DE3305280A1 - BENZOYL HYDRAZONE DERIVATIVES AND INSECTICIDES CONTAINING THEM - Google Patents

Description

T 53 818

Applicant: Hokko Chemical Industry Co., Ltd 2 , 4-chome, Nihonbashi-Hongoku-cho Kanagawa-ken
Japan

^ q Benzoylhydrazone derivatives and insecticides containing them

The invention relates to a new class of Benzoylhydra zonderivaten and insecticides containing them; it concerns in particular a new benzoylhydrazone derivative of the JL5 general formula

,1,

wherein R., R ", R, R. and η are those given below Have meanings

and an insecticide which has at least one benzoylhydrazone derivative of the aforementioned as an active ingredient or active ingredient Formula contains.

Recently, a variety of synthetic chemicals including organophosphorus compounds, carbamates, synthetic pyrethroids and the like ₃ q as agents for combating various harmful

Insects, including those on farms and the land (cultivated or uncultivated land) and forest as well as populate residential areas.

o _R A group of new benzoylhydrazone derivatives has now been synthesized and their insecticidal activity

seeks. It was found that the benzoylhydrazone derivatives of the general formula (I) given above have a strong insecticidal activity against various insects, as stated above, and that they are surprisingly effective, even against insects of the organophosphorus-sensitive strains. In addition, the new Benzoylhydrazonderivate have the advantage of ex- tremely low IQ toxicity to mammals and fish.

The compounds according to the invention are suitable for Control or control of a large number of insects, including in particular mosquitoes (Culex pipiens pallens, Culex pipiens molestus, Aedes aegypti, Aedes togoi, Anopheles sinensis, etc.), the house fly (Musca domestica), Meat flies or meat gnats, rice schnake (Tipula aino), rice gnat (Chironomus oryzae), soybean pod gall gnat (Asphondylia sp.), Oriental fruit fly (Dacus dorsalis), melon fly (Dacus cucurbitae), rice leaf bonrer (Hydrellia griscola), rice whisk maggot or larva (Hydrellia sasakii), rice stem maggot or larva (Chlorops oryzae), stone onion borer (Liriomyza chinensis), onion maggot or larva (Hylemya antiqua), seed grain maggot or larva (Hylemya platura) and the like.

There are already some compounds known that the invention Connections are similar. These compounds can be defined as those of the general formula

QQ mel (I), where η is the number 0, R _{2 is} acetyl, benzoyl, p-nitrobenzoyl or phenyl, and R and R are both methyl. and they are described in "J. Pharm. Soc, Japan", 79 ^, 103-104 (1959). However, only the process for the preparation of the compounds is given therein, as found

or- was only weak against mosquitoes and flies have insecticidal effects. The compounds of the present invention are those obtained by introducing

a special substituent (R ₁ ) in the benzoyl part of the abovementioned known compounds, as a result of which the unsubstituted parent benzoyl compounds are given a surprisingly high insecticidal effect or activity.

The compounds according to the invention can be used in good yield be prepared according to each of the following reaction schemes:

Reaction scheme (a)

-CNHN = C _n

Acid binding agent

CHD

CID

cn

Reaction scheme (b )

Il acid

O binder

cm cvd cn

wherein R., n, R, R and R each have the same meanings as indicated above, X is a halogen atom, an alkylsulfuric acid residue or an arylsulfonic acid residue and Y represent a halogen atom. The compounds of the formula (III) can therefore be alkyl halides, acyl halides, Dialkylsulfuric acid and -arylsulfonic acid esters act according to processes as known per se are easy to manufacture. The connections

of the formula (V) are substituted benzoyl halides.

The compounds of the formula (II) can easily be prepared from a benzoylhydrazine and substituted on the nucleus an aldehyde or ketone with R, - and R- substituents by hydrazone in a manner known per se. the Compounds of the formula (IV) are also easy to manufacture steep-bar by hydrazoneation of the substituted by R_ Hydrazine in the same way.

When reacting a compound of the formula (II) with a compound of the formula (III) according to the reaction jc scheme (a) or when reacting a compound of the formula (IV) with a compound of the formula (V) a solvent not to be used, however, it is usually preferred to be an organic solvent to use. It is also preferred to use the compound of the formula (III) or the formula (V) itself as Use solvents whenever possible. About suitable solvents that can be used include, for example, hydrocarbons, halogen-substituted hydrocarbons, ethers, esters, ketones, acid gels amides, alcohols and dimethyl sulfoxides. The acid binders are organic amines such as triethylamine and pyridine, or inorganic acid salts such as potassium carbonate can be used.

