DE2150956A1 - Di-thiocarbamic acid benzyl esters - prepd by reaction of di-thiocarbamic acid salts and substd benzylhalides, herbicides - Google Patents

Abstract

Cpds. of formula (I): where X = -O or -Si; R1 = haloalkoxy (1-4C); R2 and R3 = alkyl (1-3C); are prepd. by reacting a cpd. (II) HS-C-NR2R3 with a cpd. (III): They are esp. active against weeds are difficult to eradicate such as Alopecurus myosuroides, Poa annua, Apera spica venti and Echinochloa crus-galli which is wide-spread in rice. (I) may be used in wheat-, barley, rice-, maize-, cotton-, beetsugar- and sovabean cultures etc.

Description

New (di) thiocarbamic acid benzyl esters, processes for their preparation and their use as herbicides The present invention relates to (di) thiocarbamic acid benzyl esters of the general formula wherein X is oxygen or sulfur 1 R1 is a haloalkoxy radical having 1, 2, 3 or 4 carbon atoms, and R2 and R3 are alkyl radicals having 1, 2 or 3 carbon atoms.

The invention also relates to processes for their preparation which are characterized in that a) salts of (di) thiocarbamic acids of the general formula are added with a substituted benzyl halide of the general form cl wherein Hal is Ilalogen, converts, or b) substituted benzyl meracaptans of the general formula with dialkylcarbamic acid halides of the general formula converts, or c) halo thiocarbonic acid S-benzyl ester of the general formula with dialkylamines of the formula.

Chlorine or bromine are preferred as analogues in the above formulas into consideration.

As salts of (di) thiocarbamic acids of the above formula II are those of organic or inorganic bases, such as the sodium, potassium, Ammonium, pyridinium or triethylammonium salts.

The invention also relates to the use of these thiocarbamic acid esters as herbicides, as well as herbicidal agents, characterized by a content of one the thiocarbamic acid esters mentioned as active ingredients, in addition to wetting agents, adhesives and dispersants, liquid or solid carrier materials, sewing aids, granulating agents or another biocidal active ingredient or fertilizer t te] n.

The preparation of the compounds according to the invention according to the under a) to c) mentioned methods are carried out according to methods known per se, in general using stoichiometric amounts of the starting substances.

a) The implementation of salts of a thiol or dithiocarbamic acid with Benzy halide takes place in aqueous solution at temperatures from 0 ° to 100 ° C, preferably in the range between 10 ° and 60 ° C.

b) The implementation of the substituted benzyl mercaptans or their alkali salts with dialkalcarbamic acid halides is advantageous at temperatures from + 10 ° to 100 ° C carried out, being in inert organic diluents in the presence tertiary bases such as triethylamine or pyridine is used.

c) The implementation of the halothiol carbonic acid S-benzyl ester with dialkylamines happens in inert organic solvents such as acetone, benzene, toluene, in Presence of an HCl-binding substance, for example in an excess of the dialkylamine used or an addition of a tertiary base such as triethylamine or in front of soda or potash. The implementation can also be carried out in a two-phase system Perform water / organic solvent. The reaction temperatures are between 0 ° and 80 ° C, preferably between + 10 ° and 40 ° C.

The production of the starting products in the exemplary embodiments used substituted benzyl chlorides, benzyl mercaptans and chlorothiol carbonic acid-S-benzyl ester takes place according to essentially known processes. The benzyl chlorides can by side chain chlorination of the corresponding haloalkyl tolyl ethers by means of gaseous chlorine can be obtained at temperatures from 1000 to 1800C. Through implementation these benzyl chlorides with thiourea and subsequent alkaline cleavage of the Isothiuronium salts formed (Org. Synth. 21 (1941) p. 36) are obtained appropriate Benzyl mercaptans as starting substances for process b). By implementing this Benzyl mercaptans with phosgene lead to the corresponding chlorothiolenoic acid S-benzyl esters, which were generally processed further as raw products.

In the starting and end products, the radical R1 preferably contains n = 2n atoms wise / 1 - 3 carbon atoms and is substituted by / fluorine and / or chlorine /, where s: s α-C atom contains two fluorine atoms. R and R.3 2 3 are preferred the same and contain 2 or 3 carbon atoms.

