DE2324020A1 - NON-TERPENOIDS, COMPOUNDS MIMINGING THE JUVENIL HORMONE, AND THEIR USE IN INSECT CONTROL - Google Patents

Description

Non-terpenoid compounds mimicking the juvenile hormone and their use for insect control.

The present invention relates to certain 1,2-bis / ~ alkyl- (tb.io) -oarbamoyl7ethanes and their use to control insect pests

A new class of selective compounds has been discovered that disrupt the normal development of insects. These Compounds hinder the metamorphosis of the larvae into pupae and the pupae into insects, leading to the formation of abnormal ones Leads to specimens of the treated species, which may also be non-viable or sterile. This treatment leads to

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■ .. 2 -

at least indirectly to the destruction of the population.

The compounds according to the invention apparently have the Another advantage is that they are non-toxic to warm-blooded animals and highly effective for combating insects at low doses are.

The present invention also relates to new pesticide mixtures, the pesticidal active ingredient of these mixtures and a method for controlling insects, in which the metamorphosis and Multiplication of the insects is prevented or made more difficult.

The compounds of the present invention useful in insect control are of the formula

0 R ¹ E ² O

It I · tt 1 -Z

RXO-HCH ₂ GH ₂ NGX ¹ -R ^

in which R is an alkyl radical having 1 to 8 and preferably 2 to 6 carbon atoms, R is hydrogen or an alkyl radical

with 1 to 4 carbon atoms, preferably hydrogen,

2 ~

R is hydrogen or preferably eiss ^ i alkyl radical with 1 to Carbon atoms, particularly preferably with 1 to 3 carbon

■ x

atoms, Br is an alkyl radical having 1 to 8 and preferably 2 to 2 carbon atoms, X is oxygen or sulfur and X is oxygen or sulfur.

As mentioned earlier, the above compounds are useful to hinder the metamorphosis and / or reproduction of insects. The effectiveness of the compounds is such that the insects are effective at every stage of development can be treated.

3 0 9 8 U 9/1 2 k 3

The compounds of the present invention can be prepared by the following reaction are formed:

0 R ¹ R ² 0 NaOH / H ₂ O RXG-Gl + HNCH ₂ GH ₂ NH + ClS-X ¹ -R ³ >

0 S ¹ R ² O RXC-NCH ₂ CH ₂ NC -X '-R ^

Preferably the reaction is water carried out in a solvent such as, wherein the chlorine (thio) formate or mixture, the chlorine (thio) formate slowly with stirring the diamine in the presence of a Säureakzeptorst for example a sodium hydroxide solution, at a temperature of about ⁰ ° C. is added, followed by further stirring at room temperature to terminate the exothermic reaction. The reaction product is worked up in a conventional manner, for example by extraction with methylene chloride, washing the solvent phase with water and drying over anhydrous magnesium sulfate. Finally, it is filtered and the solvent is stripped off in vacuo.

Preferably, equimolar amounts of the reactants are used in the reaction, although a smaller amount Excess of a reactant can be used

For compounds where R and Έ? and / or X and X are different from one another, a mixture of the desired compounds is obtained, which can be separated by conventional methods.

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example 1

N, N'-diethyl ~ 1,2-bis (n-propylthiocarbanioyl) -ätfa.an.

? 2 ^H 5? 2 ^H 5 ⁰ I | °

CC

2.9 g (o, o25 mol) Ν, Ν'-diethylethylenediamine, 25 ml of water, 4.0 g (50 $) sodium hydroxide solution (0.05 moles) are added to one equipped with a dropping funnel and mechanical stirrer Three neck flasks mixed and stirred in an ice bath. Then 6.9 g (0.05 mol) of chlorothioformic acid n-propyl ester slowly added dropwise into the mixture, resulting in an exothermic reaction. The ice bath is removed and the reaction mixture is stirred at room temperature for 1/2 hour. The reaction product is extracted with 1oo ml of methylene chloride, then washed with 75 ml of water and dried over magnesium sulfate. The organic phase is filtered and stripped off, thereby obtaining 6.9 g of the desired product with a refractive index n «° = 1.5o22. The IR and the NMR spectrum confirmed the structure.

The following table contains certain selected compounds that were produced by the method described here can be produced. The digits used in the iCabelle are also used in the rest of the description.

