DE2131135A1 - Pest repellants - Google Patents

Description

CLBA-GEIGY AG, CH-4002 Basel

Dr. F. Zumstein Sr. - Dr. E. Assmann 9 1? 1 1

Dr. R. Koenigaberger - Dipl. Phys. R. Holzbauer / ■ -ΙΟΙ I

Dr. F. Zumstein jun.

Patent attorneys

8 Munich 2, Bräuhausstraße 4 / III

5-7096 *

Pesticides

The present invention relates to the use of dithiocarbamates of the general formula

for controlling weeds in rice crops, especially for controlling grass-like weeds,

109882/1969

in which R ₁ and R 0 each denote an alkyl radical with 2 to 4 carbon atoms or an alkenyl radical with 3 to 4 carbon atoms or in which R 1 and R 1 together with the N atom connected to them denote a 5- to 7-membered group Form heterocyclic ring with a hetero atom which is optionally substituted by one or two methyl or ethyl groups, R- means an alkenyl radical with 3 to 4 carbon atoms or a haloalkenyl radical with 3 to 4 carbon atoms and 1 or 2 halogen atoms.

An alkyl radical with 2 to 4 carbon atoms is understood to mean ethyl, n-propyl, isopropyl, η-butyl, isobutyl and sec-butyl.

Above all, allyl, methallyl and crotyl are to be mentioned as alkenyl radicals with 3 to 4 carbon atoms. Haloalkenyl radicals are in primarily to mention chlorallyl and bromallyl, which should include all positions of the halogen.

Heterocyclic rings that are formed from the N atom and the substituents R ₁ and R 0 can be saturated or unsaturated. Examples are pyrrolidine, tetrahydropyridine, piperidine, α-, β- or 7-methylpiperidine, 2,6-dimethylpiperidine or hexamethyleneimine.

Particularly noteworthy are compounds of the formula I in which R _{1 and R 2,} independently of one another, denote an ethyl _f propyl, isopropyl, isobutyl, alkyl or methallyl radical.

The present invention also relates to the new compounds of the formula II, which are preferably used for combating rice weeds be used,

R ₁ S

"" ^ NCS-CH ₀ -C = CH ₀ II

R ₀ CHo

109882/1969

and where R-. and R "have the meaning given for formula I. Among these compounds there should be mentioned in particular those representatives in which R ₁ and R ~ independently of one another denote ethyl, n-propyl, isopropyl, η-butyl, isobutyl or sec-butyl. Examples of such compounds are methallyl-N, N-di- (n-propyl) -dithiocarbamate, methallyl-N, N-di- (isopropyl) -dithiocarbamate, methalllyl-N, N-di- (isobutyl) -dithiocarbamate, methallyl- N- (n-propyl) -N-isopropyl-dithiocarbamate, methallyl-N-ethyl-N-isopropyl-dithiocarbamate, methallyl-N, N-bis (methallyl) -dithiocarbamate, methaliyl-N-isopropyl-N-allyl dithiocarbamate, Methallyl-N-methallyl-N-ethyl-dithiocarbamate, methallyl-N-methallyl-N-isopropyl-dithiocarbamate or methallyl-N-ethyl-N-propyl-dithiocarbamate.

The compounds of the formula I or the new compounds of the formula II can be prepared in a simple manner by for example, an amine of the formula

H.

where R .. and R ~ have the meaning given for the formula I, with carbon disulfide in the presence of a tertiary amine or alkali metal hydroxide and the resulting salt of dithiocarbamic acid the formula

N-C-SH

with a halide of the formula R "- Hai, where R-, the for the formula

109882/1969

1 "or with a halide of the formula. CH ₉ = C (CHo) -CH ₉ where Hai is a halogen atom, preferably chlorine or

"■ shark
Bromine means further converts.

The reaction is advantageously carried out in a lower alcohol solvent, for example in methanol or A-ethanol.

The compounds of the formula I have a total or selective herbicidal activity. This effect is used in particular to combat weeds such as Echinochloa, Eleocharis ₅ Scirpus, ™ Fimbristylis and Alisma in transplanted rice ». -

Strangely, transplanted rice (water rice), which is of outstanding importance mainly in Asia _{, is tolerant of the compounds of formula (I) 5} even if these are used in high concentrations, while very important grass weeds and weeds are completely destroyed.

This finding is surprising; because a persistent, search for herbicides carried out from different sides for Control of grass-like weeds in rice crops has not yet led to the desired success of sufficient selectivity between crops and weeds.

Surprisingly, it was also found that mixtures of dithiocarbamates of the formula (I) with ureas and triazines act synergistically.

If the compounds of the formula I are used as herbicides, the application rates can vary within wide limits, e.g. between 0.1 to 10 kg of active ingredient per hectare, but preferably 0.5 to 5 kg per hectare.

10 9 8 8 2/1969

The active ingredients of the formula I or II can be used as pests alone or together with suitable carriers and / or other additives pesticides are used. Suitable carriers and additives can be solid or liquid and correspond to the substances common in formulation technology, such as natural or regenerated mineral substances, solvent, Dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Further biocidal compounds can also be added. Such biocidal compounds can e.g. the class of ureas, saturated or unsaturated halogenated fatty acids, halogenobenzonitriles, halogenobenzoic acids, Phenoxycarboxylic acids, carbamates, triazines, nitroalkylphenols, org. Phosphoric acid compounds, quaternary ammonium salts, sulfamic acids, arsenates, arsenites, borates or chlorates. In the production of herbicidally active agents, for example, the following components are used in combination Question:

109882/1969

A) Substituted ureas

N-phenyl-N ¹ , N ¹ -dimethyl urea N-phenyl-N-hydroxy-N ¹ , N ¹ -dimethylurea N - (^ - chlorophenyl) -N ^l _> N ^l -dirnethyl urea N- (3 _J 4-dichlorophenyl) -N ^l , N ^! -dimethyl urea N- (3> ² 5-dichlorophenyl) -N-benzoyl-N ^l , N ¹ -dime thy urea N- (ty-chlorophenyl) ~ N ^! methoxy-N ¹ -methyl urea

N- ( ⁱ l-chlorophenyl) ~ N ^l -isobutinyl-N ¹ -methyl-urea NO * 4-dichlorophenyl) -N '-methoxy-N ¹ -methyl-urea N- (' i-bromophenyl) -M '- raethoxy-ri '-methyl-urea N- (U-chlorophenyl) -N ¹ -methyl-W ¹ -butyl-urea H- (ίί-chlorophenyl) -N'-raethyl-K'-isobutyl-urea N- (2 -Chlorophenoxyphenyl) -M ^l , N ^l -dirnethylha ^ ¹ nstoff} i_ (A-chlorophenoxj'-phenyl) -N ', H' -dimethyl-urea f N- (il-chlorophenyl) -N * -methyl-N ¹ - (l-butyn-2-yl) ~ urea

N-Benzthiazol-2-yl-N ¹ , N'-dimethylurea ·;

K-Benzthiazol-2-yl-N ¹ -methyl urea

M- (5-Trifluoi'methyl - ^ - methoxyphenyl) -! ·! ' jK '-dimethylurea N_ (^ j-trifluoroniethyl- ^{J. l} -isopropoxyphenyl) -N' , Ii '-dirnethylurea

N- (3-Trifluorraethylphenyl) -N ¹ ^ M ¹ -dimethylurea

109882/1969

N- (4-Triflucnr, ethylphenyl) -N ¹ , N ¹ -dirnethylurea

H- (^ -Chlorophenyl) -M '- (3 ¹ -trifluoromethyl- ^' -chlorophenyl) urea

N- (3, H- dichlorophenyl) -N'-methyl-ϊί ¹ -butyl urine

N- (> -Chlor- ^J f-trifluoroniethylphenyl) -H ', N' -dimethylurea

K- (2-chloroethylphenyl) -W ', H'-dirnethylurea.

