CS270430B2 - Herbicide - Google Patents

Abstract

2-Imidazolinyl-substd. thieno- and furo-pyridine derivs. (Ia) and (Ib), their pyridine N-oxides (when W is O or S and A is COOR3), their optical isomers (when R1 and R2 are different), and acid addn salts (when R3 is other than a salt-forming cation) are new. (One of X' and X'' being a direct bond and the other X, and broken lines indicating optional bonds; R1=1-4C alkyl; R2=1-4C alkyl or 3-6C cycloalkyl; or R1+R2=opt. methyl-substd. 3-6C cycloalkyl; A=COOR3, CHO, CH2OH, COCH2OH, CONHCH2CH2OH, CONHOH or a gp. of the formula (Ic) R3=H; 1-12C alkyl opt interrupted and/or substd. halogen OH, 3-6C cycloalkyl, benzyloxy, furyl, phenyl, furfuryl, halophenyl, (lower alkyl)phenyl, (lower alkoxy)phenyl, niteophenyl, COOH, lower alkoxycarbonyl, or, 1-4C alkylthio or tri(lower alkyl) ammonio) 3-6C alkenyl opt. monosubstd. disubstd.; 3-6C cycloalkyl opt. mono- or disubstd.; 3-10C alkynyl opt. substd. or an alkali metal, Ca, Ba, Mn, Cu, Fe, ammonium or organic ammonium cation; RC, RD=H or CH3; B=H, COR4 or SO2R5, provided that when B is other than H and A is COOR3, then R3 is other than H or a salt -forming cation; R4=1-11C alkyl, chloromethyl, or phenyl opt. substd. by Cl, NO2, CH3 or OCH3; R5=1-5C alkyl, or phenyl opt. substd. by CH3, Cl or NO2; W=O or S; X=O, S or (when ---- is a single bond) SO; Y,Y',Z,Z'=H; halogen; 1-6C alkyl; 1-4C hydroxyalkyl; 1-6C alkoxy; 1-6C acyloxy; benzoyloxy opt. mono- or disubstd.; 1-4C alkylthio; phenoxy; 1-4C haloalkyl; 1-4C haloalkoxy; NO2;CN; 1-4C alkylamino; 1-4C dialkylamino-1-4C alkylsulphonyl; phenyl mono- or disubstd. by 1-4C alkyl, 1-4C alkoxy and/or halogen; Y and Z being identical when they represent H, halogen; alkyl or alkoxy; and Y and Y' and/or Z and Z' only identical when H or alkyl; or Y+Z = -(CH2)3, -(CH2)4-, or -CL=CM-CQ=CR7-; L, M, Q, R7=H, halogen, NO2, 1-4C alkyl, 1-4C alkoxy, phenyl or phenoxy, only one of L, M, Q and R7 other than H, halogen, 1-4C alkyl or 1-4C alkoxy).

Description

The present invention relates to a novel herbidide composition for controlling annual and perennial weeds in soybean and certain flax crops.

Some substituted pyridines and quinolin-2-imidazolin-2-yl acids, esters and salts with herbicidal properties are known.

The present invention is characterized in that the herbicidal composition comprises, as the active substance, a substituted Ihieno- and furoimldazopyrrolopyrldinedione compound of the formula I

where X and Y is an oxygen, sulfur or -CH- group and the condition that each one of X and Y represents a -CH- group ·

These compounds have unexpectedly been found to be potent herbicides · This new group of herbicides is highly effective in pre-emergence or post-emergence treatment · Individual members of this group show unusual selectivity in soy and cereals such as wheat, barley, rice, vein and oats · Some the compounds of this group show unexpected effects of regulating plant growth, such as lowering plant height, anti-lodging, and increasing plant (cereal) tillering ·

The novel thieno- and furoimidazopyrrolopyridinediones of the invention can be conveniently prepared, for example, from acids of the general formula:

CH ₃ -CH-CH ₃

Wherein each substituent is as defined above, with one equivalent of dicyclohexylcarbodiimide in an inert solvent such as methylene chloride, according to the above reaction scheme.

