DE2017842A1 - New thiadiazole ureas, herbicidal compositions and methods of regulating plant growth - Google Patents

Description

DR.E.WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

Munich Hamburg

phone. 555476 8000 MONCHEN 15, 13 April 197o

TELEGRAMS: KARPATENT, NUSSBAUMSTRASSE 10

W. 14 692/70 - Ko / B

Mobil Oil Corporation New York, N.Y. (V.St.A.)

New thiadiazole ureas, herbicidal masses and method for regulating the flow of plants

Addition to the patent (patent application P 19 oil 672.9)

The invention relates to new thiadiazole ureas, their use as herbicides and a method for regulating or control plant growth with them. In particular, the invention relates to thiadiazole urea herbicides and the control of plant growth, particularly undesirable plants, with them.

The main patent (patent application P 19 oil 672.9) concerns new thiadiazole ureas which are useful herbicides. The present invention provides a modification of the invention of the main patent and relates to similar Thiadiazole ureas with thio substituents in the thiadlazole ring.

On the basis of the invention, there are connections of the lOrmel

_N γ

1 "

RC CNONR _n

^X R
^R 2

wherein R an alkenylthio group (pp "" ^c i2 ^ » ^an alkynylthio group (02" -C ₁₂ ) * ^θ1ηθ benzyl thio group substituted

009848/1939

ORIGINAL INSPECTED ^

Benzylthio, Epoxyalkylthiogruppe, haloalkylthio (C ₁ -C ₁₂₎ * Halogenalkenylthiogruppe (C ₂ -C ₁₂₎ * Cyanalkylthiogruppe, Oxocyclohexylthiogruppe, Carbalkoxyalkylthiogruppe, Thiocyanäthylthiogruppe, cycloalkylthio (C ^ -C ₁₂₎ Phenylalkenylthiogruppe, arylthio, substituted arylthio, Acylalkylthiogruppe, heteroarylthio, Aminoalkylthiοgruppe, dialkyl -aminoalkylthiogruppe (C ₁ -C ₁ 2) or represent a Aziridinylalkylthiogruppe and R _1, R ₂ and R have the same meaning, have, as in the above-mentioned invention, that R ₁ is a hydrogen atom, an alkyl group (C ₁ -C.) Or a cyeloalkyl group (C, -C ^), R _{2 is} a hydrogen atom, an alkyl group (C ₁ -C.), A haloalkyl group (C ₁ -C.), An alkoxy group (C ₁ -C.), an alkenyl group (C ₂ -C.), an alkynyl group (C ₂ -C>), an aryl or haloaryl group or the radicals R ₁ and R ₂ together with the M atom form a ring with at least 3ι but not more than 6 To articulate t ^ ii ^ ^ IHirerfcl R, a hydrogen atom or an alkyl group (C ₁ -Cg) and X is oxygen or sulfur

The starting materials for numerous compounds in the context of the invention are 2-amino- or alkylamino-5-substituted-1 _f 3i4-thiadiaBols. The starting materials can be prepared according to the method of Lasari and Sharghi, J. of Hat. Chem., Volume 3 »page 336 (1966) or according to other known literature methods.

You can use thiadiaasolurea according to the invention from the corresponding 2-A »ino- or 2-Alkrlamlno-5-Bubetituitrten-1,3,4-thiadia» ols duroh conversion »it of an isocyanate, for example methyl isocyanate, carbonyl sulfide and its suitable amine, for example dieethylamine, or carbamylochloride or a substituted one

009845/1939

Carbamylohlorid, such as mine made tliylcarbainyl chlorid will. Explanations for these implementations are given in the examples »

In accordance with the invention, there is also a method to combat plant growth ^, being on the Plant or its seeds contain a growth regulating amount of one of the thiadiazole ureas listed above is applied.

The thiadiazole drugs according to the invention & ind stable and well defined and are particularly suitable for herbicidal use when used alone or in combination with inert carriers such as those generally used in the field of Herbicides can be applied. The porter aid smit te 1 can be liquid or solid, v / as from the hu area to be treated, the type of plant to be controlled and the type of plant available for application Equipment is dependent. When using 'liquid' approaches they can be in the form of real solutions, diaper- · sions or emulsions are present, which preferably have a Contain a small amount of a wetting agent. The compositions contain a small amount of the herbicidally active compound and a major amount of carrier.

