KR820000008B1 - Process for preparing esters of phthal imido methyl cyclopropane carboxylic acid - Google Patents

Abstract

Title compds. [I; X1 = H, F, Cl, Br; X2 = F, Cl, Br; X3 = Cl, Br, I; R = IV(R6,R7,R8,R9 = H, C1, Me; S/I = aromatic, dihydro, tetrahydro ring), useful as insecticide, were prepared by reacting compds. (III) with R-OH or its derivs. The intermediates(III) were obtained from compd. (II) and halogenation agent. Thus, the CCl4 100 ml soln. of (S) α-cyano-3-phenoxybenzyl(1R, cis)2,2-dimethyl-3-(2',2'-dibromo vinyl)cyclopropane-1-carboxylate 7.57 g was mixed with bromine 2.4 g dissolved CCl4 15 ml soln. and stirred at 20≰C for 45 min. The residue 10 g of the intermediate was separated with silica gel chromatography and the developed to give compd.(I).

Description

[Name of invention]

Method for preparing phthalimidomethyl cyclopropane carboxylic acid ester

[Detailed description of footing]

The present invention relates to a method for producing a new cyclopropane carboxylic acid ester represented by the following general formula (I).

X ₁ in the above structural formula is selected from the group consisting of hydrogen, fluorine, chlorine and bromine,

X ₂ is selected from the group consisting of fluorine, chlorine and bromine,

X ₃ represents chlorine, fluorine or iodine,

R is an alkyl group containing 1 to 4 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, an alkenyloxy group containing 2 to 6 carbon atoms, an alkadienyl group containing 4 to 8 carbon atoms, and a methylenedioxyl group , Benzyl group or a benzyl group which may be substituted by at least one group selected from the group consisting of halogen atoms, or selected from the group consisting of groups represented by the following structural formula.

R ₁ in the above structural formula represents a hydrogen atom or a methyl group,

R ₂ is a monocyclic aryl group, or

-CH ₂ -C≡CH

The group represented by is shown.

R ₄ represents a hydrogen atom, a -C≡N group, or a -C≡CH group,

R ₅ represents a combustion atom or a methyl group, and n represents an integer such as 0, 1, or 2.

And R ₆ , R ₇ , R ₈ and R ₉ represent a hydrogen atom, a chlorine atom or a methyl group, and S / RI ₂ represents an aromatic ring or a similar dihydro or tetrahydro ring.

Common examples of the compound of formula (I) include R ₂ being 5-benzyl-3-furyl-methyl, R ₃ being vinyl, propenyl-yl, buta-1, 3-dienyl or bute-1-yl; _And pentavalent is 3-phenoxy-bentyl, α-cyano-3-phenoxy-benzyl, or α-ethynyl-3-phenoxy-benzyl.

For convenience, the ring to which the R ₅ substituent is attached in the alcohol moiety of the ester of formula (I) in which n is 0 is the benzene ring.

Esters represented by formula (I) exist in multiple isomeric forms. In fact, cyclopropanecarboxylic acids forming acid components in the esters of general formula (I) generally have three asymmetric carbon atoms, i.e., asymmetric carbon atoms at the 1 and 3 positions of the cyclopropane ring and 1 of the polyhalogenated ethyl at the 3 position. It has a positionally asymmetric carbon atom.

When the three substituents X ₁ , X ₂ and X ₃ are different, a secondary asymmetric carbon atom may be present at the 2 ′ position of the polyhalogenated ethyl group.

The alcohol R-OH constituting the alcohol component in the ester of general formula (I) may contain one or more asymmetric carbon atoms and one or more double bonds causing E / Z isomerization.

Esters of formula (I) also include racemic mixtures or combinations of compounds present as optical isomers resulting from the presence of asymmetric carbon atoms in the acid and alcohol moieties.