NO-chloro-'Vfiiethylphehyl) -N ', N'-dimethylurea M- (5-chloro-ethoxyphenyl) ^-N-methyl-f W'-methoxyurea H - (> chloro- ⁱ i ~ .T: ethoxyphenyl) -N ^l , U ^! -dimethylurea

ίί - (- Hexahydro- *, 7 -: nefchanoindan-5-yl) -lI ^I _J N ^t -diraethylurea f

N- (S-MGtIIyICyClOhGXyI) -H ¹ -phenylurea N- ( ^} }, 6-dichloro-i? -Pyriayl) rii ^! -dimethylurea N ¹ -cyclooctyl-NN-diinethy! .urea

Dichlorourea · ·

! ^ '»^" (Ii-MethoxyphenoxyJphenyl-N.N-dimethylurea

■ · ■ ■

N'- O-methylphenyl) -N.N-dimethylthiourea

1,1-Dimethyl-3-p5- (N-tert-butylcarbarnoyloxy) -phenyi] -urea

Ο, Ν, Ν-Trimethyl-N ¹ - ² I-chlorophenyl isourea 1) _ ^ / 4 _Dichlorophenyl-N ', N'-dimethyl-α-chloroformamidine ΪΙ, N-dimethyl-N'-phenyl-hams toff-trichloroacetate MjN -dimethyl -W ¹ - ^ l -chlorphenyl -hams toff tr ichlor, ace tat

109882/1969 BAD ORtGlNAL

B) Substituted triazines

2-Ch.tor-4,6-bis (ethylamino) -s-triazine "■".

2-chloro - ^ - ethylamino-6-isopropylamino-s-triazine 2 ~ chloro-4,6 ~ bis (inethoxypropylamino) -s-triazine 2-IAe khoxy-H to 6 ^(r i'soprop5 larriino) -s ₁ triazine 2- diethylamino - ^ - isopropylacetarnido-ö-methoxy-s-triazln 2 ~ ⁱ Isopropylarnino- l-methoxyäthylamino - -o-niethyl-rncrcapto-.o-triazine 2-Meth5 ^r lir.ercapto-J {,, 6 -bir5 {isopropylanrino) -s-triazine 2 ~ i> iethylinercapto- ^j T ^ 6-bis (äthylarnino.) -s-triazine 2-i- ⁱ ethylmercapto - ^ - aethylamino-6-tcrt.butylarnino-s-triazine 2 -Methylrnercapto- ⁱ } -äthylamino - 6-isopropylarnino-s-triazine 2 - ^! Ethylrnercapto- ^ί ^ - ■ l '^ ethylarnino-6-isoprGpyla / nino-5-tria.zin 2-methoxy-'i _J 6- bis (äthylarnino) ~ s-triazine ψ 2.-ViQtYiOY ^ y ~ h- äthylarnino-ö-isopropylamlno-s-triazine

r - ^, 6 ~ bis (isopropylamino) -S "triazine 2-Azido - ^ - methylmarcapto-6-isopropyla: nino-s-triazxn 2-A-ZIdO- ^ I -nie thyimor cap to- 6-soc. bu tylainino ~ s- triazine 2-chloro - ^ - isoiDrop5'lamlno-6- (7-inethoxypropylß2nino) -s-triazine 2- (6-Aethylamino-4-chloro-s-triazin-2-yl-amino) -2-methylpropionitri.l -Chior- ^ f-diethylarnino- · 6 »isopropylamino- s ~ triazine ·.

" ^J l ^ 6-bis- (3-wethoxypropyla: nino) - s-triazine

-Mc thy! Mercapto -H- isopropylamino- 6- {^ - rnethoxypropy lätni no) · « ^; ■., -. 109882/1969

BAD ORiGiNAL

s-triazine

2-chloro ^/ 'l-diethylari) ino-6-ethylamino-s-triazine. 2 _} ^ -Bi3 (~ 2-methoxypropylamino-6-methylthio ~ l, 3j5 2 ~ methylthio - ^ - isopropylamino ~ 6- (7-methoxypropylamino) 1,2., 5-triazine 2-chloro - ^ - ethylamino-6-tert.butylamino-s-briazine 2 - (^ - chloro-6-ethylainino-1,2j5 ~ triazin-2 ~ yl-amino) ~ 2 ~ methyl ~ propionitrile. '': _. ·

C) phenols *

Dinitro-sec-butylphenol or salts thereof pentachlorophenol or salts thereof. jJ ^ -DInifcro-o-cresol
2, 6 ~ dibro; n- ¹ I-cy anphenol 2,6-dichloro - ^ - eyanphenol dinitro-tert-butylphenol r

Dinitro-sec-amyl-phenol 2- / iethoxyi'nethyl- ⁱ , 6-dinitrophenol 2 »tert-butyl- ^ _J 6-dinitrp-5-mefchylphenol

Salts + esters salts + lister

Salts + esters salts -1- esters salts + esters

109882/1969

BAD ORlGlNAl

D) carboxylic acids, 'salts and esters'

2, h, o-trichlorophenyl acetic acid

2, j5j6 ~ trichloroborozoic acid and salts

2,3j5> 6-tetrachlorobenzoic acid and salts

ν ■

2,3,5,6-tetrachloroterephthalic acid ⁽

2-f '! Ethoxy-3j5j 6-trichlorobenzoic acid and salts. "

_{Cyclopropanecarboxylate-2>} 4-dinitro ~ 6-sec.butylphenylester Cyciopentancarbonsäure-2 _J ^ -dinltro-ö-sec.butylphcnylester ·

a-methoxy-Jjc-dichlorobenzoic acid and salts of 2-An} ino-2,5 ^ ichlorbenzoesäure salts and 3-nitro-2,5-Qichlorbenzoesäure and salts 2-i'iethyl-3/6-dichIorbenzoesäure and salts 2 _J ⁱ i-dichlorophenoxyacetic acid _J salts and esters 2jhj ^ -Trichlorphenoxyacetic acid j salts and esters (2-methyl - ^ - chlorophenoxy) acetic acid _J salts and esters 2- (2, ^, 5-trichlorophenoxy) propionic acid, salts and esters

2- (2, 'J, 5-triehlophenoxy) ethyl -2,2-dichloropropionic acid, salts

and esters

4 ~ (2, Jf-Diehio.i * phenoxy) butboric acid, salts and esters

BAD ORlSiNAL '

109 ^ 82/196 9

- 11 - h »(2 -Me th j'l - H - chlorophenoxy) but boric acid,

ttethyl-S-chloro -, -? ^ ¹ chlorophenyl) propionate, 2-chloro-9-hydroxy-fluoro-9-en carboiisäure Endo-oxo-hexahydrophthalic acid · Te trachlorph thalsäur ed.imethylester ² l ~ chloro-2 _r oxobenzothiazolin -> - yl-acetic acid 2 _J 2 _J ^ 5-trichloropropionic acid 2,2-dichloropropionic acid "·

(ψ) 2 ~ (2, Jr-Dichlcrphenoxy) -propionäure 7-0xabicyclo (2 _J 2 ^ l) heptano-2 _J ^ -dicar'oonaure * i -Ch 1 or ph en oxy acetic acid e

Gibberellic acid ·. .

