IL27197A - 4-dimethylaminomethylphenyl-n-methylcarbamates,their preparation and pesticidal compositions containing them - Google Patents

Description

•niUJ i f Π3 Τ5ΪΠ1"Τ 'Π PATENTS AND DESIGNS ORDINANCE SPECIFICATION Hovel 4-!-dimethylam-tnomethylphenyl-tf-methylcarbamates, their preparation and peeticidal compositions containing them ZjniK ni *3Dn ο*ρ*το m tnp mainyni I/We H.V. PHILIPS* GLOEILAMPEMFABBIEK , a company incorporated under the laws of the Netherlands, of 29 Emmasingel, Eindhoven, e Netherlands do hereby declare the nature of this invention and in what manner the same is to be performed, to be particularly described and ascertained in and by the following statement:- ι 27Ϊ97/2 The. invention relates to a group of novel 4-dimethylamino- methylphenyl-N-methylcarbamates, substituted in the benzene nucleus by 1, 2 or 3 alkyl groups having each 1 to 3 caibon atoms.

This group comprises the following compounds: 1) 2-methyl-4-dimethylaminomethyl-5-isopropyl-phenyl-N-methylcarbamate, ' 2) 2-isopropyl-4-dimethylaminomethyl-5-methyl-phenyl-N-methylcarbamate, 3) 3-methyl-4-dimethylaminomethyl-5-ethyl-phenyl-N-methylcarbamate, · cinnabarinus, also against ovules thereof and against Leptinotorsa decemlineata. The compound (5) is active against Aphis fabae and Tetra-nychus cinnabarinus. The compounds are active in concentra ions between 10 and 100 mgs per litre of the liquido Of these compounds particularly 2, 3-dimethyl-4-d.imethylamino-methyl-phenyl-N-methyl-carbamate exhibits an excellent activity. Compositions containing said compound were found to be capable of preventing and combating the following infections? a) leptinotorsa cinnabarimus on solanum tuberosum, b) pieris brassicae on brassica oleracea L var. c) aphis fabae scop, on vicia faba L d) myzus persicae salt on solanum tuberosum, e) brevicoryne brassicae on brassica oleracea (L) f ) eriophyes sp on EM IX apples.

The compounds according to the invention are novel compounds, which can be produced in known manner.

A very suitable method consists in starting from a phenol which does not contain other substituents at the benzene nucleus than the alkyl-groups present in the desired final product in the benzene nucleus. This phenol is etherified, for example, obtained is reacted in a solution, duced, with (para) formaldehyde. During the reaction an intermediate compound is formed, which contains at the para position, with respect to the phenol-ether group, the group CICH^* This compound is then convert-ed by means of dimethylamine into the corresponding dimethylaminomethyl-compound. After splitting of the ether function, preferably by boiling with a HBr solution, the resultant 4~dimethylaminomethylphenol, substit^ . uted by alkyl groups, is converted with methyl isocyanate into the desired N-methy1carbamates.

The biological activities were measured by the following tests; Aphis fabae: (Brevicoryne brassicae, Mygoura viciae, Myzus persicae) The bean plants or cabbage leaves were dipped in an aqueous solution or suspension containing 10 to 100 mgs per litre of liquid of the compound to be examinedo After drying the plants or leaves were put in 1 00 ml flasks filled with water and placed on wooden standso Plastic cylinders were slipped on the plants or leaves, which were then infected with 20 adult Aphis fabae. The mortality was assessed after 3 and 5 days.

Tetranychus cinnabarinuss About 10 cm high seedlings of Phaseolus vulgaris were dipped in a liquid containing the compound to be tested, after which they were dried, the leaves were enveloped in small plastic cages of a diameter of about 2¾-cms, into which the female anit«s were introduced- The infected plants were kept in a room at a temperature of 23° C, illuminated permanently with fluorescent lamps- The relative humidity was held constantly at 60 to 70o, The first check was made after 2 or 3 days, the last after 5 or 6 daySo Tetranychus cinnabarinus (ovicide test): The same kind of plants were used as for the test of the adult stage-Some of the seedlings were infected with 7 to 8 female Tetranychus cinna-barinus per cage. After 2 days the animals and the cages were carefully removed. In the meantime ovules had been deposited on the plants. The plants provided with ova were then dipped in an aqueous emulsion or suspension of the compound to be tested. After drying the plants were placed in the climatologically conditioned room and the number of ovules deposited on the leaves was counted. A second portion of the seedlings was dipped into the emulsion or suspension before infection with females of the red spider. Also in this case the females and the plastic cages were removed after two days, the further treatment being as in the foregoing. This instant was about 8 days after counting of the ovules. Living and dead ovules and living and dead larvae or nymphs or rest stages were counted.