Examples for the remainder R1 are: -OCF3, -OCHF2, -OCF2-CHF2, -OCF2-CHFCl, -OCF2-CHCl2, -OCF2-CHF-CF3.

The new compounds of formula I are mostly viscous oils, which cannot be distilled or can only be distilled with decomposition.

These products are designed to prevent unwanted plant growth suitable. They can be used as wettable powders, emulsifiable concentrates, dusts or granules alone or optionally in combination with other ilericides, Soil insecticides or fertilizers can be used.

Wettable powders are preparations that can be uniformly dispersed in water, which, in addition to an inert substance, are wetting agents, e.g. polyoxyethylated alkylphenols, polyoxyethylated Oleyl or stearyl amines, alkyl or alkylphenyl sulfonates and dispersants, z.n. sodium lignosulfonic acid, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, Sodium dibutylnaphthalenesulfonic acid or sodium oleylmethyltaurine acid contain.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, di-methylformamide, Get xylene or higher-boiling aromatics.

In order to achieve good suspensions or emulsions in water furthermore wetting agents from the above. Row added.

Dust is obtained by grinding the active ingredients with finely divided, solid substances, e.g. talc, natural clays, Pyrophillite or Diatomaceous earth.

Granules can either be sprayed onto absorbent, Granulated inert material can be produced, or by applying active ingredient concentrates by means of adhesives, e.g. polyvinyl alcohol, polyacrylic acid sodium or mineral oils on the surface of granulated inert material.

Suitable active ingredients can also be used in the production of fertilizer granules the usual way - if desired in a mixture with fertilizers - processed.

In addition, the active compounds according to the invention can be combined with other elericides and soil insecticides can be combined.

As known herbicides that are suitable for a combination with the claimed Suitable for new products, for example: Urea derivatives: Noruron (N- (Hexahydro-4,7-methanindan-5-yl) - N ', N'-dimethylurea) Cycluron (N-Cyclooctyl-N ', N'-dimethylurea) Methabenzthiazuron (N- (2-Benzthiazolyl) -N', N'-dimethylurea Linuron, Ohloroxuron, Monolinuron, Fluometuron, Diuron; Triazine derivatives: simazine, Atrazine, ametryn, prometryn, desmetryn, nethoprotryn; Urazil derivatives: Lenacil, Bromacil; Pyrazone derivatives: 1-phenyl-4-amino-5-chloropyrazidone- (6); Growth substances preparations: 2,4-dichloro-phenoxy-acetic acid, 4-chloro-2-methylphenoxy-acetic acid, 2,4,5-trichlorophenoxy-acetic acid, 4-chloro-2-methyl-phenoxybutyric acid, 2,3,6-trichlorobenzoic acid, 2- (2-methyl-4-chlorophenoxy) propionic acid; Carbamic acid derivatives: Barban, Phenmedipham, Triallate, Diallate, Vernolate, Cycloate (N-ethyl-N-cyclohexylthioethylcarbamate Monilate (iiexahydro- 1-Jl-azep in-1-carbamic acid thioethyl ester), EPTC (N, N-dipropylthioethylcarbama t), Chlorpropham and Swep; Dinitrophenol derivatives: dinitro-o-cresol, dinitro-sec.-butylphenol (Dinoseb), uinoseh acetate; Chlorinated aliphatic acids: sodium trichlorace tat, Dalapon (2,2-dichloropropionic acid sodium) Amiben (3-amino-2,5-dichlorobenzoic acid) Picloram (4-amino-3,5,6-trichloro-pyridinethylpropionamide); Amides: Diphenamide (N, N-diallylchloroacetamide) Carbetamide (2- (phenylcarbamoyloxy) -N-ethylpropionamide) N- (1 ', 1-dimethylpropionyl) -3,5-dichlorobenzamide; Dipyridylium compounds: Paraquats Diquat, Morfainquat; Anilides: N (3-dichlorophenyl) methacrylamide, Propanil, Solan, Monalide, 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide, propachlor, Methacryl-3, 4-dichloroanilide; Nitriles: dichlobenil, ioxynil; Other preparations: Flurenol, monosodium methyl arsonate t trifluralin, endothal (3,6-endo-oxohexahydrophthalic acid), Nitrofen (2,4-dichlorophenyl-4'-nitrophenyl ether), pyriclor (2,3,5-trichloro-4-pyridinol, α- (2,2,2-trichloroethyl) styrene), benzulide, aminotriazole.

