DE1949234A1 - N-substituted aryl carbamates and their use as insecticides - Google Patents

Description

N-substituted aryl carbamates and their use as insecticides

The invention relates to new aryl carbamates in which a proton of the nitrogen atom of the carbamyl group is replaced by an organic radical derived from a sulfenyl halide is. The carbamates according to the invention have the IOrmel

OR ¹

! I I

ROCFSR ²

in which R stands for an aryl group of 6 to 20 carbon atoms, R stands for hydrogen or an alkyl group with 1 to 6

2
Carbon atoms and R stands for an alkyl group with 1 to 10 carbon atoms or a monocyclic aryl group with 6 to 12 carbon atoms, which with O to 2 alkyl groups whose total number of carbon atoms is 1 to 6, or O to 2 halogen atoms with atomic numbers from 17 to 35 , ie chlorine or bromine or with O to 2 trifluoromethyl groups sub-

009816/1894

is established. The term "aryl" is intended to denote a radical derived from benzene or a compound having the benzene nucleus.

.In the above formula, R preferably has 6 to 20 carbon atoms and is a monocycli ;; cher Mcyclischer or aryl group 17 by 0 to 2 halogen atoms of atomic numbers "to 35 * alkyl radicals having 1 to 6 ι ohlenstoffatomen, alkoxy of 1 to 3 carbon atoms, alkylthio radicals with 1 to 3 carbon atoms in the alkyl group or by 0 to 1 dialkylamino radicals with 1 to 3 carbon atoms in the alkyl radicals. The total number of substituents on these monocyclic or bieyclic rings should not be more than 3. They can be the same or be different.

Particularly preferred are compounds in which R is a naphthyl radical, a 3-alkylphenyl radical with 3 to 6 carbon atoms in the alkyl radical, a 3,5-dialkyl-4-dialkylaminophenyl radical with 1 to 3 carbon atoms in each alkyl group, an alkoxyphenyl radical with 1 to 3 carbon atoms in the alkyl group, a 3-alkyl-4-ai _ky ithiophenylre _s t having 1 to 3 carbon atoms in the individual alkyl groups, a 3,5-dialkyl-4-alkylthiophenylrest having 1 to 3 carbon atoms in the individual alkyl groups, a 3-alkyl-4-dialkylamino radical with 1 to 3 carbon atoms in the individual alkyl groups, a 3-alkyl-4-alkoxyphenyl radical with 1 to 3 carbon atoms in the individual alkyl groups, a 3,5-dialkyl-4-alkoxyphenyl radical with 1 to 3 carbon atoms in the individual alkyl groups or an alkylthiophenyl radical with 1 to 3 carbon

1 2

atoms in the alkyl group, R is methyl and R is

Is methyl, 4-chlorophenyl, tolyl or phenyl radical.

Examples of radicals that can be represented by R, are:

Phenyl, 3-n-propylphenyl, 3-isopropylphenyl, 3- sec .butylphenyl, 3-tert.butylphenyl, 3-methyl ~ 5-sec.butylphenyl, 3-propyl-5 - sec.amylphenyl. 3-Dodecylphenyl, 3-Tetradecylphenyl, 3-Amylphenyl, 3-Hexylphenyl, Benzyl, 4-Tolyl, 3-ToIJrI ₁ 3-