Indolylacetic acid - ■

Indolylbutyric acid

(j ^) 2 - ('r-chloro -2-methylphenoxy) propionic acid Nj.N-diallyl chloroacetamide

Naphthylacetic acid. '

N-1-naphthylphthalimidic acid ^ -Amino- ^ 5,5j 6-trichloro-pieolinsa'ure Trichloroacetic acid

^l \ - {2., h, 5-trichlorophenoxy) butyric acid c

Salts -l esters

Gasoline idoxyacetic acid

Ethylene glycol bis trichloroacetate Chloreijsißrjäurndiäl / nylojnid

Salts + esters salts + esters salts + esters

Salts \ esters

Salts + esters

Salts + esters Salts -ι- esters

Salts' + esters salts + esters salts + esters

109882/1969

BATH ORIGINAL

· "■■■ ·

2,6-dichlorothiobenzamide. ■

2,6-dichlorobenzonitrile N., N-Dime thy Ι-α, α-diphenyl acetamide

Dipheny! Acetonitrile · ■ "

W-hydroxymethyl-2 ^ 6-dichlorothiobenzamide. ^%

E) carbamic acid derivatives

Isopropyl carbaniate "-."

3ί ^ -Dichlorocarbanilic acid methyl ester. . ·

m-chloro-carbani! acid-isopropyl ester m-chloro-carbanilic acid - ^ - chloro-S-butynyl ester ra-trifluoromethyl-carbanilic acid-isopropyl ester 2,6-di-tert-butyl - ^ - tolyl-N-methylcarbarnafc ^ - ( nethoxycarbonylaminoJphenyl-H - ^ - tolylcarbamat ^J ^ -chloro-2-yl-l Butir ^ ·} - (3-chlorophenyl) carbamate .- .f-iethyl 2 ~ isopropyl ~ ^l} ~ (inethylcarbarnoyloxy) carbanilate further diallate ^ M ^ N-Dipropyl-S- äthylthiocarbamate Molinate and Dithiocarbamate of the formula

^ P

R, - ^ ti

Ii-C-S-IU

wherein R., Rp and R _{7 represent} a lower alkyl or alkenyl radical, or wherein. R, and R "together with the nitrogen atom connected to them a 5-, 6- or Y

BAD ORiGfNAU

109882/1969

optionally alkylated ring with a total of 6 or 7 carbon atoms represent, the exo-alkyl groups on the., the nitrogen atom adjacent carbon atoms must be bound, and ■ 'R, the ethyl, propyl, n-butyl radical or isobutyl radical, including especially. . '»

K-butyl-N-ethyl-S-propyl-dithiocarbamafc, "'·".

Ν, Ν-diisobutyl-S-propyl-dithioGarbamate · ".

K, N, S ~ tripropyldithiocarbamate '.... ·.

M-isobutyl-H-allyl-S-propyldithiocarbamate N-isobutyl-N-methallyl-S-ethyldithiocarbamate

K-Isobutyl-N-methallyl-S-propyldithiocarbamate · _.

! •!, Li-dimethallyl-S-propyldithiocarbamafc '. '. ·

K-Butyl-M-ethyl-S-propyl-thiocarbamate and NjNjS-tripropylthiocarbamate, as well as M- ( ⁱ T-aninobenzsulfonyl) ir, ethyl carbamate

l-methylprop-2-yl-N- (3 ~ chlorophenyl) carbamate '

Isopropyl N- (5-chlorophenyl) carbarnate

S-Sj ^ -Dichloral-lyl-NjlI-diisopropylthiocai'bamate '· ..

S-ethyl-i ^ N-dipropylthiol carbonate ■

N-methyl di thiocarbamic acid. '.: "· ■

S-propyl-N-butyl-M-ethylthiol carbonate 5- (rn-tolylcarbarnoyloxy) phenylcarbamate Isopropyl II-phenyl carbamate

S-chloroallyl-NSlI-diethyldithiocarbamafc "...

Methyl-!. ¹ - (j5, ^ -dichlorophenyl) carbamate

109882/1969 bad original

S-2, jJ ^ -Trichlorallyl-NjH-diisopropylthiolcarbarnafc S-propyl-M ^ N-dipropylthiolcarbaniat S-ethyl-tf-ethylthiocyclphexanecarbamafc ^, ^ - dicblorbenzylrne'chyl-azydcarbiolate S-ethyl-^ -Di-t-butyl - ^ - inothylphenyl-il -. 'Uslhyl -o ^ rbainab Methyl-N- ( ² i-nitrobenzsulfonyl) carbai7iate Ν, Ν-Hexatnsthylen-S-isopropyl thiocarbamat' S-ethyl-NjN-diisobutylthiolcarbamafc 2 -Chlorbufcinyl-N - (^ - chlorophenyl) carbamate S-ethyl-N, K-diisobutyl-thiolcarbamafc methyl-N'- (U '-methoxycarbamoyl-sulfanilyl) carbainate

F) anilides ■ -

'β, Jj-dichloropropionanilide
jJ-chloro - ^ - bromopropionanilide ^ -Bromo - ^ - chloropropionanilide ₍

CyclopropancarboriGäure-J ^ ^ -dichloranilid Cyclopropahcarbonsäure - ^ - chloro - ^ - brornanilid Cyclopropanecarbonsäure - ^ - brorn-ty -chloranilid N- (5ί ^ -dichlorphcnyl) -2-methylpentanarnid M-1-Kaphthyl-phthalamic acid N- (2 ~ Tolyl) -phtha3.cjninsäure 2-Methacryl- ^ ¹ , ^J l '--dichLor ^ iLid

BATH

H- ( ⁱ l - Chlorpheny.l) -2,2-dirnethylvaieram.ld '·

} -} _ (jj-chloro-'l-methyl phenyl) -2-iricthylpentanamide oc-chloro-H-isopropylacefcanilide.

2- (a-naphthoxy) "MJs ^! -Äiäthylpropionaniid.

2-chloro-N- (2-methyl ~ 6-tert-butylphenyl) äcetamid 2-chloro-N-2,6-diäthylp'nenyl-li-irjcthoxyrnctbylacetamid 6-I ^i-ir-jethyl inethoxymothyl-2-t-buty .l ~ a-bromoacetanilide · 2 - [(^ - chloro-o-tolyl) oxy] "- N-methoxyacetamide ^: -; 2-chloro-li-isopropy.l-acetanilide.

