DE2033454A1 - Carbamic acid ester - Google Patents

Description

"Carbatinic acid ester"

Priority: July 7, 1969, ViSt.A., No. 839 641 April 13, 1970, V.St.Ä., No. 28.097

Synthetic carbamates with insecticidal properties are known since 1947. In many cases the one that contains hydroxyl groups Component in these carbamates is a substituted phenol, a naphthol or a heterocyclic hydroxy compound. U.S. Patent 3,223,585 are substituted Carbamic acid esters of oximes of cyclic ketosulfides and substituted carbamic acid esters of cyclic thiohydrojtajnic acids the following general formulas are known

009886/3214

■ 'BATH

(D

(H)

in which the radicals R, to Rg are hydrogen atoms or lower alkyl create, η has the value O or 1, Rg is a hydrogen atom or a lower alkyl radical and R 1 is a lower alkyl radical. In these compounds the sulfur atom in the ring is in the oC or ^ position to the carbony group. With regard to the relationship between the structure and the biocidal activity of the alkyl carbamates and the activity of the cyclic compounds known from the USA patent, one should not expect that compounds "which these groupings are in a position other than 1, 2- or 1 ₉ 4-position exhibit each other, have high biocidal activity. According to the invention, it was found “that Üi-alky! Carbamates of Osimen are cyclic ketosulfides in which the residual sulfur atom is in the β-position to the carbamy!” Carbon atoms, that is, in which these groups are separated from one another by a carbon atom, surprisingly in © excellent

BAD ORIGfNAL

develop biocidal activity.

The invention thus relates to new carbamic acid esters of general formula III

(III)

in which X is the group -0-, -S- or -N-, η is the value

< ^δ > η »11,. .

O, 1 or 2, m has the value 0 or 1, the radicals R to R «are hydrogen atoms, alkyl radicals with 1 to 6 carbon atoms, a cycloalkyl ring, alkenyl, alkoxy, thioalkoxy or carbalkoxy radicals or phenyl groups, or R , and R ₂ , R ^ and R., Rr and Rg or R- and R _Q together form a · new cyclohexane or cyclohexene group and the radicals R _q to R ,, form carbon atoms or alkyl radicals with 1 to 6 _# carbon atoms.

• ■ »

The invention also relates to new intermediates with biocider Effect, namely 2,4t ^ trimethyltetrahydrothiophene - ^ - QEf 2,2-dimethyl-3-carfeäthoxytetΓahydΓothiΌphen-4-one and

009885/2284

BATHROOM 0BJ6INÄL

2,2-dimethyltetrahydrothiophene-J ^ -one.

Specific examples of preferred carbamic acid esters of the invention are: . .

• '3-methylcarbamyloximinotetrahydrothiophene

.NOCNHCH ₃

3-carbomethoxy-4-methylcarbamyloximinotetrahydrothiophene

H ₅ COC

OCNHCH:

2-carbomethoxy-3-i

/ OCWHCH,

BATH ORIGINAL

(Pl (P) ^ ¹ ^ RK ff 1) ¹ ^ <s \

y y ä θ θ s / ^ s & ®

m, 5 a.

3,3-ethyl-4-methylcarbamyloximinotetrahydrothiophene

CH

H, C

3 / NOCNHCH

3,3-Dimethyl-4-ethylcarl-DamyloximinotetΓahydΓothiophene

OCNHC ₂ H ₅

2,2-Bimethyl-4-methylcarbamyloximinotetrahydrothio ^ hen

Ii

NOGNHCH,

HjC

2 _# 4- »4-Trimethyl-3-methylcarban] yloxiTninotetrahydrothiophene

NOCNHCH,

009885/2284

ORIGINAL INSPiCTED

3-methylcarbamyloximinotetrahydrothiapyran

Ii

NOCNHCH,

3 »3-diethyl-4-methylcarbamyloximinotetrahydrothiophene

C ₂ H ₅

-NÖCNHCH,

3-Ethyl-3-πlethyl-4-ynethylcaΓbamyToxiπίinotetrahydrothiophene

H ₃ C,

^C 2 ^H 5

NOCNHCH,

009885/2284

■ - 7 -

JiOCNHCH ₅

4-methylcarbamyloximino-2-thlaspirojU, 5J dec-7-en

jU, 5J

NHCH,

2,3 _f 3-TΓimethyl-4-methylcaΓbaπlyloxitninotetΓahydΓothiophen

H ^ C H, C.

NOCNHCH ₃

2-n-propyl-3,3-dimethyl-4-methylcarbarayloximine-tetrahydrothiopheja

CH-

^H 3 ^C nJ

NQCNHCH-

Q093GS / 22S4 originally inspected

2-isopropyl-3f3-dimethyl-4-methylcarbamyloximinotetrahydro-

CH,

₃ C

H ₃ C,

H ₃ C

'OCNHCH,

3-methyl-3-methylthio-4 »methylcart) amyloxiininotetrahydro thiophene

SCH ₃ '0

H ₃ C ^ JJOCNHCH,

3-methyl-3-ethylthio-4-methylcarbamyloximinotetraHydro »thiophene ^<v

SC ₂ H ₅

NOCNHCH

3- 5 "* 'iinethyl ~ ii - => iaeth; / Icar.taniyloximinotetrahydrothiophene« = l' => oxide

OCKHCK

v /

ORIQiNAL INSPECTED

>, 3-Dimethyl-4-methylcarbamyloximinotetrahydrothiophene-r,]

dioxide ■

CH- * f. _Tr

H, C, 3 NC

_{3-MethylcarbamyloximinotetΓahydrothiop>} hen-l, l-dioxide

3,3-Diniethyl-4-methylcarbamyloxiinotetrahydrofuran

CH,

OCNHCH,

3-methyl-3-methylthio-4-methylcarbamyloximinotetrahydrofuran

NOCNHCH-z

009885 / 228A

ORIGINAL INSPECTED

3-methylcarbamyloximinotetrahydrothiapyran-1-oxide

it

OCNHCH,

3-MethylcaΓbamyloximino-4,4-dimethyltetrahyd.? OthiapyΓan

CH, 0

NOC

NHCH,

3-methylcarbamyloximino-4f4-dimethyltetrahydrothia ^< pyran - l-oxide

NOCNHCH,

009885/2284

ORIGINAL IMSPEGTED

- Ii -

3-MethylcaΓbamyloximino-4 ♦ 4-dimethyltetΓahydΓothiapyΓan-l, ldioxid

H ₃ C OH,

δ *

ν / ν

3 _t 3-dimethyl-4-allylcaΓbaιnyloximinotetΓahydrothiophene

2,4,4-trimethyl 1-3-allylcarbamyloximinotetrahydrotbiophene

NOCNHCh ₂ CH = CH ₂ CH,

4-methyl-3-methylcarbamyloximinotetrahyäΓothiophene

^ΟΗ-Ζ nocWh,

ORIGINAL INSPECTED

ι ϊ. ·! U Λ '^.

4-methyl-3-diethylcarbamyloximinotetrahydrothiapyran

NOCNHCH.

2,4 »4-Trimethyltetrahyärothiophen-3-one-oxime

2,2-Eimethyl-3-carbethoxytetrahydrothiophen-4-one

vs.

Ii.