_a0 The reaction can be carried out at room temperature. As a rule, however, it is preferable to conduct it with heating. After the reaction has ended, the acid-binding agent salt which separates out of the reaction mixture is filtered off and the filtrate is distilled,

_oc to remove the solvent, whereby the invented

proper connection receives. The compound of the invention can also be produced by adding an organic one

Solvents such as benzene, chloroform, ether or tetrahydrofuran and water to the reaction mixture, separating the resulting organic layer, and then Distilling off the solvent therefrom.

The processes for making the compounds of the invention according to reaction scheme (a) and (b) are each described in Examples 1 and 2 below.

Reaction scheme (c)

CONHR '

* ~ ^x CNHNC + R'NC0->

CHD CM) CVD

wherein R ₁ , n, R- and R each have the same meanings as given above. The process according to reaction scheme (c) can be used when R in the general formula (I) denotes a lower alkylcarbamol group. In the reaction scheme (c), when a compound of the formula (II) is reacted with a compound of the formula (VI), a solvent need not be used; however, it is usually preferred to use a solvent which does not react with the compound of the formula (VI), for example an organic solvent such as hydrocarbons, halogen-substituted hydrocarbons, ethers, esters, ketones. Occasionally, the compound (VI) itself can be used as a solvent. The reaction can proceed very smoothly by adding an organic amine such as triethylamine and pyridine in a small amount as a catalyst.

Although the reaction can be carried out satisfactorily at room temperature, it can also be used if necessary get heated. The connection according to the invention can be established by filtering off the crystals isolated in the reaction mixture or by distilling off the used Solvent.

Example 3 below explains the production of the compound according to the invention according to reaction scheme (C).

Example 1 Preparation of compound N ° 2 according to the Reaction scheme (a)

10.5 g of i-p-chlorobenzoyl-2-isopropylidene hydrazine, 5.3 g Triethylamine and 100 ml of tetrahydrofuran were placed in a 200 ml round-bottom flask and while stirring with

2Q ice water was cooled, 3.9 g of acetyl chloride gradually became added dropwise. After the dropwise addition, the mixture was refluxed for one hour to effect the reaction to complete. The reaction mixture was cooled to room temperature and the precipitated salts

"C were filtered off and then the filtrate was concentrated, yellow-brown crystals were obtained which were then recrystallized from a hexane / acetone mixed solvent were, 10.4 g (82%) of yellow crystalline 1-p-chlorobenzoyl-i-acetyl-2-isopropylidene hydrazine with a

_ΟΛ Melting point (F) of 73 to 74 ⁰ C received.

Example 2 Preparation of compound N ° 24 according to the Reaction scheme (b)

"_ 6.5 g of i-methoxycarbonyl-2-isopropylidene hydrazine (manufactured from methoxycarbonylhydrazine and acetone), 5.3 g of triethylamine and 100 ml of acetone were in a 200 ml

Adding a round bottom flask and stirring while cooling with ice water, there was added 11.0 g of p-bromobenzoyl chloride added dropwise. Thereafter, the resulting mixture was stirred at room temperature for one hour to complete the reaction to complete. The reaction mixture was admixed with 50 ml each of benzene and water. The severed one organic layer was removed by fractionation, dried with anhydrous sodium carbonate and then distilled to remove the solvent. The white crystalline mass thus obtained became solid recrystallized from a hexane / acetone solvent mixture,

λ "wherein one 13.6 g (87%) of 1-p-bromobenzoyl-i-methoxycarbonyl-2-isopropylidenhydrazin in the form of white crystals having a melting point of 103-104 ⁰ C obtained.

Example 3 Preparation of the compound N ° 10 according to reaction scheme (c)

10.5 g of ip-chlorobenzoyl-2-isopropylidene hydrazine, 2.9 g of methyl isocyanate and 100 ml of acetone were placed in a 200 ml round bottom flask and 3 drops of trimethylamine were added. The mixture was stirred for one hour at room temperature. The precipitated crystalline was collected to give 12.7 g (95%) of 1-p-chlorobenzoyl-1-mßthylcarbamoyl-2-isopropylidenhydrazin in the form of white crystals having a melting point of 119-123 ⁰ C obtained.

Typical compounds of formula (I), prepared in the same way as in the previous examples, are given in Table I below. The connection number specified therein is referred to below in the the following test and examples are referred to.

10 15

link

Table I.