The thieno- and furoimidazopyrrolopyridinediones of the present invention are particularly effective herbicidal compositions useful for controlling a particularly wide range of herbaceous and woody monocotyledonous and dicotyledonous plants. In addition, these compounds are herbicidally effective for controlling weeds growing in both dry and wet locations. They are also useful as aqueous herbicides. They are unique in their effectiveness in controlling the above-mentioned plants when applied to their leaves or in soil or water containing seeds or other reproductive organs of such plants, such as tubers, roots or processes, in amounts ranging from about 16 kg / ha to about 4.0 kg / ha, and preferably in amounts from 0.032 kg / ha to 2.0 kg / ha.

Use in quantities above 4.0 kg / ha It is possible to effectively destroy unwanted plants; however, amounts greater than the amount of undesirable plant need to be used, since unnecessary overpricing occurs and excess herbicides have no useful environmental function.

Plants that can be regulated by the compounds of this invention include tristra (Peat trlandra); arrowhead (Sagittaria pygmaea); Scirpus hotarul; Flatsedge (Cypress serotinus); Eclipta alba; Cyperus dlíformls; Rotala indica; Tawny Owl (Lindemla pyrldoria); Schinoehloa crus-galli; Common Dew (Digltaria sanguinalls); Green grass (Setaria vlridis); Common Flatsedge (Cyperus rotundus); Field Bindweed (Convolvulus arvensis); Agropyron repens; Durman (Datura stramonium); foxtail (Alopecurus myosuroides); flea (ipomoea spp ·); Sida spin axis; ragweed (Ambrosia artemlsilfolla); water hyacinth (Elchhornia crasslpes); Xanthium pensylvanlcum; Ses bani and exaltata; deaf oats (Avena fatua); Abutilon theophrastl Theophrast; roof brome (Bromu tectorum); Sorghum halepense; Ryegrass (Lollum spp ·); millet (Panicum dlchotomlflorum); camomile (Marrlcaria spp.); Amaranthus re trolle x ue; thistle seed (Clrslum arvense); and Japanese Sorrel (Rumex Japonicus) ·

Said thieno- and furoimidazopyrrolopyridinediones of the invention may be prepared, for example, in the form of wettable powders, liquid concentrates, emulsifiable concentrates, granular mixtures and the like.

Wettable powders may be prepared by co-grinding 20% to 45% by weight of a fine carrier such as kaolin, bentonite, diatomaceous earth, attapulglt or the like, 45% to 80% by weight of the active compound, 2 to 5% by weight of a dispersant such as sodium lignosulfonate and % to 5% by weight of a nonionic surfactant such as octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol or the like.

A typical liquefying liquid may be prepared by mixing about 40% by weight of the active ingredient with about 2% by weight of a gelling agent such as bentonite, 3% by weight of a dispersing agent such as sodium lignosulfonate, 1% by weight polyethylene glycol and 54% by weight water.

Typical emulsifiable concentrates may be prepared by dissolving about 5 to 25% by weight of the active ingredient in about 65 to 90% by weight of 14-methylpyrrolidone, isophorone, butylcellosolv, methyl acetate or the like and dispersing the mixture in about 5 to 10% by weight nonionic surfactant such as is an alkylphenoxypolyethoxy alcohol · This concentrate is dispersed in water for liquid spray applications.

When the compounds of the invention are to be used as soil herbicides, the compounds can be prepared and applied as granular products. The preparation of the granular products can be carried out by dissolving the active compound in a solvent such as methylene chloride, N-methyl pyrrolldone or the like and spraying the thus prepared solution onto the granular carrier such as corn residues, sand, attapulglt, kaolin or the like.

CS 27o43o B2

The granular product thus prepared usually contains from about 3% to about 20% by weight of the active ingredient and from about 97% to about 75% by weight of the particulate carrier.

In order to facilitate further understanding of the present invention, the following examples are presented, in particular to illustrate certain more specific details of the present invention. The invention is not limited thereto and is limited only by the definition of the subject matter of the invention.