• PF

N ₃ /

CH,

-O

, - = 1 "■ -.:; ■: f.: *"! Tetrahydroti * ir phen = -i = on

BAD ORIGWAL

The compounds of the invention have biocidal activity that This means that they are suitable for killing and / or combating of insects, nematodes, mites and other pathogens from plants zen diseases. The compounds of the invention can be used in neat Form can be applied to the plants or other substances to be protected. Often times it is desirable to have the connections in a mixture with either solid or liquid inert ones Use auxiliaries, for example as sprays in the form of dispersions, in water or organic solvents. The choice of the suitable solvent depends all depends on the concentration of the active ingredient in which it is to be used, on the required volatility of the Solvent, the cost of the solvent, and the type of material being treated. Typical examples of solvents that can be used are hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, heating oil, petroleum, · naphtha, ketones, such as Acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichlorethylene, Perchlorethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, the monoalkyl ethers of ethylene glycol, for Example ethylene glycol monoethyl ether, the monoalkyl ethers of diethylene glycol, such as diethylene glycol monoethyl ether, alcohols, such as ethanol, isopropanol and amyl alcohol. ·

The compounds of the invention can also be applied to plants and other substances together with an inert, solid carrier

00988S / 2284

2033484

are applied, such as talc, pyrophyllite, attapulgite _{9 s} kieselguhr, chalk, diatomaceous earth, calcium carbonate, bentonite, fuller's earth, cottonseed hulls .Y _f / eizenmehl, soybean flour, pumice, tripoli, sawdust, walnut shell flour and lignin.

Frequently pesticidal agents contain compounds of the invention also another surfactant ,, these surfactants Agents are preferably used in both solid and liquid preparations, the surface-active Agent can be anionic, cationic or nonionic «,

Typical surfactants are the alkyl sulfonates, Al- ' kylarylsulfonate, alkylsulfates, alkylamidsulfonates ,, alkylaryl » polyether alcohols, fatty acid esters, polyhydric alcohols, ethylene oxide adducts such esters, Additiönsprodukte- of long-chain Mercaptans and ethylene oxide, latriumalkylbenzenesulfonates with 14 to 18 carbon atoms, alkylphenol-ethylene oxide adducts, derived for example from p-isooetylphenol ,, and soaps, Sodium stearate and sodium oleate «,

The solid and liquid biocidal agents can be used according to the usual Process to be produced »

The compounds of the invention of general formula III, in where one of the radicals Rq and R- is a hydrogen atom and the other radical signified by an alkyl radical can be prepared either by reacting a lower one. Älkylisocyanats with the

009885/2284

corresponding oxime or by reacting the corresponding oxime with phosgene and then reacting the chlorocarbonic acid ester obtained with the corresponding primary amine. The compounds of general formula III in which the radicals Rq and R _{1 (J} mean radicals other than hydrogen atoms can be prepared either by reacting the corresponding oxime with phosgene and then reacting the chlorocarbonic acid ester obtained with the corresponding secondary amine, or by reacting the corresponding oxime with the corresponding garbamyl halide, '

The oximes used according to the process are produced from the corresponding cyclic ketones by reaction with hydroxylamine. The ketones themselves are produced by Dieckma'nn condensation or by thermal decomposition of the barium salts of the

. ■ ■ s'

speaking aliphatic dicarboxylic acids obtained, slide examples illustrate the invention.

■ "■■. '■' '· EXAMPLE 1 ■. ■.

Production of T-'iethylcarbaiayloxiinotetrahydrcthiophen-

5 g (O _$ O43 mole) of tetrahydrothiophene-3-OH-OXiB (hergestelltnach in the H-ülvetica C> J, mica Acta 27 ₉ p 1285 (1944) angegebe-- men regulation) ^ ^ eräen it 20 ml Methylisocsraaat on the whole run? -aclit # Sobeifl '3i3 initial amount esothermal reaction

"5 ρ ß"

BAD ORlGiNAL

has subsided, the mixture is heated under reflux for 5 hours, then cooled and freed from volatile constituents . 9-3 g of the specified product are obtained as an amber-colored / liquid; njp - 1.5528 ,,

EXAMPLE · '2

Manufacture of 3-carbometho: ^^ '- methylcarbarayloximino-

tetrahydrothiophene _. "__ ^ _ _ ._

A mixture aas 5.3 g of (O "Q3 mole) of S-Carbomethoxytetrahydrothiophen» 4 OE oxiii "(bergetteilt after OCE ia Journal of Organic Chemistry 18, p 138 (1953) aageg @" b @ ¥ aea or§ eteift) mä 25 ml methyl isocyaaat are 5 S'taaiaa aste]? Volatile components are stripped off from Hüelsfleaß © rhitat. This gives 8 ₉ 5 g given product as a dark brown viscous liquid., IR absorption spectrum and the analysis confirm the structure "" _u

EXAMPLE 5

7 j * <ύ <= 1 ° - ι

starting from v © a 2 = carb © =

BAD ORIQiNAL.

A solution of 20 g (0.125 moles) of 2-carbomethoxytetrahydrothiophen-3-one and 20 g (0.288 mol) of hydroxylamine hydrochloride in 300 ml of methanol are mixed with 22.9 g (0.29 mol) of pyridine and heated under reflux for 16 hours. After that, the solvent becomes distilled off and the residue partitioned between ethyl acetate and water. The organic solution is separated off, dried and evaporated. 14.3 g of 2-carbomethoxytetrahyärothiophen-3-one oxime are obtained as a dark brown liquid. The IR absorption spectrum confirms the structure.

A mixture of 5.3 g (0.03 mol) of the resulting oxime of 25 ml Methyl isocyanate is refluxed for 5 hours and then freed from volatile components. 9.0 g of the specified product are obtained as a dark brown viscous liquid. The IR absorption spectrum confirms the S structure.

. '■ S

• EXAMPLE 4 ',

Preparation of 3,3-dimethyl-4-methylcarbamyloximino tetrahydrothiophene . "

A solution of 32.6 g (0.25 mol) of 3,3-dimethyltetrahydro-. thiophen-4-one (prepared according to the procedure given in Journal of the Chemical Society (1961), p.650),, 34.8 g (0.5 mole) hydroxylamine hydrochloride and 68 g (0.5 mole) sodium acetate trihydrate in 200 ml of ethanol and 100 ml of water is refluxed for 4 hours. Then the reaction mixture is concentrated in a rotary evaporator and the residue partitioned between ethyl acetate and water · the ethyl acetate solution

009885/2284. '. "

is washed with aqueous sodium bicarbonate solution, dried and evaporated. There remain behind 26 g 3f.3-Dimethyltetrahydrothiophen-4-one oxime in the form of pink crystals, P. 53-54 ⁰ C. The infrared absorption spectrum confirms the structure.

A mixture of 14.5 g (0.1 mol) of the oxime obtained *, 7 ml of methyl isocyanate, three drops of triethylamine and 50 ml of diethyl ether is refluxed for 3 1/2 hours and then left to stand for 16 to 18 hours. Volatile components are then distilled off. There remain 20 _β 7 g of a yellowish colored pesticide. The IR absorption analysis shows that the product still contains starting material. Therefore, the product is again mixed with 7 ml of methyl isocyanate, three drops of triethylamine and 50 ml of diethyl ether and heated for a further three hours. After evaporation of volatiles ier remain behind 20 g of the product as a yellowish brown Peststoff from P. 64-65 ⁰ C. The infrared absorption spectrum confirms the assumed structure *

EXAMPLE. 5 _.

Production of 3,3-dimethyl »4» allylearbamyloximinö · » tetrahydrothiophene

A solution of 7 "3 g (0.05 mol)" 3 ^^ DiraethyItetrahydro ». ' ■ thiophen-4-one oxime, 4.1 g (0 ^ 05 mol) allyl isocyanate 'in 100 ml

anhydrous diethyl ether is kept under pressure for 1 hours

009885/2284

heated and then evaporated in a rotary evaporator. There are 11.5 g of the specified product as a viscous yellow get oil; njp = 1.5276. Yield 10Q # of theory.

EXAMPLE 6th

Preparation of 3,3-DJmethyl-4- & thylcarbamyl oxyminotetrahydrothiophene

A mixture of 7.3 g (0.05 mol) of 3t3-dimethyltetrahydrothiophene «-4-one oxime (prepared according to Example 4) ₉ 3.9 g (0.05 mol) of ethyl isocyanate, 3 drops of triethylamine and about 60 ml of anhydrous diethyl ether is refluxed for 24 hours, then cooled and evaporated in a rotary evaporator. 9.5 g of the specified product are obtained as white crystals from F, 92 to 94 ° C. The product softens at 87 ⁰ C.

