US2911337A

US2911337A - Method of combating insects comprising contacting with a dichloro-1, 3, 5-triazine

Info

Publication number: US2911337A
Application number: US664461A
Authority: US
Inventors: Uhlenbroek Jan Hendrik; Haeck Hans Heinz; Bijloo Johan Dirk
Original assignee: US Philips Corp
Current assignee: US Philips Corp; North American Philips Co Inc
Priority date: 1956-06-15
Filing date: 1957-06-10
Publication date: 1959-11-03
Anticipated expiration: 1976-11-03
Also published as: NL208063A; FR1176716A; CH359563A; DE1125226B; BE558354A; GB818437A

Description

United States Patent "ice METHOD OF COMBATING INSECTS COMPRISING CONTACTING WITH A DICHLOR-1;3,5 -TRI- AZINE J Jan Hen'dr'ik Uhlenbroek, "Harmannusf Koopman, .Hans Heinz'Hae'ck, Jasper Dams, and Johan Dirk Bijloo, Van 'Houtenlaan, Weesp, Netherlands, assignors to North American Philips Company-Ina, New York, N.Y., a-corporation of Delaware No Drawing. Application June' 10, I957 Serial-'N0. *664;461'

Claims priority, application Netherlands June '15, 1956 9- Claims. (Cl. '1'67--'33) ,7 y I It is'known that various derivatives of 1,3,5-t1-iaz'ines are suitable for combating noxious organisms. Reference may, for example, be made to compounds of the general formula:

TWAIClzh-n In this formula Ar designateslan aryl-group, n a number of the value 1 or 2 and x a'number of the value 0, 1, 2, '3

These compounds are said to have a pronouncedfung icidal effect and be phytotoxical under particular circumstances.

Other compounds also having a fungicidal eifect are 2,911,337 Patented Nov. 3, 1%59 2 aliphatic or alicyclic hydrocarbon. residue, have an insecticidal activity. 1 I

Of the compounds having a harmful eifect on plants we may mentio'n those in which R is an aliphatic hydrocarbonfr'esidue containing 2 to '11 carbon atoms. phytotoxical' compounds according to the invention have a particular activity against herbaceous. plants, the more ligneo'us kinds are also aifected by the said means, but to'a' lesser'ex-tent. Of the kinds of plants, of which the growth is impeded or terminated by the said phytotoxical compounds,- we may mention: starwort (Szellaria media), White goosefoot' (Chenopodium album), broador narrowleavedyJayb'read (Plantago media and lancealata), stingingmettleKUrtica ureus),'s'orrel (Rumex ace tosella) and'charl'ock (Raphanus) From -tests with tomatoes and garden beans it was found that of the combating compounds according to the invention particularly'the mercapto-compounds have a phytoto'x-ical effect on plants. Of the mercapto-compoundsspecial mention may be made of those, in which the group of R contains 3 to 5 carbon atoms, for example,

'5 the n-propyl-, allyl-, n-butyl-, isoamyl-, n-amyl-, isobutyland '3 methylbutyl-derivatives of '2-inercapto-4,6-dichlor 1,3,5-triazines. It has been found that 2 alkylmercapto- 4,6-dichlor-1,3,5-triazines with a carbon chain having more than'll carbon atoms has hardly any photytoxical effect. The compounds in which X is -O- and R designates the groups referred to above, were found to have approximately the same phytotoxical effect with tomatoand bean-tests. 2-methoxy-4,6-dichlor-triazine, infa"con'cen'tration of 1 to 3%, was found to be only -slightly effective, as well as those compounds in which '4,6-dichlor-triazines, which are'substituted'atthe' position I '2 by an aryl-a'mine-group and of which-the aryl' g-roup may have on'e -or more alkyl or'negative*groups,for example, a chlorine atom or a nitro-group. Reference rnay furthermore be made to the compounds 2 chloro-'4,6(-diarylamino) l,3, 5-triazine and 2,4-'dichlor-6-arylamino- 1,3,5-tri-azine. These compounds could also be used as fungicides. v

'Finally we may mention the compound 2-chlor 4',6'bisdiethylaniino-1,3,5-triazine. This compound is said to 'have herbicidal effects, but be free from fungicidal eifects.

This compound is moreover said to havea slight insecticidal activity.