009816/1894

BATH ORIGINAL

194923A

Methyl-5-hexylphenyl, 3,5-X, rlyl, 4-ethylphenyl, 4-cumyl, 4-butylbenyl, 2,4-chlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 3, ^ - Dibromophenyl, 2-Ch.lor-5-terteT-butylph.enyl, x \ nphthyl, 4-indanyl, 5-indanyl, 2-chloro-5-sec _o amylphenyl, b-chloronaphthyl, 4-methylthio-3-tolyl, 3- Propylthiophenyl, 2-isopropoxyphenyl, 3,5-di (metl ^ lthio) phenyl, 2-ethoxyphenyl, 4-ric-itJiox-irpiienyl, 2-isopropoxy-3,5-dichlorophenyl, 4-dimethylamino-3-tolyl, 4-iiethylthio-3, 5-X3 ^T lyl »4-dimethylamino-3, 5-xylyl, 5-methoxynaphthyl, 2,4-dichloronaphthyl, 5,6 | 7,8-tetrahydronaphthyl, 4-propylthiophenyl, 5-bromonaphthyl, 4-diethylaraino-3-tolyl, 4-dipropylamino-3-tolyl, 4-dietirylaminophenyl, 2-chloro-4-diinethylaminophenyl and 4-methylethylanino-3,5-xylyl "

iju belong to the R -ALkj groups:

Met'iyl, / ithyl, Isopropyl, II-I-ropyl, Butyl, Isobutyl, AmyI ^ and Hexylo

R in the formula below can be: methyl, ethyl, propyl, butyl, sec-butyl, arnyl, hexyl, heptyl, decyl, phenyl, benzyl, 4-carbon or benzyl, 4-ethylbenzyl, 2-butylbenz3'l, 2,4-dichlorophen3'l, 2-3-romplieiiyl, 3-chlorophenj ^r l, 4- ^r - ^^ ^> ii'luoromethylbenyl, 4-trifluoromethylphenyl, 3f5-dibromophenyl, 3-trifluoromethylplienyl, 4 - rifluorometh3a-2-tolyl, Tolyl, xylyl, 4-JPropyl-2-tolyl, 4-ethylphenyl, 2-eth3 ^ 1phen3 ^ 1, 4-cumyl, irichlor-νίη; Ί, tribromovinyl, 1-chloro-2,2-dibromovinyl etc.

Typical carba''ates according to the above formula are: ii-Mfithyltiiio-phenylcarbamate, L ^T -'Isopropylthio-lI-meth3'l-bensylcerV - ^ '. Iat, HA:: yltliio-K "-butyl ~ 3-isopropylp} ien; /lcarba.mat, Ii-Jvtl]; / l-Ii-octylt: iio-3- sec: "Amylphenylcarbamat, üi-Hethyl-N-decyltiiio-4-tolylcarbainat, l ¹ ii ^v iethyl-N-trichlorovinylthio- 3- £ | k * amyl-phenyl-carbanate, H-butyl-K-tribromamylthio - ^ - dimethyia ^1111110 -3,5-xylylcarbanate, N-methylthio-N-methyl-2,4-dichlorophenylcarbamate, ii-hexylthio-W -hexyl-2,4 ', 5-triochlorophenylcarbamate,