Pieris brassica; Cabbage leaves were introduced into 100 mis wide-necked flasks after being dipped in aqueous emulsions or suspensions. The flasks were filled with water and the space between the stems in the neck of the flask were filled with cottonwool. After drying of the plants the flasks were placed to the neck in low wooden stands, provided with holes and they were covered with a perforated sheet of white paper, closing tightly around the neck of the flask and lying otherwise flat on the wooden stand. A plastics cylinder of 12 cms in diameter was slipped over the stems. By means of a brush 10 young caterpillars of about 2 cms (third stage) were counted and deposited on the leaves. The cylinders were then closed at the top with a sheet of soft, porous paper, which was fastened around the top end by means of a rubber band. Check was made after 5 days.

Leptinotorsa deoemlineatag This test was carried out in the same manner as described for Pieris brassica. The mother plants were formed by cut potato leaves. Per cylinder 10 young larvae of about 6 mms (= third stage) were counted and deposited. Check was made after 5 days.

The compositions according to the invention contain the aforesaid substancies in which the active substance is mixed with or dissolved in a solid or liquid carrier, to which a surface-active substance or a dispersing agent of an adhesive may be added. Apart from such water dis-persible compositions,for example dusts, smoke generators, aerosols, dis-persions and emulsions may be made.

The concentration of the active substance in the compositions according to the invention may be varied within wide limits, for example, from 95 by weight in a wettable powder containing only a wetting- and dispersing agent apart from the active substance down to 0.001 % by weight in the aqueous liquid to be sprayed.

Dusts according to the invention are obtained by thoroughly mixing an active substance for example by grinding, with an inert, solid carrier, for example in a concentration from 1 to 50 by weight. Examples of suitable solid carriers are talcum, kaolin, pipe clay, diatome-ceous earth, dolomite, gypsum, chalk, bentonite, attapulgite and mixtures of these and similar substances. Organic carriers may be used, for example, ground nutshells. ettable powders according to the invention contain an active substance, at least one dispersing age t, for example well-known agents such as lignine sulphonates, alkylnaphthalene sulphonates and furthermore preferably also a wetting agent, for example fatty alcohol sulphates, alkylarylsulphonates, fatty acid condensation products such as known under the trademark of "Igepon", whilst to this mixture may be added an inert, solid carrier. A wettable powder may be obtained by mixing the active substance with 1 to 5 parts by weight of a dispersing agent, 1 to 5 parts by weight of a wetting agent and 10 to 80 parts by weight of the aforesaid solid, inert carriers. For producing miscible oils the active compound is dissolved or finely divided into a suitable solvent, which is preferably sparingly miscible with water, to which solution an emul-sifier is added. Suitable solvents are, for example, xylene, toluene, petroleum distillates rioh in aromates, for example solventnaphtha, distilled tar oil and mixtures of these solvents. Suitable emulsifiers are, for example, alkylphenoxypolyglycol ethers, polyoxyethylene sorbitane esters of fatty acids or polyoxyethylene sorbitol esters of fatty acids. The concentration of active compounds in these miscible oils is not restricted to narrow limitsj it may vary between 2 and 0 by weight. Apart from these wettable powders and miscible oils, there may be mentioned as a high-concentration, primary composition a solution of the active substance in a liquid satisfactorily miscible with water, for example, acetone or glycolethers to which solution a dispersing agent and, if desired, a wetting agent are added. When diluted with water shortly "before or during the spraying operation, an aqueous dispersion of the active substance is obtained.