Structural formula

CH ₅

CCX) H ₃
I.

/ CH ₅ ^ CH ₅

/ CH ₅ ^ CH ₅

COC2H5

CH ₅ CH ₅

physicochemical property

_F.

20th

COC ₅ H ₇ -Ii I.

COC ₅ H ₇ -IBO I .CH ₅

II CH ₅

^F · 50-52TC

30th 35

COC5H-1 -j -n

C £

I! ^ CH ₅

O
COCH ₂ C ^

I / CH ₅

CN-N = C _n II
0

1.4989

4 9-51

Table I (continued)

F. "7 5-76t:

II "CH ₅

COOCH3

CH ₅ CH ₅

95-97C

1 CONHCH3

CH ₅ 5

11 9-1 2 5t:

1 COCH3

CH3

F. 78 ~ 80t:

1 COCH3

55-55C

1 δ C £

COCH3

I / CH ₅

N-N = C ^

C4H9-1BO

"15548

Al

Table I (continued)

COCH ₅ ι

1.5469

10 1 5 COCH ₅

. 50-53Χ:

1 6 CH ₅

■ Η

F. 148-1 5Ot

20 1 7

25th

1 8

COCH ₅

. .H

F. 128-1 29C

1 9

30th

COCH ₅ >

f. 65-67C

2 0

COCH ₅

^F 50-35X:

Table I (continued)

2

ce

COCH ₅ ι

N-N = C '

15721

10

2 2

Cl

COCH ₅ ι
CN-N = C

• CH3 • CH3

F. 142-1

2 COCH3

.CH ₅ "CH ₅

2

COOCH ₅ ι

N-N = C

'CH ₅

F. 105-1

2 COCH ₅

15458

2

COCH ₅ ι
CN-N = C

15050

Table I (continued)

2

COCHj

/ CH ₅

69-71C

2

C0CB3
ι

F. 78-81

20th 25th 30th 35

33Q5280

For the use of the compounds according to the invention as insecticides, the compounds can be used as such or they can be diluted with a suitable vehicle, for example water or a solid powder to which an adjuvant is added. If necessary, adjuvants such as wetting agents, distributing agents, dispersing agents, emulsifying agents, binders and .Q the like can be added to the mixture for use in the form of different types of preparations, such as wettable powders, solutions, emulsions, brines (flowable) , Dusts (dusts of the DL type (driftless dusts), Granules and fine granules.

In the manufacture of these chemicals are called liquid

Carrier water, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, esters, r, ketones, acid amides and highly polar solvents such as dimethylformamide, dimethyl sulfoxide and the like; than more solid to

Carrier mineral powder such as clay, talc, kaolin, bentonite, diatomaceous earth, calcium carbonate, silica and the like, and organic powders such as wood flour; and as adjuvant non-ionic, anionic, cationic and amphoteric Surface-active agents, lignosulfonic acid or its salts, gums, fatty acid salts, pastes, for example those made of methyl cellulose and the like are used.

The preparations, such as the wettable powders, solutions

and emulsions, can contain the active ingredient (active ingredient) 30th

or, the active ingredients (active ingredients) in an amount of 1-95 percent by weight, preferably from 2 to 75 percent by weight. These preparations are mixed with water up to a concentration of 0.0001 to 10

__ weight percent diluted. Dusts and granulates are contained in 35

typically 0.1 to 10 ww% of the active ingredient (Active ingredient) or the active ingredients (active ingredients).

The liquid concentrates, such as the emulsions and brines (flowable agent), can be used as such without dilution be used.

In using the compound of the present invention for insecticidal purposes, it is possible / to expand its scope by mixing it with other -Q insecticides, fungicides, herbicides and plant growth regulators, and it is also possible to achieve synergistic effects occasionally. The insecticidal effect of the compound according to the invention can be greatly improved by adding a synergist, such as, for example, propenyl- _K butylate (PB), octachlorodipropyl ether, N-octylbicycloheptenedicarboximide.

The invention is described in more detail in the following examples, without, however, being restricted thereto. the The parts given therein relate to weight.

Example 4 Emulsion

20 parts of the compound N ⁰ 1, 30 parts of dimethylformamide, 35 parts of xylene and 15 parts of polyoxyethylene alkylaryl ether were uniformly mixed with one another to give an emulsion which contained 20% of the active ingredient.

