IL31212A

IL31212A - Triazine derivatives

Info

Publication number: IL31212A
Application number: IL3121268A
Authority: IL
Original assignee: Basf Ag
Priority date: 1967-12-06
Filing date: 1968-12-03
Publication date: 1972-06-28
Also published as: CS171674B2; DE1670291A1; SE351215B; NL6817464A; DE1670291B2; IE32581L; GB1241228A; DE1670291C3; IE32581B1; CA939669A; AT284539B; BE725064A; FR1594172A

Description

1 »τκ'ΐο nnVin — Triazine derivatives BADISCHB ANILIN- & SODA-FABRIK A TIENGESELLSCHAFT 0:29451 TRIAZINE DERIVATIVES It is known to use triazine derivatives, for example 2-chloro- , 6-bis-(ethylamino)-s-triazine , for weed control. Compatibility with, crop plants, such as wheat and "barley, is, however, unsatisfactory.

We have now found that triazine derivatives having the general formula;- R^ N N R¾N-C ^.C-NHR1 hydrocarbyl in which R denotes an aliphatic/or alkoxyalkyl radical having not more than four carbon atoms, R 2 denotes the group ,CH3 CH3 HC=C-CH- or CH=C-C- CH3 , thio and R denotes chlorine or the methoxy or ethylB3«e?oe^4e- radical or the radical -CN, have good herbicidal action. e The new active ingredients may he prepared for example hy reaction of cyanuric chloride in the presence of an agent which hinds hydrogen halide with the corresponding alkylamine, alkynylamine or alkoxyalkyla ine and, when R does not denote chlorine, with an alkal metal ethylate or an alkali metal ethylmercaptide or an alkali me- tal cyanide in any sequence. 2-chloro-4-ethylamino-6-(butyn-1-yl-3-amino)-s-triazine may be prepared as follows: At a temperature of -10° to -20°C, 135 parts "by weight of eth-ylamine is dripped into a solution of 276 parts by weight of cyanu-ric chloride. The mixture is then stirred for another hour at -10° to -20°C and the precipitate formed is suction filtered. The filtrate is freed from solvent in vacuo at room temperature and the crystalline residue is recrystallized from cyclohexane. 233 parts by weight of 2,4-dichloro-6-ethylamino-s-triazine is obtained having a melting point of from 103° to 105°C. 9.65 parts by weight of 2,4-dichloro-6-ethylamino-2-triazine is dissolved in 50 parts by weight of acetone and at a temperature of from 15° to 20°C a solution of 7 parts by weight of butyn-1-yl-3-amine in 25 parts by weight of acetone is added. The mixture is stirred for another twenty hours at room temperature (20°C) and the precipitate formed is suction filtered. The filtrate is freed from solvent in vacuo and the crystalline residue is recrystallized from cyclohexane. 10.5 parts by weight of 2-chloro-4-ethylamino-6-(butyn- 1-yl-3-amino)-s-triazine is obtained having a melting point of 140°C. 2-methyl¾^s»eaI^*e--4-ethylamino-6-(butyn-1-yl-3-amino) -s-triazine may be prepared as follows: 184 parts by weight of cyanuric chloride is dissolved in 3000 parts by weight of ethyl acetate and at a temperature of from -10° to -20°C a solution of 48 parts by weight of methyl ercaptan and a solution of 40 parts by weight of sodium hydroxide dissolved in 360 parts of water are added at the same time from two dropping funnels.

The mixture is stirred for another two hours at a temperature of -10°C, the organic layer is separated, dried with magnesium sulfate and the solvent is removed in vacuo at a temperature of up to 35°C.

