NL8301659A - NEW HERBICIDE COMPOUNDS AND PREPARATIONS CONTAINING THEM. - Google Patents

Description

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New herbicidal compounds and preparations containing them.

This invention relates to new compounds, and more particularly compounds of formula 1 or formula 2, wherein R is lower alkyl, n may be 0 or 1 and m are 0 to 6.

The preferred compounds are those of formula 1.

These compounds unexpectedly prove to be useful as herbicides.

By "lower alkyl" here is meant straight chained or branched alkyl groups with up to 6 carbon atoms.

The compounds of the invention can be prepared by reacting a dimer of an isocyanate of formula 3 or formula 4 with double the amount (calculated as mill) of an amine of formula 5. This reaction can be carried out by a mixture of the isocyanate dimer and the amine in an inert medium such as toluene under stirring and heating until the starting materials have dissolved. After this is done, the product can be separated by standard solvent removal techniques and purified with other standard techniques.

The isocyanate dimer of formula 3 can be prepared by reacting a compound of formula 6 or formula 7 with an excess of phosgene. That reaction can be carried out by adding a suspension or solution of the compound of formula 6 or 7 in a suitable solvent such as toluene to a saturated solution of phosgene in a solvent such as toluene. That mixture is then stirred at room temperature for 4 to 24 hours. To remove unreacted phosgene, one can either blow out with nitrogen, then filter when the desired product has precipitated, or evaporate the solution to dryness if the product is soluble. It can be used as 8301659 i i 2, but it can also be subjected to further purification.

The invention is further illustrated by the following examples.

Example I

Preparation of the suspension of 5-t-butylisoxazolyl-3-isocyanate.

80 ml of 12% phosgene in toluene were placed in a glass flask with stirrer. A suspension of 4 g of 5-t-butyl 3-aminoisoxazole in 20 ml of toluene was added and that mixture was stirred for about 16 hours to give a precipitate.

The reaction mixture was purged with nitrogen so that unreacted phosgene disappeared. The blown-out mixture was filtered to give the desired solid solids. Example II

Preparation of 1- (5-t-butylisoxazolyl-3) -3-methyl-1-3- (1,3-dioxolanyl-2-methyl) urea.

In a glass flask equipped with stirrer and thermometer, a mixture of 5-t-butylisoxazolyl-3-iso-cyanate dimer, 4 g of N- (1,3-dioxolanyl-2-methyl) -methyl amine and 100 ml of toluene was added stirring heated until everything had dissolved. After this, the reaction mixture was stripped of solvent and the residue crystallized from ethyl acetate to give the desired product as a solid, mp 130-131 ° C. The elemental analysis was:

25 C Η N

Calculated (%) 55.11 7.47 14.83

Found (% 3 54.36; 54.56 7.47; 7.48 14.45; 14.52

Example III

Preparation of 1- (5-t-butylisoxazolyl-3) -3-methyl-3- (1,3-dioxa-3 CL nyl-2-methyl-1) urea.

In a glass flask equipped with stirrer and thermometer, a mixture of 5 g of 5-t-butylisoxazolyl-3-isocyanate dimer, 4.5 g of N- (1,3-dioxanyl-2-methyl) methylamine and 100 ml of toluene was added. heated with stirring until everything had gone into solution 35. Now 50 ml of hexane was added to precipitate the desired product, this precipitate was separated and 8301659 * 3 was found to have a melting point of 171-173 ° C after drying. The elemental analysis was:

C Η N

Calculated (%) 56.55 7.8 14.13 Found (%) 55.79; 55.96 7.8; 7.94 13.85; 13.96

Examples of compounds within the scope of this invention that can be prepared by the methods of the preceding examples are: 1- (3-t-butylisaxazolyl-5) -3-methyl-1-3- (1,3-dioxolanyl-2-methyl ) -10 urea 1- (3-t-butylisaxazolyl-5) -3-methyl-1-3- (1,3-dioxanyl-2-methyl) -. urea 1- (5-t-butylisoxazoly1-3) -3-methyl-1-3- (4,5-dimethyl-1,3-dioxolany1-2-methyl} urea 15 l- (5-t-butylisaxazolyl-3) - 3-methyl-3- (4,5,6-triethyl-1,3-dioxanyl-2-methyl) urea 1- (3-t-butylisoxazolyl-5) -3-methyl-3- (4-hexy1-1 , 3-dioxol-nyl-2-methyl) urea 1- (3-t-butyl-isoxazol-1-5) -3-methyl-1-3- (5,6-dipenty1-1,3-20-dioxanyl-2-methyl-1) urea 1- (5-t-butylisoxazolyl-3) -3-methyl-3- (4-isopropy1-1,3-dioxolanyl-2-methyl) urea 1- (5-t-butylisoxazolyl-3) -3-methy1 -3- (4,5-dibutyl-1,3-dioxanyl-2-methyl) urea 25 1- (3-t-butylisoxazolyl-5) -3-methyl-1-3- (5-pentyl-1,3-dioxo - lany1-2-methyl) urea 1- (3-t-butylisoxazolyl-5) -3-methyl-3- (4-methyl-5-ethyl-1,3-dioxanyl-2-methyl) urea 1- (5 -t-butylisoxazolyl-3) -3-methyl-3- (4-ethyl-5-propyl-1,3-30 dioxolanyl-2-methyl) urea 1- (5-t-butylisoxazolyl-3) -3-methy1 -3- (4-ethyl-5,6-diisopropy-1,3-dioxanyl-2-methyl) urea 1- (3-t-butylisoxazolyl-5 -) - 3-methyl-3- (4-hexyl-5 -pentyl-1,3-dioxolanyl-2-methyl) urea 830 1 65 9 ♦ 4 l- (3-t-butylisoxazolyl-5) -3-methyl-3- (5-butyl-6-propyl-1, 3-d ioxany1-2-methyl) urea.

For use as herbicides, the compounds of this invention are generally included in formulations containing an effective amount of such a compound and an inert carrier. These herbicidal preparations, also called "formulations", allow the active compound to be easily applied to the weed-infested site in any desired dosage.

These preparations can be solid, such as dusting powders, granules and wettable powders, and they can also be liquids such as solutions, aerosols and emulsifiable concentrates.

For example, dusting powders can be prepared by grinding the active substance together with an inert carrier such as talc, clay, silicate, pyrophyllite, etc. Granular preparations can be prepared by impregnating a granular carrier such as attapulgite or vermiculite, usually with grain sizes of 0.3 to 0.5 mm, with the compound, the latter usually in a suitable solvent. Wettable powders, which can be diluted in water or oil to the desired active ingredient concentration, may be prepared by incorporating humectants in a concentrated dusting powder.

In some cases, the active compounds are sufficiently soluble in common solvents, such as kerosene and xylene, to use them directly as solutions in these liquids. Often solutions of herbicides can be dispersed under increased pressure as aerosols. However, the 8301603 liquid herbicidal compositions are preferably emulsifiable concentrates which contain an active compound of this invention and as an inert carrier a solvent with an emulsifier. Such self-emulsifying concentrates can be diluted to any desired concentration with water and / or oil before spraying. The most commonly used emulsifiers in these concentrates are nonionic or mixtures of nonionic with anionic surfactants. With the aid of some emulsifier systems, an inverted emulsion (water in oil) can be prepared for direct application to present weeds.

A representative herbicidal composition of this invention is illustrated in the following example, in which the parts are parts by weight.

Example IV

15 Preparation of a dusting powder

Product of example H 10

Talcum powder 90

These ingredients are mixed together in a mill and ground into a homogeneous, free-flowing powder of the desired particle size. This dusting powder is suitable for direct application to the weed area.

The compounds of the invention can be used as herbicides in any manner known in this art. A method of controlling weeds consists in that the site where that weed grows is contacted with a composition according to the invention containing as an active ingredient an effective amount of the compound according to the invention. The concentration of the new compounds of the invention in the herbicidal compositions will vary widely with the type of formulation and the intended purpose, but generally the herbicidal compositions will contain from 0.05 to 95% by weight of active substance. Preferably they contain 5 to 75% by weight of active substance. The compositions may also contain other substances such as other pesticides, insecticides, nematocides, fungicides, etc., and further stabilizers, dispersants, inactivators, adhesives, fertilizers, activators, synergists, 830 1 6 5 9 •.

6 "r etc.

The compounds of the invention are also useful in combination with other herbicides and other defoliators, dryers, growth inhibitors and the like of herbicidal compositions previously described. These other substances can make up 5 to 95% of the active substances of the total preparation. Combining these other herbicides and / or defoliators, dehydrators, etc. with the compounds of the invention results in new separate herbicidal compositions.

These other herbicides, defoliators, dehydrators and plant growth inhibitors that can be used in conjunction with the compounds of the invention include chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 4 (2.4-DB), 2.4-DEB, 4-CPB, 4-XPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex, ed, 15 carbamate herbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, ed, thiocarbamate and dithiocarbamate herbicides, such as DCEC, methane sodium, EPTC, diallate, PEBC, perbulate, vernolate, etc., substituted urea herbicides, such as norea , disuron, dichloral urea, chloroxuron, cycluron, fenuron, monuron,.