When the substituents X ₁ and X ₂ are identical, the clear stereoconfiguration of the asymmetric carbon atoms at the 1 and 3 positions of the cyclopropane ring and the alcohol moiety (which itself constitutes at least one asymmetric carbon atom and at least one double bond causing E / Z isomerization) In order to determine the structure of the present invention, there may be esters of general formula (I) due to the presence of the asymmetric carbon atom at the 1 'position or a diastereomer of the corresponding free acid, and in fact their NMR (nuclear magnetic resonance) ) Or their speed of movement in thin layer chromatography.

The two dimers mentioned above are represented by isomers (A) and (B).

Among the esters of the general formula (I) to be dealt with in the present invention, among the cyclopropanecarboxylic acids (k) constituting the acid component of the esters, the following may be mentioned.

-2, 2-dimethyl 3- (2'-2'- dibromo 1 ', 2'- dichloroethyl) cyclo propane- carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrachloroethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (2 ', 2'- difluoro 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (2 ', 2'-dichloro 1: 2'- dibromoethyl) cyclopropane-1-carboxylic acid;

2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid,

-2, 2-dimethyl 3- (1 ', 2', 2, 2'- tetrabromoethyl) cyclopropane- 1-carboxylic acid;

-2, 2-dimethyl 3- (2 ', 2'- difluoro 2', 1 '1'- diiodoethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (2 ', 2'- dichloro 2', 1'- diiodoethyl) cyclo propane- 1-carboxylic acid;

-2, 2-dimethyl 3- (2 ', 2'- dibromo 2', 1'- diiodoethyl) cyclo propane- carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2', 2'- tribromoethyl) cyclopropane- 1-carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2'- dichloro 2'-bromoethyl) cyclopropane- carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2', 2'-trichloroethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2'- dibromo 2'- chloromethyl) cyclopropane- carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2'- dichloro 2'-fluoroethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2'- dibromo 2'-fluoroethyl) cyclopropane- 1-carboxylic acid;

-2, 2-dimethyl 3- (2'-fluoro 2 ', 1'- diiodoethyl) cyclopropane- 1- carboxylic acid;

-2, 2-dimethyl 3- (2'-chloro 2 ', 1'- diiodoethyl) cyclopropane- 1-carboxylic acid;

-2, 2-dimethyl 3- (2'-bromo 2 ', 1'- diiodoethyl) cyclopropane- 1- carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2', 2'-trichloro 2'-fluoroethyl) cyclopropane- 1-carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2'- dibromo 2'- chloro 2'- fluoroethyl) cyclopropane- carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2', 2'-trichloro 2'-bromoethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (1 ', 2', 2'- tribromo 2'- chloroethyl) cyclo propane- 1- carboxylic acid;

-2, 2-dimethyl 3- (2'-fluoro 1 ', 2', 2'-tribromoethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (2'-bromo 2'-fluoro 1 ', 2'-dichloroethyl) cyclopropane-1-carboxylic acid;

-2, 2-dimethyl 3- (2'-fluoro 2'- chloro 2 ', 1'- diiodoethyl) cyclopropane- 1- carboxylic acid;

-2, 2-dimethyl 3- (2'-fluoro 2'-bromo 2 ', 1'- diiodoethyl) cyclopropane- carboxylic acid; And

-2, 2-dimethyl 3- (2'- chloro 2'- bromo 2 ', 1'- diiodoethyl) cyclopropane- carboxylic acid;

Common ones of the compounds of formula (I) include those wherein X ₁ and X ₂ are the same and are selected from the group consisting of fluorine, bromine or chlorine; X ₂ is different from X ₁ ; R is 5-benzyl-3-furyl-methanol, 1-oxo-2- allyl- 3-methyl- cyclophen-2-ten- 4-yl alcohol, 3-phenoxy- benzyl alcohol, or (alpha) -cyano- 3-phenoxy-benzyl alcohol; And X ₁ and X ₂ are the same and are selected from the group consisting of bromine, chlorine and fluorine and R is derived from 5-benzyl-3-furyl-methanol.