The present invention'relates to a method of producing means for combating noxious organisms, comprising a derivative of 1,3,S-triazine and is characterized in that a compound of the general formula:

wherein X designates NH, -'0- or -S* and R a the group of R had more than 11 carbon atoms. Of the combating means according to the invention, which are derivatives of 2-oxy-4,6-dichlor-l,3,5triazine particularly those are important, in which theflgroup of R contains 3 to'll. carbon atoms.

The'active compounds or a mixture thereof can be worked up to obtain combating means in a conventional manner. To this end'the active compounds are mixed with solid or liquid carriers or, if necessary, dissolved therein, and, if desired, enriched with dispersion agents,

emulsifiers or wetting agents. Preparations thus obtained may be'sprayed, pulverized or nebulized in air either as such or emulsified or dispersed in a liquid, for example water. 'Of the various'preparati'ons which may be used and which may be obtained by means of the active compounds, mention may be made ofthe so-called mixable oils, spray. powders and atomizing powders. These forms are referred to only by way of example and do not intend to restrict the invention.

In order to produce mixable oils the mixture of active compounds-is dissolved in a suitable solvent, which is immiscible with water, and to this solution is added an emulsifier. Suitable solvents are, for example, xylene, toluene dioxane, petroleum distillates rich in aromatic compounds, for example, solvent naphtha, distilled tar oil, furthermore tetraline, cyclohexane or mixtures of these liquids. As emulsifiers may beu-sed alkyl phenoxypoly .glycolethers, poly-oxyethylene sorbitane esters of fatty acids or poly oxy-ethylene sorbitol esters of fatty acids. Some of these types of emulsifiers are known under the registered tradename of Triton, Tween and Atlox.

The concentration of the active compounds in the liquidmi-xable with water is not subjected to narrow limits. It may vary,-for example, between 2 and 50% by weight. When using'these solutions, the mixable oils are emulsified in 'water and this emulsion is sprayed. Usually the concentration of active compounds in these aqueous emulsions 1iesbetween0.01 and 0.5% by weight.

The

Thespray powders may be produced by mixing the active compounds with a solid, inert carrier, usually in the presence of a dispersion agent and/ or wetting agent.

Prior to their use the spray powders are dispersed in liquid, preferably in water and this dispersion is sprayed.

any auxiliary substances may in addition be ground.

The carrier material may, for example, be alum earth, diatomaceous earth, kaolin, dolomite, talcum, gypsum, chalk, bentonite, attapulgite, infuson'al earth, celite, wood meal, tobacco dust or ground coconut shells. Suitable dispersion agents are lignine sulphonates and naphthalene sulphonates. Wetting agents may be fatty alcohol sulphates, alkyl-aryl-sulphonates or fatty acid condensation products, for example those known under the trade name of Igepon.

Also with the spray powders the concentration of the active compounds is not subjected to narrow limits. In general, the concentration will be chosen to lie between 10 and 80% by weight.

Atomizing powders may be produced by applying an active compound or mixtures thereof, as such, or dissolved in a solvent, to a solid carrier. When used, the preparation thus obtained is atomized in the air in a dry, finely pulverulent state. duced, when suitable light carriers are employed, also in the manner described for the production of spray powders. The carrier material may be the products referred to above for the production of spray powders. Usually, the concentration of active compounds in the atomizing powders is lower than that of the spray powders or mixable oils, but it exceeds the concentration of active compounds in dispersions or emulsions, obtained by diluting spray powders or mixable oils with liquids. The atomizing powders often contain 1 to 20% of active compounds. It may be superfluous to observe that the mixable oils, the spray powders or the atomizing powders according to the invention may be produced by mixing two mixable oils (or spray powders and atomizing powders), each of which contains one of the active compounds.

The compounds according to the invention have a comparatively high chlorine content and are capable of splitting ofi hydrochloric acid. 7 This may be undesirable. In order to avoid the harmful effect of the hydro chloric acid, a compound may be added to the combating substances, which compound is capable of binding the hydrochloric acid set free. To this end use may be made of propylene oxide. A concentration of about 1 to of this compound usually yields satisfactory results.

