DE1770027C - Substituted 2 ammo 4 (1 methyl 1 thiocarbamoy1 ethyl) amino s triazine - Google Patents

Description

The invention relates to substituted 2-Λιηίηο-4- ( 1-methyl-1-thiocarbamoyl-ethylHimino-s-triazine of the general formula I.

X
C.

N '' N

CH ₃ S

N-C C -NH-C C-NH, (I)

in the X a c liloratom. a methyl mercapto or represents a methoxy group and R 'and R- are identical or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, as well as containing them as effective ingredients herbicidal agents.

Thiocarbamoylalkylamino-s-triazines are in the Literature has not yet been described, they are derived from Aminoessigsüure-lhionmid, that am n-Kohlensioff is twice substituted. Triazine derivatives. the ein.cn amino acid or amino acid amide sulfide are already known.

It has been found that the thioearhamoylalkylammo-s-triazines in contrast to the corresponding (arbamoyl- and carboxyalkylamino-s-triazines, surprising possess potent and selective herbicidal properties. .is

The compounds according to the invention can according to different methods can be produced. For their production is within the scope of this invention no protection claimed.

Introducing the i-methyl-l-thioearbamoyl- 40 nc: äthylaminogruppc can, for example, by reacting cyanuric chloride with - / - Aminoisobuttersäurcthioamid take place, which according to Λ s i η g e r. W. Schäfer. 11. K e r s t e η and A. Saus (Monthly booklets for chemistry 9X. P. 1K43 to IKM [1% 7 || imidazolidinthione-4 substituted by hydrolysis.

CH,

CS

NH NH

R ¹ R ²

CH, CSNII ₂

CW, NH ₂
Γη .: HWC

The imidazolidinthine-4s which are oiled for the process are in any case covered by conventional methods (11. T. Bucherer and W. S lei η e rs Prakt. Chemie, 140, 308 [1934]).
The reaction of the n-Aminoisobutlersäurethioamids with cyanuric chloride takes place according to processes which are analogous to those described in the literature for the reaction with amines. Also the introduction of the second amino group in da ;; Triazine molecule

ίο takes place in a manner known per se (J.T. Thurston and coworkers, J. Am. Chem. Soc, 73, p. 29Sl [1951T).

The claimed methoxy and methyl mercaptotriazines can be z. B. by converting the 2-alkylamino-4- (l -methyl-1 -thiocarbamoyl-ethyU-amino-6-halogen-s-triazine obtained with methanol or iviethyl mercaptan in the presence of acid acceptors. But you can also proceed in such a way that methoxy- and Meihylmercaptü- (1-methyl-1-cyanoethyl) aminotriazines with hydrogen sulfide in the presence of strong and weak bases, e.g. B. pyridine or triethylamine.

Methyl mercapto derivatives of (1-methyl-1-tliiocarbamoylethyl) - amino - s - triazines can also be made from appropriately substituted chlorine! l-melhyll-cyano-ethyl) -amino-s-triazines can be obtained by treating them with IFS in pyridine. Man thus receives the 2-alkyl-amino-4- (1 -methyl-1 -thiocarbanioylethyl) -amino- (S-mercapto-s-triazine, which then e.g. with dimethyl sulfate in the presence of alkali, to the corresponding i'i-methylmerciiptos-triazine implemented.

The compounds according to the invention are distinguished by their superior natural properties and can be used both as pre-emergence and post-emergence herbicides. Even in low concentrations, they are able to influence the growth of plants. You can, depending on the type of Substituenlen R 'and ^R: to eradicate or selective suppression of I nkräutern under crops and the complete destruction and prevent unwanted Pflanzeiiwachstums serve.!.

You can also use the new compounds for defoliation. Reduction of the fruit set. Use delay animal flowering etc. They can be used individually or in a mixture with one another or together be used with anile herbicides. You can also use insecticides to do this. Fungicides and

y> Use mixed fertilizers. The compounds are mostly crystalline substances that are organic in many '. ¹ »Solvents are very soluble.

Examples of suitable solvents for the new compounds are: alcohols. Ketones.

v, hydrocarbons, h.ilogcnicrtc hydrocarbons, z. B. (hlornaplithalin. Mineral oils, such as diesel oil. Vegetable oils oiler mixtures of the substances mentioned.