009816 / 189Λ

N-ethylthio ^ -bromophenylcarbamate, N-methylthio-N-methyl ~ 2-chloro-3-isop-ropylph.enylcarbamate, 1: \ i-octylthio-H-propyl-3-amyl-4-chlorophenylcarbamate, M-decylthio -N-methyl-4-cLiraethy] .- aminophenylcarbamate, N-methylthio-4-dia? Propylamino-3f 5-xylylcarbamate, N-ethylthio-N-methyl-2-chloro-4-dimethylaminophenylcarbamate, E-r-phenylthiophenylcarbamate, Phenyl ~ thio-N-methyl-benzylcarbamate, N-phenylthio-naphthyl-carbamate, N-methylthio-N-methyl-naphthyl-carbamate, H-phenylthio-N-propyl-4-tolyl-carbamate, ltf-butyl-N-phenylthio-3- isopropylphenylcarbamate, N-ethyl-N-phenylthio-4-dimethylamino-3,5-xylylcarbamate, N-methyl-IT-phenylthio-2,4-dibromophenylcarbamate, H ■ -ätl·lyl-H-methylthio ~ 4-bromophenylcarbamaΐ, N -4-chlorophenylthio-4'-methoxyphenylcarbamate, N-4-oloropheiiylthio-lT-methyl-2-isopropoxyphenylcarbamate, N-methyl-1-1-4-tolylthio-2 '-isopropoxypenylcarbamate, N-4-bromophenylthio- -4 ^l -dipropylamino-3 > 5-xylylcarbamate, N-ethylthio-3 % 5-xylylcarba.-raat, E'-I-ethyl-lT-pllenylthio-3-raethyl-4-π Lethylthiophenylcarbamat, IT-3,4-I) chloroplienylthio-l'i-raethyl-2'-propylthioplienylcarbaraat, N-methylthio-l'ί-propyl-4-ethylthio-3-t ■ olylcarbaπlat _> IJ-4-Oumylthio -N-methyl-3'-ethyl-4'-dimethylaminophenylcarbaniate, lT-2-Metb.yl-4-chlorophenylthio-li-propyl-3 ' t 5' -dipropylphenylcarbamate, H-butyl-ir - 4-trifluoromet] iylphenylthio-5'-brora-1'-naphthylcarbamate, I \ * -4 ~ chlorophenylthio-4'-chloro-1 '-naphthylcarbamate, N-butyl-K-4-tolylthio-5'-indanylcarbamate, N-hexylthio-iT -methyl-5 '-propoxy ^ - ^ «jjppjj ^ hy ^ carbaiKat, 17-kethyl-W-phenolthio-2,4-dichloro-1-naphthylcarbamate, U-butyl-li-4-ehlorpheiiylthio-1'-naphths' carbamate _t N-methylthio-H-niethyl-1-naphthylcarbamate, IT-3, S-dichlorophenylthio-N-ynethyl-iJ -methylthio-1'-naphthylcarbamate, N-methyl-N-4-trifluoromethylphenylthio-5'-ethyl- 1'-naphthylcarbamate, H-4-chlorophenylthio-N-methyl-4'-indanylcarbamate and N-methylthio-N-propyl-1 · - (i? * »6 *, 7 ' 1 8-tetraJ: iydronaphthyl) carbamate

The compounds according to the invention can be produced by reacting an aryl carbamate with a sulfenyl halide will. The implementation proceeds according to the equation

009816/1894

BAD ORIGSNAL

11th

R t

O ti

-R ι

R-O-O-N-M + XSR '

ROGH- SR ' ¹ + MX

in which X is a halogen with an atomic number of 17 to 35 and M is hydrogen or an alkali metal cation,

1 2
and R, R and R have the meaning indicated above, This reaction dimethylformamide, in pyridine, with or without an acid acceptor or in another solvent such as iiethylenchlor, chloroform, acetonitrile or Oimethoxyäthan be carried out in the presence of an acid acceptor _e Among the acid acceptors which together May be used with dimethylformamide or the other solvents include pyridine, alkylpyridiii, quinoline and similar heterocyclic bases, Pyridine is the preferred acid acceptor, When pyridine is used alone it acts as both a diluent and an acid acceptor «The preferred medium for performing these Implementation is dimethylformamide with pyridine as the acid acceptor ,, ·

The pressures and temperatures at which the reaction was carried out are not critical, temperatures between skin temperature and about 60 C are normally used, however, lower or higher temperatures can up to the decomposition temperature of the reaction partners or products can be used, usually atmospheric pressure or autogenous reaction pressure is used, but sub-atmospheric or super-atmospheric pressures can be used will. Implementation is usually within about 1 to about 4 hours completed.

