DE2503216A1 - HERBICIDAL AGENTS - Google Patents

Description

Priority: January 29, 1974, Japan, No. 11425/74

The invention relates to that characterized in the claims Object.

Preference is given to using compounds of the general formula I in which the alkyl and alkoxy radicals have 1 to 4 carbon atoms contain. Specific examples of these radicals are the methyl, ethyl, propyl and butyl groups and the methoxy, Ethoxy, propoxy and butoxy groups. Preferred halogen atoms are chlorine and bromine atoms.

The compounds of the general formula Ia '' ■ 'are particularly preferred

(I-a)

S 5

509831/0890

in which X _{1 represents} a hydrogen or bromine atom, a methyl or ethyl group, R. ^a hydrogen or bromine atom or a methyl or methoxy group and R "represents a hydrogen atom or a methyl group.

In Table I are specific examples of the invention compounds used:

Table I.

attachment

No.

link

co

CH,

OCH "

CO

F. or Kp.

F.

56.5-57

^Κ Ρ ο /
135-135.5 C /

h torr

5. Torr

'Appearance

pale yellow crystals

70 _t 5-72.5 ° C

177.5 ° C /
3. Torr

white liquid

blue liquid

pale green crystals

Slightly brown liquid

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δ ■ . "· '/ ^0CH 3' Kp.
^: 155.5-156 ⁰ C /
• 2. Torr colorless
liquid 7th F.
72.5-73.5 ° C- white
Crystals 8th
> o ^co -o ^A 65-66 ° C weak green
Crystals 9 0- ^c0 -O- ^ci 98-100 ° C white
Crystals 10 Br _: - *
0- ^co -0 Kp.
164-166 ° C /
3 torr weak green
Crystals 11 - ■ "* -""*. ^CH 3
. ^ yco - ^ - ch ₃ Kp.
lftl _r 5-1 ^ 2, 5 ° C /
"2 torr colorless
liquid 12th Q-CO-Q-OCH ₃ Kp. "
167-170.5 ⁰ C /
2, torr colorless
liquid 13th CH
/ "VCO- fl ~ \ -OCH ₀
\ s / ν = / 3 F.
■ 61.5-63 ° C white
Crystals

509831/0890

CH

5-CO-0 ₊

(^ mixture ratio '

C ₂ H ₅ -

CH,

, -CO-

CH CH ■ J

»-CO--

Mixing ratio s 1 «τ. ρ \

CH,
\

CH,

CH ₃ CH,

, -CO-,

3 "

Mis clause ratio s 1.6: fi

Kp.; volume

F.

89-91 ° C

Kp. 'Torr

Bp 151-151-5 ° C /

Torr

136-138 ° C /

Torr

159-162 ° c /

b ratine
liquid

white
Crystals

yellow
liquid

pale yellow crystals

colorless liquid

colorless liquid

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Kp

150.5-155.5 ° C /
3. Torr

(Mixing ratio 1: 2.2) green
Liquid ice

72-73 ° C

pale yellow crystals

Br-

KP. . '

147-150 ⁰ C /

pale yellow liquid

Kp.
166-167 ° C /

Ij 5th torr

yellow
liquid

76-78 ° C

yellow
Crystals

OCH ₃

Br-

F. yellow
Crystals

Br-

F.

-Cl pale green crystals

Kp ;. C /
Torr

colorless liquid

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-α ·

CH "~ V VCO

CH.

Kp ..

158-159 C /
Torr

colorless liquid

72-73.5 C.

weak, green liquid

•, oh ,.

-O"

CH ff VCO

h5-h6 ° C

white
Crystals

CH,

.-o- ^co -

-OH,

70-71.5 C

faint, yellow crystals

Cl.

F. 39- ^ 0.5 C

schiiach yellow Crystals

-Cl 9O-9l,., 5 C

pale yellow crystals

^1H 3

Bp 153-156 ° C /

Torr

brown liquid

F. 70.5-71 C.

white
Crystals

OCH,

F. pale yellow crystals

5 09831/0890

'37 - C ₂ H ₅ - ^ "Vco- / A-ocH ₃ F.
49-50 ° C weak, green
Crystals 38. Kp.
'J.51-151, 5 ° C /
2.5 Torr pale yellow
liquid 39 Br- ^ / \ - C0-CH ₂ - ^ \
f -IY
66-68 ° C white
Crystals 40 Q-OO-QO ₂ U ₅ F.
39.5-4.O ⁰ C " pale yellow
Crystals 4l Q-OO-QL ₃ F. '.
45-47.5 ° C pale yellow
Crystals 42 ci- ^ Vco- ^ F.
V 57-59 ° c white
Crystals

