waste liquors and methy! Cellulose.

Powder, litter and dust can be produced by mixing or grinding the active substances with one

- 24 -

509831/0903

- 24 - Ο, Ζ. > ■ 234

solid ™ oxygen produced.

Granules, for example coated, impregnated and homogeneous granules, can be produced by binding the active ingredients to solid carriers. Solid carriers are ZoB ₀ kinetic earths such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, talc, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, fertilizers , such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal mash, tree bark, wood and osscale flour, CeXLulose powder and other solid carriers.

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

In addition to the mixtures or individual active ingredients, oils can be different Type, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoam agents (e.g. silicones), growth regulators, antidote agents oda? other herbicidally active compounds such as substituted anilines

substituted aryloxycarboxylic acids and their salts, esters and amides
substituted ethers

substituted arsonic acids and their salts, esters and amides substituted benzimidazoles
substituted benzisothiazoles
Substituted Benzthladiazinond ioxides Substituted Benzoxazines
substituted benzoxazinones
substituted benzothiadiazoles
substituted biurets
substituted quinolines
substituted carbamates

substituted aliphatic carboxylic acids and their salts, esters and amides

50983Ί / 0903

240237Q

- 25 - OZ. 3) 0

substituted aromatic carboxylic acids and their salts,

Esters and amides

substituted carbamoylalkyl thiol or ditbiophosphate

substituted quinazolines

substituted Cycloalkylaaiidocarbontbiolsäuren and their

Salts, esters and amides

substituted Oycloalkylcarbonamido-thiazole substituted dicarboxylic acids and their salts, esters and amide e

substituted dibydrobenzofuranylsulfonates substituted disulfides

substituted dipyridylium salts

substituted dithiocarbamates

substituted dithiophosphoric acids and their salts, esters and amides

substituted ureas

substituted hexabydro-1-H-carbotbioate substituted hydantoins

substituted hydrazides

substituted hydrazonium salts

substituted Isooxazolpyrimid one substituted imidazoles

substituted isouhiazole pyrimidones substituted ketones

substituted naphthoquinones

substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles

substituted oxadiazinones

substituted oxadiazolidinediones substituted oxadiazinediones

substituted phenols and their salts and esters, substituted phosphonic acids and their salts, esters and amides

substituted phosphonium chlorides substituted phosphonoalkylglyzines substituted phosphites

substituted phosphoric acids and their salts, esters and amides

- 26 509831/0903

"2δ · - ο.?.,

substituted piperidines substituted pyrazoles substituted pyrazolakylcarboxylic acids and their salts, esters and amides substituted pyrazoliura salts substituted pyrazoliura alkylsulfates substituted pyridazines substituted pyridazones substituted pyridinecarboxylic acids and their salts, esters and amides substituted pyridines, substituted pyridinecarboxylates, substituted pyridines, substituted pyridinecarboxylates, substituted pyridinecarboxylates, substituted pyridimidinones, substituted pyridimidinones and their esters, substituted pyridimidinones, substituted pyridimidones and their salts, esters and amides substituted pyrazoliura salts, substituted pyridimidinones Amide-substituted pyrrolidines, substituted pyrrolidones, substituted arysulfonic acids and their salts, esters and amides, substituted styrenes, substituted tetrabydro-oxadiazinediones, substituted tetrahydro-oxadiazole-diones, substituted tetrahydrometbanoindenes, substituted tetrahydro-diazol-thiones, substituted tetrahydro-tydiazine-substituted, aromatic, tetrahydro-thiadiazine-substituted, aromatic, tetrahydro-thiadiazine-substituted, aromatic, tetrahydro-thiadiazine-substituted, aromatic, tetrahydro-thiadiazine-substituted thiocarboxylic and their S _a lze, esters and Amide-substituted thiolcarbaraates substituted thioureas substituted thiophosphoric acids and their salts, esters and amides substituted triazines substituted triazoles substituted uracils substituted uretidinediones

509831/0903

- * a? ~ ο, ζ. 30 33 ² Y-

if necessary, it can only be peeled off before use (Tanlcffiix) eye sets. The last mentioned herbicides Compounds can also be used before or after the individual active ingredients or mixtures according to the invention will.