»> · EXAMPLE 7 's *

Production of 4-methyl «-3-methylcarbamyloximino · -. tetrahydrothlophs

A 500 ml three-necked flask, which is equipped with a reflux cooler and heating jacket, is filled with 23 "2 g (0.2 mol) of ^ -methyltetrahydrothiophene-J-one (prepared according to the Svensk Kemisk Tidskrift 57" p. 24 ( 1945) specified regulation), 172 ial 95 prose-ntigem ltfeanol ₉ 2T ₉ 8 g (O ₉ 4 mol) hydroxylamine !: drocalorid la 45 ml 'tessef waü 2O ₀ I g (O ₉ 19 mol) anhydrous IlF ^ L'ioaear-'boaat ia 45 ml 'barrel® :? lb @ sehickt ₀ 3Di® 'solution y / ird i "./Il ../'"anead eater Hüe & flis® erlii & st WMä öasaefe

. ..; ... . ~. : _. , BAD ORIGINAL

the ethanol is evaporated in a rotary evaporator «The two layers of the residue are extracted three times with ethyl acetate. The combined ethyl acetate extracts are dried over anhydrous magnesium sulfate and then evaporated in a rotary evaporator. There remain behind 24 g of _4-f 6 Methyltetrehydrothiophen-3-one-oxime as an orange-colored white moist Peststoff. The IR absorption spectrum confirms the assumed structure,

A dried, 200 ml flask, which is equipped with a reflux condenser with a drying tube and a heating mantle, is filled with 10.5 g (0.08 mol) of the oxime obtained, 100 ml of anhydrous diethyl ether, 5 g (0.088 mol ) Methyliso.cyanat and 4 drops of triethylamine charged. the pale yellow solution is heated β hours under reflux and -anschlieseend iri ^x einen_ rotary evaporator evaporated · are obtained 5 '8'g an amber-colored, viscous liquid which dissolved ia 50 ml of anhydrous diethyl ether and again treated with 2 ₉ 6 g (0 _{φ 04β} mol) Metbylisocyanat and 3 drops of triethylamine and 24 hours is boiled under reflux for. Then, evaporate the reaction mixture in the rotary evaporator. There are 6 ₉ 2 g of the. product as a viscous amber liquid. -The IR absorption spectrum confirms the assumed structure? · '

0098S5 / -2284

EXAMPLE 8 *

Production of 2,2-dimethyl-4-methylcarbamylox ~. iminotetrahydrothiophene

A suspension of sodium ethylate in benzene made from 64 g (1.5 moles) of a 56.2 percent sodium hydride dispersion, 69 g (1.5 moles) of anhydrous ethanol and 300 ml of benzene is within a period of 20 minutes with a solution of 162 g (1.35 mol) of 2-mercaptoacetic acid ethyl ester in 100 ml of benzene added, the mixture refluxing gently. The resulting slurry is for 25 minutes with a Solution of 179 g (1.4 mol) of ethyl 3,3-dimethylaerylate in 50 ml of benzene are added and the mixture is then refluxed for 75 minutes heated. The brown colored reaction mixture is extracted with four portions of ice water. The combined aqueous extracts are immediately 'acidified' with cold concentrated hydrochloric acid and extracted with three portions of benzene. The combined benzene extracts are evaporated and the residue is distilled. There are 198 g of 2,2-dimethyl-3-cactäthoxytetrahydrothiophen-4-one

OK

in three fractions with refractive indices from n £ - 1.4850 to

1.4874 and with boiling points from 69 ° / 0.08 Torr to 77 ° θ / σ, 55 Torr . obtain. The IR absorption spectra confirm the assumed Structure. ,

^: A mixture of 151.7 g (0.75 mol) of 2,2-dimethyl-3-carbethoxy- ₍ 'tetrahydrothiophen-4-one, 200 ml of EBsiga acid, 105 ml of concentrated sulfuric acid and 750 ml of water is refluxed for 8 hours

009885/2284

heated and stirred. The mixture is then cooled, extracted with two portions of benzene, the combined benzene extracts are washed with 10 percent sodium hydroxide solution and dried over anhydrous magnesium sulphate. The solution is then passed through a microcolumn measuring 2 "54 x 15 cm distilled. There are 79 g of 2,2-Dimethyltetrahydrothiophen-4 ° one as colorless liquid into two ^fractions: deri '/ Bre "ehungsindiees a ^ = 1.4926 get to 1 ₃ 4929" The "XR-down absorption spectra confirm the assumed Structure ■

A solution of 32 _f 6 g (O ₉ 25 mol) 2 ₉ 2 = dimethyltetrabydrothiophene ~ 4-QB _t 34.8 g (0.5 mol) Hjelroxylaiiin-faydr © chloride and 68 g (0.5 mol) sodium acetate trifaydrate The reaction mixture is then evaporated under reduced pressure and the residue is distributed between ethyl acetate and water. The ethyl acetate solution is washed with an aqueous solution of mineral carbonate , dried and evaporated * There are 33.5 g of 2,2-Dimethyltetrahjdrothi0phea = 4 ^c = on <= © xime as clear,

pe

orange-red colored liquid erialtaag nzr = l _f 5292 _e The IR absorption spectrum confirms the anomraene structure «,

A solution of 14.5 g ( ₀ l mol) of Ses © ffealteadia Osims and 10 ml of methyl isocyanate in 60 ml of Beasol is mixed with ir © i drops of triethyl. amine mixed · Bs takes place an ex © tta @ i ° ® © B © aktioa ₀ Baaach is the Reaktioasgeiiiseii S Stuaäea natQi? Httekflöi © rfeitzt and-

then evaporated in a rotary evaporator. It will 23 g of the specified product were obtained as a red-brown viscous liquid. The IR absorption spectrum confirms the assumed Structure.

EXAMPLE 9

Production of 2,4,4-trimethyl-3-methylcarbamyl oxime-tetrahydrothiophene '___

A solution of 21.6 g (0.15 mol) 2,4,4-trimethyltetrahydrothiophen-3-one (prepared according to the procedure given in Journal of the Chemical Society (1961), p.650), 20.9 g (0.3 mol) Hydroxylamine hydrochloride and 24.6 g (0.3 mole) sodium acetate trihydrate in 200 ml of 95 percent ethanol and 110 ml of water is refluxed for 4 hours and then in one Rotary evaporator evaporated. The resulting crystal slurry is filtered off, washed with water and placed in a vacuum desiccator dried over sodium hydroxide. It will be 19.5 g of the corresponding oxime in the form of white crystals from F. 81 to 83 ^ C obtained. -

A solution of 9.6 g (0.06 mol) of the resulting oxime, 5 ml Methyl isocyanate and four drops of triethylamine in 150 ml of diet hy lather is refluxed for 6 hours, then stand left and evaporated in a rotary evaporator · It will be 12.5 g of a cloudy liquid is obtained, which is removed when standing transformed into a pasty solid. The IR absorption

009885/2284 _BAD origwal

apektrum confirms the assumed structure for the named product. P. 73 to 76 ⁰ C.