509831/0890

The compounds of general formula I have excellent properties herbicidal effect on a wide variety of weeds, e. B. grasses such as fingergrass (Digitaris adscendes HENR.), Chicken millet (Echinochloa crusgalli BEAUV), green meadow foxtail (Setaria viridis BEAUV.), ¥ aster foxtail

(Alopecurus aequalis SOBOL), annual bluegrass (Poa annua and

L,), / sticky herb (Eleusine indica (L.) GAERTM), sedge, such as the tiger nut (Cyperus microiria STEUD), broad-leaved weed, such as buckhorn (Portulaca oleracea L.), knotweed (Polygonum longisetum DE BRUYN), bluish amaranth (Amaranthus lividis L.), goosefoot (Chenopodium album L.), carpet grass (Mollugo stricta L.), green amaranth (Amaranthus viridis L.), Commeline (Commelina communis L.), milkweed plant (Euphorbia supina RAFIN.), shepherd's purse (Capsella bursapastorxs MEDIK.), chickweed (Stellaria media VXLL), chickweed (Stellaria alsine GRIMM), yellow cress (Rorippa indica HIERON), Lamium amplexicaule L., Hornwort (Cerastium vulgatum L.), Fleabane (Erigero linifolius IiILLD.), Speedwell (Veronica didyna TENORE.) and common ragwort (Senecio vulgaris L.), as well as against grasses in the rice field, such as chicken millet (Echinochloa crusgalli BEAUV), sedge (Cyperus microiria STEUD), Cyperus serotinus ROTTB or sea ledges (Scirpus erectus POIR) and broad-leaved weeds in the rice field, such as Monochoria vaginalis PRESL, false pimpernelle (Lindernia procumbens PHILCOX), Dopatorium junceum HAMILT, water seasoning (Elatine triandra SCHK), Rotala indica KOEHNE, American composites (Eclipta prostrata L.) or two teeth (Bidens tripartita L.).

5 0 9 8 31/0890

The compounds used according to the invention are particularly valuable as herbicides for rice fields, since they cause only very little damage to the rice seeds and the young rice plants that have been moved.

The compounds of general formula I can in per se be prepared in a known manner by (a) a compound of the general formula II

in which X has the preceding meaning with the compound the general formula

Cl-CO-R

(III)

in which R has the preceding meaning, or (b) a compound of the general formula JE

U-COCl

in which X has the preceding meaning, with a compound the general formula

MR
in which R, - is a phenyl group of the general formula

509831/0890

in which R ₁ and R _{2 have} the above meaning, or a thienyl radical of the general formula

'S

represents, in which R "has the preceding meaning, in the presence a condensing agent such as tin tetrachloride, zinc chloride or alurainium chloride in a solvent such as Asleep! Carbon, condensed.

The examples explain the preparation of the compounds of general formula I,

Example 1

Preparation of 2-bromo ~ 5- (2 ^! -Methylbenzoyl) -thiophene (compound no. 22)

A solution of 65.2 g (0.4 mol) of 2-bromothiophene and 61.8 g (0.4 mol) of 2-methylbenzoyl chloride in 100 ml of carbon disulfide is added in portions with 104 g (0, 4 moles) of anhydrous tin tetrachloride was added, then heated gradually to room temperature and then stirred for 2 hours. The reaction mixture obtained is treated with 200 ml of ice-cold 5gewichtsprozentiger hydrochloric acid and then extracted with 200 ml of benzene. The benzene extract is washed with 200 ml

509831/0890

- 11 -

5 weight percent sodium hydroxide solution and water, dried over sodium sulfate and evaporated under reduced pressure. The brown liquid residue obtained is distilled. Yield 82g. (86.6 ° / o of theory) of pure, pale yellow title compound, bp. 147 to 15O ° C / 2 Torr.