The starting carbamate can and usually will be a commercially available insecticidal carbamate. Customary processes for preparing such carbamates either in situ or in a separate step can be used. Such starting carbamates are described in U.S. Patents 3,062,707, 3,062,864, 3,062 865, 2 903.478, 3 084 096, 3 203 853,

009816/1894

BATH. Original

3,167,472 and 3,256,145, British Patent 982,235 and in the Pesticide Index, 3rd edition, D.E.H.I'rear (1965)

Examples

The following examples illustrate processes by which the carbamates according to the invention are produced can «These examples are in no way intended to limit the invention» The percentages relate to the G-weight, unless otherwise stated.

example 1

5.5 g of m-sec.amylphenyl IT-methylcarbamate in 40 ml of dimethylformamide are mixed with 2.2 g of pyridine in a tube. 4.9 g of p-chlorophenylsulfenyl chloride are added to this mixture. The foreign is stirred for 2 hours at room temperature, then 500 ml of ice water are added, and the mixture is extracted with ethyl ether. The extract is washed with sodium bicarbonate and water and dried. The ether is removed, leaving an oily product. This oily product is chromatographed on silica gel with hexane and 5% ethyl ether in hexane. About 7 g of Np-chlorophenylthio-IT-methyl-m-seke-amylphenyl carbamate are obtained. This' material is an oil and shows the following S- and Cl-A ^ s.lyse: S calculated: 8.80'p; found: $ 8.94; Cl calculated: 9.75 '^ i found: _9f 80 $ _e

Other carbamates according to this invention were prepared according to the in Method described in Example 1. These carbamates and their physical properties are shown in Table I. reproduced «,

. ORIGINAL BATHROOM

00-9816 / 1894

Tabel

3eisp «

ITr.

'' C

II — p_ — Chi ο rph e rrj / l t M ο -Iv-

aetriyl-1-η ^ ρ} ·; ethyl chloride 109-11 4

H-Ihenylthio- ^ -raethyl-1-naphthylcarbamate '66-70

N-methylthio-W-methyl-1 naphthyl carbamate fluid

A ^T -O-Tolylthio-II-methyl-1-naphthylcarbamate 96-99

U-phenylthio-N-methyl-m-

sec-butylphenylcarbamate liquid

N-p-chlorophenyl thi o-H-methyl-m-sec-butylphenyl carbamate fluid

H-Me thy 1 thi ο-ϊΤ-Jne thyl-msek, butyl phenyl carbamate fluid

U-Me thy 1 thi ο-ΪΓ-methyl-m-2-pentylphen37lcarbamate fluid

U-JD-T ο lylthi o-U-methyl-msec.Butylphenylcarbamate fluid

U- £ -chlorophenylthio-F-methylphenylcarbamate 76-78

ST-IIe thyl-N-p_-chl ο rphenylthio-4-dimeth37lamino-3., 5- xylyl carbamate liquid

N-methyl-N-p_-chloro rphenyl thio O-isopropoxyphenyl carbamate fluid

H-methyl-N-trichlorovinyl

thio-1-naphthyl carbamate liquid

Elemental analysis

r *

calculate found. calculate sefund «

5.50

5.00

4.17

9.15 9.16

12.65 10.58

11.97 10.67

9.72

8.99

10.81 10.92

9.02 9.10

9.10 '8.58

8.83 8.90

Cl

calculate ε efund

4.43 9o32 8.93 10.32 9.72 4.53 5.49 10.35 9.8B 5o66 4.28 12.95 12.72 4.33 4 «64 9.90 9.81 4.44 10.18 10.45

10.15 10.38

February 12, December 12

9.72 10.02

10.10

29.30 29.48

The carbamates according to the invention can be used for combating by insects such as aphids, cockroaches, cabbage moths, * burrow beetles, mosquitoes etc. are used. Insecticidal effective amounts of one or more of the carbamates are used directly on the insect or to control applied to its environment. In many cases the carbamates according to the invention show significantly better insecticidal properties Effectiveness than the carbamates from which they are derived.