G) Organic phosphorus compounds

tris- (2. H-D.ichlorphenoxyethyl) phosphbit

0- (2 _> ¹ ! -Dichlorophenyl) O ^l -methyl-N-isopropyl-arnidothiophosphab ^ - (2- (O, O-di-isopropyldithiophosphoryl) ethyl | benzenesulfonaroid S ^ S ^ S-tributyl-thiophosphate. '

H) Various connections

2-chloroethyl-triirethyl-arimoniuri-chloride Haleinic acid lydrazide

Methylarsinic acid-di-Na-aal-z ^J l, 5,7-Tr-dichlorobenzthiodia- / ol-2, l ",?

5-Amlno-l, 2, ¹ I-UrIaZOl · ·

Trichlorobcriayl Chloride '

2-phenyl-jJ, l-bcn ^ oxazinone

109882/1 -9 69

BATH ORIGINAL.

. 7th

N-Butyl-N-ethyl-2,6 ₇ dinitro - '»- trifluoromethylaniline * ·''"' · · ϊί jN-Di- (n-pro? Yl) -2,6-dinitro - ^ - trifluoromethylaniline 4- Trifluoroethyl-2,4'-dinitro-diphenyl ether · 2, hj S-trichloro-h ^t -nitrodipheriyl ether · "·

2,4-dichloro- * r ^f -nitro-diphenyläfcher '·

J-chloro-δ-methyl-J-tert-butyluracil. *. · ". *

"Ammonium sulfamate -". . '' · ·

.5-Bromo-6-niethyl-3- (l-methyl-K ^I -propyl) -uracii \

1,2 ^, 5, β, 7,10,10-octachlor ~ ¹ h Y ₁ 8,9-tetrahydro- **, 7-ra ethylenindanm-isopropyl-xanthate ....., ..- * '. ''

^ -Eroin-J-isopropyl-ö-iTiethyluracil ^ -Cyclohexyl-ö-mothyluracil ■

5 ~ cyclchexyl-6-sec-butyluraeil

5-CyGlohexyl ~ 5-bromouracil. ■; .

^ -Cyclohexyl-5-chloruracil

35-isopropyl-5 ~ chloruracil ■■ ·

5-isopropyl-5-bronmracil · '·'. "■

2-chloro-1 · I-ethyl- ^; l-rhodaΓ.oaniline 2 j Jij 6-trichlorobenzyloxypropanol hexachloro-2-propanone. ·

Sodium 2- (2,4,5-trichlorophenoxy) ~ ethyl sulfate Potassium cyanate · ·. · ·

BATH ORIGINAL

10 9882/1969.

2, 5 ~ ⁱ J-Dibrorn- hyclroxybenzaldoxim-2 '/ V -dinitrophenyläther 2,5-diiodo ~ ty-hydroxybenzaldozim-2', V -dinitrophcnyläther

Acrolein

Arsenates. ·· "·..

All3'l alcohol. '. ...

2, ^ - _r dinitrophenyl _i 2, ⁱ i-dinitro-6-sec.but5 ⁱ lphenyl carbonate

5-chloro-2-isopropylbenzimidazoX ·. '

5-iodo-2-trifluorine-3-ethylbenzimidazole ·· ■ ' ^ -Cyclohexyl-β, T-dihydro-1H-cyclopentapyrimidine -> *

l: l-ethylene-2: 2-bipyridyliunibro: nid ■

Di (methoxythiocarbonyl) disulfide. · '

2-methyl- ^; ^ - (^ ^l -trifluoΓmethylphenyl) ~ tetrahydro-l _J 2 _ί 4-

l-phenyl- ^ l-, 5 ~ ^<
6-chloro-2-difluoromethyl ^ H-imida / jo (^, 5-.b) '- pyr.idin.

ι. ■

2 ~ tert-butyl-6 ~ chlorimidazo-4,5-pyridine ^ ^:

Hexafluoroacetone hydrafc

Kakodyl ' ^- ·. . '

ⁱ ~ (methylsulphonyl) -2 _/ 6-dinitro-N _, N-dipropylaniline 4lMethyl-2,6-d'initro ~ H, N-dipropylaniline

. * ' BATH

'109882/1969.

- 18 - r

5- ^{Amino- i} l -chlor-2-phenyl -2-pyridazon 2,3,5-Trichlor- ^j 4-pyridinol *

5,4,5,6-tetrahydro-5,5-dimethyl-l,; 5, -5-thiadiazine-2-thione sodium 2- (2,4-dichlorophenoxy) ethyl sulfate 2,3-dichloro ~ l, ⁱ ! - ~ naphthoquinone ...

Di (ethoxythiocarbonyl) disulfide; . '. j5,5-dichloro-2,6-difluoro * ^J i - hydroxy-pyridine

Such agents can be used in the form of solutions, suspensions, granules or dusts reach. The application forms depend on the intended use and must have a fine distributability of the ' Ensure active substance. Especially with the total eradication of vegetation, with premature dehydration as well as defoliation, the effect can be exerted by the use of inherently phytotoxic carriers, such as high-boiling Mineral oil fractions or chlorinated hydrocarbons, are strengthened; on the other hand, there is the selectivity of the V / achsturnshemmung when using carriers that are indifferent to plants, e.g. in selective weed control, in general clearly shown to advantage.

109882/1969

Solvents are used to prepare solutions, such as in particular alcohols, e.g. ethyl or isopropyl alcohol, Ketones, such as acetone or cyclohexanone, aliphatic hydrocarbons, such as kerosene and cyclic hydrocarbons such as benzene, toluene, xylene, tetrahydronaphthalene, alkylated Naphthalenes, also chlorinated hydrocarbons, such as tetrachloroethane, Ethylene chloride, and finally also mineral and vegetable oils or mixtures of the substances mentioned above in question.

The aqueous preparations are dispersions. The active ingredients are used as such or in one of the abovementioned solvents, preferably by means of dispersants, homogenized in water. On cation-active Examples of dispersants are quaternary ammonium compounds called; of anion-active e.g. soaps, aliphatic long-chain sulfuric acid monoesters, aliphatic-aromatic Sulfonic acids, long-chain alkoxyacetic acids; of nonionic polyglycol ethers of fatty alcohols or p-tert. Alkyl phenols with ethylene oxide. On the other hand, concentrates consisting of active ingredient, dispersant and possibly solvent can also be used getting produced. Such concentrates can be diluted with water before use, for example, and then lie as emulsions or suspensions.

109882/196 9

Dusts can be produced by mixing or grinding together of active substance with a solid carrier. Examples of these are: talc, diatomaceous earth, kaolin, Bentonite, calcium carbonate, boric acid, tricalcium phosphate, but also Wood flour, coal and other materials of vegetable origin. The active ingredients can also be mixed with a volatile solvent are drawn onto the carrier materials. By adding wetting agents and protective colloids, powdered preparations and pastes can be made suspendable in water and usable as wettable powders.