The compounds of the invention are fairly stable, when kept in stock; some of them lose their activity rather soon when they are applied to the soil or mixed therein. Owing to this property these compounds, of which we may mention particularly 2n-butylmercapto-, and 2n-butoxy-, -4,6-dichlor-1,3,5-triazine are particularly suitable to destroy weed like plants from agricultural or horticultural fields before the cultural plants have come up. To this end the compounds may be employed in a quantity of 2 to 20 kgs. per hectare. A quantity of about kgs. per hectare often gives satisfactory results.

The phytocidal effect of the compounds of the given formula was determined by tests on tomatoes and garden bean plants in the following manner.

A compound to be examined was dissolved in acetone (concentration 1% by weight). Then this liquid was sprayed on a number of tomatoand garden bean-plants in a quantity which corresponded to 10 kgs. of active substance per hectare. A similar test was made with a 3% acetone solution, which was applied to plants in a These powders may be pror quantity which corresponded to 30 kgs. of active substance per hectare. Each series of tests was carried out on two tomato plants and two garden bean plants, the age of which was 3 to 4 weeks. Ten days after the application it was fixed to what extent the plants had suffered from the treatment. The following standard was fixed:

No traces of burnin 0- 0 to A part of the surface of the plant burnt 1 A /a part of the surface of the plant burnt 2 A to /3 part of the surface of the plant burnt 3 /3 to part of the surface of the plant burnt 4 W to 1 part of the surface of the plant burnt 5 Quite dead. 6

The numerals thus fixed were united in the Tables I, II, III.

TABLE I Phytotoxic effect of Z-alklymercapt0-4,6-dichlor-1,3,5-triazines Test plant Tomato garden bean Tested compound concentration concentration 2 ethyl mercapto 4,6 dlchlor 1,3,5 trlazine 1 5 4 6 2 n propyl mercapt 4,6 dlchlor 1,3,5-trlazine 4 6 6 6 2 -lso propyl mercapto 4, 6 diohlor-1,3,5-triazine 1 6 3 6 2 allyl mercapto 4, 6 dichlor 1,3,5-triazine 4 6 6 6 2 n butyl mercapto 4,6 dichlor- 1,3,5-triazlne 5 5 4 6 2 (1, 1' dlmethyl ethyl) mercapto- 4,6-dichlor-L3,5-trlazlne l 3 3 5 2 (3- methyl butyl) mercapto 4,6-dlchlor-1,3,5-trlazine 3 6 6 6 2 n octyl mercapto 4 6 dichlor- 1,3,5-triazine 2 3 4 4 2 n amyl mercapto 1,3,5-triazine 6 6 6 6 2 (2 methyl propyl) mercapto -4,6-

dlchlor-l,3,5-triazine 6 6 6 6 2 (1' methyl propyl) mercapto 4,6-

dlchlor-1,8,5-tr1azlne 6 6 6 6 TABLE H Phytotoxic efiect of Z-alkyloxy 4,6 dichlor 1,3,5-triazins Test plant Tomato garden bean Tested compound concentration concentration 2 ethoxy 4,6,- diehlor 1,3,5-trlazine--- 3 5 3 4 2 n-propoxy 4,6,-dlchl0r 1,3,5-triazlne- 5 5 2 5 2lso prODOXY 4,6,-d.lchlor 1,3,5-trlazlne. 4 5 4 4 2 (propene-2) oxy-1' 4,6,-diel1lor 1,3,5-

trlazine 3 6 4 6 2 (propynyl-Z') oxy-l 4,6,-dlchlor 1,3,

5-tr zine 2 5 3 5 2 n-butoxy 4, 6,-dlchlor 1,3,5-triazine 3 6 3 5 2 (1 methylpropoxy) 4,6, dichlor 1,3,5-trlazine 2 6 3 5 2 cycle hexoxy 4,6,- dichlor 1,3,5-

trlazlne 3 5 3 5 2 octoxy 4,6,-dlchlor 1,3,5-triazine 5 5 3 4 2 (lmethylheptoxy) 4,6,-d ichlor 1,3,5-trlazine 2 3 1 2 2 amyloxy 4,6,-dlchlor 1,3,5-trlazine 5 6 6 6 The insecticidal effect of the compounds of the formula whereinlX: designates.- O-. or --S' was fhundstoioccuri particularly. withthose compounds; .iniwhichlRi designates an aliphatic residuehavingl toll-=1 carbon. atoms; The insecticidal effect wastestedon twov kinds of; insects i.e. Musca and Sitophilus in two concentrations i.e. of 1000 p.p.m. andof 300 p.-p.rn. The tests were carried out as follows.