The crystalline residue is recrystallized from petroleum ether. 9 .8 parts by weight of 2- ethyli^-»eerp-t- -4 , 6-dichloro-s-triazine is suspended in 25 parts by weight of water and 1 5 parts by weight of acetone and then 5 . 25 parts by weight of butyn- 1-yl-3-amine hydro chloride dissolved in 1 0 parts by weight of water is added. A solution of 4 parts of sodium hydroxide in 1 5 parts by weight of water is subsequently dripped into the mixture at a temperature of from 25° to 40°C. The reaction mixture is stirred for some hours at 35°C, the oil which has separated is shaken with methylene chloride, the methylene chloride solution is dried with magnesium sulfate and the solvent is removed in vacuo. The oily residue is ground with petro- thio leum ether and becomes solid. 9 parts by weight of 2-methylffe*&a-pt«-4-chloro-6-(butyn-1-yl-3-amino)-s-triazine is obtained having a melt ing point of from 56° to 58°C. /thio . 7 parts by weight of 2-methyl»e*e«rp-t-e-4-chloro-6-(butyn-1 -yl-3-amino)-s-triazine is suspended in 25 parts by weight of water, 1 0 parts by weight of acetone and 3 . 5 parts by weight of 35$ aqueous ethylamine, the mixture is boiled under reflux and at this temperature a solution of 1 part by weight of sodium hydroxide in 5 parts by weight of water is dripped in.

The mixture is then stirred for three hours at boiling temperature, cooled to room temperature and the oil which separates is shaken with methylne chloride, the organic layer is dried and the solvent is removed in vacuo. The oily residue becomes crystalline when toluene is added and the whole is cooled. 4 .8 parts by weight .thio) of 2-methylflreroapio-4-ethylamino-6-(butyn- 1-yl-3-amino)-s-triazine is obtained having a melting point of 95° to 97°C. Examples of the new ingredients are as follows: 2-chloro-4-ethylamino-6- ( 3-methylbutyn-1 -yl-3-amino )-s-triazine ; melting point 1 35° to 1 37°C , 2-chloro-4-isopropylamino-6- ( 3-methylbutyn- 1-yl-3-amino)-s-triazine ; melting point 146° to 148°G , *~ t 2-chloro-4-isopropylamino-6-(butyn-1-yl-3-amino)-s-triazine ; melting point 170°C, 2-chloro-4-ethylamino-6-(butyn-1-yl-3-amino)-s-triazine ; melting point 140°C, 2-chloro-4 , 6-bis-(butyn-1-yl-3-amino)-s-triazine ; melting point 161 °C.

Other compounds are mentioned in the Examples. Herbicides may be prepared in a conventional manner from the compounds according to this invention by mixing the compounds with solid or liquid carriers, for example water, hydrocarbons, organic solvents, clay, fertilizers, borax or diato aceous earth. It is also possible to add wetting agents, dispersing agents, adhesives and fungicides, insecticides or other herbicidally active compounds. The herbicides may also be applied in granular form.

The following Examples illustrate the superiority of the compounds according to this invention over known active ingredients.

EXAMPLE 1 Plastic^ pots having a diameter of 8 cm are filled with loamy sandy soil in a greenhouse and sown with seeds of barley (Hordeum vulgare), wheat (Triticura sativum), Indian corn (Zea mays), annual meadow grass (poa annua) , slender foxtail (Alopecurus yosuroides) , small nettle (Urtica urens), wild mustard (Sinapis arvensis), white goosefoot (Chenapodium album), vetch (Vicia sp.), chamomile (Matricaria chamomilla) and chickweed (Stellaria media) and then treated with 1.5 kg per hectare of 2-chloro-4-ethylamino-6-(butyn-1-yl-3-amino)-s-triazine (I) and, for comparison, with 1.5 kg per hectare of 2-chlor-4 , 6-bis-(ethylamino)-s-triazine (II), these amounts of the active ingredients each being dispersed in 500 liters of water. After four to five weeks (I) exhibits a better plant compatibility with barley (Hordeum vulgare) and wheat (Triticum sativum) and at the same time a stronger herbicidal action on the weeds.