The use of granules for the uniform release of active ingredients over a longer period of time is particularly advantageous. Such carriers can be obtained by dissolving the active ingredient in an organic solvent, absorbing this solution through granules Produce mineral, e.g. attapulgite or SiCL and remove the solvent. They can also be manufactured so that the active ingredients of the formula I are mixed with polymerizable compounds, whereupon a polymerization is carried out, of which the Active substances remain unaffected, and granulation is still carried out during the polymerization. Certain artificial ones High polymers such as urea / formaldehyde resin or polyacrylonitrile can be used as porous microgranulates with a high specific surface area and with an adsorption-desorption ratio that is favorable for biological agents and as active ingredient granules by applying active ingredient solutions and removing the solvent insert. One of the advantages of such polymer-based granules is their increased specific weight, which is a rapid decline when used in water rice guaranteed [BeIg. P. 736.508].

109882/196 9

The content of active ingredient in the agents described above is between 0.1 and 95 %; it should be mentioned that when applied from an aircraft or by means of other suitable application devices, concentrations of up to 99.5% or even pure active ingredient are used.

109882/1969

Example 1 describes the production of two active ingredients. All temperature data in this description relate to degrees Celsius.

example 1
Production of 2-chloroallyl-N-ethyl-N-isopropyl-dithiocarbamate

202 g of ethyl-isopropylamine (2.3 moles) have been proposed in 500 ml of water added to 184 g w and 50% NaOH (2.3 mole) added with cooling. Then 175 g of CS “(2.3 moles) were added dropwise with cooling at 5-10 °. The ethyl isopropyl ammonium salt of ethyl isopropyldithio-carbamic acid temporarily precipitated out. The reaction mixture was stirred at room temperature until a homogeneous yellow solution was formed and then left to stand overnight. Sodium dithiocarbamate partially crystallized out in the process. 238 g of 2,3-dichloro-1-propene (2.15 moles) were added dropwise to this suspension at 20-25 ° with slight cooling. The batch was stirred for 1 hour at room temperature and 5 hours at 45-50 °, then the deposited oil was taken up in 500 ml of ethylene chloride. The organic phase was separated off, dried over Na ^ SO, and the solvent was distilled off in vacuo. The desired compound remained as a dark yellow oil.

Yield 473 g = 87% of theory

Cl -CS-S-CH ₂ -C = CH ₂ [comp. Number 1]

109882/1969

Analysis: Ber. N: 5.89 % Cl: 14.91% Found N: 5.8% Cl: 15.0%

Production of methallyl-N, N-di- (isopropyl) -dithiocarbamate

202 g of diisopropylamine (2 moles) are placed in 1000 ml of water. 160 g of 50% strength NaOH (2 moles) are added and 152 g of CS _{2 are} then added dropwise at 10 ° while cooling with ice. The suspension of the salt formed is stirred at room temperature for 4-5 hours. Then 176 g of 2-methylallyl chloride 1.95 moles in 300 ml of toluene are added dropwise and the mixture is stirred for one hour at room temperature and for 3 hours at 50-60 °. After cooling, the organic phase is separated, dried over Na SO _0, dried and concentrated in vacuo. This gives 429 g ( «95.5% of theory) of a yellowish red ÖIS, τι £ ^υ 1.5584, bp. 96-97 ° 0.02.

(iso O ₃ HJ ₀ N-CS-S-CH ₀ -C = CH ₀ [Comp. No. 24]

CH ₃

Analysis: Ber. S: 27.71% Gef: S: 27.8 %

The following connections can be made in the same way:

109882/1969

^R l characterization

CHg = C-CHg CH,

. Il

CHg = C-CHg

CH, "

C ₂ H ₅ .

7th

8 9 10

.11 "

12th

15 "

^1C 3 ^H 7

^C 2 ^H 5

-CH. 2-CH = CHg -CH, _o -C = CH ₀
^ t <=.
Cl -CH, 2-C = CHg
CH, -CH g-CH = CHg -CH g-C = CHg. Cl -CH gC = CHg-
CH, -CHg -CH = CHg -CH ₂ -C = CHg Cl -CH ₂ -C = CHp
t ■ £ ■
Br -CH ₂ -C = CH ₀
t ^
CH -CH " -CH = CHCl

-CH ₂ -CH = CH-CH-

ber.

^{N found} . ⁶ '3 *

5.75Si

ber. ^ * - ¹ " ¹ ^ ■

jber. Cl: 13.44 %
13.0 %

5.8 %

6.2

approx.

CO

N: 5.31 5.I

KP IO5-IO5VO.O2 mm. Ed

L / tiX * * Va ^ KJ m {J / O / Ii · { ·

found: 51.I # 8.0 % 7-5 ^. 55.9 KP IO7-IIOVO.O2 mmHg

Br, 29.79
oer.

Br $ 31.2

KP 105-107 ° / 0.01 mmHg

Calcd .: Cl: 15-84;
Igef.i. I5.O j

^S ber.51.53 ^

6.26 ^ / S: 28.6βί?

6.5 fo

^{S found} . 31.1

29.4 fo

to cn co

^R l nC.H ₇ -CHg-CH = CHg characterization s _ 29.5 %
found ^{N found} . ^βΛ ^ cn 14 η Il -CH ₂ -C = CHg
Cl ber. ^{N found} . ⁵ * ³ ^ mm Hg 15th <-. ti -CH ₂ -C = CHg
Br ^Br gef. ²⁷ · ² ^ S: 25.46 £ Cl:
25.2 fo 14.08 %
14.2 ■ fo- 16 "1 -CHg-CH = CHCl ^3r ber. ^{26 '97} ^ % N: 5.56 JS
Year 5.4 JS N _ 28.0 %
found 17th If ti -CHp-C = CHp
cz, τ cL Ber. Cl: 14, O8
sef. 14.1 KP 113-115 ° / 0.02. mm Hg. Hg (decomp.) ■ 18 Il CH, mm Hg Ca) // -CH ^ -CH = CHCH-
2 3 N. 6.Ο5 fo
ber. ^ ' 00
/ in 19th Il IC ₅ H ₇ ■ - ■ -CHg-CH = CHg κ? 95-96V0.03 O .ρ £ 1 (. W / 20 i C ₅ H ₇ * -CHp-C = CHp
Cl calc. N: 5.56 %
found 21 H - ti 2 ι 2
Br Br _ber . _{26th 97} * 22nd I * (I. -CHg-CH = CHCl KP 140 ° / 0.3 mm 23 M. Il -CHg-C = CH ₂ K? 96-97 ° / 0.02 24 Il CH ₃ J / -CH ₂ -CH = CH-CH ₃ S _{V / ivi} 27 * 71 ^
Of the. 25th U