Monuron TCA, diuronm linuron, molinuron, neburon, buturon, trimeturon, etc., herbicides derived from symmetrical triazine such as simazine, chlorazine, atraon, desmetryne, norazine, ipazine, prometryn, atrazine, trietazine, simeton, prometon, propazine, ametryne, ed chloroacetamide herbicides, such as α-chloro-N, n-dimethylacetamide, CDEA, CDAA, α-chloro-N-iso-propylacetamide, 2-chloro-N-isopropyl-acetanilide, 4- (chloroacetyl) -morpholine, 1 - (chloroacetyl) piperidine, ed, chloro fatty acid, herbicides such as TCA, dalapon, 2,3-dichloro.

propionic acid, 2,2,3-TPA, ed, chlorine-containing benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, fenac, PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy-3,4,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoic acid, etc., and compounds such as aminotriazole, maleic hydrazide, phenyl-35 mercuric acetate, endothal, biuret, technical chlordan, dimethyl-2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, ©

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8301659 9 ·· 7, r dichlorobenil, DPA, diphenamid, dipropalin, trifluoralin, sólan, dicry1, merphos, DMPA, DSMA, MSMA, potassium azide, acrolexes, benefin, bensulide, AMS, bromacil, 2- (3,4-dichlorophenyl) -4-methyl-1,2,4-oxadiazolidine-3,5-dione, bromoxynil, cacodyl acid, 5 DMA, DPMF, cypromid, DCB, DCPA, dichlone, diphenatrile, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocril, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH paraquat, PCP, picloram, DPA, PCA, pyrichlor, seson, terbacil, terbutol, 'TCBA, brominil, CP-50144, H 17.6-1, H-732, M-2091, planavin, sodium tetraborate, calcium cyanamide, DEF, ethylcanthogen disulfide, sindon, sindon-B, propanil and the like.

When using the substances and preparations according to the invention, these herbicides can also be used in the form of salts, esters, amides and other derivatives, if so appropriate.

Weeds are unwanted plants that grow in places where they are not wanted, have no economic value and interfere with the production of useful crops or ornamentals or interfere with the welfare of livestock. 20 Many types of weeds are known, including annuals such as goose feet , foxtail, millet, wild mustard, field cherry, ryegrass, ot, peach leafwort, purslane, cepa, knotweed, bollard, buckwheat, kochia, mugwort, milk thistle, coffee plague, croton, cuphea, ragwort, cinquefoil, hemp nettle, hemp nettle , wild rice, fountain - herb, fennel, day blooms, woodruff, duckweed and nymph herbs, biennials such as wild carrot, feverfew, wild millet, cuckoo flower, chamomile, burdock, torch and mothwort, round-leaved mallow, thistle, dog's tongue and spear thistle, and perennials such as perennial ryegrass, cultivation, alpe pye millet, field thistle, bindweed and bindweed, Bermuda grass, sheep sorrel and curled sorrel, pearl grass, bird wall , dandelion, bells, flax snapdragon, yarrow, pearl seed, horsetail, iron-hard, Sesbania, various Russians, loosestrife and winter cherry. It is economical «. Desirable to control the growth of such weeds without damaging useful crops or livestock.

8301659 8

The new compounds of the invention are particularly valuable for weed control because they are toxic to many weed species and groups, but relatively little to many beneficial crops. The exact amount of compound one needs depends on several factors, including the toughness of the type of weeds, the weather, the soil type, the method of application, which useful crops are in the same area, and the like. So while one or two ounces of active substance per hectare can be enough for a sufficient suppression of light weed growth under unfavorable conditions, up to 10 kg / ha or more of active substance may be required in dense growth with tough weeds grow under favorable conditions.

The herbicidal activity of the new compounds can be demonstrated by test methods known in the art, both before and after weed emergence.