Another application form of the present active ingredients consists in Mixing them with fertilizers, making them both herbicidal and herbicidal can be obtained.

The weed control agents according to the invention can be used in those for plant protection agents Commercially available formulations with a more or less high active ingredient content will. So these formulations show in addition to the usual formulation additives e.g. an active ingredient content of 10 - 95%. When mixed with other active ingredients and / or In fertilizers, the content of the active ingredient according to the invention can be lower, e.g. 10 to 1% or less.

The application of the means takes place in the for weed control means usual dilutions, whereby these are increased according to the weeds to be controlled sclionenden cultivated plants, the climatic conditions, the season, the Soil quality and the like. Can direct. In practice, dilutions are made in the field from 0.001 to 1.0, O / o is customary, although deviations therefrom are also possible. As a comparative figure is often the part by weight applied per unit of floor area specified.

The claimed new compounds have a very good effect against a number of weeds that are difficult to control1 e.g. Alopecurus myosuroides (black foxtail), Poa annua (annual panicle), Apera spica venti (wind stalk) and Echinochloa crus-galli (Chicken millet), one of the most common weeds in irrigated rice. They are superior to known compounds in terms of effectiveness and are as gentle as this one Number of crops such as wheat, barley, rice, maize, cotton, sugar pulp and soybean.

Example 1: (bp 79 ° / 1.6 mm) 22 g (0.116 mol) p-difluoromethoxybenzyl mercaptan / in 80 ml of benzene, 8.1 ml of phosgene were added at OOC, and then 11.7 at OOC g (0.116 mol) of triethylamine were added dropwise. After stirring for one hour at room temperature Was heated to 40 ° C. for 30 minutes, shaken out with water after cooling and that Solvent removed in vacuo. The resulting liquid S-p-difluoromethoxybenzylthiocarbonic acid chloride became a solution of 17 g (0.232 mol) diethylamine in 150, kept at + 5 ° C ml of methylene chloride was added dropwise and the mixture was subsequently stirred at room temperature for 2 hours. After shaking out the product was dried at 1 mm Hg / 80 ° C. with water and evaporation of the solvent.

Yield: 31.6 g slightly yellowish oil Analysis: C13H17F2NO2S MW 289.5 calc .: C 54.0%; H 5.9%; N 4.8%; F 13.1% Found: C 53.8; H 5.9%; N 4.7; F 13.1 y Example 2: 0.1 mol (7.3 g) of diethylamine in 100 ml of water containing 4-.0 g of sodium hydroxide solution was added dropwise at + 10 ° C. with stirring with 0.1 mol (7 , 6 g) carbon disulfide added. It was continued for a further 20 minutes without cooling, then 0.1 mol (19.3 g) of p-difluoromethoxybenzyl chloride / was added and the mixture was kept at 60 ° C. for 3 hours. After cooling to room temperature, it was extracted with methylene chloride, the organic phase was washed several times with water and the solvent was stripped off. The dithiocarbamate remained behind in the form of a light yellow colored oil, which was dried at 80.degree. C. at 1 min Hg.

* (Bp 98-100 ° / 10mm) Yield: Analysis: C13H17F2NOS2 MW 305.4 calc .: C 51.1%; H 5.6%; N 4.6 0 Measured values: C 50.9%; H 5.5%; N 4.9 ß Example D: A kept at OOC to +, 5 ° C solution of 0.1 mol (7.3 g) diethylamine and 0.1 mol (4.0 g) sodium hydroxide solution in 40 ml of water was slowly added 0.1 mol (7.05 g) of 85% carbon oxysulphide are added to the mixture. 0.1 mol (25.9 g) of p- (1,1,2-trifluoro-2-chloroethoxy) benzyl chloride * were then added and the mixture was allowed to come to room temperature in 4 hours with stirring. After standing for one day at room temperature, the mixture was extracted by shaking with methylene chloride, the organic phase was washed several times with water and the solvent was distilled off. The crude product was dried at 1 mm Hg and 80 ° C.