Dusting and spraying of the compositions according to the in-vention are carried out in a conventional manner in a concentration matching the prevailing conditions? this concentration is not subjected to narrow limits and may lie between 0.01 and 5f usually between 0.01 and 0.5 % by weight.

An aerosol composition according to the invention is obtained in a classical manner by incorporating the active substance if necessary in a solvent, in a volatile liquid to be used as a propellant gas, for example the commercially available mixture of chlorofluorine-derivatives of methane and ethane, known under the tradename of "Preon".

Smoke generators or fumigant powders, that is to say, compo-sitions capable of developing a pesticidal fume, when burning, are obtained by incorporating an active substance in a combustible mixture containing, for example, as a fuel sugar or wood flour, preferably in a ground state, a substance supporting the combustion, for example ammonium nitrate or potassium chlorate and, furthermore, a substance delaying the combustion, for example kaolin, bentonite and/or colloidal silicic acid.

Apart from the aforesaid ingredients the compositions according to the invention may contain other substances known for use in this kind of compositions.

To a dust may be added, for example, a "conditioner" such as calcium stearate or magnesium stearate. For example "adhesives" such as polyvinylalcohol , cellulose derivatives or other colloidal materials such as caseine may be added to improve adhesion of the pesticidal composition to the surface to be protected.

The method of producing the compounds according to the invention will be described more fully with reference to the examples.

EXAMPLE 1 2-MethylM-^imethylaminomet carbamate , (compound 1) a. Carvacrol methylether Carvacrol was methylated by standard methods with dimethyl sulphate in the presence of aqueous NaOH. Yield 95 . Boiling point 96 - 98°/l2 ram Hg. b. 2<- ethyl»4^imethylaminomethyl~^--lsoproT?ylanisole A mixture of 50 mis of benzene, 100 mis of concentrated hydrochloric acid and 82 gs of carvacrol methylether was saturated at 5°C with gaseous HC1. A solution of 17 g of paraformaldehyde in 200 ml concentrated hydrochloric acid was added dropwise over one hour whilst the mixture was thoroughly stirred. During this addition the temperature was kept at +1°C to +5°C, whilst a slight current of HC1 gas was passed through. After the addition stirring was continued for one hour at about +5°G, after which 200 ml of benzene and 200 g of ice water were added. The organic layer was separated off and washed three times with 150 ml of ice water. After drying over the benzene solution of 2-methyl-4~chloromethyl -5-isopropylanisole was added to a cold solution of 60 g of di-methylamine in 400 ml of tetrahydrofuran. The mixture was allowed slowly to assume the room temperature, left to stand for one day and then was heated in a water bath for 8 hours at 70 to 80°G, The mixture was concentrated in vacuo to a volume of about 300 ml and then extracted three times with 150 ml of 4H hydrochloric acid. The hydrochloric acid layers were collected and rendered strongly alkaline with a concentrated NaOH solution. with ether (200 mli. After drying over Na^O^ and distilling off the solvent, the product was dietilled. Yield 63 g (about 60 ), Boiling point 92°C/0.5 mm. It was found by gas-chromatography that the product consists of a single substance. c. 2-i¾thyil-4-difflethylaj3iinomet^ The above mentioned anisole (30.7 g) was refluxed with 120 ml of 48# HBr for ten hours. After evaporation in vacuo to about 80 g 100 ml of water was added and the solution was rendered strongly alkaline by adding a concentrated NaOH solution. After continuous extraction with diethyl ether the product was recrystallised from cyclohexane. Yield 24 g (about 84$). Melting point 120 - 125°C. d. 2-Methyl«4^imethylaminomethyl»^ carbamate .. . . nr . .M .., , The above mentioned phenol (5 g) was dissolved in 60 ml of diethyl ether, to which solution were added 3ml o methyl isocyanate and three drops of triethylamine. After standing or two days the mixture was refluxed ir 1»o hours.

After evaporation in vacuo the residue was recrystallised from petroleum-ether (boiling point 60 to 80°C). Yield 6.1 g ( 5 )* Melting point 94 - 95°C.