EXAMPLE IO

Production of 2 _l 4t4 "trimethyl-3" allylbamylox · iffllnotetrahydrothiophene

A solution of 4.0 g (0.025 mol) of 2 _# 4,4-trimethyltetrahydrothiophen-3-one oxime (prepared according to Example 9), 2 g (0.025 mol) of allyl isocyanate and 3 drops of triethyleraia in 40 ml of anhydrous diethyl ether is 5 Heated for 1/2 hour under direct flow and then evaporated in a rotary evaporator. 6.0 g (100 percent of theory) of the stated product are obtained as a clear yellow oil! nt = 1 "5242"

EXAMPLE II

Production of 3 »lthyl ™ 3 ™ methyl« 4 »iBetfaylearbemyl oximinotetrahydrot hipphen -

'A solution of 132 g (0 "68 mol) of 2» bromomethyl-2 = .methylbuttersäure (prepared according FransösisctiwS Pateat 1,231,163) in 350 ml ^r * 25prosentigem -ethanol and 980 ml of water EIA © probe solution of 28 g (O ₉ 7 mol) of sodium hydroxide in 265 ml of water are converted into a solution of 69 g (O _g 75 MeI) in a quantity ratio of 2% within 2 hours! acid in 400 ml v / ater given @ b @ a,> that holds 6. Wire '53, © performed for 45 minutes during the rest of the year

BATH ORIGINAL

009885 / 22.84

conditions. The resulting mixture is refluxed for 6 hours, left to stand for 16 to 18 hours, the ethanol is distilled off and the residue is poured into ice and hydrochloric acid. , The acidic mixture is extracted with 4 portions of diethyl ether. The combined ether extracts are then extracted with 4 parts of 10 percent aqueous sodium carbonate solution. The combined sodium carbonate extracts are acidified and extracted with diethyl ether. After drying the ether extract and evaporation, 79 S 2-ethyl-2-methyl-4-thiaadipic acid are obtained as a pale yellow viscous liquid.

A mixture of 79 g (0.38 mol) of the thiaadipic acid obtained and 3.0 g of barium hydroxide is placed in a 100 ml three-necked flask equipped with a stirrer, thermometer, distillation attachment, reflux condenser and flask. While stirring, the mixture is ^{heated to 200 to 310 °} C. in a metal bath until the distillation has ended. The organic solution of the distillate is separated from the aqueous layer by means of ether. The ether solution is dried over magnesium sulfate and evaporated. The residue is distilled through a Vigreux column with the dimensions 13 xl _f 6 cm, which is equipped with a Claisen attachment. After a short forerun, the following fractions of 3-ethyl-3-methyltetrahydrothiophen-4-one are collected: -.

009885/2284

First fraction: boiling point 81.5 ° C / 9 Torrj 5 ₉ 5 g yellow liquid?

n <p » ⁵ = 1.4967

Second fraction: Kp _e 80 ° "C 81.5 ^0/9 _f 9 Torr; 5" 5 g of yellow

Liquid;

njp = 1.4960

Third fraction: Bp, Bl _t 5 ° C / 9t5 Torrj 3.0 g almost "colorless liquid!"

njp = 1.4975-Daa IR absorption spectrum confirms the assumed structure »

A solution of 28.0 g (Ο «2 mol) of 3-ethyl-3-methyltetrahydrothiophen-4-one in 172 ml of 95 percent ethanol is mixed with 27.8 g (0.4 mol) of hydroxylamine hydrochloride in 45 ml of water as well 21.2 g (0.2 mol) of sodium carbonate in 45 ml of water are added and the mixture is refluxed in a 500 ml flask 6. The clear, light yellow solution is freed from ethanol in a rotary evaporator using a water jet pump layers existing residue is taken up in ethyl acetate, -the itfaylacetatlösung dried and evaporated. There are 29 s "5 S 3-ethyl-3-mei

27 4-one oxime obtained as a viscous liquid ^ a ₀ "- 1 ₉ 529O.

A solution of H ₉ 2 g '(0.07 mol) of the oxime obtained "in

50 ml of anhydrous Diet FayISther is mixed with 4 ₉ 4 g (Ο ₉ Ο77 mol)

009885/2284

Methyl isocyanate and 4 drops of triethylamine are added and 6 hours heated under reflux. Thereafter, the reaction mixture evaporated in a rotary evaporator under reduced pressure. 14.7 g of the product mentioned remain as an amber color viscous liquid; nj = 1.5282. The IR absorption spectrum confirms the assumed structure,

EXAMPLE 12

Preparation of 3,3-diethyl-4-methylcarbamyl. oximinotetrahydrothiophene

A solution of 42.4 g (0.6 mol) of sodium carbonate in 450 Water is mixed with 160 g (0.77 mol) of 2-bromomethyl-2-ethylbutyric acid offset, the production of which is described in French patent specification 1,231,163. A water-

insoluble top layer. This mixture becomes a solution of 78.3 g (0.85 mol) of mercaptoacetic acid in 175 ml of water containing 52.2 g of potassium hydroxide. The resulting mixture is refluxed for 13 1/2 hours and stirred, then cooled and poured into ice and hydrochloric acid. Dae The mixture is extracted with diethyl ether, the ether extract then extracted with saturated aqueous sodium bicarbonate solution. The sodium bicarbonate solution is acidified and extracted with diethyl ether. The ether extract is dried and evaporated. 68 g of 2,2-diethyl-4-thiaadipic acid are obtained as an almost colorless viscous liquid.

0098 85/22 8 4

A mixture of 67 g (0.3 mol) of 2,2 ~ Diethyl-4-thiaadipinsäure and 2.1 g of barium hydroxide is as long as' heated in a simple distillation apparatus in a metal bath at 220 to 240 ⁰ G, until the distillation ended, _{"A layer of water (4 f} 5 g) is separated from the distillate (33.9 g)," The organic solution is dried and then distilled. "11.4 g of a distillate are divided into two fractions with a boiling point of 93 to 97 ° C / 7.3 to 9 Torr (nj " ⁵ = 1 _f 4965 to n ^ ⁴ = 1.4994) obtained * The IR absorption spectrum confirms the structure of 3,3-diethyltetrahydrothiophene-4-oa8 _t ,

A solution of 11.0 g (0.07 mol) 3i, 3 ° diethyltetrahydrothio-

phen-4-one in 60 ml of 95 percent ethanol is 9 ^ 8 g

(0 _f 14 mol) of hydroxylamine hydrochloride in 15 ml of water and 7.4 g (0.07 mol) of sodium carbonate in 16 ml of water and placed in a 200 ml flask equipped with a heating jacket Refluxed. When sowing for 15 1/2 hours, the clear yellow solution is evaporated in a rotary evaporator on the water jet pump and the residue is suctioned off through a filter. The yellow Kristall® iverden in a vacuum desiccator ^ · About calcium chloride dried yield 1O ₉ 4 g of 3,3-Diäthyltetrahydrothiopheft-4> oa ° oxiifflo the g®Th ° m @ Crystal © melt at 69 to 75 ⁰ G. ''

A solution of 7 g (0 «04 mol)" # &. anhydrous diethyl ether

009881/2214 bad oronal.

Methyl isocyanate and 4 drops of triethylamine are added. The "mixture is refluxed for 6 hours in an oil bath and then evaporated under reduced pressure in a rotary evaporator.

8.5 g of the specified product remain as light

26 5 • amber colored viscous liquid; Q-n = 1.5252.

EXAMPLE 13

Preparation of 3-methyl-3-methylthio-4-methylcarb amyloximinotetrahydrothiophene

A cooled solution of 131 g (1.3 mol) of methyl methacrylate in 400 ml of anhydrous diethyl ether is g within a period of 1 hour at 0 to 5 ⁰ C under stirring with a solution of 108.7. (1.3 mole) of methanesulfenyl chloride in 330 ml of anhydrous diethyl ether are added. The resulting solution is stirred for another hour at 0 to 5 ⁰ C, subsequently 'stripped of solvent and distilled through a ¥ cm igreux column with dimensions of 2.5 x 18th There are 186 g (83 $> of theory) of 3-chloro-2-methy1-2-methylthiopropionsäuremethylester as a light yellow liquid into two fractions of boiling point 76 to 77 ⁰ C / 5, .3 to 5.5 Torr · (n ^ ⁴ = 1.4850) and boiling point. 76 to 77 ° C / 5.1 to 5.3 Torr (n ^ ⁶ = 1 ^ 4850) was obtained.