The scaling back of these agents to those according to the invention Herbicides can be used in a weight ratio of 1:10 to 10; 1 take place. The same applies to oils, fungicides, nematocides, Insecticides, bactericides, antidotes and growth regulators.

The herbicides according to the invention can, inter alia, im

Planting procedure Subsequent balancing procedure Pre-sowing procedure Pre-emergence procedure Post-emergence method

or during the emergence of the culture or unwanted plants

be applied one or more times.

Example 9

In the greenhouse, loamy sandy soil was placed in test vessels filled and sown with the seeds of various plants. Immediately thereafter, the treatment with 2,3-dihydro-3,3-diraethyl-2-ethoxybenzofuran-5-ylmethylaminosulfonate sodium salt took place (I)

2,3-Dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-y1-N-raethylcarbonyl-methylaminosulfonate (II)

2,3-Mhydro-3,3-dimethyl-2'-ethoxybenzofuran-5-y 1-N-chloromethylcarbonyl-methylarainosulfonate (III)

2,3-Dibydro-3,3-dimethyl-2-methoxybenzofuran-5-y1-N-methylcarbonyl-methylaminosulfonate (IV)

- 28 509831/0903

- SS ~ ο.ζ. 30 3>'l

2,3-Dibydrc-3 »3-dimethyl-2-methoxybenzofuran-5-y1-N-methyl-methyl-carbon-1-methyl-arainosulfonate (V)

2,3-Dibydro-3,3-dimethyl-2-methylcarbonyloxybenzofuran-5-y1 ~ K-raetbylcarbonyl-methylaminosulfonat (YI)

2,3-dibydro-3 »3 _? -dimetby1-2-ätboxybenzofuran-5-y1-N-metboxycarbonyl-metbylaminosulfonate (TII)

2,3-dibydro-3,3-dimefbyl-2-ethboxybenzofuran-5-y1-N-ethboxycarbonyl-methylaminosulfonate (YIII)

2,3-Dibydro-3,3 ~ dimetby1-2-ethboxybenzofuran-5-y1-H-isopropoxyoarbonyl-raetbylaidinosulfonate (IX)

2,3-Dibydro-3,3-diraetbyl-metboxycarbonyloxybenzofuran-5-yΙα imetbylaminosulfonate (X)

2,3-Dibydro-3,3-dimetby1-2-ethboxycarbonyloxybenzofuran-5-yldimetbylaainosulfonate (XI)

2,3-Dibydro-3,3-airaethyl-2-metboxycarbonyloxy "benzofuran-5-yl dimethylaminosulfonate (XII)

in the context of the active ingredients

2-Etboxy-2,3-dibydro-3,3-dimethyl-5-benzofuranyl-metbarsulfonate (XIII)

2,3-Dibydro-3,3-dimethyl-2-isopropoxybenzofuran-5-y1-ethylaminosulfonate (XIY).

The application rate was 2 kg per hectare and was in ' 500 liters of water per hectare dispersed, emulsified or solved"

After 4 to 5 weeks it was found that the active ingredients I up to XII showed a better herbicidal action with the same tolerance on the cultivated plants than the active ingredients XIII and

The Yersuob result can be seen from the following table:

- 29 -

509831/0903

Active ingredient I II III IT Y YI YII YIII IX XIY X XI XII XIII

kg / na a.S. 2 2 2 2 2 2 2 2 2 2 2 2 2 2

Beta spp «0000000000 0 0 0 10

Brassioa napus 10 5 0 0 00000 10 0005

Pbaseolus vulgaris 0 0 000 0 0 00 0 0 0 0 5

_m Helianthus annuus 000000000000010

to H ££ -Desired plants:

ω Avena fatua 100 100 98 95 95 90 95 95 90 90 100 95 95 80

\ Alopecurus myosuroides 100 100 100 100 100 90 100 95 90 30 100 100 95 85

2 EcMnocbloa orus galli 100 95 95 96 95 90 95 95 95 30 100 95 90 80

° Lolium raultiflorum 100 100 100 100 100 80 100 95 95 50 100 95 90 80

^ω Poa annua 100 100 97 100 100 90 100 98 95 65 100 100 95 85

Sinapis arvensis 80 65 55 50 50 40 60 45 40 30 75 60 55 20

0 = above damage

100 = total damage '

30 - ° · ^ζ ·

Example 10

In the greenhouse, various plants at a height of 2 "to 15 cm were treated with the active ingredients I" to XIV (as in the preceding Example defined). The application rate was 2 kg per hectare and was in each case 500 liters of water per hectare dispersed, emulsified or dissolved.

After 2 to 3 weeks it was found that the active ingredients I to XII had a better herbicidal effect with the same tolerance on the crop plants showed as the active ingredients XIII and XIV,

The test result is shown in the table below see?

- 31 509831/0903

Active ingredient I II III IY Y YI YII YIII IX XIY X XI XII XIII

kg / ha a.S. 2 2 2 2 2 222 2 2 2 2 2 2

^ J Beta sppo 00000000000 0 0 20 q

co Brassic.a napus 0 0 00 0 0 0 0 0 010 0 5 30 ^l

CO -Jt

co Avena fatua

_ω Echinochloa crus galIi

Poa annua

Alopecurus myosuroides

0 = without damage ^

100 = total damage ^

100 98 90 95 95 90 95 96 90 90 95 90 85 75 90 90 85 85 85 85 85 86 85 85 100 95 90 70 100 97 90 98 95 90 95 97 90 85 100 95 90 70 95 95 90 95 95 85 95 97 85 80 100 100 95 90

Correspondingly biologically effective as the compounds in the The above examples are the following compounds:

2,3-Dibydro-3,3-dimethyl-2-metboxybenzofuran-5-yl-H-methylsulfonyl-methylaminosulfonate

2,3-Dihydro-3,3-dimethyl-2-methoxycarbonyloxybenzofuran-5-yl diethylaminosulfonate

2,3-Dihydro-3j3-ditethyl-2-t-ethoxycarbonyloxyben2iofuran-5-yldiraethylaminosulfonate

2,3-dihydro-3, 3-d imetbyl-2-äthoxycarbonyloxybenzofuran-5-yldimetbylaminosulfonat.

Example 11

Experimental pots with a loamy sandy soil were used in the greenhouse filled and sown with various seeds. Immediately thereafter, the treatment with the active ingredients took place

2,3-Dibydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-N-metbyicarbonyl-methylaminosulfonate (II)

2,3-Dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-yl-H-chloroethylcarbonyl-methylaminosulfonate (ill)

2,3-Dihydro-3,3-dimethyl-2-ethoxybenzofuran-5-y1-J-methoxycarbonyl-methylaminosulfonate (VII)

2,3-Dihydro-3,3-d imethyl-2-ethoxybenzofuran-5-y 1-IT-ethoxycarbonyl-methylaminosulfonate (VIII)

compared to the active ingredient

2-ethoxy-2,3-dibydro-3,3-diraethyl-5-benzofuranyl-metbane sulfonate (XIII)

each dispersed or emulsified in 500 liters of water per hectare. The application rate was 3 kg per hectare of active substance. During the experiment, the plants became very much kept moist.

- 33, 509 83 1/0903

- 33 - o.z. 30 334

After 3 "to 4 weeks it was found that the active ingredients. II, III, YII and VIII showed better tolerance on the crop plants with the same herbicidal effect than the active ingredient XIII.