Example 1

Preparation of 2-isopropyl-2-mothyl-5H-imidazo [1 ^# »* 2: 1,2] pyrrolo [3,4-b] thieno [3,2-e] -pyridln-3 (2H)

Of 5-dione

Dicyclohexylcarbodilmld (1.0 g · ο, οοδ mol) in methylene chloride (20 ml) was added dropwise to a stirred methylene chloride (30 ml) suspension of 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolinyl) thieno [2,3 b] -pyridine-3-carboxylic acid (1.5 g, 0 · 47 mol) under nitrogen · After stirring the reaction mixture for 16 hours, the mixture was purified by filtration »concentrated to dryness and the resulting material purified by column chromatography on Silica gel eluting with acetonitrile / methylene chloride (1: 2) · The solid product was crystallized from toluene »to give pure

3,5-dione as white crystals, m.p. 214.5-216.5 ° C *

Example 2

Preparation of 2-Isopropyl-2-methyl-5H-imidazo- [2 ', 2 * 1,2] -pyrrolo [3,4b] furo [2,3e] -pyridin-3 (2H), 5 -dibnu

CS 27o43o В2

- = О

- ₃ ) ₂

СН ₃ acetic anhydride dimethoxy ethane pyridine

сн ₃

To a suspension of 6- (4-isopropyl) -4-methyl-5-oxo-2-imidazolin-2-yl) furo [2,3-b] pyridine-5-carboxylic acid (11.7 g, o, o39 mol) ) in loo ml of DME, to 7.3 ml of acetic anhydride and 3.9 ml of pyridine. After stirring at room temperature for 24 hours, the solid is filtered off and washed with ether and the mother liquor and concentrated by addition of xylene to The residue was triturated with ether to give a solid which was combined with the first yield to give 11.1 g (loo%) of the product. Recrystallization from ethyl acetate / hexane 2: 1 gives an analytical sample, melting point 193 to 25 ° C *

Post-emergence herbicidal evaluation of test compounds

The post-emergence herbicidal activity of the compounds of the invention is demonstrated by the following tests in which various monocotyledons and dicotyledons are treated with test compounds dispersed in aqueous acetone mixtures.

In these tests, plant seedlings are grown in pots for approximately 2 weeks. * Test compounds are dispersed in acetone / water mixtures at a ratio of 5o: 5o containing 0.5% TWEEN 2o, which is a polyethylene sorbitan monolaurate surfactant from Atlas Chemical Industries in sufficient amounts to provide an equivalent of about 16-16 kg / ha for the active compound when applied to these plants by spraying at a pH of 274 kPa for a predetermined period of time * After spraying, the plants are placed on greenhouse workbenches and treated in a conventional manner comparable to conventional greenhouse practices *

From 4 to 5 weeks after Jaou treatment, plant seedlings were evaluated and distributed according to the evaluation system shown below * Jaou values obtained are recorded in the following Table I.

CS 27o43o B2

Evaluation system of% difference in growth compared to control

O - no effect

- possible effect 1 - lo

- weak effect 11 -25

- slight effect 26 -4o

- Some damage 41 -6o

- herbicidal effect61-75

- good herbicidal effect 76 -9o

- almost total destruction 91 -99

- complete destruction

- abnormal growth, ie some physiological malformation, but with an overall effect of less than grade 5 on the evaluation scale.

In most cases, the data are for Individual Tests, but in a few cases they are average values obtained from more than One Test ·

Used plant species

Hedgehog corns leg green green oat round oat deaf pupil morning glory peasant rape pensylvanian lamb purple ambrosia pelletsColly opaque Theophrast's barley corn maize sown rice soya sunflower annual wheat

Bchinochloa crusgalli Setaria vlridis (Cyperus rotundus L), Avena íatua

Agropyron repens Convolvulus arvensis L. Xanthlum pensylvanicum Ipomoea purpure and Ambrosia artemlsilíolla Abutilon theophrastl Horde um vulgare

Zea mays

Oryza suck in a

Glycine max Hellanthus annus - Triticum aestivum

CS 27o43o B2

Table 1

Post-emergence tests - doses in kg / ha

Compound:

2-Isopropyl-2-methyl-5H-imidazo [1,2 * 2: 1,2] pyrrolo [3,4-b] thieno [3,2-e] pyridin-3 (2H), 5-dione

dose It's Scarf bér šáchor oat Ž & k morning glory chamomile povíjnice Ι, οοο 9.0 7.0 8, o 9 * o 8.0 9.o 3.0 4.o o, 5oo 9, o 4.0 8 * o 9 * o 8.0 9.0 l.o 2, o o, 25o 8, o 4.0 7.o 6.0 9.0 9.0 0.0 0.0 o, 125 9.0 2 * o 4.0 2 * 0 8.0 7.0 0.0 0.0 o, o63 * 7.0 1.0 2.0 1 * 0 8 * o 0.0 0.0 o, o32 2 * o 0 * 0 0.0 0.0 6 * 0 4.0 0.0 0.0 dose ambrosia mraČňák Barley maize cotton rice sdja wheat Ι, οοο 9, o 9.0 9.o 9.0 to 2,0 2,0 o, 5oo 9.o 7 * o 9 * 0 9.0 8.0 l.ó 2,0 o, 25o 9.0 3.o 9.0 6.0 6.0 l.o l.o 0.125 4.0 l.o 9.0 6.0 6.0 l.o 0.0 o, o63 l.o l.o 9.0 3.0 4.o 0.0 0.0 o, o32 0.0 0.0 6.0 2.0 2,0 0.0 0.0

Evaluation of pre-emergence herbicidal activity of test compounds

The pre-emergence herbicidal activity of the compounds of this invention is tested by the following tests (tests) in which the seeds of various monocotyledonous and dicotyledonous plants are spaced apart with horticultural soil and grown to a layer of approximately 2.5 cm thick soil in spaced trays.

After sowing, the dishes are sprayed with selected aqueous acetone solutions containing the test compounds in sufficient quantity to provide an approximate dose of about 0.1-6 kg test compound per hectare for each dish. The treated dishes are then placed on greenhouse worktops, watered and treated with conventional greenhouse procedures.

After 4 to 5 weeks after treatment, the tests are terminated and each milk is evaluated according to the evaluation system described above. more than One test for a given compound * Are dd ^ J · averaged ·

CS 27o43o B2

Table II

Pre-emergence tests - doses in kg / ha

Compound:

2-Isopropyl-2-methyl-5H-imidazole [1 * 2 *: 1,2] pyrrolo [3,4-b] thieno [3,2-e] pyridin-3 (2H), 5-dione

dose Ježatka bér šáchor oat žlftk morning glory chamomile povíjnlce o, 5oo 9, o 9.0 9, o 9, o 9.0 9.0 9, o 6.0 o, 25o 9, o 6.0 9, o 9, o 9.0 9.0 9, o 4, o o, 125 9, o 7.0 9.0 8.0 9.0 9.0 9.0 4, o o, o63 3, o 2, o 8, o 7.0 9.0 9.0 6.0 1.0 o, o32 0.0 0.0 8, o 3, o 4, o 9.0 3, o 0.0 o, ol6 0.0 0.0 6.0 l.o 0.0 7.0 1.0 0.0 dose ambrosia cloud Barley maize cotton rice sdja wheat o, 5oo 9, o 8, o 9 * o 9, o 9.0 9.0 4.0 7.0 o, 25o 9.0 7, o 8, o 9, o 8, o 7.0 3, o 2, o 0.125 7, o 5, o 8, o 9, o 8, o 6.0 l.o 2, o o, o63 7.0 3.0 7.0 6.0 6.0 4, o l.o 2,0 o, o32 0.0 2, o 5, o 4.0 4.0 2, o l.o l, o o, ol6 0.0 0.0 3, o 2,0 2.0 1.0 1.0 0.0

Table Ш

Prw emergence tests - doses in kg / ha

Compound:

2-Isopropyl-2-methyl-5H-imidazo [1 *, 2 * 1,2] pyrrolo [3,4-b] thieno [3,2-e] pyridin-3 (2H), 5-dione