. A solution of Na.tr i amme thy la t prepared from 16.1 g (0.7 gram atom) of sodium and 600 ml of anhydrous methanol is iodide with 74.3 g (0.7 mol) of methyl thioglycolate, a trace of sodium and 128 g (0.7 mol) of 3-chloro-2rmethyl-2-methylthio .. propionic acid methyl ester added under nitrogen,

009885/2284

After 4 hours of heating under Riiokfliai, the reaction mixture is filtered and the piltrate is freed from methanol under reduced pressure. The residue is taken up in chloroform, the chloroform solution is washed with water, dried and evaporated. 123 g (70 % of theory) of 2-methyl-2-methylthio-4- »thiaadipic acid dimetfaylter are obtained as an amber-colored liquid? n ^ ⁵ = 1 _S 4963 *

A by reacting 16.6 g (0.52 mol) Methanol 22 3 ₉ g (0.52 mol) of sodium hydride dispersion 56,2'prozentiger ISS ■ 1100 ml of anhydrous toluene prepared slurry of sodium-is within a space of the tent 30 minutes at 37 to 42 ^° C. with a solution of 118.5 g (0 ^ 47 mol) of 2-methyl-2-methylthiQ-4-thieedipiasäax »eaimethylester in 200 ml of toluene. The mixture is "heated 52 ⁰ C, then cooled and 'a' to 5 Standen 48'bis mixture of ice and salt," acid poured. The organic LÖsaag is combined with the ether extract of the aqueous solution "dried ,, freed from the solvent and distilled ₀ There are 52 g (50 $> of theory) of 2-carbomethoxy-4-methyl-4 ~ m © thyltfaiotetrahydrothiophen-3-one as yellow liquid obtained in four Fraktioaea from the boiling range 70 to 82 ° C / 0.19 Torr (n ^ ⁵ = 1 ₉ 500 9 ^ is 1.5035) '°. Since @ IR absorption spectrum confirmed ate accepted® Strwktar »

A mixture of 48 g (0 ^ 22 mol) of 2 ° C
methylthiotetrahydrothiophene ~ 3 ° OB eai 304 al 10prog © atiger

009835/2384

aqueous sulfuric acid is refluxed and stirred for 4 hours. After cooling, the reaction mixture is extracted with diethyl ether, the ether solution is dried and evaporated and the residue is distilled. 21 g (43 l> of theory) of 3-methyl-3-methylthiotetrahydrothiophen-4-one are obtained as a pale yellow liquid with a boiling point of 70 ° C./9.1 torr; njp = 1.5080. ■.

A solution of 11.7 g (0.072 mol) of 3-methyl-3-methylthiotetrahydrothiophen-4-one, 10 g (0.14 mol) of hydroxylamine hydrochloride and 7.6 g (0.072 mol) of sodium carbonate in 62 ml of ethanol and 32 ml of water is refluxed for 5 1/2 hours and then freed from the solvent. The residue is taken up in ethyl acetate, the ethyl acetate solution is washed with water, dried and evaporated. There remain behind 12.2 g * ^x 3-methyl-3-methylthiotetrahydrothiophen-4-one oxime as a dark brown solid which melts at 40 to 50 ⁰ C. '

A dried 100 ml flask, which is provided with a reflux condenser with an attached drying tube and heating mantle, is filled with 5.3 g (0.03 mol) of the oxime obtained, 50 ml of anhydrous diethyl ether, 1.9 g (0.033 mol) of methyl isocyanate and 3 drops of triethylamine are added as a catalyst. The mixture is heated for 6 hours under reflux, then evaporated in a rotary evaporator under reduced pressure _m. There are 7.6 g of the product mentioned as a dark amber-colored, very

■ * · ■

- I.

-009885/2284

viscous liquid obtained · IR absorption spectrum confirmed the adopted structure. ·

EXAMPLE 14

Preparation of 3-methylcarbamyloximinötrahydrO "· thlapyran

A solution of 7.9 g (0.06 mol) of tetrahydro-3-thiapyran oxime (prepared according to the procedure given in Journal of the American Chemical Society 74, p. 917 (1952)), 5 ml of methyl isocyanate 3 drops of triethylamine and 50 ml of anhydrous diethyl ether is refluxed for 3 hours, left to stand for 16 to 18 hours and then in a rotary evaporator of free of volatile substances »12.5 g of the specified Product as a yellow "viscous" cloudy liquid;

nzr = 1.5495. The IR absorption spectrum confirms the assumed structure. _rt S

EXAMPLE 15

Production of 4,4 »dimethyl · = j ^ methylcarbamyl oxlminotetrahy drothiapyran

A solution of 14.4 g (0.1 mol) of 4 '4-Dimettayltetrehydrothia "pyran-3-one (prepared by the in Tetrahedrpn 22 S" instructions given 285 (1966), _f) in 100 ml ^r 95prozentigem Itfaaa ©! is added with a solution of 14 g (0.2 mol) hyiroxyleain-hyelroefelorid in 35 ml water and an amount of 10 "6 g. (0 »l Eüol) sodium carbonate in 35 ml water, vereetat _o

The 4i4-dimethyltetrahydrothiapyran-3-one oxime separates out almost immediately in the form of white crystals. The crystals are filtered off, washed thoroughly with water and air-dried. Yield 12.5 g, '• F. 147 to 149 ^° C. A further 2.4 g are obtained from the filtrate; F. 145 to 147 ⁰ C. The IR absorption spectrum shows the absence of a carbonyl group and the presence of

OH and C = N groups.

A solution of 4 _f 8 g (0.03 mol) of the obtained oxime, 1.8 g (0.031 mol) of methyl isocyanate and 3 drops of triethylamine in 200 ml of anhydrous Triäthyläther 17 is heated hours under reflux. The reaction mixture is evaporated in a rotary evaporator. 6.6 g of the stated product remain as a clear liquid residue, which solidified to a white, semi-solid mass on standing. The IR absorption spectrum confirms the assumed structure. (-NH at 2-, 9xt and-C = O at 5.85Zt).

' EXAMPLE 16

Production of 3t3-dimethyl-4-methyl-earbamyl oximinotetrahydrofuran __

A solution of 6.9 g (0.054 mol) of 3,3-dimethyltetrahydrofuran-4-one oxime (produced according to the in Bulletin de la Societe Chimique de France 1967 »8.1909 specified regulation), 3.9 g (0.068 mol) methyl isocyanate and 4 drops of triethylamine in 30 ml

009085/2234

anhydrous diethyl ether is refluxed for 6 hours and then evaporated in a rotary evaporator. 10 g of the specified product are obtained as a colorless, viscous liquid; n £ ⁵ = 1.4740.

The experiments below explain the use of the compounds of the invention for killing and / or controlling insects, mites, bacteria, viruses and nematodes.

Attempt 1

In this experiment, the insecticidal activity of the compounds to be investigated against black bean aphids (Aphis fabae) is investigated. Stock solutions are prepared which each contain 500 ppm of the compound to be tested. For this, 0.05 g of the test compound or 0.05 ml, if the compound is a liquid, 4.0 ml of acetone, which is 0.25 percent by volume of a wetting agent (Triton X-155) and contains 96.0 ml of deionized water. The stock solutions are diluted to the appropriate desired concentrations. The bean aphids are grown on Nasturtium plants var "Tall Single. In these experiments insects of various ages are used. Individual Nasturtium test plants are infected in 5 "7 cm large flower pots with populations of 100 to 200 bean aphids",

When used as a spray, 50 ml of the stock solution

or spray the diluted solution evenly on the plants. When used as a bystemic agent, 11.2 al of the caulking solution or the diluted solution are added to the Soil applied «A dose of 11.2 ml of the preparation containing 500 parts of the test compound corresponds to one Dose of 18 kg / ha.