( I ) ( ID barley 10-20 20-30 wheat 10 20-30 Indian corn 0-10 0-10 annual meadow grass 90 80 slender foxtail 80 70 small bettle 100 90-100 wild mustard 100 90 white goosefoot 90-100 80-90 vetch 90-100 80 chamomile 90 80-90 chickweed 90-100 80-90 0 = no damage 100 = total destruction The following substances have the same biological effect as the substance ( I ) in any o*f Examples 1 to 4. 2-chloro-4-isopropylamino-6-(butyn-1-yl-3-amino)-s-triazine , 2-chloro-4-tertiary-butylamino-6-(butyn-1-yl-3-amino)-s-striazine , 2-chlor0-4- ( 3-methoxypropyl)-amino-6- (butyn- 1-yl-3-amino)-s-triazine 2-chloro-4-ethylamino-6-( 3-methylbutyn-1-yl-3-amino)-s-triazine , 2-chloro-4 , 6-bis-(butyn-1-yl-3-amino)-s-triazine , 2-methyl¾ie*-&apte-4-isopropylamino-6-(butyn- 1 -yl-3-amino)-s-triazine , thio » 2-methylTjie»eapte-4-ethylamino-6- ( 3-methylbutyn- 1-yl-3-amino -s-tn- azine , 2-methylBS-»eap*«-4--( 3-methoxypropyl)-amino-6-(butyn- 1-yl-3-amino)- s-triazine, 2-methy ©*«apt-e-4-ethylamino-6- (butyn- 1-yl-3-amino)-s-triazine , 2-meth.oxy-4-ethylamino-6- (butyn- 1-yl-3-amino)-s-triazine , 2-methoxy-4-isopropylamino-6- (butyn- 1-yl-3-amino)-s-triazine , 2-methoxy-4-ethylamino-6- ( 3-methylbutyn- 1-yl-3-amino)-s-triazine , 2-cyano-4-ethylamino-6- (butyn- 1 -yl-3-amino)-s-triazine , V · 2-methyl^:g!<-¾¼^ EXAMPLE 2 In a greenhouse, the plants "barley (Hordeum vulgare), wheat (Triticum sativum), Indian corn (Zea mays), annual meadow grass (Poa annua), slender foxtail (Alopecus myosuroides) , barnyard grass (Pani-cum crus-galli), wild mustard (Sinapis arvensis) , white goosefoot (Chenopodiu album) , small nettle (Urtica urens) , chickweed (Stel-laria media) and chamomile (Matricaria chamo illa) are treated at a growth height of 3 to 18 cm with 1.5 kg per hectare of 2-chloro-4-ethylamino-6-(butyn-1-yl-3-amino)-s-triazine (I) and, for comparison, with 1.5 kg per hectare of 2-chloro-4, 6-bis-(ethylamino)-s-triazine (II), these amounts of the active ingredients each being dispersed in 500 liters of water.

After three weeks it is found that active ingredient (I) has a better selectivity on barley (Hordeum vulgare) and wheat (Triticum sativum) than (II) and a stronger herbicidal action on the weeds.

The herbicidals action may be seen from the following Table: Active ingredient (I) (ID barley 0-10 20-30 wheat 10 20-30 Indian corn 0-10 0-10 annual meadow grass 90-100 90 slender foxtail 90 80 barnyard grass 80 · 50-60 wild mustard 100 90-100 white goosefoot 100 90-100 small nettle 90-100 90-100 chickweed 90-100 90 - - . . , v. · EXAMPLE 3 In a greenhouse, seeds of annual meadow grass (Poa annua), slender foxtail (Alopecurus myosuroides) , small nettle (Urtica urens), wild mustard (Sinapis arvensis), white goosefoot (Chenopo-diu album), betch (Vicia sp.)» chamomile (Matricaria chamomilla) and chickweed (Stellaria media) are planted in loamy sandy soil and which is then treated with 5 kg per hectare of 2-chloro-4-ethyl-amino-6-(butyn-1-yl-3-amino)-s-triazine (I) and, for comparison, with 5 kg per hectare of 2-chloro-4 , 6-bis-(ethylamino)-s-triazine (II) these amounts of the active ingredients each being dispersed in 500 liters of water per hectare.