The compounds according to the invention are general insoluble in water, so that they require an organic solvent when using solutions. cheap or necessary. For example, acetone can be used as a solvent. Others surrender for the professionals without further ^.

If dispersions are used, this is the dispersion medium generally watery, can jödooh. even contain small amounts of an organic solvent, i.e. quantities that are not sufficient to dissolve dee

009845/1939

BATH ORIGINAL

active ingredient ^ as well as a small amount of a wetting agent to keep the particles in suspension hold au.

The wetting agents are out of their effect Suspension of the toxic particles is also useful as an aid in distributing the active material uniformly over the surface to be treated »In other words, the wetting agent helps prevent this the build-up of droplets on certain parts of the surface while leaving other parts untouched or inadequately treated by the toxic agents. Such means are well known and do not need to be listed here individually. An example of a useful wetting agent is Tween-20, a polyethylene aorbiton monolaurate.

The solid approaches in question can consist of dusts or granules, the herbicidal active substances I! Close to thiadiaolureas contain »numerous Solids are known in the art as all useful carriers for herbicides. Examples of such carriers Bind kaolin, talc, kieselguhr, diatomaceous earth, pyrophyllite, Bentonite, calcium carbonate, powdered cork, hole, walnut shells and brownnut shells, fuller's earth and tricalcium phoephate. Approaches using these carriers can be prepared in a known manner.

In addition, the compounds can be applied as aerosols, in which case ee can favorably "tin , dissolve them in any suitable solvent" and disperse this solution in the propellant, for example dichlorofluoromethane or other chlorofluoroalkanes at boiling points below barely any temperature at normal pressures.

009845/1939

The concentrations of the chemicals in the masses can vary within a wide range when the herbicidal activity or toxic exposure of the active ingredient is brought onto the plant or in its immediate vicinity. Thus the important considerations are not the minimum and maximum concentration, but the most economical concentration. The herbicides of the present invention are useful in the treatment within a range of about 0.27 to 3.3 kg / hectare (0.25 pounds to about 30 pounds per acre) of active agent and the most favorable ratio of carrier to active ingredient is determined by the The amount of vehicle required is determined to give an even distribution of a growth-inhibiting amount of the active material over the area to be treated.

When combating unwanted plants with the chemicals listed as a treatment agent before Germination, the toxic agent or masses containing it can be sprayed onto the soil, if any is liquid, or is spread out, it falls into place Solid is · Subsequently, the material can be natural The effect of cherishing can be overloaded or ea can be plowed or plowed and rolled into the ground · When used as a means for after germination, a solid mass can be applied to the plants close to the same Method "as it is used for the application of other known solid herbicide masses, can be dusted on. When spraying fluids to treat Plants are used, the liquid mass can then until IU the Stell · the PlUselgksitsalilattfons sprayed on will.

Following the general description of the In the invention, examples of chemicals according to the invention and their use as herbicides are given below. The examples serve only to illustrate the Invention based on specific embodiments, without limit them. In the examples, files are by weight unless otherwise specified.

example 1

1-methyl-3- / 5-allylthio-2- (1,3,4-thiadiazolyl1 / -. Urea

5 g of 2-amino-5-allylthio-1,3,4-thiadiazolyl (0.03 mol, melting point 116 to 116 ° C), prepared by alkylating 2-amino-5-meroapto-1,3,4-thiadiazol with allyl bromide , were slurried with 50 ml of acetone in a 125 ml pressure bottle. 1.8 g of methyl isooyanate (0.032 mole) was added thereto . Gemisoh obtained with && b was heated by placing the bottle in a steam bath for 2 1/2 hours. The bottle was removed from the bath and the contents ^{cooled to about 20 4} C; on cooling the contents separated from the reaction mixture in a white solid.

The solid was filtered from the Reaktionsgenisch and dried in a vacuum oven at 6Q ⁰ C. The solid weighed 4.1 g (61 ft yield) and had a melting point of 171 to 172 ¹¹ C. Additional solid was obtained by concentrating the filtrate, for which the filtrate was heated to remove the acetone.