A moisture resistant piece of a thermoplastic Foil with the dimensions 10 χ 10 cm is applied to the center cut open and so in the base of the trunk of the test plant attached to form a funnel. These test plants are placed under fluorescent lamps during the Duration of experiment watered from the bottom of the flower pots. Dead bean aphids fall into the funnel so they can be counted easily. The percent mortality will be 3 days determined after treatment. In Table I are the results compiled.

■ nnifi'NAL INSPECTED

009885/2284 orig.nal

Tatelle I.

Application as a spray application as a system! rope Percent mortality for medium Concentration in tpm " Test connection

250 128 64

3-methylcarbamyloximinotetrahydrothiophene 100 100 100

3 «0ai'boTnethoxy-4-methylcarbainyloximinotetrahydrothiophene

3 ^ -DimethyW-methylcarbamyloximinotetrahydrothiophene

2,2-33imethyl-4-methylcaΓbaιnyloximinotetrshydrothiophene

• ^ ^ methylearbamyloximinotetrahydro- ® thiapjran

® ° 3 _t 3-3Dts®tfeyl-4-allylcarbamyloximino-

';. **>:' tatrahydrothiophene ⁰ ^ 3 gJ ^ Biffisthyl ^ -äthylcarbamyloximino- · ^ ^: ^ h \ tetrahydrothiophene

2§4t 4 " ³⁶ TrImS thy l-3-methylear'batnyloximinotetrahydrothiophene

: 3 ₉ 3 «dimethyl = 4-methylcarbamyloximino-

: tetrahydrofuran

3- «ethylcarbainyloximinotetra-

hydrothiophene

100 100 100 0 90 100 100 100 100 100 100 100 lOO ¹ 37 100 100 100 100 100 -1 ^ ₅ 100 82 0 - 66 100 100 93 100 - 100 100 100 - 100 100 100> 100 100 100

percent mortality
Concentration in kg / ha 90 i ± 51 2.26 - 63 70 - 84 - 43 April 9 100 100 100 100 78 25th - * 100 100 76 81 - 16 fO
O
I CO 100 78 38 , cn
-Pv 100 100 68 100 43 100 100 - 29 83 100

... J Table I (continued)

. Application as a spray · Application as a systemiscb.es

Percent mortality for medium

Concentration in tpm percent mortality

■. ' Concentration in kg / ha

£ 50 128 _64 _32 9.04 4.52 2.26 1.1

ο 4f4-I) imβthyl-3-methylcarbaπ ^ yloximino- ·, ....

«> Tetrahydrothiapyran · 100 100. 100 100 100 100 100 100

2 _t "4 _t 4-trimethyl-3-allylcarbamyloximino-

tetrahydrothiophene 100 100 61 - 59 0

33

cö. ■ ■ '

ti ■

K) O CO CJ

cn

Attempt 2

In this experiment, the insecticide residual activity of the too investigated compound against black bean aphids (Aphis fabae) determined. The one described in Experiment 1 The procedure is repeated, with readings being taken on the third and seventh day after spraying and soaking, respectively will. The results are summarized in Table II:

ORIGINAL INSPECTED

009885/2284

co 00 09 cn

Concentration, TABLE II as spray concentration Application as ΤυΜ application ke / ha systemiaches middle •? middle . Test connection mortality 7 days Mortality. % ? Ta <re 3 tnpre 7 days . 256
128
64
32
16 95
60
49
41
42 9 »O4
4.52
2.26
■ 1.13 100 100
76 47
81 56
25 46 3 _t 3-dimethyl-4-methylcarb-
amyloximinotetrahy-
drothiophene 100
100
100
100
83

K) ΙΌ CO

■ z.

■ ζ.

N> O

CXI

Attempt 3

In this experiment, the acaricidal effect of the compounds to be investigated against red spider mites (Tetranychus ep.). According to experiment 1, stock solutions are prepared which contain 500 ppm of the test compound. These stock solutions are used both as sprays and as systemic Funds used. A supply of spider mites is kept on the leaves of scarlet firebeans. About 18 to 24 hours before the experiment, the spider mites are transferred to the primary leaves of lima beans (var.Sieve), which in Flower pots with the diameter of 5.7 cm can be pulled.

According to Experiment 1, the test preparations are used as systemic agents and sprinkling agents. After 3 days there will be two of the four treated leaves examined and the mortality determined. If a test compound is an effective acaricide, the other two sheets are available to determine the residual activity of the preparation bu «The results are in Table III compiled

ORIGINAL INSPECTED

009885/2284

Table III Test connection

3-methylcarbamyloximinotetrahydrothiophene

3 _f 3-Dimethyl-4-methylcarbamylox -_ 'iminotetrahydrothiophene

2 _t 2-dimethyl-4-methylcarbainylox ^ - ^ iminotetrahydrothipphen

3-methylcarbamyloximinotetrahydrothiapyran .

3,3-dimethyl-4-allylcarbamyloximino tetrahydrothiophene

3 _t 3-I) imethyl-4-ethylcarbamyloxlinino tetrahydrothlophen ■

* j 3Tethyl-3 ^ methyl-4-methylcarbamyloximinotetrahydrothiophene

Use as a spray

percentage; Mortality '', ■ at concentration TpM

500 250 128 64

100 15

100 100 100 100

100 100 100 .100 100 43 100 73 97 0

55

Application as see systemic with «TeT ~~~ ^

percentage mortality at concentration in kg / ha

9.04 4.52 ' 2.26 1.13

100

100

43

Tt »

—Ι FfI

O CO CJ)

Table III (port setting)

it
as
m

Test connection

3-methyl-3-methylthio-4-methylcarbianayloximinotetrahydrothiophene

4-methyl-3-methylcarbamyloximinote.trahydrothiophene

4f4-dimethyl "= 3-methyroarbamyloximinotetrahydrothiapyran ·

oximiaotetrahydrothiophene application as a spray application as systemic percentage mortality for agents

Concentration TpM percent mortality at

Concentration in kg / ha

April 9, 4.52 2.26

500 250 128 64

97 85 0 97 81 11

100 100 99
91 58

1.13

100 100 100

86

rfä

S. ω -ο m

NJ CD OJ U)

Attempt 4

In this experiment, the residual acaricidal activity of the too investigating compound against red spider mites (Tetranychus sp ") determined. The attempt is made according to the attempt carried out, but the readings are taken on the 3rd and 7th Done days after application of the means The results are summarized in Table IV:

¹ ORIGINAL INSPECTED

009885/2284

Tea tvarbind mm

3,3-Dime thy1-4-methyleer b amyloximonotetrahydrοthiophane

Tabel JV 89 Sprits » concentration ce 9.04 Application as use al 26th k «/ ha 4.52 systemic means middle 11 · 2.26 Mortality, % Consumption Mortality, % 7th 1.13 3 days 7 days TtA 3 ropes 100 100 126 r tai 100 100 64 100 100 100 100 32 100 43 39. 16 100 8th 98 4th 99 23

S>

TtJ

CD OJ OJ

cn

Attempt 5 '

In this experiment the acaricidal activity is examined Connection to a strain of red spider mite, investigated that is resistant to organophosphoric acid esters, as well as to another strain that is resistant to organophosphoric acid esters is sensitive.

The experiment is carried out according to Experiment 3, however the readings are taken on the 3rd and 7th day after application. The results are shown in Table V.

Table V. Use as a spray

Test Compound Concentration Mortality,%

TpM sensitive resistant

5 days 3 days ""

3,3-dimethyl-4-

methylcarbamyl- 64 100 '100

oximinotetrahydro- 16 99 ,, loo.

thiophene use as a systemic agent

Concentration '^'., Mortality, % ' kg / ha sensitive resistant

3 days e 7 days 3 days 7 tape

9.04 100 100 100 100

4.52 95 98 .9.4 100

2.26 50 68 50 88

1.13 6 71 43 83

Attempt 6 ,

In this experiment, the insecticidal activity of the compounds to be investigated against adult houseflies _t (Musca domestica) is determined. According to experiment 1, stock solutions are prepared which contain 500 ppm of the test compound. These stock solutions become the appropriate ones you want

* ^. 009885/2284 'originally inspected

"Lift *" V - * ■ "■■ ν, ^τ tvf

Concentrations diluted.