^R l R ₂ • It ^R 3 characterization Cl found 25, 1 % ■ 26 IC ₅ H ₇ ■ ^iC 3 ^H 7 -CHg-CCl = CHCl Cl bar. 24; 77 ^ Vf. 5 .8th fo ^
co 27 nC ₄ H ₉ TiC ₄ H ₉ . -CHg-CH = CHg N. 5.7I %
ber. ^J ' ^S sef. .22 • 9 28 / I • -CHg - C = CHg
Cl S. '22 .91 %
ber. ^ ^{/ C1} sef. 11 • 3 co
cn 29 -CHg-CH = CHCl Cl. 12.67 %
ber. ■ mm Hg 30 " f -CHg-C = CHg KP 131-133 ° / o 25 CH ₅ mm Hg 31 sec C ₄ H ₉ sec. C ₄ H ₉ , -CH ₂ -CH = CHg KP 98-100V0.01 mm Hg 32 " «« .-CH ₀ -C = CH KP 124-125 ° / 0.02 Cm J ti.
Cl mm Hg ■ 33 " α -CH ₂ -C = CHg KP 108-105V0.01 O * £ * 1
c3 ^ - * ^ · 25th 4th 34 IC ₄ H ₉ • ^1C 4 ^H 9 '-CHg-CH = CHg s, 26.13 %.
ber. ^{C1 found} 11. 6th 35 It -CHg-C = CHg
Cl ci. 12.67 fo
ber. 36 -CHp-CH = CClCH, S: 24
24 .71
.7 I. 37 iber. N: 5-40 fo
\ found 5-7 pounds

KNKN

OJ OJ

CO

mm

Φ φ

X) fcO

OJ

Φ faO CO

VO O

-ο

KN

ω χ »

CO

<ί-ι

bO

KN

Φ .Ω

ϋ ^-

VO OJ ΙΛ VO

«In Vi

Φ Φ

bO faO

525 S3

VO

νο

m νο

5η

φ χ)

te:

φ χ>

νο m

OJ

OJ OJ

CO CVl

m KN

OJ

to

? 3 • W. « W. * CO Q) • Φ ■ t I. U co Ϊ3. Cj faO U bO
CO U OJ Q) φ rl
Φ φ φ O \ R X) X) X) X) O VO CO «R 53 CO \ r-i KN O O m O • « « * CO OJ m VO VO m m « • r-l OJ LTV KN ri
I. «· OJ 1
KN S3 iH • iH Century Φ CM vX> - \ "* & DO • LfN • Φ bOj i - '

ΚΛ

ϋ Ä O

Il

O 1

OJ

te

CVI

Il

ta

O CVI

ta ο

OJ

Il M

ο-ο

CVI

ία ο

r-1 O

Il

OJ ΐΠ O

OJ

K O

Il K O -O

CVI

O I

KN

KN CV)
ία CVi CVI KN CV!
ία OJ CVf ? ο
H ία
ο ία
ο ία O
, Il do
O f ta
ο * τ * Il H Il O ta I! .H Ii ta Il
ta O
I. ο-ο O-
I. ο
I. Ο-Ο ο-ο ο CVI CVI
ΐτ-ι CVI
ία
O
I. CVI CVJ CVI
ία CVl -Cr > Ίη
O
I. Μ- #
O -CI ο ία
ο ι

ON

ta ο

CVl

ta

ία ο

Ii CVI

ta ο ία ο -

• Η

CVJ

ta

KN

ο-ο CVJ

ta ο

• Η

co

KN

CM

ta ο

ta ο

Il CVl

ία ο

ON KN cm

ία

ία ο-ο

ία ο

OJ

νθ

CVI

ία

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• ία ο-ο =

CVl

ο-

OO

On

1098-8 & /

V ^R 2 \
N- Ί • * ^R 3 Choir act eration ι N: 7.48
: 7.4. - ^C1 ber. ¹ S-SS '' 6.96 % 1 N: 6.50 %
6.9%
N: 6.5Ο ft>
6.4 # S: 54
33 .23
.8th D / 0 28 1 rf
• X JO .50 Jl. -CHg-CH = CHg Jber. PP 48-50 ° ^N ber 31.85 fo N: 6.5Ο fo
6.4 year 9% 29 »5 / ° 51 ο- -CH ₀ -C = CH ₀ ber N: 6.96 fo
7.2 $, Cl: 14.19
14.3 4 % Il Cl Jber.
\ found FP 45-48 ° 27.95 % ^{C1 found} 16. I. 25th .7 # 52 -CHg-CH = CHCl 29 «Ύ7 # ^{N found} . 6th .8 fo 53 Il -CH ₂ -C = CHg Vf. 31. 54 Il
H -CH ₀ -CH = CH-CH-, ⁰¹ calc. ¹ S- ⁰ '* * 25.67 Ji S: 31
31 VJTCO
VJl X / 0 55 Ά -CH ₂ -CH = CHg fber.
| found
jber. 27.95 # fo ' 56 Ο "' -CHg-C = CHg fber.
% ef. ί Il Cl jber.
v_ ^{C1 found} 15th S: 25.67 % ■
25.6 % 57 Q- -CHg-CH = CHCl ber. S: 29.
29
S: 29.
28. 77
5
77
5 Vf. 58
59 CH-,
3 -CH ₀ -C = CH ₀
d. , egg
CH ₃
-CH ₀ -CH = CH-CH-,
^ 3 ber. S: 29.
29 77
8th Vf. 60 Il
Ä -CHg-CH = CHg 61 Il -CH ₀ -C-CH ₀
c. ι d.
Cl ^S ber. Vf. 62 -CHg-C = CHg Vf. 63 -CHg-CH = CHg 64 -CHg-C = CHg.
Cl 65 O ΐιι QOO ^ t
C. il U φ φ Q £ f CIL,

V ^R 2 R ₃ . 19th characterization 29-77 % Vf. 29 .7 * fo 66 CH ₃ - / ~~ N- -CFl -CH = CH ₀
2 ^d ber. 25.67 i Vf. 25th .6 fo 67 ' -CH ₀ -C = CH ₀
<; ι ^
Cl ber. 27.95 fo Vf. 27 .95 % 68 * -CHp-C = CHp
CH ₃ ^S ber. 69 * -CHg-CH = CH-CH 6.11 % IN THE
D * (- ^ T 5 .6 % 70 <C <N- -CHg-CH = CHg ^N ber. 13.44 % ^{C1 found} 13th .4 % . ^CH 3
71 * ^y -CH ₂ -C = CHg
Cl ^C1 ber. 7.03 % Vf. 7th ,1 % 72 <Q <- -CHg-CH = CHg ^N ber. 27.43 % Vf. 27 .7 * .75 ' -CHg-C = CHg
Cl ^S ber. 06/30 # Vf. 29 , 6 74 ■ -CHg-C = CHg
CH ₃ ^S ber. 6.50 %
6.6 <$>
5.61 ^
5.5 % CQ CQ
ro ro ro ro
UlUl VOVO .77
.6
.67
.7 ⁷⁵ O-
76 ■ -CHp-CH = CHp
-CH ₂ -C = CHg
Cl ber. N:
found '
ber. N:
found 27.15 % ^Br gef 26th ;.8th * 77 "■ -CHg-C = CHg '
Br ^r ber. : 14.19 %
16.4 % S: 25
23 .67
.9 78 ". -CHg-CH = CHCl ber. Cl
found 6.11 #
5.9, " S: 27
27 .95
.3 79 " -CHg-C = CH ₂
CH ₃ ber. N:
found 27.95 ζ » Vf. 27 .8th 80 " -CH ₂ -CH = CH-CH ₃ ^S ber. 109882 / 59 -