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τ- Ο LfN Ο VO O tO τ— to O CVJ τ— O ιη Ln LT * volume • ν • k d τ- τ— Τ τ—

to

CVJ I. α> pcj ro , —J I. H »} 2y Φ "CvJ Xi W. Ct) O EH τ— CvJ Pl W. O O - ■ f = o

O =!

CSJ

U Φ

co

ιη

OO OO

σ * ο ο ιλοο

t ιτ \ νο * ι ι in ι ι

ο ο t—

I I T- T-

C-C-

c-c-cno

to

MM WW WWWW

^ r ^^ f ^ Lt ^ κ ^ κ ^ - ^ - ■ * ι ■ * ι ο ο W ο ο too o ^ oooooo

I I <AJ I I K I I 1 «X I I I I I I

d ClO d · Η O d Ή «Q 4» · Η d Ή · Η · Η

into | τ] θ

CVJl

CvJCVJCMCMCMCMCvJ

C- W to

in W CJ

O dWOOOOOOOW-HWWO

c— c— W W to to

OO II

• H -H W

intoin in in in m in in in WoW WWWWWWW

CVJl CvJ CVJCVJCVJCVJCVJCVJOJ

ο dowoooooooW

CC- CC- WW WW totointoto

ο ο w ο ο

I | CV | I cn W

cn cn »* ■ cn c- c- c— cn cn WWowWWWWW

· <Φ- ^ · | ^ to ιλ to ■ * ■ + too ο, μοοοοοο

KII

|| IKIII | d O d Ή O d · Η CQ + »· Η ti

CD

to

30984 9/1243

! Table I (cont.)

ω ο co co

CD

lsi

Verb.
No. R. X E ¹ R ² X r5 _a 3o, _{p )} 16 sec-C, H 3 H C ₂ H ₅ S. sec-C ₄ H ₉ 1.5o5o 17th I * aJ O ° 2 ^H 5 H 0 1-C ₄ H ₉ 1.4482 18th
19th
2o HG ₃ H ₇
i "c ³ H ⁷ S.
S.
S. GH ₃
G ₂ H ₅
CH ₅ G ₂ H ₅
CH ₃
C ₂ H ₅ S.
S.
S. 1.512o
1.5o85
1.5o65 21 QG ₃ H ₇ S. H CH ₃ S. UC ₅ H ₇ 1.52oo 22nd
23 XC ₃ H ₇ co co CH ₅
GH H
H co co 1-C ₃ H ₇
4 9 38-4o ° C 24 ⁱ ~ ^G 4 ^H 9 S. H H S. 4 9 94-96 ⁰ G 25th 2-Me-
ethyl
butyl S. H C ₂ H ₅ S. 2-methyl
butyl

cn I

a = compound from example 1

Test for insecticidal effect:

The effectiveness of a test compound of the hindrance or the prevention of the metamorphosis of insects is determined with regard by treating an insect with the compound and examined after the last transformation to the mature form of _a uf undeveloped features the penultimate stage larvae.

Larvae of the yellow mealworm, Tenebrio molitor, L. are? Kept 4iger humidity at 28 ⁰ C and 4o and fed with bran flakes, the prepupae are selected from the culture and maintained in separate containers. ^The pupae collected once a day are 1 to 25 hours old at the time of treatment. Suitable amounts of the test compound in 0.5 or 1.0 μl acetone are applied to the ventral side of the Tenebrio molitor, L. pupae by means of a spray device. The treated dolls are maintained at 28 ⁰ C and 4o ^c / cent moisture until the adult insects occur (usually within 6 to 8 days). The adult animals are rated as follows: positive, negative or dead. The result is rated positive in the presence of a typical epidermis, urogomphi, abnormal wings and the like. A group of 10 pupae was used in each test.

The dose of test compound required to produce a positive result in 5 of the pupae is determined. Table II shows this dose in the column

98/3 /) 2 4 3

(Table II connection no.