One can also use the triazine compounds apply solid supports. Everyone comes as such

<> o known for this, /. B. Sound. Kaolin. Kieselguhr. Bentonite. Talc, finely ground calcium carbonate. Charcoal. Wood flour and the like.

The active ingredients can be mixed with the carrier substances in dry form. But you can

fi.s also solutions or emulsions on the carrier materials spray on or mix with these and then dry the mixture.

To better adhere the active ingredients to the

Iiiigern to achieve, one can know KIeIv SU) ITe, such as glue, casein, alginic acid salts uiul similar SiolTe, use.

You can finally prevent the triazine, if necessary mix together with the TriigersloITen, with suspension mills and stabilizers, /. Process H. into a paste or powder, and then add water to form a suspension touch.

Wetting agents, emulsifiers and stabilizers can be unionic, cationic or non-ionic use hekannle fabrics! will, /. B. Turkish oil, Salts of fatty acids, alkylarylsulphonates, secondary alkylsulphates, acidic with resin: salts, polyethylene ethers of fatty alcohols, fatty acids or fetiamines, quaternary Ammonium compounds, ligninsulphonic acid, saponin, cielatine, casein alone or in a mixture together.

Examples of compounds corresponding to general formula I are:

Cl

Cl

Cl

Cl

OCH

OCII

SCII ₁

SCH,

Cl

II

.11

H
Il

R-H

cn.,

i-C, ll.

cm'i,

CH,
CH,

CIU
CMI,

I '. (Ci

over 300 164.5 (Decomposition) ISO 140.5 (Decomposition) 163.5 until 134 (Decomposition) 1 Χ ^ι λ5 until 1.66.5 (Decomposition) 133 until 172 (Decomposition I. 165.5 until 160 (Decomposition) 171 hl ·, (Decomposition) 159 until (Decomposition 200

white
white
white
white
white
white
white
white
white

Crystals
Crystals
Crystal
Crystals
Crystals
Crystals
Crystals
Crystals
Crystals

I .-, isi already e; .the series of substituted bis-alkylaminolria / inen bekannlgeword '-' i. Some of them In practice, they have proven to be excellent herbicides preserved, like the 2.4-bis-ät'ylamino-6-chloro-N-triazine and the 2-Ätliylamino-4-i-propylamino-6-chl (M-s-tria / in. In contrast to these compounds / own triazine compounds with a substilnierh-n Aniinoessigsäureamidrcsl no or no, very limited herbicidal effect. Example igt a compound of the general formula II

IUCNII

Cl N NII Cl I, Y I, C. C. C. N Cl C. N '

in (ki Y the COOII- or the CONIU-C Ii lip means no herbicidal effect, whereas Y means CSNH ₂ , then there is a very strong effect.

It was surprising and unforeseeable that the claimed s-triazines, which have a tertiary carbon atom on an amino group and a thionamide group directly connected to it, are very strong herbicides.

The 6-Clilor-s-triazine compounds according to the invention are / .. B. very selective in maize crops. In this they resemble z. B. the 2.4-8

But they have the great advantage over this that their persistence / in the soil is less. you will be degraded in the soil in the period of a cultivation period to substances without a herbicidal effect. One is out for this reason, no longer forced to plant maize on the same fields again the following year. To test the herbicidal effectiveness, compounds of the claimed type are in the form of Solutions or suspensions iii a mixture of

Equal parts of water and acetone, which also contains 1% of a commercially available dispersant and 2% glycerin, are used. The following types of plants are treated: maize, wheat, ryegrass, ground peas, linseed, mustard, sugar beet.

4s When treating the leaves, the formulated Connections with the help of a spray device sprayed the leaves. The device used makes it possible. I or 10 kg / ha of active ingredient in one Spray volume of 630 l / h.

For the treatment of the soil after the sowing has been carried out, the tea plants are used in Hrdc. which are in Plastic bowls located, sown. The sowing unu Watering takes place shortly before the treatment, and that at the same time as the foliage treatment, so that the

s ". equal amounts of active ingredient are used.

At the end of the investigation (7 days at

the foliage treatment and 11 days in the soil tandhing before sprouting) the results are determined by visual inspection.

fo kung is classified on a scale from 0 to 9. Here, 0 means no effect and 9 means total damage to the plant. The phytotomacy of all seven plant species using an active ingredient concentration of 1 kg / ha is in the following

f> s the table together with the information about the The constitution of the compound used is shown. The table also gives the comparison with known connections again.