The following examples demonstrate the insecticidal effectiveness of N- p -chlorophenylthio-N-methyl-i-naphthylcarbamate and its superiority as an aphicide over W-methyl-1-naphthy1-carbamate *

Example 15

Each compound was dissolved in a suitable organic solvent dissolved and then with water that is a low Amount of surfactant was diluted to a concentration of 1.9 ppm. Four corresponding Cucumber leaf sections infected with at least 20 cotton aphids (Aphis gossypii Glover) per section were immersed in this mixture. Excess solution was drained from each section. Everyone "Section was thinly placed on a '-ί-'eller, which in turn placed in an incubator for 24 hours on 20 randomly selected aphids on each leaf section mortality counts were then made. from these numbers were the percent mortality as the average of the four leaf sections calculated.

That the N-p-Chlorophenylthio-N-methyl-i-naphthylcarbamate containing mixture caused a mortality of $ 100, while the mixture containing the N-methyl-1-naphthylcarbarnate only caused a mortality of 23 »5 #,

00981671894

Example 16

M-phenylthio-N-methyl-i-naphthyl carbamate and N-methylthio-N-methyl-1-naphthyl carbamate were tested at 0.98 ppm or 1.9 ppm as aphicides according to the method of Example 15, N-phenylthio-H-methyl-1-naphthyloarbamate caused 98.5% mortality and N-methylthio-N-methyl-1-naphthyl-carbamate 92.5 $ mortality rate,

Episode 17

F-p-Tolylthio-N-methyl-i-naphthyl carbamate and N-p -chlorophenylthlo-N-methyl-1-naphthyl carbamate were used against the beetle larvae (Gastrophysa oyanea Melsh.) After the following Method tested. This method is intended to determine to what extent leaves are protected against insect damage.

Each test compound was dissolved in a suitable solvent and then washed with water containing a small amount of one surfactant was diluted to a concentration of 15.6 ppm. Four corresponding rows of 5 20 mm wide leaf disks were made from pilot root— scroll cut out. Each row of these leaf disks was dipped in the test compound mixture and allowed to drain and placed on a J-'eller. Each row was then of freed of excess moisture and infected with 5 larvae. The series were incubated for 24 hours, after which time mortality counts were made on each disc and the percentage mortality calculated as the average, N-p-tolylthio-N-raethyl-i-naphthylcarbamate caused 100% Control and N-p-Chlorophenylthio-N-methyl-i-naphthyloarbamate 90 # fight,

Example 18

N-p-Tolylthio-N ^ methyl-1-naphthylcarbamate was used against cabbage moth larvae (Trichoplusia ni) at a concentration of

009816/1894.

500 ppm by the method of Example 17 using cucumber leaf slices and caused a 96 ' destruction.

Example 19

'■ Typical carbamates according to this invention were based on their Efficacy against cockroaches (Periplaneta amerioana L.) tested by the following method · Each test compound was dissolved in a suitable solvent and then diluted with water so that a 2.5 microliter dose 1250 ng per insect. Am an arbitrary mix of male and female cockroaches were anesthetized with COg, and 3 corresponding groups of 10 cockroaches each were sorted out and placed in corrugated cardboard troughs. A 2.5 microliter dose of the test compound solution was added injected with a micrometer hypodermic syringe into the abdomen of each cockroach. Each group was put in a cage. After 24 hours, mortality counts were made on each group and the percent mortality calculated as the average of these counts. The test results are shown in Table II.

Table II

Link . mortality

U-p_-chlorophenylthio-N? -Niethyl-m-sec. Butylphenyl carbamate 70

N-Phenylthio-N-methyl-m-secTButylphenylcarbamate ^- 78

IT-methyl thio-N-methyl-m-sec. Butyl phenyl carbamate - ^ ₀₀

N-methylthio-N-methyl-m-2-pentylphenyloarbamate "" 100

N-methylthio-N-methyl-1-naphthyl-

oarbamate 96

Studies of toxicity to mammals show-

009816/1894

ί *

ten that the carbamates according to the invention are significantly less are more toxic than their chemical predecessors. For example, toxicity tests carried out orally have shown that the W-wethylthio, the W-phenylthio and the IT-chlorophenylthio derivative of 3-sec-butylphenyl-ii-methylcarbamate is about 2 to 4 times less toxic than 3 sec. Butyl phenyl IT-diethyl carbamate.