Example 5 Wettable Powder
30th

20 parts of the compound N ° 2, 5 parts of polyoxyethylene alkylaryl ether, 3 parts calcium lignosulfonate and 72 parts diatomaceous earth were mixed evenly with one another,

a wettable powder was obtained which contained 20% of the 35

active ingredient (active ingredient) contained.

Example 6 dust

3 parts of compound N ° 10, 0.5 part of anhydrous silica, 50 parts of clay and 46.5 parts of talc were evenly mixed with each other to obtain a dust which Contained 3% of the active ingredient (active ingredient).

The experiments described below are intended to illustrate the usefulness of the insecticides according to the invention, which contain the active ingredients (active ingredients) according to the invention.

.._ Experiment 1 (Tes t to combat or control Culex

'*

pipiens pallens)

250 ml of a test liquid with the specified concentration an emulsion prepared according to Example 4

was placed in a petri dish with a diameter of 9 cm 20

and a height of 6 cm at which 20 4th instar larvae were released. After standing for 24 hours at a constant temperature of 25 ^° C., the mortality (%) was determined. This experiment was carried out three times

__ leads and the average mortality became er-2b

calculates. The results are summarized in Table II below.

3305280 AU - - '' - - - ■ link
Ν ^β Io
Table II
Active ingredient conc
tration (ppm) mortality
(%) 1
2
• δ
4th
5
6th
7th 1
ff
ff
ff
ff
ff
If 1 0 0
1 0 0
1 0 0
1 0 0
1 0 0
1 0 0
1 0 0 8th dd 1 0 0 9 ff 1 0 0 1 O Il 1 0 0 1 1 Il 1 0 0 1 2 It 10 0 1 δ U 1 0 0 1 4 H 1 0 0 1 5. ff 1 0 0 1 6 ff 1 0 0 1 7 ff 1 0.0 1 8 ff 1 0 0 1 9 ff 1 0 0 2 0 dd 1 0 0

Table II (continued)

2 2

2 3 A.
B. H 2 4 C. I / • 2 5 D. Il 2 6 E. Il 2 7 ti 2 8 Il Comparative
chemical
η Il
ff η Il It Il It Il untreated
group -

1 0 1 Or 1 0 1 0 1 Ü 1 0 1 0 1 0 5 4th 4th 4th 9 0 0 0 ü U Ü 0 0 0 8th A. 6th 4th 5

In the table above, it concerns the comparison chemicals A-D to the compounds described in "J. Pharm, Soc, Japan" 79, 103-104 (1959) and the individual chemical names are for "A" 1, i-dibenzoyl-2-isopropylidene hydrazine, for "B" 1-benzoyl-1-p-n-trobenzoyl-2-isopropylidene hydrazine, for "C" i-Benzoyl-i-acetyl-2-isopropylidene hydrazine and for "D" IQ i-Benzoyl-i-pfaanyl-2-isopropylidene hydrazine. "E" stands for a fungicidal preparation available on the market under the general name EMP and 0,0-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate contains.

Experiment 2 (test for combating or controlling

Musca domestica)

On the bottom of a petri glass dish with a diameter of 9 cm, a filter paper was placed on which 1 ml

OQ of a test liquid with the specified concentration an emulsion prepared according to Example 4 was added dropwise. 10 house flies from Takatsuki strain (organophosphorus sensitive strain) or de s third Yumenoshlma tribe (multi-resistant tribe)

2g released. After standing for 48 hours on one At a constant temperature of 25 * C, the number of insects lying below was counted to determine mortality (%). This experiment was carried out three times for each concentration. It became the average mortality

ο «is calculated and the results are in the following table III summarized.

3305280 ^ -
Table III Mortality (%) 100 Yumeno 100 House fly (Takatsuki house fly (3.
Tribe) shima-tribe) 87 Active ingredient concentrations
tration (ppm) 83 Connect Active ingredient concentrations
tration (ppm) 1 00 300 00 dung N ° 300 93 1 00 93 100 90 100 1 93 1 1 00 1 00 1 00 97 2 1 00 87 1 00 80 3 1 00 90 1 00 90 4th 1 00 93 1 00 93 5 1 0 0 1 00 1 00 93 6th 1 00 87 1 0 0 90 7th 1 00 1 00 1 00 00 8th 1 00 1 00 1 00 00 9 1 00 97 10 0 1 93 1 O 100. 90 100 1 9 3 1 1. 1 00 87 1 00 83 1 2 100 90 1 00 90 13th 100 90 1 00 81 1 4 1 00 90 1 00 83 1 5 1 00 1 00 1 6. 1 00 1 00 1 7 1 00 1 8 "