K '

CI *

Cl *)

OCH,

SCHSCH,

SCH,

Cl

N N

ι II

| <> C Γ K ¹

u-

Cl

Vcrplciclissubslan / cii:

Cl

NO.,

NHC ₂ H ₅

NHCH,

NHCH,

NIIC ₂ H ₅

NII,

NIIi-C ,!

NO,

NHC ₂ H,

Cl

Ί Compounds tolerate corn

NHC ₂ II ₅

NII-C-CSNH, CH ₃ CH,

NH C CSNII,

Nile C-CSNH,

CH,

CH, NH C-CSNII,

CH,

cn,

Nile C CSNII ₂

NH · ■ (■■ CSNH,

CH, Nile C CSNH,

NIIC ₂ IU CH .. NH-C-CONH ₂

ei I ₃

CH ₃ NH -C-COOH

lil.iH hulKiiul Ιιιιιμ

5.9

6.3

> l) l-ii liL - li.i iuI in 11}!

5.7

5.3

5.4

3.6

5.0

5.1

6.0

5.7

6.7

6.0

3.3

example 1

10 parts 2-Ethylamino-4- (l -methyl-1 -thioearhanioyl - ethyl) - amino - 6 - chloro - s - triazine. 89 pieces Hentonite and 1 part of a finely divided, on pyroonem Silicic acid produced in this way is ground in a ball mill to the fineness of the dust. This Mixture can be used as a dusting agent.

B e i s ρ i e I 2

10 parts of 2-methylamino-4- (1 -methyl-1-thiocarbamoyl - η - propyl) - amino - 6 - chloros - s - triazine and 90 parts of diatomaceous earth are in a ball mill up to grind to the greatest fineness. They can be used as a dust.

Example 3

Prepare a mixture of 20 parts of isopropylamino - 4 - (1 - methyl - 1 · ■ thiocarbamoylethyl) amino - 6 - methylmercapto - s - triazine. 70 parts Chlorobenzene and 10 parts of a commercially available dispersant based on a di- • butyl-phenol and 10 to 12 moles of ethylene oxide obtained oligoglycol ethers. This preparation gives with water a stable dispersion.

50 parts of 2-ethylamino-4- (1-methyl-1-thiocarbamoylpropyl) -amino-6-methoxy-s-triazine one dissolves kerosene in 450 parts. The solution can be sprayed immediately.

Example 5

22.2 g of 2-methylamino-4- (1-methyl-1-cyanoethyl) -imino-6-methoxy-s-triazine are dissolved in a mixture of 100 ml of pyridine and 10 ml of triethylamine. At a temperature of 50 to 60 ° C., H ₂ S is passed in until saturation is reached. let stand overnight and then pour the crystalline solidified contents of the flask into water. You get off. washes thoroughly with water and dries in vacuo at 50C. 23.7 g of 2-methylamino-4- (1-methyl-1-thiocarbamoyl-ethyl) -amino-6-methoxy-s-triazine are obtained. F. 165.5 to 166.5 C. Yield: 92.5% of theory. Light colored crystals.

45 Example 6

a) Dissolve 184.5 g of cyanuric chloride (= 1 mol) in 2 l of acetonitrile. While cooling, 236 g of finely powdered are added at 0 to 1 ° C. -Aminoisobutyl acid thioamide (= 2 mol) (m.p. 109 C) was added. A snow-white precipitate forms immediately. The mixture is stirred for a few more hours at a temperature of 20 ^: C. It is then evaporated to dryness. The crystalline residue is treated with water, suction filtered and dried in vacuo at 30 ° C. Yellowish white crystals are obtained which slowly dissolve above 160 ° C. decompose.

Analysis: CH ₀ N ₅ SCIj (molecular weight 266).
Calculated:

C 31.6. H 3.4. N 26.3. S Ί2. C! 26.7;
Findings:

C 31.4. H 3.2. N 26.1. S 11.8. Cl 26.4.

b) 26.6 g of 2,4-bis-chloro-6- (l-methyl-1-thiocarbamoyl-ethyl) -amino-s-triazine suspended in KK) ml of acetone. While stirring, one drips between 20 and 30 C 9 g of a 50% ethylamine solution

60 and then 50 ml of 2N Na () ll to / u. The final temperature can be 40 to 45 ° C. The mixture is stirred until a pH value of 7 is reached. Acetone is then evaporated off in vacuo. A thick slurry of crystals remains, which is filtered off with suction and washed with water. Drying takes place in the Vacuum at 40 C.