10 adult houseflies are placed in a cylindrical cage with the dimensions 3 »8 χ 10 cm, which is made of fly screen with a mesh size of 0.83 mm. The flies are then sprayed with 50 ml of the stock solution or the diluted preparations. The flies are offered food and water with a glucose solution so that they can eat as they please. The percentage mortality is determined three days after the treatment. The results are summarized in Table VI:

ORIGINAL IiMSPECTED

009885/2214

Table VI Mortality. f>. at concentration TpW Tea connection 500 250 128 64 3 2

3-methylcarbamyloxirainotetrahydrothiophene 100 100 100 100 90

3-carbomethoxy-4 * methylca3sbaiJurloxlainötrahydrothie-

phen 100 30

3,3-Dimet hy 1-4-methy lcarbafflyloximinottthiophene 100 100 100 100 100

2 _f 2-Dime thy 1-4-me thy lcarbatnyloximino tetrahydro thiophene 90 70

3-methylcarbamyloxiffiinotetrahydrothiapyren - 100 '100 90 30

3,3-Dimethyl-4-allylcarbaiiyloximinotetriihydrothiophene 100 100 100 10

ο 3,3-Dime thy 1-4-ethylcarbaiiyloximinotetra hydro thiophene 100 100 100 100 60

^ 3 "· Xthyl-3-methyl-4-methylcarban ^ yloxίmlnotβtrahydΓO-

O _{0 t} thiophene 70 0 - -. ', .- ■

^ ¹ * 3 * "methyl-3-methylthio-4-« ethylcarbamyloximinotetra-.J2 hydro thiophene, 100 100 100 100 100

■ • ° '4-Methyl-3-methylcapba! NyloximinotetrahydΓothiophane 100 100 100 100 100

* - '! 2,4,4-Trime thy 1-3-mathylcarbaayloxlpinotetrahyäro-

• · thiophene "- 100 100 50

4,4-Ilimethyl-3-mβthyle rbamyloximlnotβtrahydΓothiapyΓan -, 70 50

■ z. ■ ■ ■.

ω ■ ■. . ■■■■■ ... '. · ■. ■. ■

~ ® ■ ■. ■ · .. ■■. ^

■ rn. '. ■. ■■■ ■'

ro CD Ca>

-48- 2033A5A

Trial 7

In this experiment, the insecticidal activity of the investigated Compounds determined against Argyrotaenia velutinana.

Freshly hatched larvae of the insect are used. Paired fully expanded primary leaves of winter beans are kept in a water culture and sprayed with 50 ml of the stock solution or the diluted preparation into a rotatable spray hood. The stock solution contains 1000 pU of the compound to be investigated and it is prepared according to Experiment 1, but 0.1 g of the test compound is used _{instead of O 9 O5 g.} The stock solutions are diluted in the same way to produce preparations with a correspondingly lower concentration.

As soon as the solvent of the preparations on the leaves evaporates is, the paired leaves are separated from each other. One leaf is on one. ~ Tj, 5pro! Sentigen water agar in placed on a petri dish. Ten newly hatched larvae are placed on the leaf and the Petri dish is covered. The larvae are kept at 22 ° C for three days. Then the mortality is determined; The results are in the table VII compiled: ■ -

ORIGINAL INSPECTED

009885/2284

ί. - ■■. . "._ .. '" Table VII

ν ■

Test connection

3-methylcarbainyloxiffiinotetrahydrothiophene

3-GaΓbomethoxy-4-methylcarbamyloximinotetΓahydrothiophene

^ »I-Dimethyl-A-methylcarbatnyloxiininotetrahydrothiophene o ·

■ ■

3-methylcarbamyloximinotetrahydrothiapyran

Mortality, fo, at
TpM " concentration 1000 500 250 100 70 70 hydro
80 O drothiophene - 80 25th 62 14th

«O ^^^ - trimethyl - ^ - methylcarbamyloximinotetrahydro · -" ■

»- thiophene - · -. * 65

IM · · ■

-η '■ ■ ■

Trial 8

In this experiment, the insecticidal activity of the compounds to be investigated against the Mexican bean beetle (Epilachna varivestis) is determined. The experiment is carried out as in Experiment 7, but one-day-old larvae of the beetle are used. The larvae are ^{kept at 22 °} C. for three days. Then the mortality and the inhibition of food intake are determined. The habitat of the food intake is an indication that the compound being investigated has a repulsive effect. The results are summarized in Table VIII:

INSPECTED

Table VIII

Test connection

Mortality, ^, at concentration tpm

3-methy lcarbamyloximinotetrahydro thiophene 3-carbomethoxy-4-methylcarbarayloximinotetra-

hydrothiophene 80 *

3,3-Pimethyl-4-methylcarbBmyloximinotetra-

hydrothiophene ~

a ^ -Dimethyl- ^ methylcarbamyloximinotetrahydro-

"thiophene -

J-methylcarbarayloximinotetrahydrothiapyran 3ι3-dimethyl-4-allylcarbamyloximinotetrahyaΓo-

thiophene -

3 _t 3-dimethyl-.4-äthylcarbaπlyloximinotetrahyärothiophene

2 _f 4,4-trimethyl-3-methylcarbamyloximinctetrahydro- thiophene

2 _t 4 »4-trimethyl-3-allylcarbamyloximine-tetrahydrothiophene

3-ethyl-3-methyl-4-methylcarbamylόximifi ₁ ot ^ tra- »

hydrothiophene -

3 »3-diraethyl-4-methylcarbamyloximinotetrahydrofuran 3-methyl-3-raethylthio-4-methylcarbaπlyloximino ~

tetrahydrothiophene -

4-methyl-3-methylcarbaπlyloxitninotetrahydΓethiophene 4 ♦ 4-Dimethyl-3-methylcarbaInyloximinotetrahydΓo-

thiapyran / ^% -

Inhibition of food intake 500
100 *

C.
100 *

100 *
100 *

100 *
100 *

250 128 .64 _22 100 * 100 * 80 * 10

100 * 100 * 100 * 100 *

100 * 100 * 100 *

100 * 100 * 100 *

100 * 100 * 100 *

100 * 100 * 30

100 * 100 *

80 *

100 * 90 80 ο - O
Ca) 100 * 100 * 80 * 30th 50 100 *
100 * 100 *
100 * 100 *
100 * 100 *
40 - 100 80 40

Attempt 9

The compounds are examined for their ability to combat the "Southern Bean Mosaic" on pinto beans and Maize Dwarf Virus on maize (Golden Bantam) an amount of O ₉ I g was used instead of 0.05 g. The leaves are both sprayed and the earth soaked. 1 to 2 hours before the treatment, the leaves are rubbed with silicon carbide sandpaper and infected with the viruses.

When used as a spray, 67 ml of the stock solution are sprayed evenly onto the plants at 1000 ppm. For systemic use, the stock solution is applied to the surface of the soil of each flower pot before spraying in a dose of 72.4 or 36.2 kg / ha applied «10 days after the infection, the plants are examined for the symptoms of a virus. The results are summarized in Table IX:

ORIGINAL INSPECTED

009885/2284

Test connection

2,2-Dimethyl-4-methylcarbamyloxy-ininotetrahydrothiophene

2,2-dimethyl-3-carbethoxytetrahydrothiophen-4-one

J-methyl ^ -methylthiotetrahydrothiophene M-one oxime

Tabel IX concentration TpM kg / ha 1000 72.4 1000 ) thiophene 72.4 500 ■ on 36.2 > xim

Oppression · «^ beans corn ■■ '■

100

100

100

ο to m a> cn

■ z

-ο

'■ CaJ CaJ

Vers-uch 10

In this experiment, the effectiveness of the compounds to be investigated against infection by root knot nematodes (Meloidegyne spp.).

em Composted greenhouse soil, one / third with clean washed sand is diluted, is infected with about 2 g of root galls containing tomato roots per flower pot. Then be Put 25 ml of the preparation to be examined on the infected soil. The preparation contains 0.056 g of the substance to be examined Compound, 1.0 ml of an emulsifier stock solution (0.25 percent Triton X-155 emulsifier in acetone) and 24.0 ml of deionized water. The concentration is 2240 ppm. Lower concentrations are obtained by dilution.