The solid consisted of 1-methjl-3- / 5-allylthio-2- (1 »3» 4-thiadlazolyl! / - urea, such as by IR and IMR

09845/1939

BAp

Spectrum confirms wurdes

H H O

H ₀ C-GH-GH ₀ -SC CHCH-CH-,

^{2 2} V ι ι '

HH

The 2-araino-5-mercapto-1 _f 3t4-thiadiazole (melting point 234 ° E) was prepared by reacting carbon disulfide with thlosemicarbazide in dimethylformamide.

' Example 2

1-methyl-3- / 5-isopropylthio-2- (1 , 3 , a- thiadiazolyl} / -

urea

5g 2-Amino-5-isopropylthio-1,3,4-thiadiazole (0.03 mole, melting point 145 to 147 * 0) prepared duroh alkylation of 2-amino-5-Niex 3apto ^i-1 _s ~ 3i4 thiadiazol with " 2-bromopropane were slurried with 50 ml of acetone in a pressure bottle of 125 ml. 1.8 g of methyl isoeyanate (0 _s 032 mol) was added thereto and the resulting solution was heated by placing the bottle in a steam bath for 3 hours. The bottle was removed from the bath and the contents cooled by placing the bottle in an ice bath was asked. After the bottle cooled, a white solid separated from the reaction mixture. The solid was then filtered off from the reaction mixture. The solid was dried ^{at 60 °} C. in a vacuum oven. The leetetoff weighed 3.9 g (Auebeute £ 58) and had a melting point of 170-172 ⁰ C. Another solid was duroh concentration dee Filtrates'erhalten, ie the Aotton-

009845 / 193Q

BATH ORIGINAL

solution which contained part of the reaction mixture a. The structure assumed was determined by the IR and NMR spectrum confirmedι

H IT M O

I I! P Il

H ₁₁ CCSC CNCH-CH, H ₃ C ⁰ HH

Example 5

1-methyl-3- / 5-n-propylthio-2- (1,3,4-thiadiazolyl) / - ; urea

5.0 g of 2-amino-5-n-propylthio-1 _f 3 »4 thiadiasol (0.03 mole, melting point 113-114 ⁰ C) prepared duroh alkylation of 2-amino-5-mercapto-1,3 , 4-thiadiazole with 1-bromopropane, were slurried with 50 ml of acetone in a 125 ml pressure flask. 1.8 g of methyl cyanate (0.032 mole) was added thereto and the resulting mixture was heated by placing the flask on a steam bath for two and a half hours. The flask was removed from the bath and cooled in an egg bath, whereupon a white precipitate evaporated. The white solid was filtered off and dried in a vacuum oven at 60 ° C. The solid weighed ¼.4 g (yield $ 78) and had a melting point of 173 to 175 ⁸ C. IR and IMR periods indicated the following structure:

IL N 0

ü Il I!

H ₇₁ C-CH ₉ -CH ₉ -SC C-JI-CN-CH,

⁸ HH

009845/1939

Examples 4 to 13

The following compounds were prepared according to the corresponding preparation processes as in Examples 1 to 3 of the patent application

P 19 01 672.9 produced. In these compounds, the radical R ₁ denotes hydrogen, Rg denotes the group CH ,, R-hydrogen, Z denotes the group 0 and R denotes one of the following groupings!

Example Mr. R.

4 methallylthio

3-methyl-2-pentenylthio

CH ₂ -CCHgS-

CH ₃ CHgC-CHCH ₂ S-CH,

Chlörpropylthio ClCH ₂ CH ₂ CH ₂ S- Beneylthio Phenäthytthio

\ cHgCHgS

p-nitrobeneylthy

O ₂ I \ y CH ₂ S

10

Aoetonylthio

009845/1939

ORIGINAL INSPECTED

Example no, r

11 Phenacylfchi © f TCCH ₉ S-

12 methylacetozythio CH ₃ OCCH ₂ S-

13 cyanopropylthio NCCH ₂ CH ₂ S-

Further compounds, which were prepared in the same way, are the following, in which R- is a hydrogen atom, R _{2 is} the group CH *, R _{3 is} a hydrogen atom, X is the group 0 and R is one of the following groupings:

H ₂ C-CHCH ₂ S-, HC-CCH ₂ S-, 2,4-dichlorobenzylthio »