Example 2

Preparation of a mixture of ^ - methyl-2- (3 '-methylbenzoyl) -thiophene and 3-methyl-2- (3 ^f -methylbenzoyl) -thiophene

A solution of 39 »2 g (0.4 mol) of 3-methylthiophene and 61.8 g (0.4 mol) of 3-methylbenzoyl chloride in 100 ml of carbon disulfide is added in portions with 5 ^» 5 g ( 0.4 mol) of anhydrous zinc chloride are added, then gradually warmed to room temperature and then stirred for 2 hours. The reaction mixture obtained is mixed with 200 ml of ice-cold 5 percent strength by weight hydrochloric acid and then extracted with 200 ml of benzene. The benzene extract is washed with 200 ml of 5 percent strength by weight sodium hydroxide solution and water, dried over sodium sulfate and evaporated under reduced pressure. The residue is distilled. Yield 65.7 g (75 »9 i ° of theory) of a mixture of 4-methyl-2- (3-methylbenzoyl) -thiophene and 3-methyl-2- (3'-methylbenzoyl) -thiophene with a boiling point of 159 up to 162 c / 3 Torr. Gas chromatographic analysis shows a quantitative ratio of 4-methyl-2- (3 ^l -methylbenzoyl) thiophene to 3-methyl-2- (3'-methylbenzoyl) thiophene of 1.6: 1.

509831/0890

- 12 -

Example 3 Preparation of
2- (2'-methyl-4'-metlioxybenzoyl) thiophene

A solution of 4.9 g (0.04 mol) of 3-methylianisole and 5.58 g (θ, θ4 mol) of 2-thenoyl chloride in 30 ml of sulfurous carbon is added in portions at a temperature of below 5 ° C. at 5 »3 S (O, .O4 mol) aluminum chloride added. The resulting solution is then gradually warmed to room temperature and stirred for 3 hours. The reaction mixture is mixed with 60 ml of ice-cold 5 weight percent hydrochloric acid and then extracted with ethyl acetate. The Athylacetatextrakt is washed with 5g ^e weight percent sodium hydroxide solution and water and dried over sodium sulfate evaporated. The residue is distilled. The pure title compound with a boiling point of 17 to 170.5 C / 2 Torr is obtained as a colorless liquid.

Examples 4 to 9

According to Example 1, the compounds listed in Table II from the starting compounds given in Table II under the reaction conditions also given there manufactured.

509831/0890

Table II

¹ HO ■ ■ Ρ Pt

Exit pre-bindings

^x tJ

• ö ·

X and
his
position

Weight (β) Cl-CO-R

-R

Weight - '■ weight'. (G)

12.5

CH.

.15.5

3.8

7.7

3.8

7.9

2-Br

2.2

CH 3

2.3

"29

2-

CH ₃

-CH.

7.1

CH,

6.8

509831/0890

Table II (continued)

13,, 3 kt i onsb edinpH-inff 20th Reaction _T
tempera
door
( ⁰ C) Realctions
Time
(H) the end
prey
i ^0/0) F. or Kp. Rea 6.0 Solution with
tel and vo
lumen
(ml) ■ 30 40 1 63.9. Kp.
145-146 ° C /
3.5 torr catalyst
and weight
U) 6.0 cs ₂ 30th Reflux JVJ 58.6 Kp.
155.5-156 ⁰ Q /
2. Torr AlCl ₃ CS ₂ η - - - 2 86,, 8 ^F
65-66 ⁰ C AlCl ₃ 3.5 CS ₂ 30th AlCl ₃ 10.4 30th . Il . a 72 _f 3 43-45 ° C 6. ^ O CS ₂ 20th 3 77 h 72-73.5 ° C ■ SnCl ^ ^CS 2 Il ² 74.0 Kp.
153-156 ^O C /
2. Torr SnCl ^ ^CS 2. AlCl ₃

509831/0690

The compounds of the general formula I can be used with or without auxiliaries. Preferably they will be with

as

conventional excipients mixed and / emulsifiable concentrates, wettable powders, dusts, granules or tablets used. Such auxiliaries are "e.g. carriers, Diluents, emulsifiers, wetting agents, adhesives and surface active agents. The carrier material is used for application of the active ingredient on the plants. It can also be a diluent. Solid carriers are e.g. B. clay, kaolin, talc, Diatomaceous earth, silicon dioxide and calcium carbonates Liquid carriers are e.g. B. benzene, alcohol, acetone, xylene, methylnaphthalene, cyclohexanone, dimethylformamide, diethyl sulfoxide, animal and vegetable oils, fatty acids and their esters as well as various surfactants.

The herbicidal compositions of the invention contain about 0.5 to 95 » preferably 2 to 70 percent by weight of the active ingredient and about 99 »5 to 5» preferably 98 to 30 percent by weight, one or more auxiliaries. ·

The amount of a compound of the general formula I that must be used to prevent the growth of weeds, is different and depends e.g. B. on the local conditions, the type of preparation and the method of application, the prevailing weather conditions and the active ingredient used. Because of these numerous factors, it is difficult to specify a certain preferred or even suitable amount for all situations. However, the average specialist

L '-I

509 831/0890.