CL 269135 l o, 5oo o, 25o 0.125 o, o63 o, o32 0.016 It's a scarf 9, o 9.0 9.0 3.0 0.0 0.0 sveřep 9, o 9.0 8, o 3.0 0.0 rosička 9, o 9.P 6.0 6.0 4, o 2, o 0.0 bér 9.0 8, o 7.0 2, o 0.0 0.0 šáchor 9.0 9.0 9.0 8.0 8.0 6.0 oat deaf 9, o 8.5 8, o 7.5 5.5 2.5 0.5 žňk 9, o 9, ° 8.5 9.0 7.5 3.5 0.0 morning glory 9, o 9.0 9.0 9.0 8.5 9.0 6.0 chamomile 9, o 9.0 8.5 7.5 3.5 1.5 o, 5 povíjnlce 8, o 6.5 5.5 5.0 2, o 0.5 0.0 mustard (wild) 9, o 8.0 8, o 8, o 7.0 6.0 6.0

CS 27o43o B2

Continuation tables lil number l o, 5oo o, 25o o, 125 o, o63 o, o32 o, ol6 CL 269135 ambrosia 9, o 8.5 8.5 7.0 5.5 l.o 0.0 mračflák 9.0 8, o 7.5 6.0 4,5 3.5 0.0 Barley bar bush 9, o 9, o ’9.0 9.0 5.0 0.0 Maury barley 9, o 9.0 8.0 8, o 7.0 5.0 3.0 diabetes 9, o 9.0 9, o 9.0 8, o 7.0 maize 9, o 8.5 9.0 9, o 7.0 3.5 l.o cotton 9.0 8.0 8, o 6.0 4, o 2, o rice 9, o 7.0 6.0 4, o 2 »o l.o soya Bragg 4.0 3, o l, o Uo l.o l.o soya WlUiams 6.0 2.0 2.0 1.0 1.0 0.0 sunflower 9.0 8, o 9, o 7.0 7, o 7.0 wheat Era (spring) 7, o 7, o 3.5 2.5 1.0 o, 5 0.0 spring wheat (Anza) 9, o 7.0 5, o 4, o 3, o 2, o l.o winter wheat (Nuga i) 9.0 7.0 6.0 5, o 3, o 3, o 0.0

Table IV

Pre-emergence rates - kg / ha

Compound:

2-Isopropyl-2-methyl-5H-furo [2,3-b] imidazo [2 * 1, 5,1] pyrrolo [3,4-e] pyrimidin-3 (2H), 5-dione

Cb 260057 l o, 5oo o, 25o Otl25 o, o63 Oto32 OtO16 hedgehog 9.0 5, o 6.0 2, o 0.0 0.0 bér 9, o 9, o 6.0 4.0 1.0 0.0 šáchor 9.0 9.0 9.0 9.0 6.0 7.0 oat deaf 9, o 7.0 6.0 2, o 0.0 0.0 žňk 9, o β, ο 9.0 3, o l.o 0.0 morning glory 9, o 9.0 9, o 9.0 8.0 chamomile 9.0 5, o l, o 0.0 0.0 0.0 povíjnice 9, o 9.0 9, o 2.0 1.0 0.0 ambrosia 8 _t o 7.0 7, o 2.0 l.o 0.0 diabetes 9, o 9, o 9, o 6.0 9.0 9.0 maize 9.0 9, o 8, o 6.0 2,0 2, o cotton 9.0 9.0 9, o 5.0 6.0 2, o rice 9, o 8.0 7.0 4.0 4, o 2, o soya Bragg 6.0 3, o 2, o 2, o l.o l.o Williams 6.0 4, o 3, o 3, o 2, o l.o

CS 27o43o B2

Continuation of Table IV

CL 28oo57 o, 5oo o, 25o 0.125 o, o63 o, o32 o, ol6 sunflower 9, o 9, o 9.0 7, o 5.0 2, o Wheat Spring 7.0 3 _t o 2.0 l.o 0.0 0.0

Table V

Post-emergence tests - doses in kg / ha

Compound i

2-Isopropyl-2-methyl-5H-imidazo [1 * 2 * 1,2] pyrrolo [3,4-b] thieno [3,2-a] pyridin-3 (2H), 5-dione

Number

CL 269135 Hedgehog barch oats deaf pupil bindweed chamomile povQnice ambrosia meerpea corn sugar cotton rice soy Bragg soybean WiUiams sunflower wheat Spring ltooo