1. cc. of an acetone solution ofthe compound'to be tested in one of, the said concentrations was, brought into a Petri dish, having a content value. of about 64 cc. After the solvent had been evaporated, muscas were introduced into the dishes. With the Sitophilus test both the bottom and the lid of thePetri dish were painted with: l cc. of an acetone-solution and after the solvent-had been evaporated, the insects were introduced into the dish; ForzMusca after 21 hours and for Sitophilusafter 5 days is was fixed what percentage of the insects had been killed. Blank testswere. carried. out, in, a similar manner. The results ofthese-tests are indicated in the Tables III and IV. The values indicated (percentages of" kill)';- are average values of a series of tests. From these tests it is evident that the insecticidal effect of the mercapto-compounds is slightly greater than that of the' oxy-compounds.

TABLE III Insecticidal efiect of 2-alkylmercapt0-4,6-dichlor-I,3,5-

triazines Test insect Tested compound Musea Sitophilus 1,000 300 1,000 300 p.p.m. p.p.m. p.p.n1. p.p.m.

2-ethyl-mercapto-4, 6-dichl0r-1, 3, 5--

triazine -r 100 87 100 100 211-.propyl, mereaptoi, 6-diehlor-l,3,

fi-triazlne 100 100 100 100 2n-allyl'mercapto-4, fi-dichlor-l, 3, 5-

tliazine 100 97 100 100 2n-lsopropy1 mercapto-et, fi-dichlor-l,

. 3 fi-triazln 100 96 100 100 2n-bu 100 100 100 100 2(1 1 dlrnethylethy1) 100 94 100 100 2(3fmethylbutyl) 100 97 100 f 100 TABLE IV Insecticidal efiect of 2-alkoxy-4,6-dichl0r-1,3,5-triazine Test insect.

Tested compound Musca I Sitophilus 1,000 300 1,000 300 ,p.p.m. p.p.m. p.p.m. p.-p.m.

2*eth0xyF4, G-dichlor-l, 3, 5-triazines. 100 16 100 8 211-propoxy-4, fi dichlor-l, 3, S-triazines 100 100 100 100 2n;allylo xy 4; 6-dich1or-1, 3, 5-triazines 100 52 100 100 2 (propene-2-oxy-1) 4, 6-dichlor-1, 3,

5-triazines. 100 33 100 72 2-ls oprop,oxy 4; G-dichlor-l, 3, 5-triafi'trlaziiihs q i 100 61 100 2woetoxy. 4-,.6-dichlor-1, 3, 5-tnazines 90 71 99 84 2=(1'-methyl heptoxy) 4, G-rlichlor 1, 3,

5triazines 92 67 100 100 2-.cyclohexoxy. 4, G-dichlor-l, 3, 5-triazines 100 100' 100 100 It can furthermore be stated that the compounds gin.- dicated in table have a knock-down effect, particularly with the Musca insects. Also in this respect the mercapto-compounds proved to have a greater activity than the. oxy-compounds; The. compounds having an insecticidalzeffectamayibe worked up in the mannerdescribed for thepliytoeidali compounds to obtain mixable oils, spray powders; or: atomizing: powders. an. alternative, the.

6 compounds maybe dissolved, in hydrocarbons, forex. ample, mineral oils or coal tar distillates without: the. addition of auxiliary substances, such as wettingagents or dispersion agents. Moreover, the insecticides according, to the, invention may be dissolved in readily condensable, inert liquids, which are gaseous at room temperature; Assuch use may be made, for example, of fluorine-chlorine-methanes, for instance Freon. If

desired, diluents may be added to these solutions, for I example, methylene" chloride. These solutions can be readily nebulized.

The compounds of the general formula:

7 01 wherein X designates O-., orS- and R a saturated or an, unsaturated or alicyclic hydrocarbon residue, are produced-by reacting compounds of the general formula HXR with cyanuric acid chloride, preferably in the presence of an acid binder.