CM Vi • YR ■ Η • YR φ I. « OS « CO * • VO a YR « 30th Φ O r-i - CM YA • ■ - = YR , • 2131 sr 135 • - YR t a O fa C- O U VO J ₄ O U £ - « CM YR &O O P ^- ; U CO co U O CO ί-ι CM C-- φ φ VO φ KS φ ω φ ΟΛ Φ CA CO rH O νό φ co eH Φ φ OS YR φ OS Φ H , Q hO ys. r> co CM bD CT \ ! I rH Xl hO Xi ^ r χι CM. Xl YR KS CO vd CM φ YR O-O CO CO ιή S3 CO CM Φ r-i O ¥ - · in CM • YA bO co CM CM Φ bO CM •
ri CM O O O φ CM bO CM Φ CM bO O CM - = 1- O W. \ R in C. bO YR O III bO Il r-I O KS Jt φ O O OS 'Ά O KS in Il Φ O co O KS O Il S &O Il in CM H K co W. ε faO ■ Il & Il S b
I. Il ri o-o O
I. O- cn O-O i-l O ε S3 Ο-Ώ . Ο-Ο YR CM oo
I. CM CM CM CM Φ YR CM KS CM CM CU Υ & CM CO O CM O O O Xl in O O O O t- O co I. O I. I. Φ r-i O I. *
O YR. 1 I. VO £ 1 O vd CJS in in Φ co in O O CM CM CM ar ^ CM CM O ιή O sr O Si O r-1
I. O CM VO Il co W. O O r-i C- KS O O
Il
Oi " ¹ KS ^K ks CM O Pi O _ O
•H = 3r O O σ \ r-i KS in I. co r-i CO CM co co co t— CM CO JT *, O O Il rH OO
I. CM O C- I. O
•H VO co W) P. P. φ cn
■ rl ■ φ
I \ + ■ * CO O K ^ ft; -

109882/1969

co co to

^R l R ₂ -CHg-CH = CHg ' characterization 6.50 % 27.95 % ^{N found} . 6.4 % 6.2 f ψ
1 31135 I.
93 CHg = CH-CHg- iCJHL -CHg-C = CHg
Cl ^N ber. '5-61 % 29.80 %
14.19 % Vf. 5.7 % 6.2 5
5.0 f
i 94 '' u -CHg-C = CHg
Br ^N ber. ber. Br: 27-15 %
found 26.8 % 6.11 Si N: 4.76 %
4.4 5S 26.34 «g
26.0 % f
3 95 " (I. -CH ₂ -C = CHg ^S ber. 6.11 #
5.31 % Vf. 28.0 $ 1 ■ 96 ti -CHg-CH = CHg
-CH ₂ -C = CH ₂
Cl ber.
^C1 ber calc. N: 5-75 %
found 5.64 % Vf. ^{29 6} *
^c Vf. ^{13 9} '* * 97
98 CHp = CH-CHp
it ir -CH ₂ -C = CH ₂ ·
CH, ^N ber. Vf. 1 99 11 -CHg-CH = CHg
-CHg-C = CHg
Cl ^N ber.
^N ber. Vf
Vf 100
.101 CHg = CH-CHg
fi nC ^ Hg -CHg-C = CHg
CH, S: 102 U

1 109 R-, Λ Il Il R ₂ ' ^R 3 'Characterization 6.11 fo N: 5.04 % ^{N found} . ^{N found} . 6.0 % % fo 1 Q ^ Oo • ro 103 110 CH ₂ = CK-CH ₂ I "-CH ₂ -CH = CH ₂ * ber Cl: 13.44 * 5.2 fo ι S: 24.30 '% fo .6 "% co 104 H CH ₂ = C-CH ₂ Il -CH tC = CH ber. 13-1 % £ 24.79 1 ^{S found} . 24.2 rf
/ 0 OJ 111 ι / CH ₂ = C-CH ₂ -
, 1 ^CH 3 Cl found 5.75 # ^{C1 found} 5.6 12 76 105 "■ ■ -CH ₀ -C = CH ₀ 5-44 % ^{N found} . · 12 .'l % 112
i CH, 3T-S ₅ ^ 32nd 23.6 106 113 . ^CH 2 -CH ₂ -CH = CH ₂ ber. ' 15.0 « 14.7 107 '' Il -CH ₂ -C = CH ₂
Cl ^C1 ber. 6.5 % ^{N found} . 6.9 5.8 • 108 114 CH ₂ = C-CH ₂ Il -CH ₀ -C = CH ₀
* - »* - ¹ ber. 6.46iö . ^CH 3 CH, 6.7 % 115 3 27.95 6.5 H C ₂ H ₅
I / -CH ₂ -CH = CH ₂ '" ^T ber. : 48.O8 # H: 28.2 Cl: l4 -CH-C = CH ₀ ber. C .49.I % mm Hg 14th Cl found : 6.1155 S: Cl: Il -CH _p -C = CH _o oer. N 6.1 % 3ef. KP 110-112 ° / 0.01 ^Br gef. .nC ₄ H ₉ -CH ₂ -CH = CH ₂ Jber. II -CH ₂ -C = CK ₂ Igef. Cl ' Br _ber Il -CH ₂ -C = CH ₂ Br N. _nori -CH ₂ -C = CH ₂

- 33 - ■

Example 2

formulation

Dust

Equal parts of an active ingredient according to the invention and precipitated silica are finely ground. By mixing with kaolin or talc, dust ¹ with a preferably 1-θ? O active ingredient content can be produced therefrom. Wettable powder

To produce a wettable powder, for example, the following components are mixed and finely ground: 50 parts of active ingredient according to the present invention 20 parts of Koch adsorptive silica 25 parts of Bolus alba (kaolin)
1.5 parts l-benzyl ~ 2 ~ stearyl-benzimidazole ~ 6.3 ¹ -disulfone-

acidic sodium. ·. .

3j5 parts of reaction product from p-tert. Octylphenol and

Ethylene oxide. Enml sion concentrate

Easily soluble active ingredients can also be formulated as an emulsion concentrate according to the following rule: 20 parts active ingredient
70 parts of xylene
10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecyl

109882/196 9

benzoliuilfonat · _nArN __, «.,., '

_CO py BATH ORIGINAL

are mixed. When diluting with water to the desired Concentration creates a sprayable emulsion.

Granules

a) 7.5 g of one of the active ingredients of the formula I are dissolved in 100 ml of acetone and the acetone solution thus obtained is increased to 92 g granulated attapulgite given. The whole thing is mixed well and the solvent is drawn off in a rotary evaporator. One receives a Granules with 7.5% active ingredient content.

b) To produce a 7.5% polymer granulate 77Og of one of the active ingredients of the formula I in 2.5 liters of trichlorethylene dissolved and sprayed onto 9230 g of urea / formaldehyde granules at 1.5 at spray pressure. By heating the The solvent can be removed again in a fluidized air at approx. 50 °.

c) For the production of polymer granules with 10 percent by weight Active ingredient 3.3 liters of a 30% formulation of an active ingredient of the formula I as an emulsion concentrate (EC-30) per 9000 g sprayed on a presented granulated urea / formaldehyde resin. In this case the solvent remains on the granulate.

d) If the switching weight of a polymer granulate is to be additionally increased, 770 g of a technically pure active ingredient of the formula I, 500 g of BaSO ₄ , 1000 g of urea and 7730 g of the dry crude polymer [ eg polyacrylonitrile or urea / formaldehyde resin (UF)] on a roller mill and then break to the desired grain size.