• 0

Il 0

H ₂ C-CH-CH ₂ S-, NGOH ₂ CH ₂ S-, C J ^ H ₃ COCCH ₂ CH ₂ S-,

ITCSCH ₂ CH ₂ S-, H ₂ q-pH-S-, C ₆ H ₅ -CH-CHCH ₂ S-,

H ₂ 5 0 ⁸

(H ₃ C) ₂ C-CH (CH ₂ ) ₂ C-CHCH ₂ S-, H ₃ COCH ₂ S-,

0 9 8 4 6/1939 oriq, nal inspected

₂₂ S-, ClCH ₂ -CH-CH ₂ S-, ClCH ₂ CH = CHS- and ^H 3 ^C Cl

- C «C -

H ₃ C

Herbicide Versuoh

Herbicide Versuohe. before germination and after germination Method of spreading the experimental garden

Crab grass (CGr) * Digitariasanguinalis yellow fox sohwanE (YF) = Setaria glauca Johnson grass (^ S) "Sorgum helepenee Barnyard grass (BS) * EohinocHloa crus-galli Araaranth thistle (PW)" Amaranthus retroflexus Turnip (TP). «Bratsica sp.

Cotton (CT) * Soeeypium Mrsutua Tar.DPL-smooth-

leafy

Haie (CK) .m Zea-Maie

Beans (BH) * Phaseolus vulgaris yar. Black Valentine

All types of herbaceous plants and weeds were individually planted in plastic pots hair dryer 75 mm, which contained potting soil. Four seeds each of corn, cotton and beans became eu a depth equal to the diameter of the seed sown. All other species were sown on the surface and sprayed with sifted soil in sufficient quantity to cover the seeds. Direct after planting, all the pots were through

009845/1939

ORIGINAL iNSPECTED

Irrigation watered from below in greenhouse soils. The pots for pre-germination study became one Sown the day before treatment.

The planting values for the near germination phase were varied so that all the seedlings reached the desired stage of development at the same time. The suitable « The stage of germination for treatment in the early germination phase was as follows

Grazing height 50 mm (2 inches) Thistle and Turnip ι 1 or 2 real leaves above

of the visible cotyledons cotton First real leaf 25 mm long,

expanded cotyledons Malst height 75 to 100 mm (3-4 inches) Beans: primary leaves expanded, watch turn parts at the primary leaf node.

Treatment method

The compounds were applied in amounts equivalent to 8.9 kg / ha (8 lbe / aore) of the active compound applied in a spray volume of 554 l / ha (38 gallons / acre). The required constants of the spray head the release of the foregoing volume followed

Belt speed * 3.2 km / h

Luftdruokt Posted on releases from 354 lA »

Nozzle tip For the formation of a uniform Cross section of the flat spray

00 9845/19 3g

The spray application approaches were in volume of 50 ml made with the following three ingredients:

1. 1 _t 24 g of the compound (8.9 kg / ha)

2. 49 ml of acetone or a mixture of water and acetone

3. 1 Bl Tween-20.

Approaches for a dosage of 4 »4 kg / ha have been carried out manufactured according to · adjustment of the amount of active ingredient.

The spray applications were carried out in one head removable tape and fixed spray nozzle. A pot from each sample was used to pass through the spray head (Pre-germination phase) on the back half of the surface posed. Si · treated materials were placed in the greenhouse after spraying. You watering during The observation period was only done by watering from below. '

Procedure for recording the results

2 Woohen after the treatment, the pre-germination and germination damage or the comparative value visual and the results are summarized in the following tables. The pre-caming values are given in Table I. and the low germ levels in table XX, -

098457193g

Table I.

Pre-germination activity, j » of control

At- quantity CG YF JG BG PW XP CT CK BH game kg / ha

(ID / acre)