EXAMPLE 2 2-Isqpropyl^-dimethylaji^omethyl^5^methyl-T?henyl~H*methylcarbamatei (Compound 2) a. 2~Iaqpropyldimethylami^omethvl 5~methylanisole In a three-neck, 500 ml roundbottomed flask provided with an agitator, a thermometer, dropping funnel and a gas inlet tube, a mixture of 25 ml of benzene, 50 ml of concentrated HCl and 41 g of thymel-methylether was saturated with HCl gas.

Whilst leading in HCl at 0° - 3°C, a HCl-gas saturated solution of 8.5 g of paraformaldehyde in 100 ml of concentrated HCl was dropped in over 30 minutes. At 0° to 3° stirring was continued for one hour and then 150 ml of benzene and 150 ml of ice water were added* The benzene layer was dried (over Na2S0^), evaporated to about 100 ml and dropped into a solution of 33 g of dimethylamine in 200 ml of tetrahydrofuran (T 0°) . Without cooling, stirring was continued for one hour. The mixture was kept standing overnight and then refluxed for one hour under COg. The liquid was then evaporated to half its volume in order to remove the excess of dimethylamine. ^fee-The residue was extracted with 4N HCl. The HCl layeis ere collected, washed with benzene and then rendered strongly alkaline with NaOH and extracted with ether; the ether layer was dried and evaporated* The residue weighed 29.6 g. Fractionatin yielded 25.3 g! boiling point 85°/0.4 mm. b. 2~Isopropyl'-4~dimethylaminomethyl'<>5-*methylphenol. 24· g of 2~isopropyl«4»dimethylaminomethyl-5-methylanisole was boiled with 100 ml of HBr (48 ) for S.5 hours and the reaction mixture was evaporated. 50 ml of HgO was added to the residue and themixture was rendered strongly alkaline with NaOH. The liquid was extracted three times with 100 ml of ether. The three extracts yielded, subsequent to evaporation, 17.7, 2.5 and 1.3 g respectively of a solid substance.

Continuous extraction of the water layer (10 hours) yielded, in addition, 1,1 g of solid substance. By analysis, determination of the melting point and gas-chromatography the four fractions appeared to be identical. The fractions were recrystallised from petroleum-ether (60 - 80°). Yield 19#3 g; melting point 96°. c. 2-Isopropyl-4^imethylaminometh^^ carbamate , 14.5 g of 2-isopropyl-4-dimetbylaminomethyl-5-me hylphenol was dissolved in 70 ml of ether and cooled in ice.

Then 6 ml of methyl isooyanate and two drops of triethylamine were added to the solution. The mixture was kept standing at room temperature for 28 houre and refluxed ibr one hour and evaporated* The iBsldue (white), 20.7 g was recrystallised from petroleum-ether (60 - 80°). Yield 18 g; melting point 72-79°.

EXAMPLE 5 1-Methyl-4-dimethylaminomethyl-5-ethylTohenyl-H-methylcarbamate (Compound 3) a. 3-Methyl-4-dimethylaminomethyl-^-ethylanisole The production of the title compound from 3-methyl-5-ethylanisole was quite analogous to that of 2 isopropyl-4-dimethylaminomethyl-5-methylanisole from 2-isopropyl-5~methyl~ anisole, described in Example 2. Fractionation of the final product (32.2 g) gave three fractions ί I 87.5° - 90°/0.5 mm (a few drops), II 90° - 92°/0.5 mm (16.6 g; oil bath 135 - 140°), III 92° - 107°/0.5 mm(27 g; oil bath about 180°).

The fractions II and III were combined. The residue probably contained the anisole substituted in the ring with two dimethyl-aminomethyl groups. Yield about 40 · . ?»Methyl-4^imethylajninomethyl-5-e;vihylphenol The production of ths title compound from 3-methyl-4-dimethylaminomethy1-5-ethylanisole was quite similar to that of 2-isopropyl*=4-dimethylaminomethyl-5-methylphenol, described in Example 2. Yield about 30^· Recrystallisation from petroleum-ether (60 - 80°) . Melting point 81°. c. 3» ethyl-4^imethylaminQmethyl-5~ethylp carbamate 4 g of 3-methyl-4«dimethylaminomethyl-5-ethylphenol was dissolved in 20 ml of diethyl ether and 2»5 ml of methyl isocyanate and one drop of E ^JI were added to the mixture at 0°C. The mixture was kept standing for 48 hours and the re-fluxed for one hour and inspissated. Residue 4·5 g (theoretically 5.2 g). The residue was dissolved in 5 ml of diethyl ether and 2 ml methyl isocyanate and one drop of triethylamine were added. The mixture was kept standing for 48 |iours and then evaporated. The residue was dissolved in ether. HCl gas was led into the solution and the hydrochloric acid salt was subsequently filtered off* Yield 6 g (theoretically 6 g).