As a solvent use may be made of chloroform, tetrachlorcarbon acetone, aliphatic ethers for instance diethylether, dimethyl-ether, furthermore aromatic hydrocarbons,

for instance toluene or benzene. It has been found that inthese solvents the presence of water affects adversely the'yield'of the reaction, so that the reaction is preferably carried, out in an anhydrous medium.

As an acid binder use may particularly be made of 2,6-alkyl-substituted pyridine, for instances 2,6-dimethyl-' pyridine, 2,4, 6-trimethyl-pyridine, Zmethyl-chinoline, although also other tertiary amines may be used, for instance: dirnethylor diethyl-aniline.

The compounds according to the invention, wherein X isO or S are best produced at a temperature between 20 and +25 C.

The said compounds may, as an alternative, be obtained by causing cyanuric acid chloride to react with a compound of the formula: HXR is an excess quantity in the presence of. an inorganic acid binder, for instance sodium carbonate, sodium bicarbonate or sodium hydroxide. This reaction may be carried out in an aqueous medium.

The compounds, wherein X designates O or S-., may furthermore .be produced by reacting cyanuric acid chloride with a compound of the formula: MeX-R, wherein Me designates an alkali atom, for instance sodium ethanolate or-potassium methanolate, or an alkali compound of an aliphatic mercaptane. This reaction is carried out preferably in the presence of an excess quantity of the alcohol or the mercaptane. If desired, other organic solvents, for'instance, aliphatic or aromatic others, such as dimethylor diethyl-ether, phenetol anisol; furthermore acetone or benzene and toluene, may be used as diluents.

It should be notedthat the compounds are preferably produced by carrying out the reaction. between cyanuric acid chloride and the desiredaliphatic alcoholor, themer= captane in the presence of a 2,6-alkyl-substituted pyridine as an acid binder.

EXAMPLE I.2-METHOXY-4,6-DICHLOR-1,3,5-TRIAZINE EXAMPLE II.2-ETHOXY-4,6-DICHLOR-1,3,5-TRIAZINE 18.4 g. cyanuric chloride (0.1 mol) was dissolved in 120 mls. of acetone. While being cooled on ice, this solution had added to it in succession, 4.6 g. of ethyl alcohol (0.1 mol) and 13.5 mls. of collidine in a manner such that the temperature of the reaction mixture did not exceed C. The mixture was kept at room temperature for three hours. The hydrochloride acid salt of: collidine formed was then filtered off and washed with acetone. The filtrate was then poured out in ice water.

The 2-e'thoxy-4,6-dichlor-1,3,5triazine was precipitated in the form on an oil, which was absorbed in diethyl ether. The ethereal solution was washed four to five times with water, dried on sodium sulphate, filtered and evaporated to dryness. The remaining oil was distilled.

The yield was 10 g. (52%) of 2-ethoxy-4,6-dichlor-1,3, 5-triazine. Boiling point 14 mm.=114 C.

EXAMPLE III.2N-PROPOXY-4=, 6-DICHLOR-1,3 5-

TRIAZINE In the same manner as described in Examples I and H 18.41 g. of cyanuric acid chloride (0.1 mol), 6 g. of npropyl-alcohol and 13.5 mls. of collidine yielded 12.5 g. (60%) of 2-propoxy-4,6-dichlor-1,3,5-triazine. Boiling point 12 rnm.=124 (3.

EXAMPLE IV.-2-ISOPROPOXY-4,G-DICHLOR-l,3,5-

TRIAZINE In the same manner as described in Examples I and II 12.3 g. (0.067 mol) of cyanuric chloride, 3.9 g. of allyl-alcohol and 9 mls. of collidine yielded 7.1 g. (52%) of 2-(propene-2-oxy-1')-4,6-dichlor-1,3,5-triazine. (Boiling point 11 mm.=126 to 127 C.)

EXAMPLE VI.2-(PROPYNYL-2'-0XY l)-4,6-DICHLOR- 1,3,5-TRIAZINE In the same manner as described in Examples I and II 18.5 g. (0.10 mol) of cyanuric chloride, 5.6 g. of propargyl-alcohol and 13.5 mls. of collidine yielded 8.6 g. (42%) of 2-(propyn-2-oxy-1) 4,6-dichlor-1,3,5-triazine. (Boiling point 11 mm.=134 to 135 C.) After some time the substance solidified and melted at 39 to 40 C.