Given these factors, it is easy to determine the appropriate amount for the situation at hand. Usually amounts to the amount 2 to 100 g, preferably 5 to 70 g / are.

Example A.

Sea sand is now filled deep into petri dishes about 5. 20 seeds Chicken millet (Echinochloa crusgalli BEATJV), 50 pinger grass seeds (Digitaris adscendes HENR), 20 alfalfa seeds (Medicago sativa

fruits belonging to weeds, L.) as the legume seeds / 15 beet seeds (Brassica rapa LINN) as the cruciferous weeds and 20 tomato seeds (Lycopersium esculenta MTLL) as nightshade weeds are sown in a Petri dish Poured 10 ml of the liquid preparations, which are formulated so that the concentration of the active ingredient is 500 and 100 ppm, respectively.

The petri dishes are kept in an artificial climatic chamber for 14 days kept under light and temperature conditions that change every 12 hours. The Petri dishes are set at 8000 Lux artificially exposed. For the daytime the temperature is kept at 25 C. During the nighttime there is no exposure, and the temperature is set at 20C. The herbicidal effect is then measured. The results are in the table III summarized. "

The growth retardation is indicated with the following numbers:

509831/0890

5r more than 80 ° / o (number of plants killed)

ki more than 60. ⁰ Yes to 80 ⁰ Jo

3: more than 40 ° to 60 ° fl / o

2: more than $ 20 and up to 40 ° / o

1: not more than 20 ° / o

O: O ° ß> (the plant growth is the same as in untreated beds),

509831/0890

- 18 Table III

Ver
binding
No. Conc
tration
(ppm) Herbicidal effect Chicken
millet finger
grass alfalfa turnip tomato 1 100
500 4th
5 4th
5 5
5 4th
5 5
5 2 100
500 3
4th UiUt 5
5 5
5 UtUi 3 100
500 Ut Ut 5
5 UtUi UtUt 5
5 5 100
500 3
4th 3
5 5
5 3
5 UtUJ 6th 100
500 UtUJ 5
5 5
5 5
5 - 5th
5 8th 100
500 3
4th UtUt 5
5 UtUt 3
3 10 100
500 4th
5 5
5 5
5 UtUl UtUt 11 100
500 3
4th 5
5 5
5 UiUt UtUJ 12th 100
500 4th
4th UlUi 5
5 5
5 4th
5 14th 100
500 4th
5 UtUt UtUt UtUt 5
5 15th 100
500 4th
5 5
5 5
5 UtUi UJUJ 16 100
500 4th
5 5
5 5
5 4th
5 3
5 17th 100
500 3
5 - 5
5 5
5 UlUl UJUJ 20th 100
500 UiUt 5
5 5
5 5
5 3
3 23 100
500 3
4th UtUt UiUi UJUJ UJUJ

509831/0890

Table III - continued

Ver
binding
No. Conc
tration
(ppm) Herbicidal effect Chicken
millet finger
grass alfalfa turnip tomato 27 100
500 4th
5 UtUt 5
5 5.
5 UiUt 28 100
500 5
5 UlUt 5
5 4th
5 4th
5 29 100
500 4th
5 UtUt 5
5 3
4th 3
3 30th 100
500 4th
5 UtUt 5
5 4th
5 3
4th 3h 100
500 4th
5 5
5 UtUi 3
4th 3
4th 38 100
500 3
5 UUt, UlUt 3
5 3
5

50983 1/0890

Example B rice field: flood treatment before the weeds emerge

A certain amount of soil from a rice field is put into small vessels with the dimensions 11 χ 6 era, and that for one Usual rice field conditions are set. In every vessel will be a certain amount of millet seeds at a depth of 2 cm sown and young rice plants in the 2 to 2.5-leaved Planted stage. The water level in all vessels is adjusted to a depth of 3 cm. In every vessel a liquid, about 50 g / are of the compound according to the invention containing herbicide given, 30 days after the herbicidal Effect measured. The experiment is carried out in a greenhouse at 18 to 27 ° C. The results are shown in Table IV.