The test result can be seen from the following table,

Active ingredient - II III VII VIII 10 XIII kg / ha a.So 3 3 3 3 15th 3 1 ^ t zjsf lajnz en ° 5 G-ossypium birsutum 5 0 5 40 Zea mays 20th 5 10 10C 60 Beta spp » 10 0 5 100 30th unwanted plants ι 100 Echinochloa crus galli 100 100 100 100 100 Setaria faberii 100 100 100 100 100 Alpecurus myosuroides 100 100 100 100 Avena fatua 100 100 100 100 Goliura aparine 100 100 100 100

0 = without damage
100 = total damage

- 34- 509831/0903

Claims (1)

Claim e means in there? R ^ one optionally by halogen, Alkoxy or, alkylthio substituted alkyl, alkenyl or alkynyl radical, an alkylamino or dialkylamino radical, or one which is optionally substituted by halogen Alkoxy radical and R is hydrogen, optionally one alkyl, alkenyl or alkynyl radical substituted by halogen or alkoxy, or an acyl radical of general formula -GR ⁵ !1 means in which R is optionally replaced by halogen, Alkoxy or alkylthio substituted alkyl, alkenyl or alkynyl radical, an alkylamino or dialkylamino radical, or an alkoxy radical which is optionally substituted by halogen. 2. Herbicide containing a solid or liquid carrier and a benzofuranyl derivative according to claim 1 as Active ingredient - 35 - 509831/0903 - 35 - ο. ζ. 30? 34 3. Use of a Bensofurany! Derivative according to claim as a herbicide. 4. 2,3-Dibydro-3,3-diraetbyl-2-ethboxybenzofuran-5-yl-methylarainosulfonate, sodium salt. 5 »Z ^ aminosulfonate potassium salt. 6. 2,3-Diayaero-3,3-diiDetbyl-2-ethboxybenzofuran-5-yl-l ⁱ r-t-detnyloariDonyl-tnefbylatDinosulfonat. 7. 2,3 "-DiQydro- = 3,3-airetl] yl-2-a-b3OxyT3enzofuran-5-yl-N-chlorodethylcarbonyl-methylarainosulf onato 8. 2,3-Dinyäro-3J3 - din] etbyl-2-tDetnoxy'benzo ± uran-5-yl-l ^{i-r-nietbylcarbonyl} raetbyTatDino sulfonate 9. 2,3 ~ Dibyäro-3} 3-aiii] ethyl-2-t-detboxybenzofuran-5-yl-]! ⁱ -cblorme tbylcarbonyl-tDetby! amino sulfonate. 10. 2,3-Dibydro-3,3 ~ dimethyl ~ 2-methylcarbonyloxybenzofuran-5-ylr N-methylcarbonyl-methylaminosulfonate. 11. 2,3-Mbydro-3} 3-dimethyl-2-ethboxybenzofuran-5-yl-N-metboxycarbonyl-methylaminosulfonate. 12. 2,3-I> ibydro »3,3 ~ dimethyl-2-ethboxybenzofuran-5-yl-N-ethboxycarbonyl-methylarainosulfonate. ο 2,3-dibydro-3,3-d imetbyl-2-ethoxybenzoiuran-5-yl-N-isopropoxycarbonyl-metbylarainosulfonate. 14. 2,3-Dibydro "3,3-dimethyl-2-metboxybenzofuran-5-y1-H-methy-sulfonyl-methylaminosulfonato 15. 2,3-Dibydro-3,3-dimetbyl-2-metboxycarbonyloxybenzofuran - ^ - yldiätbylaminosulfonatο - 36 509831/0903 - 36 .... o <z. 5 ° 16ο 2.3 ~ £ -. ' ydrn - 3 _i 3-dItr _J < ^: T-: üyl "-y! -ei imetny laminosul Ivona t. 17. 2,3 "Dinydro ~ 3,3 ~ i3itDefhyl-2-ätboxycarbonyloxybenzofuran-5 · y l - cl imetbylarainosulfonat. BASI? Corporation , - 509831/0903