EXAMPLE VII.2NBUTOXY-4, G-DICHLOR-l ,3,5- TRIAZINE In "the same manner as described in Examples 1 and II 92.2 g. (0.5 mol) of cyanuric chloride, 53.5 g. of nbutyl-alcohol and 67.5 mls. of collidine yielded 95.5 g. (86%) of 2n-butoxy-4.6-dichlor-1,3,5-triazine. Boiling point 12 mm.=139 to 140 C.

EXAMPLE VIII.2-(1'-METHYL PROPOXY)-4,6- DICHLOR-1,3,5-TRIAZINE In the same manner as described in Examples I and II 12.3 g. (0.067 mol) of cyanuric chloride, 4.95 g. of

butanol and 9 mls. of collidine yielded 9.5 g. (65%) of 2(1 methyl propoxy) 4,6 dichlor 1,3,5 triazine. (Boiling point 12 mm.=127 to 128 C.). EXAMPLE 1X.2-cYcL0HEXoXY-4,e1)1cHLoR-1,3,5-

TRIAZINE In the same manner as described in Examples I and II 12.3 g. (0.067 mol) of cyanuric chloride, 6.7 g. of cyclohexanol and 9 mls. of collidine yielded 10.2 g. (62%) of 2-cyclohexoxy-4,6-dichlor-1,3,5-triaz.ine (boiling point 12mm.=168 to 169 C.).

EXAMPLE X.2-OCTOXY-4,6-DICHLOR-1,3,5-TRIAZINE In the same manner as described in Examples I and 11 18.45 g. (0.1 mol) of cyanuric acid chloride, 13 g. of octanol (0.1 mol) and 13.5 mls. of collidine yielded 16.9 g. (61%) of 2-octoxy-4,6-dichlor-1,3,5-triazine (boiling point 0.02 mm.=127 to 130 C.).

EXAMPLE XI.2(1'-METHYLHEPTOXY)-4,6-DICHLOR- 1,3,5-TRIAZINE In the same manner as described in Examples I and H 18.45 g. (0.1 mol) of cyanuric acid chloride, 13 g. of octanol-2 (0.1 mol) and 13.5 mls. of collidine yielded 13.5 g. (48%) of 2-(l'-methylheptoxy)-4.6-dichlor-1,3,5- triazine. (Boiling point 0.005 mm.=l02 to 106 C.)

EXAMPLE XII.2-METHYLMERCAPTO-4,6-DICHLOR- 1,3,5-TRIAZINE 55.6 g. (0.2 mol) of methylisothio-urea sulphate was introduced into 80 mls. of 5n-caustic soda. While being carefully heated, the sulphuric acid was bound and the methylisothio-urea was set free. The latter substance is not stable at normal temperature and decomposed into cyanic amide and methyl-mercaptane. The methylmercaptane was introduced into a solution of 18.45 g. of cyanuric chloride, dissolved in 200 mls. of acetone. The temperature of the solution was kept between 25 to 30 C. When all the methylmercaptane had been introduced, the reaction mixture had added to it 13.5 mls. of collidine at the same low temperature. The hydrochloric acid salt of collidine was immediately precipitated.

The reaction mixture was kept for one hour at a temperature not rising above 0 C. and was then poured out on ice. The 2-methylmercapto-4,6-dichlor-1,3,5 ,-triazine was precipitated in the form of a solid substance; After filtering, washing with water and drying on concentrated sulphuric acid in vacuo, 17.5 g. (89%) of 2- methylmercapto 4,6 dichlor-1,3,5-tn'azine was obtained (melting point 57 to 59 C.). Recrystallisation of the substance from petroleum ether (60 to 80) did not raise the melting point.