Table IV

link
No. dose Chicken
millet broad-leaved
Weeds ⁺ ) Damage to the
Rice plant 12th 50 4th 5 O 13th 50 4th 5 O 14th 50 4th 5 0 15th 50 5 5 0 16 50 4th 5 O 17th 50 5 5 O 19th 50 5 4th 0 21 50 5 5 · O 22nd 50 ■ 3 4th 0

50983 1/0890

Table IV - continued

link
No. dose Chicken
millet broad-leaved
Weeds ⁺ ) Damage to the
Rice plant 23 50 5 5 0 24 50 3 5 p 25th 50 5 5 0 28 50 5 5 0 34 50 3 4th 0 35. 50 3 5 0 40 50 3 5 0 41 50 3 5 0 42 50 4th 5 0

⁺ ) Broad-leaved weeds: Monochoria vaginalis PRESL Lindernia procumbens PHILCOX Rotala indica KOEHNE and Elatine triandra SCHK.

5 0 9 8 31/0890

Examples
Treating the soil before the weeds emerge

A certain amount of soil is placed in a small pot with a diameter of 9 cm and a height of 12 cm. At a depth of 1 cm, a certain amount of seeds of the fingergrass (Digitaris adscendes HENR) and the bluish Amarants (Amaranthus lividis L.) sown. ' A liquid herbicide containing the compound of the invention is thus applied sprayed the surface of the earth in the pot that the amount of active ingredient is 50 g / are. After that, the pot is placed in a greenhouse brought to a temperature of 18 to 27 ° C. 30 days then the herbicidal effect is measured. The results are shown in Table V.

Table V

link UOSXS Herbicidal effect bluish amaranth No. 50g / Ar Pingergrass 5 3 50g / " 5 5 12th 50g / " 5 5 15th 50g / » 5 5 16 50g / » 5 5 19th 50g / " 5 5 21 50g / " 3 5 22nd 50g / ' 3.5 5 28 3.5

50 9831/0 89 0

Γ "1

- 23 -

Example D

A dust of the following composition is made:

Compound No. 3 10 parts by weight

Tallcum k5 "

Tone 45 "

These substances become a biologically active dust mixed, which is sprayed to destroy the weeds in the field,

Example E.

A wettable powder of the following composition is prepared :

Compound No. 9 55 parts by weight

Kaolin 37 "Sodium Alkylbenzenesulfonate 3" Sodium Lignosulfonate '5 "' ·

These substances are mixed and finely ground. Before use the wettable powder is suspended in water. The suspension obtained is sprayed onto the weeds to be destroyed.

50983 1/0890 ', V-

Example F An emulsifiable concentrate is prepared as follows:

12 parts of compound no. 12 are dissolved in 63 parts of xylene. 17 parts of the condensation product of an alkylphenol and Ethylene oxide are dissolved in the resulting solution. An emulsifiable concentrate is obtained. Before the application, the emulsifiable concentrate diluted with water.

Example G A granulate of the following composition is prepared:

Compound No. 15 3 parts by weight

Diatomaceous earth 35 "

Bentonite 23 "

Talc 37 "

Disintegrator 2 "

These substances are mixed uniformly and with 18 parts Water added. The mixture is mixed again, whereby it becomes uniformly moist and then granulated in a granulating machine.

Example H

A wettable powder of the following composition is prepared:

509831/0 89 0

Connection no. 17 30 weight parts

water-containing silica powder kO "clay 20»

These substances are mixed and added with 10 parts of the mixture from sodium laurylate and sodium dinaphthyl methanesulfate added. The mixture obtained is mixed and ground again. A wettable powder is obtained.

509831/0 89 0

Claims (3)

Claim e (Ij herbicidal agents, consisting of 99.5 to 5 percent by weight of an excipient and 0.5 to 95 percent by weight of one or more compounds of the general formula I C-R (I) in which X is a hydrogen or a halogen atom or a represents
lower alkyl radical / and JR either a benzyl group or a phenyl group of the general formula ^R l in which R _{1 represents} a hydrogen or halogen atom, a lower alkyl or alkoxy radical and R_ represents a hydrogen atom or a lower alkyl radical, or a thienyl group of the general formula \ jr represents, in which R »means a lower alkyl radical. 2. Herbicidal agents according to claim!, Containing as active ingredient a compound of the general formula I-a 509831/0890 (i-a) in which X _{1 is} a hydrogen or bromine atom, a methyl or ethyl group, R. is a hydrogen or bromine atom, a methyl or methoxy group and R "is a hydrogen atom or .sine methyl group. 3. Use of the compounds of general formula I as herbicides, 509831/0890