01250

01125

9, o 9.0 β, ο 9, o 7.0 2,0 7.0 4.0 4.0 2,0 1.0 0.0 8.0 8.0 7.0 4, o 2,0 0.0 9, o 9, o 6.0 2, o 1.0 0.0 8, o 8, o 9.0 8, o 8.0 6.0 9, o 9, o 9.0 7.0 4.0 3, o l.o 0.0 0.0 0.0 0.0 4.0 2.0 0.0 0.0 0.0 0.0 9, o 9.0 9.0 4.0 l.o 0.0 9.0 7.0 3.0 l.o l.o 0.0 9.0 9.0 9.0 9, o 7, o 4.0 9.0 9.0 9.o 9, o 9, o 6.0 9.0 9.0 6.0 6.0 3, o 2,0 8.0 8.0 6.0 6.0 4, o 2,0 2,0 1.0 l.o l.o 0.0 0.0 l.o 1.0 0.0 0.0 0.0 0.0 9, o 9.0 9.0 9.o 9.0 9.0 2,0 2, o 1.0 0.0 0.0 0.0

Table VI

Post-emergence tests - doses in kg / ha

Compound:

2-isopropyl-2-methyl-5H-imidazo [2 ', 2 l 2 _t] pyrrolo [3 _f 4-b] furo [2,3-e] pyridin-3 (2H), 5-dione number

CL 28oo57

1,000

o, 25o

Ježatka 9, o 8.0 8, o 8.0 2, o 0.0 bér 9.0 8, o 8, o 9, o 6.0 4.o Šáchor 6.0 7, o 2,0 2, o 0.0 * 0,0

lo

CS 27o43o B2

Continuation of Table VI

CL 28oo57 Ι, οοο o, 5oo o, 25o 0.125 o «o63 o, o32 oat deaf 9.0 9, o 9, o 7.0 2.0 0.0 live & to 9, o 6.0 2, o 0.0 0.0 0.0 morning glory 9, o 8, o 9.0 7.0 4.o 0.0 chamomile 6.0 2,0 0.0 0.0 0.0 0.0 povíjnice 9, o 9.0 6.0 2,0 0.0 0.0 ambrosia 9, o 7, o 4.0 4, o 0.0 0.0 mračfták 8, o 7.0 4.0 0.0 0.0 diabetes 9.0 9.0 9.0 9, o 7.0 5.0 - maize 9.0 9.0 9.o 9, o 9.0 6.0 я cotton 9, o 9.o 9.0 7.o 7.0 4, o rice 8, o 8, o 9.0 7.0 5.0 4.o soya Bragg 2, o 2, o l.o 0.0 0.0 0.0 Williams 3, o 2, o 1.0 l, o 1.0 0.0 sunflower 9, o 9, o 9, o 7.0 3.0 wheat spring 9.0 9.0 3, o 2, o 2,0 0.0

Table VII

Pre-sowing tests - doses in kg / ha

Compound:

2-Isopropyl-2-methyl-5H-imidazo [1,2 *: 1,2] pyrrolo [3,4-b] thieno [3,2-e] pyrimidine-3 (2H) .5-dione

Number 2 _t ooo Ι, οοο o, Soo o, 25o o, 125 о, об

CL 269135

rosička 9, o 8.5 8.5 6.5 5, o 4.0 tesknice 9.0 9.0 9.0 8.5 8.0 7.0 bér 9, o 9.0 8.0 7.5 4.5 1.0 oat deaf 9.0 9.0 9.0 8.5 7.5 2.5 mustard 9.0 8.5 9.0 9.0 8, o 4,5 spring barley 9, o 9.0 8.5 9.0 6.0 2,0 winter barley 8.5 9.0 8.5 7.5 5, o 2.5 wheat spring ERA 7.5 5.5 3.5 2.5 2, o l.o wheat Spring ANZA 7.0 6.0 4.5 4,5 2.5 o, 5 winter wheat NUGA I 8, o 6.5 5, o 3.5 3.5 2.5

CS 27o43o B2

Claims (1)

A herbicidal composition characterized in that it contains a compound of the formula I as active ingredient. (I) where Y а X is oxygen, sulfur, or -CH- with the proviso that always One of the symbols Y а X is -CH- ·