Yield: 25.15 g of 2-ethylamino-4- (l-methyl-1-ihioarbamoyl-ethyl) -amino-6-chloro-s-tria / yne (= 91.6 "/" of theory). White crystals. F. 163.5 to 164.5 C (decomposition).

Analysis: CqH ₁₅ N _n SCl (molecular weight 274.5). Calculated:

C 39.3. H 5.5. N 30.6, S 11.6. Cl 12.9: found:

C 39.1. H 5.7. N 30.4. S 11.5. CI 12.7.

Example 7

184.5 g of cyanuric chloride are suspended in KHIOmI acetonitrile and cooled to 0 C. ^n. A solution of 119 g of d-aminoisobutyric acid thioamide is now added dropwise

1 l of acetonitrile added: then also at 0 to

2 C 200 ml of 5N NaOH. 85 g of a 70 ° isopropylamine solution are then added dropwise, and the temperature rises to 20 "C. Finally, 200 ml of 5 'NaOH are slowly added to the mixture. The temperature is 40 to 45" C. in the end. Once the mix is neutral. the acetonitrile is stripped off in vacuo. The remaining crystal sludge is filtered off with suction, washed and dried. F. U "9.5 to 190.5 C (decomposition). White crystals.

Yield: 257.3 g of 2-isopropylamino-4- (1-methvl-1-thiocarbamoyl-ethyl) -amino-6-chloro-s-triazine corresponding to 89.2% of theory.

Analysis: C ₁₀ HpN ^ SCl (molecular weight 288.5).

Calculated:

C 41.6. H 5.9. N 29.1. S 11.1. Cl 12.3: found:

C 41.4. H 5.8. N 28.8. S 11.0. Cl 12.1.

Example 8

27.45 g of 2-ethylamino-4 - (1-methyl-I-thiocarbamoyl-ethyl) -amino-6-chloro-s-triazine are added to a solution of 5.4 g of sodium methylate in 200 ml of methanol. The solution is 6 hours on 50 bb 55 C heated, it then reacts neutrally. It is evaporated to dryness. takes up with water and i'utschi the crystals off. Drying takes place at 40 C in a vacuum.

Yield: 25.1 g of 2 - ethylamino - 4 - (1 - methyl i -thiocarbamoyl-ethyl) -amino-6-methoxy-s-triazine White crystals. F. 133 to 134 C.

Analysis: C ₁₀ H, "N" SO (molecular weight 270). Calculated:

C-44.4. H 6.7. N 31.1. S 11.8: found:

C 44.4. H 6.6. N 9/30. S 11.6.

Example 9

25.4 g of 2-ethylamino-4- (l -methyl-! -Cyanoethyl amino-6-methylmercapto-s-triazine are dissolved i a mixture of 100 ml of pyridine and 10 ml of trihydric amine. heated to 60 C and passed at diesi Temperature hydrogen sulfide to saturation. It is left to stand overnight and then i

109 686/2 '

Claims (2)

9 10 Water a. The substance soon crystallizes out. You mean formula I. is sucked. washed and dried and then umkrislallisicrt from methanol. White crystals. K 159 up to 160 C. Yield: 19.35 g of 2-alhylamino -4- (I-methyl- 5
I-thiocarbamoyl-ethyl) -amino-6-methylmercapto-R ¹ N s-tria / in corresponding to 67.2% of theory. ^! i Analysis. C _1n ! I, "N ₍ , S, (molar weight 2SX). ^{N (} Calculated: ri2 C 41.6. H 6.9. N 29.1. S 22.2: found: _{in l) he χ cjn} chlorine atom, a methyl mercapto- C 41.4. 116./, N 2ΧΛ S ZZX). _{or cjnc} Mrthoxygruppc and R ¹ and R ^: are the same or different and for a water ".., ι"; material atom or an alkyl group with I to 1 carbon Claims: lenstolTatomen stand. 2. Herbicidal agent, characterized. I. Substituted 2-amino-4-ll -methyl-1-thin- that it is an effective ingredient of a compound carbamovl - ethyl) - amino - s - triazine of generalgemäl.l claim I contains X
I. N
I. NH- CH, S. (Il I.
C. I.
C.
j C- NHj CH, N '' · ". R τ c