Yield: 26.6 g slightly yellowish oil Analysis: MW 355.8 calc .: C 47.3%; H 4.8%; S 9.0 </ found: C 47.1%; H 5.0%; 5 9.1% * (bp 121-122 ° / 10mm) Example 4: 0.1 mol (13.6 g) diethylcarbamic acid chloride and 0.1 mol (24.0 g) para- (1,1,2, 2-Tetrafluoroethoxy) benzyl mercaptan / in 80 ml of pyridine were heated to 80 ° C for 2 hours, after cooling, poured into 500 ml of water, the organic phase was taken up in methylene chloride and washed with dilute hydrochloric acid and water.

After distilling off the solvent and drying at 80 ° C., 1 mm Hg was an almost colorless, viscous oil.

Yield: 32.2 g Analysis: MW 339.3 calc .: C 49.5%; H 5.1%; N 4.1% found: C 49.4%; H 5.2%; N 4.2% * (bp 104-105 ° / 14 mm) The following compounds were obtained analogously to the above examples: RN 4 . ~~ ~~ ~~ w ~ or 14 0 8th ! rl rl rl (IOmN rl rl a, a, a> a, a, ou ooo O 0 U) O FC16 & CF2O)? CH2S9jN (flC3hT?> 2 found: Oel m o C ~. L ~~~~~~~ S 3.5 ; ri 1 P ~. . c aE H ms e ç ç ew cs crw n < 6 rCIMC-CF2O-CH2-SCN (C2H5> 2 (n V2 uz II uz uz Oel 2 .. 45.4; H . 4.8; V \ \ 3 0 c3 (I \ c \ L c3 [ Ln n -s -; r ut rn rrrrc LV \ V \ Ln t4f ' > ~ 14 XHH z IZ F4 9 48.0; H 5.3; X 16, o oil 2 O. ~. ~. ~. ~. . ~. ~. C 0 0 O o H . C) j: C3C: C3: 0: af: rC: r ri OCI \ U \ Ln c3 t k -r * Ci; r 08 6 0 0 48.0; H cJ bsJo .D cJ bOu .Q 5 bou n O 16.0 n C) SJO ~ ~~ ~ ~~~~ ~~ ~ ~ ~~ ~ ~ o ~ s cQ cq - ß, ~ tD B FT (t2 X = I 9 ClHC-CF2 C-CH2 r vl 50.0; II 5.5; 5 8.4 - 52 V C3 H7> 2 found: = i 5.7; 5 i no z 0 49.9; CX IIIII lllll 10 x> 2 cu Frt H 4.8; N 3.9 oil 3 O vvvvvv gef. z ..r; rtOlF l 47.0; lllllt) Xo OQOOO% oooooo rq> r4 X> t 1 vl t1 vl 1 rd, Vt rol FT rd cJ V v VV r- rR rR X> wral l ì Uz vD 1> CD (> O rt 11 cdQ cV (U rd Cxl Cq rol oc according to ex. ber .: - C 48.0; H., 5 16.0 oil 2 at At uo s found: H 4.9; 5 C r1 rd rl O 48.3; 15.8 4'U a, a, a, a, ra, o0 oooo ° Um ° C 47.3; H 4.8; 5 9.0 - -CH2 -sc, -N (C2 H5 r found: -on 0 0 47.4; II 4.6; 5 9.0 OCF OO u \ Ir \ fc c. LC \ 1 o \ o \ cO cO c \ cl d ~ 50.0; H (Q;!;; 5.5; 5 tn 8.4 13 ko trx to Cn 1 O 0 49.8; H rr rr 5, r 0CF2-CHClF ber .: ;> t H 5.3; N .