Determination of melting point under the microscope: at about 70° a probable development of gas. At 100° melting and re-crystallisation. The new crystals melted at 165°« Determination of the melting point with the Buchi melting-point apparatus. At about 70° development of gas. At 95 to 100° melting and decomposition.

EXAHPIB 4 2.5-Dimeth.^4-dimethylaminoroethylphenyl-K-methylcarbamate (Compound 4) a. 2^3-Dimethyl*4 dimethylamlnomethylanisole The production of the title compound was completely similar to that of the correspondin anisole described in Example 2. Yield about 60$. Boiling point 83°/0.4 mm. - b. 2.3-I>imethyl~4~diineti'ylaminomethylphenol The production of the title compound was quite similar to that of the corresponding phenol described i Exim le 2. The four ether extracts yielded 3.8 g, 2.2 g„ 1.6 g <^4 13.6 g, respectively, of identical substances. Hecrystallisation o o from bensene-pertoleum-fther (60 - 30 ) melting point 97 .

Yield about 805¾. c. 2.3~I meth,yl-4-dimethylaminomethylphenyl-H-methylcarbamate 1Θ.74 g of 2,3-dimethyl-4-dimethylaminomethyl-phenol was dissolred in 60 ml of diethyl ether. At 10° 6 ml of methyl isocyanate and one drop of trietiylaraine rare a dded to this solution. Immediately a white precipitate was formed. The mixture was kept at 20° for 48 hours and then refluxed for tw.p hours and evaporated. The residue was recrystallised from benzene/petroleum/ether (60 ~ 80°). Yield 13.5 g. Melting point 133°.

EXAMPLE 5 2 5-Dimethyl~4^imethylaiiiinomethylphenyl-I\i-methylcarbamate (Compound 5) a. 2.5~Piraethyl»4-dimeth.ylaiainomethylanisole The production of the title compound was identical to that of the corresponding anisole, described in Example 2. Yield about 50 boiling point 80°/0.5 mm. b. 2.5~Dimethyl^4'»dimethylaminomethylphenol The production of the itle compound was quite identical to that of the corresponding phenol, described in 2.1g Example 2, The four ether extracts provided 3.1 g, 1.8 g,/and 8.9 g, respectively, of 2,5-dimethyl«4-dimethylaminomethyl- - .74 g of 2,5^imethyl-4-»dimethylaminoiaethylphenol was dissolved in 110 ml of diethyl ether. At 10° 6 ml of methyl isocyanate and one drop of triethylamine were added to this solution. The mixture was kept standing for 48 hours, refluxed for two hours and then evaporated. The residue was a thick oil which was dissolved in diethyl ether. By passing HC1 gas into the solution the HCl salt was precipated. Yield 15.6 g; melting point 229°.

Claims (1)

1. 5 Compounds of the group of substances consisting 2 and the salts of these example the hydrochloric acid the sulphuric acid salt or the phosphoric acid compositions containing as an active substance a compound claimed in Claim mixed solid or liquid method of combating noxious character ized in that an area be cleared from noxious organisms is treated with a composition as claimed in Claim the tion of active ingredient in said composition varying between and A method of producing characterized in that compounds of the formulae mentioned in 1 are produced by methods known se for the production of this type of compounds and by analogous Λ method as claimed in Claim characterized in compound of the 16 wherein X and in have one of the following X is a and Y a or X is a and Y a or X is a and Y a or X is a and Y a or X is a and Y a is reacted with the amine subsequently isolated from the reaction or an preferably being introduced into the reaction the resultant salt being subsequently separated insufficientOCRQuality