The herbicidal action of the compounds. according to this invention, tests with a variety of weeds that had not yet occurred. In these tests, small dry soil plastic pots were seeded with various weeds. 24 hours or less after sowing, the jars were sprayed with water until the soil was wet and the test substances, formulated as aqueous emulsions or acetone solutions containing emulsifiers, at the indicated dosages over the surface of sprayed the ground. The pots were then placed in greenhouses and kept at the desired temperature and watered once or several times a day. The plants were kept under these conditions for 14 to 21 days, after which their growth was noted in the form of a digit, as follows: 0 = no damage, 1 and 2 = light damage, 3 and 4 = »moderate damage, 5 and 6 = moderate to heavy damage, 7, 8 and 9 progressively worse damage, and 10 = dead. The effect of these substances can be seen from the following figures: 35 8301659

Herbicide action on plants that have not yet emerged

Product of, example II

14 days after treatment (NB * not determined) 9 5 kg / ha 1.1 0.55 0.28 0.24

Wild mustard 10 10 10 5

Bindweed 8 5 5 4

Goosefoot 8 000 10 Abutilon 8 000

Day flower 10 10 8 8

Needle needle 7 330

Cinnabar 9,000

Aleppo millet 8 878 15 Breeding 3 10 0

Note 7 4 3 0

Cynodon 9 988

Short stem 9 985

Dravik 0 000 20 Sugar beet 10 0 10 10

Soy bean 7 3 2 2

Cotton NB 0 0 0

Pinto bean 0 000

Lucerne 10 10 10 5 25 Wheat 5 0 0 0

Rice 10 877

Millet 8 722

Maize 6 5 3 0

Oats 5 7 0 0 30 8301659 - ia -

Herbicide action on plants that have not yet emerged

Product of example II

21 days after treatment 5 kg / ha 1.1 0.55 0.28 0.14

Wild mustard 10 3 10 7

Ide 10 0 0 0

Goose foot 10 10 10 0

Abutilon 10 2 9 1 10 Day flower 10 10 10 7

Needle needle 10 0 0 0

Cinnabar 10 0 0 0

Aleppo millet 98 53

Culture 5 8 0 0 15 Note 10 10 80 Cynodon 10 10 8 0

Short stem 10 10 9 0

Dravik 88 10

Sugar beet 10 10 10 10 20 Soybean 10 3 2 0

Cotton NB 0 0 0

Pinto bean 9 10 0 0

Lucerne 10 10 10 0

Wheat 10 10 5 0 25 Rice 10 10 4 2

Millet 88 10

Maize 7 8 0 0

Oats 30 10 1 0 * 8301659

Herbicide action on plants that have not yet emerged

Product of example III

14 days after treatment - π - 5 kg / ha 4.4 2.2 1.1 0.55 0.28 0.14

Yellow sedge 3 1 1 - -

Wild mustard 10 10 10 10 7 2

IDE - ~ 10 10 10 3

Goose foot 6 5 7 10 10 0 * 10 Thorn apple 3 4 2 10 7 6

Abutilon 3 10 10 9 9 1

Day flower 4 4 4 10 8 2

Needle needle 44 210 0

Cinnabar 10 83 0 0 0 15 Aleppo millet 36 200 0

Grow 3 2 3 0

Note 5 7 7 0 0 0

Cynodon 10 7 5 0 0 0

Short stem - - 9 1 0 0 20 Dravik 3 0 0 8 0 0

Sugar beet - - 10 10 10 10

Soybean - - 3 0 0 0

Cotton - - 10 10 10 9

Pinto bean - - 1 0 0 0 25 Lucerne - - 10 10 10 10

Wheat - - 10 10 0 0

Rice 0 0 0 0

Millet 2 0 0 0

Maize - - 2 0 0 0 3Q Oats - - 7 0 0 0 8 301 659

Herbicide action on plants that have not yet emerged

Product of example III

21 days after treatment - 12 - t »5 kg / ha 4.4 2.2 1.1 0.55 0.28 0.14

Yellow sedge 3 2 2 - - -

Wild mustard 10 10 10 10 10 10

IDE - - 10 10 10 7

Goose foot 7 8 8 10 10 0 10 Thorn apple 10 10 5 10 10 10

Abutilon 10 10 10 10 10 10

Day flower 10 10 10 10 10 10

Needle needle 10 10 10 1 0 0

Cinnabar 10 10 8 1 0 0 15 Aleppo millet 78 7 200

Culture - 10 10 7 0

Note 10 10 10 1 1 0

Cynodon 10 10 10 0 0 0

Short stem - - 10 7 0 0 20 Dravik 10 9 4 9 0 0

Sugar beet - - 10 10 10 10

Soybean - - 10 10 4 1

Cotton - 10 10 10 10

Pinto bean - - 10 8 7 0 25 Lucerne - - 10 10 10 10

Wheat - - 10 10 3 1

Rice - 10 0 0 0

Millet - 10 1 0 0

Corn - - 10 3 0 0 3Q Oats - 10 4 0 0 8 301 659 13

The herbicidal activity of the compounds of this invention has also been demonstrated in tests with weeds already above the ground. In these tests, the test substances were formulated as aqueous emulsions which were sprayed over the leaves of the various weeds at the specified doses after they reached a prescribed height. After watering, the plants were placed in greenhouses and watered one or more times a day. Water was not applied to the leaves of the treated plants. The severity of the damage was determined 14 to 21 days after treatment and noted in the previously indicated scale. The effect of these compounds can be seen from the following data:

Herbicidal action against already standing crop. Product of Example II

15 kg / ha 1.1 0.55 0.28 0.14

Wild mustard 10 10 10 10

Bindweed 10 10 10 10

Goose foot - - 10 10

Thorn apple 10 10 10 10 20 Abutilon 10 10 10 10

Day flower 10 10 10 10

Needle needle 8 95 0

Cinnabar 10 10 0 0

Aleppo millet 10 10 1 0 25 Breeding 10 10 10 0

Note 10 10 10 2

Cynodon 10 8 0 0

Short stem 10 10 10 1

Dravik 10 8 0 0 30 Sugar beet 10 10 10 10

Cotton 10 10 10 10

Soybean 10 10 7 6

Pinto bean 10 10 10 7

Lucerne 10 10 10 10 35 Millet IQ 3 0 0

Wheat 10 10 10 5

Rice 10 10 10 1

Maize 10 7 0 0

Oats 10 10 9 1 8301659 L> r · »14

Herbicidal action against already standing crop. Product of example III

kg / ha 4.4 2.2 1.1 0.55 0.28 0.14 0.07 0.035

Yellow sedge 10 7 8 10 10 10 - - 5 Wild mustard 10 10 10 - - 10 0 0

IDE 10 7 7 10 7 000

Goosefoot 10 10 10 10 10 10

Thorn apple 10 10 10 10 10 10 0 0

Abutilon - - - - - 000 10 Day flower 10 10 10 10 10 10 0 0

Needle needle 7 10 9 10 0 0 - -

Hanepoot 10 10 7 10 10 0 0 0

Aleppo millet 10 8 10 10 0 000

Breeding - - 7 7 0 0 - - 15 Note 10 10 10 1 0 0

Cynodon 10 10 10 5 0 0 - -

Short stem - -10 7 0 0 - -

Dravik - - 3 1 0 0

Sugar beet - - 10 10 10 10 20 Cotton - - 10 30 10 10 - -

Soybeans 10 10 10 9 1 100

Pinto bean - - 10 10 10 0 - -

Lucerne - - 10 10 10 10 - -

Millet - -10 1 0 0 - - 25 Wheat - - 10 10 0 0 - -

Rice - - 0 0 0 0 - -

Corn - -10 1 1 0 - -

Oats - -10 5 0 0 - - 30 8301659

Claims (5)

1. Compounds of formula 1 or 2, wherein R is a lower alkyl group, n is 0 or 1 and m is 0 to 6. 2. Compounds of formula 1 wherein R is an alkyl group of 1 to 6 carbon atoms and n may be 0 or 1 and m 0 to 6. 3. The compound 1- (5-t-butylisoxazolyl- ΙΟ 3) -3-methyl-1-3- (1,3-dioxolanyl-2-methyl) urea. 4. The compound 1- (5-t-butylisoxazolyl-3) -3-methyl-1-3- (1,3-dioxanyl-2-methyl) urea. 5. Herbicidal composition containing an inert carrier and an effective amount of a compound according to any one of the preceding claims as active substance. A method of controlling weeds in which said weed or the place where it grows is contacted with a herbicidal composition according to claim 5. 2Q 8301659 * Γ Η Ο CHj Ο-C Η ι ιι ι / ι CH, \ρ \ I HjC_C-1 ^ ° - \ - C r _ CH3 0 Rm Η HO CH. , 0 —- C ι η ι / I Cu --1 N-C -N CHj — C - H (CH ^ ι J \ \ ι H} CC — 1 ^ 0 0_ \ C 2 CHj Rn, 0 = C = N -] ι 0 = C = N-1 - - | I CH3 NJ — C-CHj? Hj X (T 1 ° v si) - C— CHj CHj I 3 CHj 4 HO-IC 1 / I N - CH4 — C-H / CHs) \ V I e CHj o-V— c 5 R »n 9Η * Π NHa _ Γ-. NHa II CHi 1 HjC— C -1 N ur n I H3C-C-L O CHj g CH * Xn 7 830 1 6 5 9 VELSICOL CHEMICAL CORPORATION, Chicago, Illinois, USA America