EXAMPLE XIII.2ETHYLM ERCAPTO-4,6-DICHLOR- 1,3,5-TRIAZINE 18.45 g. (0.1 mol) of cyanuric chloride was dissolved in mls. of acetone. While being cooled on ice, 10 g. (0.16 mol) of ethyl-mercaptan was added, then 13.5 mls. of collidine. During the reaction the mixture was cooled with ice. The reaction was continued for three hours at a temperature between 20 to 25 C. Then the deposit of the hydrochloride acid salt of collidine was filtered ofif, washed out with acetone. The acetonic solution was poured out in ice water, in which 2-ethylmercapto-4,6-dichlor-1,3,5-triazine was precipitated in the form of an oil. The oil was dissolved in diethyl ether, the solution was washed with water, dried on sodium sulphate, filtered and inspissated. The remaining oil was distilled in vacuo. Yield 13.5 g. (64%) of 2-ethylmercapto- 4,6-dichlor-1,3,5-triazine. (Boiling point 0.07 mm.=79 to 80 C.)

EXAMPLE XIV.-2N PROPYLMERCAPTO-4,6-DICHLOB- 1,3,5-TRIAZINE In the same manner as described in Examples X11 and )QII 18.45 g. (0.1 mol) of cyanuric chloride, 8 g. of n-propylmercaptane (0.105 mol) and 13.5 mls. of collidine yielded 20.65 g. (92%) of 2n-propylmercapto-4,6-

dichlor-1,3';5' triazine; After distillation theyield was 78% (boiling::point.0301 mm.=89 to.9.1'C.).

XV..2-ISOBROBYIMERCAPTO ae-i icrinon- 1,3,5-JEIHAZI1WEv 1 p m the same mannerasdescribed iniExamples XII and XIIjE1 8.45 'g. 0.1 mol) of-cyanuric chloride, 101g. (0.13 mol) of-isjopropylmercaptane and 13 .5 mls. of-collidine yielded 16 .17 (25%) of-'2-iso-propyl mercapto14,6-diclil'or 1,3,5-triazine. (Boiling point- 0.2. mm.=8 1=' CI) EXAMPLE XVI.25AI1DHJMERCARTQ-4-6DICHLOR-l,3,5- TRIAZINE In the same manner as described in Examples X112 and XIII 18.45 g. (0.11 mol) of cyanurica chlorida. 10. g. (0.135 mol) of allylmercaptane and 13.5 mls. of collidine yielded 16 g. (72%) of 2-allylmercapto-4,6-dichlor- 1,3,5-triazine. (Boiling point-0.25 m'm.=l11 C.).

EXAMPLE XVII.2N BUTYLMERCAPTO-,G-DICHLOR- 1,3,5-TRIAZINE In the same manner as described in Examples XII and XIII 92.25 g. (0.5 mol) of cyanuric chloride 45 g. (0.5 mol) of n-butyl-mercaptane and 13.5 mls. of collidine yielded 97.5 g. (81%) of 2n-butylmercapto-4,5-dichlor- 1,3,5-triazine. (Boiling point 1.5 mm.=116 to 119 C.)

EXAMPLE XVIII.-2-(1,1'-DIMETHYLETHYL) MER- CAPTO 4,6-DICHLORr1,3,5-'TRIAZINE In the same manner as described in Examples XII and M11 18.45 g. (0.1 mol) of cyanuric chloride, 10 g. (0.11 mol) of 1'l-dimethylethyl-mercaptane and 13.5 mls. of collidine yielded 27 g. (11%) of 2-(1',1-dimethylethyl) mercapto 4,6 dichlor 1,3,5 triazine. (Boiling point 0.01 mm.=80 C.)

EXAMPLE XIX.2-(3'-METHYLBUTYL) MERCAPTO4,6- DICHLOR-1,3,5-TRIAZINE In the same manner as described in Examples XII and XIII 18.45 g. (0.1 mol) of cyanuric chloride, 11.0 g. (0.105 mol) of 3-methylbuty1-mercaptane and 13.5 mls. of collidine yielded 19.9 g. (79%) of 3-methylbutylmercapto-4,6-dichlor-1,3,5-triazine. (Boiling point 0.005 mn1.=92 to 94 C.)

EXAMPLE XX.'2N-OCTYLMERCA-PTO-4,G-DICHLOR-l,3,5-

TRIAZINE In the same manner as described in Examples XII and XIII 18.45 g. (0.1 mol) of cyanuric chloride 18 g. (0.125 mol) of octyl-mercaptan and 13.5 mls. of collidine yielded 23.25 g. (79%) of 2n-octylmercapto-4,6-dichlor-1,3,5- tr'iazine. (Boiling point 0.4 mm.=146 to 148 C.)