Table III (continued)

1 9 A. 1 00 1 • 9 5 1 00 9 0 2 0 Ά.
B. 1 0 0 9 5 1 00 9 0 2 1 C. 1 00 00 1 00 9 7 2 2 D. 1 00 95 1 00 87 2 5 E. 1 00 1 97 1 00 9 0 in the v
2 4 F. 1 00 1 90 1 0 0 9 0 2 5 1 00 00 100 1 0 0 2 6 1 00 00 1 00 9 7 2 7 1 00 87 1 00 85 2 8 1 00 87 1 00 8 0 Comparative 85 50 80 4 5 chemical
Il 80 55 85 4 5 ti 87 55 90 50 11th 80 50 80 4 5 Il 1 00 90 0 0 η 1 00 1 00 0 0 gross trade 0 0 0 0 te group

In the table above are the comparative chemicals A-E are the same compounds as discussed above, and the comparative chemical F is an insecticide, the O, O-dimethyl-S- (1,2-εicarbät8xyäthyl) phosphorothiolothioate (Malathon) contains.

Experiment 3 (test for "combating or controlling Hyl emya platura)

In a 60 cm wide trench in a test field Fish meal incorporated and then left to its own devices for 22 days, causing Hylemya platura to lay eggs was induced. D. The fish meals were made with soil covered and the soil was with a test agent of the specified amount of the emulsion prepared according to Example 4 mixed. In the soil treated in this way, white beans (New Edogawa species) were sown and with Earth covered. On the twentieth day after the treatment, the number of germinations and the degree of damage were recorded investigated, whereby from the damage index described below the value for the control or Control (%) was determined. The results are summarized in Table IV below.

index

no 0 small amount 1 easy 3 middle 5

Degree of damage

no damage
weak damage; no effect on subsequent growth

harmed; however no effect on the subsequent growth is comparatively damaged and some adverse effect on growthastum; However, recovery is possible

a lot of 8 damaged and very bad

Growth; Recovery impossible 10 seriously damaged; Germination impossible or die off after germination

Index for each »(number of trunks _, ..,. Degree of damage) χ for each degree of damage ₌ ___Z degree of damage)

Number of tested maximum of the index th strains χ

Control or control value (%) = 100 - damage index 15th

Table IV

Connect
dung N ° A.
B. Active ingredient
amount (g / 10Ar) Germinating
rate(%) Value of
control
or fighting
fung (%) 2 C. 150 100 100 3 D. Il 98 100 9 G Il 98 100 10 It ' 100 100 20th Il 100 100 22nd It 96 100 23 It 92 100 25th Il 100 100 Comparative
chemical
It It
ti 94
92 60
56 Il ti 98 62 η Il 94 56 ti Il 100 94 untreated
te group - 100 0

In the table above, Comparative Chemicals A-D are the same as listed above and "G" stands 5 for an insecticide, the 0,0-diethyl-O- (2,4-dichlorophenyl) ■ contains phosphorothionate (ECP).

Claims (2)

T 53 818 Applicant: Hokko Chemical Industry Co., Ltd 2,4-chome, Nihonbashi-Hongoku-cho Kanagawa-ken
Japan Claims Benzoylhydrazone derivative, characterized by the general formula
15th 0 ^1X . " where mean: R _{1 represents} a lower alkyl group, a lower alkoxy group, a halogen atom or trifluoromethyl; η the number 1 or 2;
R represents a lower alkyl group, an alkylcarbonyl group, a halogenated lower alkylcarbonyl group, a benzoyl group, a lower alkoxycarbonyl group or a lower alkylcarbamoyl group; and R- and R individually each represent a hydrogen atom, a lower one Alkyl group or a phenyl group or in which R and R can together form a cyclohexane ring. 2. Insecticide, characterized in that there is at least one benzoylhydrazone derivative as the active ingredient (active ingredient) the general formula contains: ^ 'Hfl 1 T- Lj IH ~ 11 <-> IT \ where mean: R represents a lower alkyl group, a lower alkoxy group, a halogen atom or trifluoromethyl; η the number 1 or 2; R ~ a lower alkyl group, an alkylcarbonyl group, a halogenated lower alkylcarbonyl group, a benzoyl group, a lower alkoxycarbony group or a lower alkylcarbamoyl group; and R ₃ and R ₄ individually each represent a hydrogen atom, a lower alkyl group or a phenyl group, or in which R and R together can form a cyclohexane ring.