- .- .- .- L? U \ <O CN CW O CX) O CQ HO LA Ir 14 COC: COC: CIC: found: -. .- no ru ~ .. 2 0Q \ Q c3. 0.0 o 4 cs 4 zx cs U Sq mv 4 h ~ 'vch to cz to Ss t' c, s 6CF2 CHClFS o 48.2; H 5.3; N 3.4 n »O bOt) rQ O WO n Q C4» n ~ n ~~ ~~ ~ 0 50.1; H 5.5; 5 16.7 80-85 oi F2HC-Ci'20.CN2SCN (iC5H7) 2 c # t2 V 50.0; H t r. t2 s ber .: 16 -CH2-s-c11-N (c2 H5) 20 49.5; H 5.1; N 4 ', 1 2; V. I. IU = V1 I rl -CHF 0 cq U 5.0; N 4.2 a) 1 | Frt E FL | Frg c # ~ rX vv «g O Cç O (2 O t; (\ t z I tt Fz g Ft | Frt | C) iI Fh O t VVV c # V o2 l V FE., X '> 8 II Fr: R | X, | XAIU 4 ivX a ° a vO O ° o C rq V # V. E4 # Q rt OJ 1 <s1- tN \ 9 zQ rd rt r1 r1 rul rffl h Q N td NNH tH > bX. 50.1; H 5.5; N 3.6 I. p (Ln i rl rl rt I hmrI: r ( U! at go O 0 O n \ O rb F =: O 0 sm -CHF2 ber .: 291 {#} ½ei re C2 115) 2. 46.3; . 4.4; F 29 -C112 found: I n Ct OCF2 tn Cm -CMF-CF3 n (3 Q \ rrrnrrr - n CQ es Cf nn * t ds UU *. I. ~ ZZEZ% ZZZZ; Z g; ber .: C 47.1; : V: tn cU 1 I cc \ o \ O o \ O Ch O \ m - u \ n; r çD 46.9; H srx N 3.0 oil I 1 ri i XXXXXX xc 1 St. ~. ~. ~. ~. ~. ~. ~. ~. ~. ~. ~. ~ Q: ONOQ O : LCCCCLC CI) CC O os D PW r vO vrç Ji. * ^ M> n : kV \ kk -rt k-ir k6r ku \ kLT \ klr \ km kk rrr PU MO p0 WOO sC, O p C) O POh0L) PCltr) U sC) bOO nO WO f 0O .Qu WO »O 60O, StO QV 01 CV r1 54.0; fl 5.9; N c # C22 . <2 found: I nx = -; I. OCHF2 53.9; ll ZVN = O V) U] nnnll rl l | ¢ t 1 12s4 U =; QU] n d) crt c # D c2 D ll D sat EX Ci c # FE I FE-§ IS} CQ 01t ELE h V z V D4 V hl * 1, L, Flt o I = I Frl | t rq cst VVV ¢, a rX t rX W ml C rn a cc5 Q X rwl r | Qt> CO Ch O tl C \ l rl ll r ~ l rl C \ l C \ lt \ J Example 23: A powder that is easily dispersible in water is obtained by adding 50 parts by weight of p-difluoromethoxybenzyl-N, N-diethyl thiol carbamate, 20 parts by weight of finely dispersed silica, 14.5 parts by weight of quartz flour, 5.0 parts by weight of NaHCO3 (stabilizer and grinding aid) , 7% sodium dinaphthylmethane disulphonic acid (dispersant) and sodium 3.500 alkylnaphthalenesulphonic acid (wetting agent) and grinds in a pin mill.