1 2.2 (2) 60-30 50-70 50 10 40

2 4.4 (4) 50-30 40-100 30-10

3 2.2 (2) 90-70 50-60 50 10 30

4 4.4 (4) 30 10 20 60 10 20 30 50 90

5 4.4 (4) 20-10 20 10 10 30 10 100

6 4.4 (4) 3 - 10 40 20 20 30 10 80

7 4.4 (4) 20-20 10-40 30-30

8 4.4 (4) 10 - 10 20 10 10 80 30 80

9 4.4 (4) 20-20 20 10 10 50 10 80

10 4.4 (4) 30-20 40 10 10 50 10 30

11 4.4 (4) 20 - 10 10 10 10 30 50 100

12 4.4 (4) 10-20 30 20 80 30 10 80

13 4.4 (4) 20 - 10 20 10 10 50 10 50

OO984S / 1S30

! Table II

Activity: at lot after (1 ^ / acre) (2) 80 the Germination, BS i » control TP -CT c » BN game kg / d CG 2.2 (4) 90 TF Yes PW La 4.4 (25 100 1 2.2 (4) 100 90 80 100 50 100 2 4.4 (2) - 80 50 - 100 100 40 100 3 2.2 (4) 50 - 70 90 - 70 100 100 70 4th 4.4 (25 - -. 90 40 - 90 100 40 50 2.2 (45 90 40 40 - - 70 - ■ - - 5 4.4 (45 70 - 20th 100 80 80 30th 100 4.4 (D 40 - 30th - 90 60 - - - «. 6th 1f1 (45 60 - - 70 90 80 100 30th 100 7th 4.4 (25 —I around - 60 70 90 100 100 30th 90 2.2 (4) 40 - 70 50 - 100 100 40 70 8th 4.4 (25 - - 40 20th - 90 100 100 100 2.2 (45 50 - 30th - 90 70 - 9 4.4 (25 - -. " 20th 90 90 50 20th 100 2.2 (♦) ■ 20th -. 30th - 90 60 * »- .— 10 4.4 (25 - ~ 30th 90 80 90 30th 100 2.2 (4) 30th 60 30th - 90 60 - - -. 11 4.4 (4) 70 20th 60 30th 60 30th 100 4.4 20th - 100 30th - - 12th - - 20th 70 70 60 30th 50 13th - 20th 20th 60 80 100 100 100 * - 20th 80

0Q98A5 / 1939

Claims (6)

Claims Thiadiazole ureas according to patent ....... (Patent application P 19 oil 672.9), characterized by the general formula N 'N X If Il I! R_G CNCNR ₁ ^{XS /} i R wherein R is an alkenylthio group (C ₀ -C, _o ), an alkynylthio group (C _{2 -C 12} ), a benzylthio or substituted benzylthio group, an epoxyalkylthio group, haloalkylthio group (C ₁ -C ₁₂ ), haloalkenylthio group (Cp- ^ IP ^ * -aminoalkylthiogruppe Cyanalkylthiogruppe, Oxocyclohexylthiogruppe, Carbalkoxyalkylthiogruppe, Thiocyanäthylthiogruppe, cycloalkylthio group (C, -C ₁₂₎ Phenylalkenylthiogruppe, arylthio or substituted arylthio group, Acylalkylthiogruppe, heteroarylthio, Aminoalkylthiogruppe, Dialky1- (C ₁ -C ₁₂₎ or Aziridinylalkylthiogruppe, R _{1 represents} a Hydrogen atom, an alkyl group (C ₁ -C ₄ ) or a cycloalkyl group (C, -Cg), R ₂ a hydrogen atom, an alkyl group (C ₁ -C ₄ ), haloalkyl group (C ₁ -C ₄ ), alkoxy group (C _{1 -C 4} ), alkenyl group (C ₂ -C ₄ ), alkyny group (C ₂ -C ₄ ), aryl or _{haloaryl group, where R 1} and R ₂ together with the N atom can also form a ring of 3 to 6 members , R »is a hydrogen atom or an alkyl group pe (C ₁ -Cg) and X represent an oxygen or sulfur atom. 2. Thiadiazole ureas according to claim 1 with the formula - N 0 N— H ₉ C = CH-CH ₉ -SG CNCN-CH _x ^{2 2} Ns / 'II ³ H H 009845/1939 3 · thiadiazole ureas according to claim 1 with the Formula. H N-N 0 ι if ι ii HCCSC CNON-CH, ³ I N 3 / ij ³ CH ₅ HH 4. thiadiazole ureas according to claim 1 with the formula ■ N-N 0 ■ i · Ρ H HiC-CH ₉ -CH ₀ -SC CNCN-CH, ' ^{ά ά} NS ⁷ II ''* H H - 5 · Method for regulating or controlling plant growth, characterized in that the An anti-growth amount of a compound according to Claims 1 to 4 is applied to the plant or the seeds thereof. 6. Herbicidal compositions, consisting of a carrier and a compound according to claims 1 to 4. 1939