The carbamates according to the invention are thus effective agents for combating numerous anthropodal pests. For their application, the carbamates can generally be processed into formulations using the same materials and using the same methods as the carbamates from which they are derived. Liquid preparations of the carbamates according to the invention contain one or more solvents, such as hydrocarbons or polar solvents, and one or more surface-active agents. The latter are preferably nonionic. They allow easy dispersibility in water for use in the field. Such liquid preparations can be used as sprays or mists. Solid preparations of the normally solid carbamates of this invention can be prepared by one or more C _{ar] jaiTia} te, etc. mixed with a solid diluent such as clay, talc, diatomaceous earth. The normally liquid carbamates can be sprayed onto absorbent solid diluents to form granular or pylverous preparations. Such insecticide preparations can also contain other compatible pesticides, fillers, binders, additives, stabilizers, synergistic agents, etc.

009816/189 A

BATH

Claims (1)

in which ß for an aryl group with 6 to 20 carbon atoms, R for hydrogen or an alkyl group with 1 to ρ
6 carbon atoms and R stands for an alkyl radical with 1 to 10 carbon atoms or monocyclic aryl radical with 6 to 12 carbon atoms, which with G to 2 alkyl groups with a total of Ί to 6 carbon atoms, 0 to 2 halogen atoms with an atomic number between 17 and 35 or 0 to 2 Trifluoromethyl radicals can be substituted ₀ 2 «carbamates according to claim 1, characterized in that R is a monocyclic or bicyclic aryl radical with 0 to 2 halogen atoms. It has atomic numbers: 1 to 35, 0 to 2 alkyl radicals 1 to 6 carbon atoms, C to 2 alkoxy radicals with 1 to 3 carbon atcinfeü, C to 2 alkyltnio— radicals with 1 oίε 3 i o-ilenstofxatorieii in the alkyl group or 0 to 1 dialkyl3, fiiinoreste with- 1 to 3 Kc'ilenst off atoms in the individual Al ^ yIi -, ^; ppen is substituted, the total number of substituents on the Rlvit; never 't _L ; is larger than 3, 3e Carbe-ate according to claim 1, characterized in that R is a Na / phth / yl radical, a 3-alkylphenyl radical with 3 to 6 carbon atoms a 3,5-dialkyl-4-dialkylaminophenyl radical in the alkyl radical with 1 to 3 carbon atoms in each alkyl group, an alkoxyphenyl radical with 1 to 3 carbon atoms in 0098 16/189 k bad the alkyl group, a 3-alkyl-4-alkylthiophenyl radical with 1 to 3 carbon atoms in the individual alkyl groups, a 3-, 5-dialkyl-4-alkylthiophenyl radical with Ί "to 3 carbon atoms in the individual alkyl groups, a 3-alkyl-4- Dialkylamino radical with 1 to 3 carbon atoms in the individual alkyl groups, a 3-alkyl-4-alkoxypv, _eny ] radical with 1 to 3 carbon atoms in the individual alkyl groups, a 3,5-dialkyl-4-aifcoxyphenyl radical with 1 to 3 carbon atoms in the individual alkyl groups or an alkylthiophenyl radical having 1 to 3 carbon atoms in the alkyl group, R ρ
a methyl radical and R a methyl, 4-chlorophenyl, tolyl or is phenyl «, 4e carbamates according to claim 1, characterized in that 1 2 R is a 3-sec-butylphenyl radical, R is a methyl radical and R is Is phenyl, 4-chlorophenyl or methyl » 5e insecticide, characterized in that it is a carbamate according to claims 1-4 in. an insecticidally effective amount and contains a biologically inert diluent. For Chevron Research Company San Francisco, CaI ,, V ₀ St ₀ Ae Lawyer 009816/1894