1 098 82/196 9

Example 3

Rice seedlings of the variety IR 8 were transplanted in the field and treated after 3 weeks with granules (7, 5%) of compounds 1 and 84th The grass weeds (Echinochloa, Cyperus and Scirpus) were in the single-leaf to three-leaf stage at the time of treatment. The granules were applied to the rice field flooded with water 3-4 cm high; this water level was maintained for a long time. After 26 days, ratings were given for effectiveness against grass weeds and compatibility with rice plants.

109882/1969

Table 1

Connection Active ingredient

1.5 kg / ha 3 kg / ha

1.5 kg / ha 3 kg / ha

Effectiveness against
Oblig. Rice grasses

1
1

5.5 3.5

5.0 3.5

Legend: 1 = no damage to rice, complete destruction to

Weeds

9 = complete destruction in the case of rice, no damage to it the weeds.

Example 4

Three to four weeks old rice plants grown in the greenhouse (Height 12-15 cm) were transplanted in boxes 3/4 m in area. The bottom was up to a height of 4 cm with Layered water, sown in the echinochloa seeds became. When the weeds were in the two-leaf stage after 8-12 days and with the topmost stem out of the water sticked out, the plants were treated with the active ingredient 1

109882/1969

and as a comparison with N, N-di- (n-propyl) -S-n-propyl dithiocarbamate (Comp. A), N.N-Di-Methallyl-S-n-Propyl-Dithiocarbamate (Comp. B) [both disclosed in French patent 1,571,695] and with N-cyclohexyl-N-n-propyl-S-allyl dithiocarbamate (Verb. C) [in Brit. Patent 1,154,075 disclosed].

109882/1969

Table 2

link

(known from>

Ep.ρ. ι.571.695 '

^ known from
FF.P. 1

Application rate

0.5 kg / ha

1 kg / ha

2 kg / ha

1
2

1
2

kg / ha kg / ha

kg / ha kg / ha

Effect against Verpfl. R ice Eehinochloa

1 1 2

1 1

1 1

6 8 9

Table 3
link

^ known from>

fe. p. 1,154,075}

Application rate

0.5 kg / ha

1 kg / ha

• 2 kg / ha

0.5 kg / ha

1 kg / ha

2 kg / ha 4 kg / ha effect against "Verofl. Reis Echinochloa

1 1 2

1 1 1

6 7 9

1 1

Legend for Tables 2 and 3: 1 = no damage, no effect

9 = total destruction

1098 82/1969

It was found that the active ingredient suitable according to the invention 1 . leads to better results with significantly lower application rates than the comparison substances A, B and C.

109882/1969

Claims (11)

Claims 1. Use of dithiocarbamates of the formula ^R l S J) N -CSR ₃ R ₂ where R, and R _? each represents an alkyl radical with 2 to 4 carbon atoms or a P alkenyl radical with 3 to 4 carbon atoms or in which R- and R "together with the N atom connected to them represent a 5- to 7-membered heterocyclic ring with a hetero atom which is optionally substituted by one or two methyl or ethyl groups, Ro means an alkenyl radical with 3 to 4 carbon atoms or a haloalkenyl radical with 3 to 4 carbon atoms and 1 or 2 halogen atoms, for combating undesired vegetation in Rice crops. 2. Use according to claim 1 of dithiocarbamates, ψ wherein R- is an allyl, methallyl, crotyl, chlorallyl or bromoallyl radical. represents. 3. Use according to claim 1 of dithiocarbamates, in which R 1 and R 2 are, independently of one another, an ethyl, n-propyl, isopropyl, isobutyl, allyl or methallyl radical and R _{3 is} a methallyl radical. 4. Use according to claim 1 of the compound methallyl N, N-di (isopropyl) di thiocarbainate. 109882/1969 5. Use according to claim 1 of the compound methallyl-K-ethyl-N-propyl-dithiocarbamate. 6. Use according to claim 1 of the compound 2-chloroallyl-K-methallyl-N-ethyl dithiocarbamate. 7. Use according to claim 1 of the compound 2-chloroallyl-N-ethyl-N- (n-propyl) dithiocarbamate. 8. Use of the compounds according to any one of claims 1 to 7 for combating undesirable vegetation in crops of transplanted rice. 9. Use of the compounds according to any one of claims 1 to 7 for combating Echinochloa, Eleocharis, Scirpus, Fimbistylis and Alisma in Cultures of Transplanted Rice. 10. Use of the compounds according to any one of claims 1 to 7 together with one or more suitable solid or liquid Carriers. 11. Use of the compounds according to any one of claims 1 to 7 on suitable carriers in the form of active ingredient granules. 12. Use of the compounds according to any one of claims 1 to 7 on granulated mineral. 109882/1969 13. Use of the compounds according to any one of claims 1 up to 7 on granulated high polymers. 14. Use of the compounds according to any one of claims 1 up to 7 on granulated urea / formaldehyde resin or granulated polyacrylonitrile. Process for the preparation of compounds of the formula NC - S - CH ₀ - C = CH by reaction of an amine of the formula R ₁ - NH ^R 2 with carbon disulfide in the presence of a tertiary amine or alkali metal hydroxide and further conversion of the resulting salt of a Dithiocarbamic acid of the formula R ₁ -NH-C-SH ¹ I.
R ₂ with the halide of the formula Hal - CH ₂ -C = CH ₂ CH ₃ Xiorin R and R _{0 have} the meaning given in claim 1 and Hal is a halogen atom, preferably chlorine or bromine. 109882/1969 16. Compounds of the general formula ^R 1 S - 43 - N - C - S - CH ₉ - C = CH ₀ R ₂ where R and R _? each denotes an alkyl radical with 2 to 4 carbon atoms or an alkenyl radical with 3 to 4 carbon atoms or in which R- and R "together with the N-atom connected to it denote a 5- to 7-membered heterocyclic ring with a heteroatom which is optionally substituted by one or two methyl or ethyl groups. 17. Compounds according to claim 16, wherein R, and R " independently of one another an ethyl, n-propyl, isopropyl, isobutyl, Mean allyl or methallyl radical. 18. The compound methallyl-N, N-di- (isopropyl) -dithiocarbamate. 19. The compound methallyl-N-ethyl-N-propyl-dithiocarbamate. 20. Pesticides which are one of the im Claim 16 mentioned compounds together with one or more contain suitable carrier materials. 21. Pesticides according to I-atent claim 20, the contain methallyl-N, N-di- (isopropyl) -dithiocarbamate as active ingredient. 109882/1969 "22, pesticides according to claim 20, the contain methallyl-N-ethyl-N-propyl-dithiocarbamate as active ingredient. f FO 3.35 / Pk / kö June 11, 1971 109882/1969