After four to five weeks it is found that (I) has a somewhat better hericidal action than (II).

EXAMPLE 4 An experimental area having a crop of annual meadow grass (Poa annua) slender foxtail (Alopecurus myosuoides), barnyard grass (Panicu crus-galli), wild mustard (Sinapis arvensis), white goose-foot (Chenopodiu album), small nettle (Urtica urens), chickweed (Stellaria media) and chamomile (Matricaria chamomilla) is treated at a growth height of the plants of 3 to 12 cm with 5 kg per hectare of 2-chloro~4-ethylamino-6-(butyn-1-yl-3-amino)-s-triazine (I) and, for comparison with 5 kg per hectare of 2-chloro-4 , 6-bis-(ethylamino)~ s-triazine (II), these amounts of the active ingredients each being dispersed in 500 liters of water per hectare. After one to two weeks is found that herbicidal action has occurred more rapidly in the case of the abovementioned weeds and weed grasses with (I) than with (II) and after four to eight weeks all the plants are almost completely withered . 31212/2

Claims

CLAIMS It A triazine derivative having the formula! in which R^ denotes an aliphatic hydrocarbyl radical or an alkoxy- 2 dlkyl radical, R denotes the group OH- GH- I 5 I 3 HC-C-C or HCnC-G- I I H CH, j 3 and R denotes chlorine, the methoxy radical, the methylthio radical or the radical -CN.\ 2. : A .herbicide comprising a- triazine derivative having the formula 1 hydrocarbyl in which R denotes an aliphatic/radical or an alkoxyalkyl radical 2 R denotes the group and R he methylthio radical or the radical -CN. 3. A herbicide comprising a solid liquid carrier and a triazine derivative having the formula 31212/2 ' hydrocarbyl in which R denotes an aliphatic/ radical or an alkoxyalkyl radical 2 ■ ··'. R denotes the group CH„ CH, : . : -: , 3 I 5 HCSC-C or HCeC-C- 1 I H Cf^ 3 and R denotes chlorine, the methoxy radical, the methylthio radical or the radical -ON. 4· A process for the production of a herbicide which comprises mixing a solid or liquid carrier with a triazine derivative having the formula R3 - hydrocarbyl in which R denotes an aliphatic/radical or an alkoxyalkyl radical 2 R denotes the group , I 3 I HCSC-C or HC=C-C- I I H CH- and R denotes chlorine, the methoxy radical, the methylthio radical or the radical -CN. 5· A process for controlling unwanted plants which comprises treating the plant or the soil with a phytotoxic amount of a tri R3 I l . hydrocarbyl in which R denotes an aliphatic/radical or an alkoxyalkyl radical, denotes the group 3 a d R denotes chlorine, the methoxy radical, the methylthio radical or the radical -CN, 6· A process for the production of a triazine derivative having the formu T hydrocarbyl in which RI ddeennootteess aann aalliipphhaattiicc//rraaddiiccaall oorr an alkoxyalkyl radical, 2 R denotes the group and R denotes chlorine, the methoxy radical, the methylthio radical or the radical -CN, wherein cyanuric chloride is reacted, in O.Z. 25,265 the presence of an agent which binds hydrogen halide with an amine 1 ? 1 having the formula and an amine having the formula Νί^1*· (R and R having the above meanings) and the product thus obtained may or may not be treated with an alkali metal methylate, an alkali metal mercaptide or an alkali metal cyanide. 7. 2-chloro-4-ethylamino-6-(butyn-1-yl-3-amino)-s-triazine. 8. 2-chloro-4-isopropylamino-6-(butyn-1-yl-3-amino)-s-triazine . 9. Any triazine as claimed in claim 1 and herein specified.