1 2 3 4 5 6

1o 11 12 13 14 15 16 17 18 19 2o 21 22 23 24

ο, 8th 1o 0, VJl ο, o8 ο,
1 ο 2 1 ο
ο? 1 ο, 5 ο, 5 2. 3 Oi oo3 ο, o2 2 1o 1o ο, 2 0, 5 3, 0 ο, o5

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- Q _

The compounds according to the invention are generally used in Forms suitable for application are transferred. For example, the compounds can be processed into pesticide mixtures, which can be in the form of emulsions, suspensions, solutions, dusts and aerosols. These mixtures contain in general, in addition to the active ingredient, the auxiliaries normally present in pesticides. In such preparations The active ingredient according to the invention can be used as the sole pesticidally active component or together with other compounds similar usefulness exist. The pesticide mixtures according to the invention can use organic solvents as auxiliaries such as sesame oil, xylene solvents, heavy petroleum and the like, water, emulsifiers, surface-active agents Agents, talc, pyrophyllite, diatomite, gypsum, clays, propellants such as dichlorodifluoromethane and the like. Contain. If if desired, the active ingredients can also be applied directly to feed, seeds and the like that are eaten by the insects, be applied. In this application form, it is expedient to use non-volatile compounds.

The compounds can also be combined with baits in a conventional manner.

The particular application of the pesticide mixtures according to the invention is obvious to the expert. Generally the pesticidally active compound is in a liquid Mixture, for example an emulsion, suspension or an aerosol spray. Although the drug concentration can vary within wide limits, the pesticidal compound will ordinarily not exceed about 50% by weight Make up mixtures. The pesticide mixtures according to the invention are preferably present in the form of solutions or suspensions about 0.1 to 1.0% by weight of the pesticidally active compound.

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Claims (19)

Claims R is hydrogen or an alkyl radical with 1 to 4 carbon 2
atoms, RV / hydrogen or an alkyl radical with 1 to 4 Carbon atoms, R an alkyl group with 1 to 8 carbon atoms, X oxygen
Represent sulfur. atoms, X oxygen or sulfur and X oxygen or 2. A compound according to claim 1 _; in which R is an alkyl radical 1 2 with 2 to 6 carbon atoms, R hydrogen, R one • x Alkyl radical with 1 to 3 carbon atoms, R ^ an alkyl radical having 2 to 6 carbon atoms and X and X represent sulfur. 3. A compound according to claim 1, in which R is an alkyl radical having% to 6 carbon atoms, R ¹ and R ^{2 are} alkyl radicals having 1 to 3 carbon atoms, R ⁵ represents an alkyl radical having 2 to 6 carbon atoms, and X and X is sulfur. 4. N-ethyl-1,2-bis (isobutylthiocarbamoyl) ethane. 5. N-ethyl-1,2-bis (sec-butylthiocarbamoyl) ethane. 6. N-ethyl-1,2-bis (n-propylthioearbamoyl) ethane. 7 "N-ethyl-1 ^ -bis-cisopropylthiocarbamoyl / ethane. 309849/1243 8. NjN'-diethyl-i ^ -bis-cisobutylthioearbamoyl-ethane. 9. N-methyl-N'-ethyl-i ^ -bis-cisobutylthiocarbamoyl-ethane. 10. N-ethyl-1,2-bis (2-methylbutyl-tb.iocarbamoyl) -ethaa. 11. Use of the compounds according to claim. 1 for insect control. 12. Use of the compounds according to claim 2 according to claim 11. 13. Use of the compounds according to claim 3 according to claim 11. 14. Use of N-ethyl-1,2-bis (isobutylthiocarbamoyl) ethane according to claim 11. 15. Use of N-ethyl-1,2-bis (sec-butylthiocarbamoyl) ethane according to claim 11. 16. Use of N-ethyl-1,2-bis (n-propylthiocarbamoyl) ethane according to claim 11. 17. Use of N-ethyl-1,2-bis (isopropylthiocarbamoyl) ethane according to claim 11. 18. Use of N ^ '- diethyl-i ^ -bis-cisobutylthiocarbamoyl) ethane according to claim 11. 19. Use of N-methyl-N'-ethyl-1,2-bis (isobutylthiocarbamoyl) ethane according to claim 11. 309849/1243 2o. Use of N-ethyl-1,2-Ms- (2-methylbutyl-thiocarbamoyl) -ethane according to claim 11. For: Stauffer Chemical Company
Westport, Conn., V.St.A. Dr. H, J. Wolff Lawyer 3098A 9/1243