Example 24: A dust that turns out to be a weedkiller well suited, is obtained by adding 10 parts by weight of p-tetrafluoroethoxybenzyl-N, N-diethyl thiol carbamate as the active ingredient and 90 parts by weight of talc as the inert substance and in one Cross beater mill crushed.

Example 25: An emulsion concentrate consists of J5 parts by weight m-Tetrafluoroethoxybenzyl-N, N-diethyl thiol carbamate, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of polyoxyethylated nonylphenol as an emulsifier.

Example 26: Rice and chicken millet seeds (Echinochloa crus-galli) were sown in pots and the pots were placed in the greenhouse.

3 weeks later, after the plants had developed 3-4 leaves, they were coated with an aqueous emulsion of the active ingredient (Example 4) sprayed.

The following were used as comparison agents: Benthiocarb and propanil which were applied in the same way.

A week after the treatment, the pots were placed in a basin, which was filled with water so high that the water level was 1 cm above the top of the pot was standing. 3 weeks after the treatment, the result was expressed as the degree of damage in, ', the following: Echinochloa rice 0.15 2.5' 0.15 2.5 kg / ha Subst.

A 90 100 0 0 Benthiocarb 60 95 0 0 Propanil 0 80 0 0 The invention Substance is therefore much more effective on Echinochloa plants than those on the market comparison means located.

Example 27: Vessels with the dimensions 20 × 25 × 25 cm were filled with loam up to about 5 cm below the upper edge of the vessel and sown with rice and echinochloa. A week later, after the plants had just emerged, the vessels were flooded until the water was 1–2 cm above the surface of the earth. The individual active ingredients were then sprinkled into the standing water in granulate form. 2 weeks after the treatment, the water level was raised to the top of the vessel. The following active ingredients were used: (Example 4) (Example 16) (Example 1) (Example 21) The comparative agent was the benthiocarb mentioned in Example 1.

4 weeks after the treatment, the result was expressed as the degree of damage in%, determined; it read (dosages in kgXha active substance): Echinochloa Rice 1.25 2.5- 1.25 2.5 Active ingredient A 75 95 # 0 0 B 75 90 0 0 c 95 100 0 0 D 80 95 0 0 Benthiocarb 65 80 0 0 The substances according to the invention thus fight Echinochloa crus-galli, one of the most common weeds in irrigated rice better than the chemically closely related and in practice broad in some countries applied product benthiocarb.

Example 28: Seeds of various weeds and crops were made sown in pots. On the day of sowing, watery emulsions became more diverse Active ingredients sprayed on the soil surface.

In addition to the active ingredient B (example 16/27), the substance B (Example 3) and Benthiocarb used as comparison agents. 4 weeks after the treatment, the following result was shown (dosages in kg / ha of active substance): Alopecurus Poa annua Apera myosuroides annua spica lteizen / barley 0.62 1.25 0.62 1.25 0.62 1.25 0.62 1.25 Work. B 75 95 85 100 95 100 0 0 75 90 80 100 85. 100 O 0 Benthiocarb 55 75 70 90 75 95 0 0 The substances according to the invention thus control difficult-to-control grass-like weeds such as Alopecurus myosuroides (black foxtail), Poa annua (annual panicle) and Apera spica-venti (wind stalk) better than benthiocarb, without damaging cereal crops.

Example 29: In a manner similar to Example 28, pots were sown with weeds and crop plants and with the active ingredients C (cf. Example 27) and F (Example 2) and Benthiocarb treated as a comparison agent on the day of sowing. Here the result was 4 weeks after the treatment: Digitaria Eleusine Setaria Echinochloa Amaranthus sanguinalis indica faberii crus-galli retro flexus 1.25 2.5 1.25 2.5 1.25 2.5 1.25 2.5 1.25 2.5 C 100 100 90 95 100 100 95 100 80 90 F 95 100 95 100 80 95 85 90 70 85 Benthiocarb 85 95 85 90 70 90 75 90 60 70 The crops maize, cotton, sugar beet and soybean showed no damage at the tested dosages. Weeds of the species mentioned play a significant role in these crops; they were fought better by substances according to the BrfindulIÔ than by the well-known preparation Benthiocarb.

Claims (4)

Patent claims: Compounds of the formula wherein X is oxygen or sulfur, R1 is a halogenoalkoxy radical having 1, 2, 3 or 4 carbon atoms, and R2 and 113 are alkyl radicals having 1, 2 or 3 carbon atoms. 2. Process for the preparation of compounds according to claim (1), characterized in that a) salts of (di-) thiocarbamic acids he general formula in which R2, R3 and X have the meaning given under claim (1), with a substituted benzyl halide of the general formula converts, in which Hal is halogen and R1 has the meaning given under claim (1) or b) substituted benzyl mercaptans of the general formula with dialkylcarbamic acid halides of the general formula R1 converts, where Hal, / R2 and R3 have the meaning given above, or c) halothiol carbonic acid S-benzyl ester of the general formula with dialkylamines of the general formula. Ri> where Hal, / R2 and R3 have the meaning given above. 3 3. Herbicidal agents, characterized by their compound content according to claim 1 as an active ingredient. 4. A method for controlling undesirable vegetation, thereby characterized in that a herbicidal agent is applied to the areas to be treated Claim 3 applies.