EXAMPLE XXI A mixable oil was produced by dissolving 25 g. of Znbutylmercapto-4,6-dichlor-1,3,S-triazine in 65 g. of xylene and by adding thereto g. of an emulsifier of the type alkylphenoxy-polyglycol ether (Triton) and 5 g. of propylene oxide the latter substance serving to bind any free hydrochloride acid. Similar mixable oils were produced of 2-isopropylamino-4,6 dichlor-1,3,5-triazine from 2n butoxy-4,6-dichlor-1,3,5-triazine and of 2-allyloxy- 4,6-dichlor-1,3,5-triazine. For practical use these mixable oils were diluted with water in a weight ratio varying between 1:200 and 1:40. The aqueous emulsions were used as weed-killing means in a quantity of about kgs. per hectare.

EXAMPLE XXII An aerosol was produced by dissolving 0.5 g. of Znbutyl mercapto-4,6-dichlor-1,3,5 triazine in a mixture of 5 g. of xylene, 1 g. of propylene oxide, 40 g. of methylene chloride, 53.5 g. of a fluorine-chlorine-methane compound (a mixture of equal quantities of Freon-11 and Freon-12). A similar aerosol was produced, which contained the same quantity of 2-(3-methylbutyl)mercapto-4,6-dichlor-l,3,5 triazine and 2-butoxy-4,6-dichlor- 1,3,5-triazine. The aerosols were used for combating insects.

I 10 What is claimed-is: g a

1. A method of destroying insects comprising:contact; ing said insects with:an insecticidal.composition containing in: an. insecticidally effectivezamount a. compoundworrer spendingto thegeneral formula.

wherein X'designates a member of the groupconsiStingof --O-- and -S- and R designates a member ofthe group consisting of saturated aliphatic hydrocarbon radicals containing from 1 to 11 carbon atoms, the allyl radical and the cyclohexyl radical.

2. A method of destroying insects comprising contacting said insects with an insecticidal composition containing in an insecticidally eifective amount a compoundcorresponding to the general formula:

wherein X designates S and R designates a member of the group consisting of saturated aliphatic hydrocarbon radicals containing from 1 to 11 carbon atoms, the allyl radical and the cyclohexyl radical.

3. method of destroying insects comprising contacting said insects with an insecticidal composition containing in an insecticidally efiective amount a compound corresponding to the general formula:

wherein X designates a member of the group consisting of --O and S and R designates a member of the group consisting of saturated aliphatic hydrocarbon radicals containing from 1 to 11 carbon atoms, the allyl radical and the cyclohexyl radical and a solid carrier therefor.

4. A method of destroying insects comprising contacting said insects with an insecticidal composition containing in an insecticidally effective amount a compound corresponding to the general formula:

11 ing 2(n-butylmercapto)-4,6-dich1oro1,3,5-triazine in an insecticidally effective ,amount- 7. A method of destroying insects comprising contacting said insects with an insecticidal composition containing 2(n alkylmercapto)-4,6-dichloro-1,3,5-triazine in an insecticidally effective amount.

8. A method of destroying insects comprising contacting said insects with an insecticidal composition containing ,2(n-propoxy)-4,6-dichloro-1,3,5-triazine in an insecticidally eflective amount.

9. A method of destroying insects comprising contacting said insects with an insecticidal composition contain ing 2(cyclohexyD-4,6-dichloro-1,3,5-triazine in an insecticidally eflective amount.

References Cited in the file of this patent NITED STATES PATENTS Dudley June 6, 195.0 Holm-Hansen June 27, 1950 Dudley Jan. 9., 1951 DAmico Nov. 2, 1954 Feldman Feb. 8, 1955 Wolf Oct. 11, 1 955 Brassel Dec. 11, 1956 OTHER REFERENCES Hirt et al.: Helv. Chim. Acta, vol. 33, pp. 1365-1369, 1950, p. 1367 pert.

Experientia, vol. 11, pp. 107-8, 1955.

Claims

1. A METHOD OF DESTROYING INSECTS COMPRISING CONTACTING SAID INSECTS WITH AN INSECTICIDAL COMPOSITION CONTAINING IN AN INSECTICIDALLY EFFECTIVE AMOUNT A COMPOUND CORREESPONDING TO THE GENERAL FORMULA