After the treatment with the preparation, the soil, the inoculum and the active ingredient are thoroughly mixed, poured back into the flower pot, and the mixture is ^{incubated for seven days at 20 °} C. and constant humidity. After the incubation with the first test compound in Table X two seedlings of tomato plants (Rlitgers) and three windsorb bean seeds (Vicia faba) are placed in each flower pot. When incubated * with the remaining six test compounds in Table X, two seedlings of tomato plants and three nasturtium seeds (lasturtium spp.) Are placed in each pot. "After three weeks of growth, the roots are removed from the soil and checked for root knuckle formation

■ ·. 0098 85 / 2284- bad original

examined. The roots of the Y / ind Sorbonne or the Nasturtium plants are examined only when the tomato host plants Necrose showed. The extent of the infection will be on hand determined on a scale from O to IO. O means no Y / root gall or complete suppression and 10 means strong root knot formation, which is comparable with the control plants is. Each V. root system is examined separately, and the Average is multiplied by 10 and subtracted from 100. In this way you get the percentage suppression of Nematodes. The results are summarized in Table X:

009885/2284

ω -a τη

Tabel X Oppression, #. 18.1 9.05 36.2 0 - 72.4 95 100 100 100 100 0 - 100 100 40 - 100 40 0 - 100 100 30th ■ - 100 80 70 50 100 85 100

Test connection suppression. #. at a concentration of «kg / ha

4.52 2.26 1.13

3-methylearbamyloximinotetrahydrothiophene

3t3-dimethyl-4-methylcarbaniyloximino

tetrahydrothiophene 100 100 100 100 100 90

> 3 ♦ 3-Dimethyl-4-ethylcarbamyloximinotetrahydrothiophene

3 »3-dimethyl-4-allylcaΓbamyloximino-. tetrahydrothiophene

β. 2 _t 4f4-trimethyl-3-diethylcarbanjyloxi- <O; minotetrahyiarothiophene "

00

οθ! J-ethyl-S-methyl ^ -methylcarbamyloxiinicnj notetrahydrothiophene

j 3-methyl = 3 = methylthio-4-methylcarb-, oil

* amyloximinotetrahydrothiophene

ι ■

CD CJ CO

cn

Attempt 11

Young tomato plants in flower pots with a diameter of 9 cm are treated by soaking the earth with the test compound given in the table below and exposed to a population of whiteflies for 7 days in the greenhouse. The plants are treated with the test compound in an amount of 9.05 kg / ha or less *. Stock solutions containing 500 ppm of the test compound are prepared according to Experiment 1 and diluted to the desired concentration. After 7 days, numerous eggs could be found on the plants examined. All plants were placed in a holding room. Fifteen days after the treatment, the total number of living larvae on the third and fourth leaves was determined and the percentage suppression was calculated. The ·. Results are shown in Table XI. ^ -

' Table XI

Test compound concentration, suppression,

kg / ha $>

^^^ 9.05 99 oximinotetrahydrothiophene 2.26 64

0.565 41

Attempt 12

Adult cotton boll beetles (Anthonomus grandis) are found in cylindrical fly cages of the type described in Experiment 6 and kept with a suspension of the mentioned in Table XII Test compound sprayed. Then the insects are given sugar water

009885/2284

offered as food. The mortality is determined three days after the treatment. "Stock solutions containing 500 ppm of the test compound" are prepared according to experiment 1
and diluted to the desired concentration. The results are shown in Table XII.

Table XII test compound

3f3-dimethyl-4-methyjcarbamyl oximinotetrahydrothiophene

concentration Trial 13 Mortality, - TpM 1 ° .myl-
hen 243 100 81 100 27 100 9 60 3 10

Test preparations are tested for their ability to suppress the growth of Xanthomonas phaseoli (Xp) in
different concentrations examined. The stock solution contains 0.125 g or 0.125 ml of the test compound, 4.0 ml emulsifier stock solution (0.25 percent emulsifier Triton K-155 in
Acetone) and 96.0 ml of deionized water. The active ingredient concentration is 1250 ppm. Lower concentrations will be
by diluting the stock solution with distilled water

■ j

posed.

Two ml of the test preparation are placed in a test tube

00988S / 2284

BATH ORIGINAL

bottled, which is then placed in a water bath held ^{at 47 0 G.} 8 ml of Difco nutrient agar are filled in the test tube, so that the dilution of a 1 maintained at 47 ⁰ C stock solution: 5 and the final concentration of test compound is 250 ppm in the agar. The contents of the test tube are thoroughly mixed while still warm and immediately afterwards poured into a sterile Petri dish with dimensions of 100 χ 15 mm made of polystyrene. -As soon as the agar has solidified, a suspension of Xanthomonas phaseoli is spread on its surface. The plate is then incubated for 24 to 48 hours at 3O ⁰ C. The inhibition of growth of the microorganism is then determined visually. The percentage growth inhibition is determined relative to the growth of a streak colony on control plates. The results are shown in Table XIII. ... ■ "* '■

Table XIII Test Compound Concentration, TPM Suppression, #

2,4,4-trimethyltetrahydro-

thiophene-3-one oxime 128 50

2,2-dimethyltetrahydro-

thiophene-4-one 250 50

009885/2284

Claims (3)

Patent claims 1, carbamic acid esters of the general formula: in which X is the group »0-, -S- or -N-, η the value O, 1 or 2, m has the value 0 or 1, the radicals R, to Rg 5 alkyl radicals with 1 to 6 carbon atoms, a cycloalkyl ring, Alkenyl ™, alkoxy, thioalkoxy or Mean carbalkoxy radicals or phenyl groups, or R ^ and Rp, R, and R., Rc and Rg or R ™ and Rg together form a cyclohexane or cyclohexene group, and the radicals Rq to R, ^ hydrogen atoms or alkyl radicals with Are 1 to 6 carbon atoms. 2. Tetrahydrothiophene derivatives of the general formula: 009885/2284 ^l 2 ~ R. in the R-, a hydrogen atom, a methyl group or a carbo-lower-alkoxy radical, Rp a hydrogen atom or a methyl group, R, and R. Hydrogen atoms or Are methyl groups and X is a carbonyl oxygen atom or the oximino group (NOH), 3. 2,4,4-trimethyltetrahydrothiophen-3-one oxime; 2,2-dimethyl-3-carbethoxytetrahydrothiophen-4-one · 2,2-dimethyltetrahydrothiophen-4-one; 3-methyl-3-methylthiotetrahydrothiophen-4-one oxime; 3-methyl-3-methylthiotetrahydrothiophen-4-one; 2-carbomethoxy-4-methyl-4-methylthiotetrahydrothiophen-3-one; 4 »4-dimethyltetrahydrothiapyran-3-one oxime; 3 »3-dimethyl tetrahydrothiophene-4-one oxime; 3-cyano-2-methyltetrahydrothiophen-4-one; 3 _f 3- ^ diethyl tetrahydrothiophen-4-one oxime; 3-ethyl-3-methyltetrahydrothiophen-4-one; 3-ethyl-3-methyltetrahydrothiophen-4-one; 'A-methyltetrahydrothiophene-1-one oxime. 009885/2284