Compounds of formula (I) or mixtures thereof in the form of isomers (A) or isomers (B) due to the presence of the 1 'positional asymmetric carbon atom in formula (I) There are things like

-(S) α-cyano 3-phenoxybenzyl 1R, cis 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane-1-carboxylate;

-(S) α-cyano 3-phenoxybenzyl 1R, cis 2, 2'-dimethyl 3- (2 ', 2'-dichloro 1', 2'- dibromoethyl) cyclopropane-1-carboxylate ,

Formula (I) in the form of isomers (A) or isomers (B) due to the presence of the 1 'positional asymmetric carbon atom of formula (I) or in the form of a mixture of these isomers which will be specifically mentioned in the examples below Esters are also common.

The present invention includes compounds of formula (I) in the form of mixtures of stereoisomers of cis and trans structures.

More specifically, mention may be made of stereoisomer mixtures of cis and trans structures in 20/80, 50/50, and 80/20 weight ratios.

In a new process according to the invention for preparing esters of formula (I), chlorinating agents, brominating agents, or iodine, in which the esters of general formula (II) can be added to the side chain double bonds of cyclopropane carboxylic acids, Reacts with the topic. This method will be referred to as the α method.

X ₁ , X ₂ and R have the same meanings as above.

As the halogenating agent, chlorine, fluorine or iodine can be used, and the reaction is carried out in an organic solvent which does not react with chlorine, fluorine or iodine, for example acetic acid, carbon tetrachloride, chloroform or methylene chloride.

In the process according to the present invention for preparing a compound of formula (I), a compound of formula (IV) is obtained by reacting an acid of general formula (III) with a chlorinating agent, brominating agent, or iodide The derivative is reacted with an alcohol or a functional derivative of the structure R-OH. Hereinafter, this method will be referred to as β process.

As the halogenating agent of acid (III), chlorine, fluorine or iodine is used, and the reaction is carried out in an organic solvent which does not react with chlorine, cancellation or iodine, for example, acetic acid, carbon tetrachloride, chloroform or methylene chloride. .

Functional derivatives of acid (IV) used for esterification with alcohol ROH or esterification with functional derivatives of alcohols, in particular chlorides, anhydrides, mixed anhydrides, lower alkyl esters, metal salts of acid (III) or organic basic Salts, chlorides, fluorides of these alcohols, or functional derivatives of alcohols which may be sulfonates.

In one variation of method β, the functional derivative of the carboxylic acid of formula (III) is reacted with a brominating agent, a chlorinating agent, or an iodide to form the corresponding functional derivative of the acid of formula (IV), which is then reacted with an alcohol ROH There is a method of forming the corresponding ester of I). This is called the method γ.

As the halogenating agent used to halogenate the functional derivative of the acid (III), chlorine, fluorine or iodine is preferable, and then an organic solvent which does not react with chlorine, fluorine or iodine such as acetic acid, carbon tetrachloride, It is preferable to carry out the reaction in an organic solvent such as chloroform or methylene chloride.

In the methods β and α of the present invention, one of the acids (V) or one of its functional derivatives is reacted with an alcohol ROH or a functional derivative of this alcohol to obtain compound (I) from the acid (IV) or its functional derivative.

For example, the esterification can be carried out on the alcohol ROH by the action of acid (IV) or chlorides, anhydrides or mixed anhydrides of this acid.

The transesterification process can also be used in which the lower alcohol ester of acid (IV) is reacted with alcohol ROH in the presence of a basic catalyst.

As a salt of an acid (IV), an alkali metal salt, a silver salt, or a triethylamine salt is mentioned, for example.

Other methods of esterifying an acid (IV) or a functional derivative thereof with an alcohol ROH or a functional derivative thereof can be used without departing from the scope of the present invention.

An advantageous advantage of carrying out the method β of the present invention is the use of chlorides of these acids as functional derivatives of acids (III) or (IV).

The esterification of the chloride of acid (IV) with alcohol ROH is then conventionally carried out in the presence of a tertiary base such as pyridine or triethylamine.

The functional derivatives of ester (II), acid (III) and acid (III) used as starting materials in the process of the present invention are described in French Patent Nos. 2,185,612 and 2,240,914 and are similar to the methods described in these patents. Can be manufactured by

When X ₁ and X ₂ represent a halogen atom and X ₁ is different from X ₂ , esters (II), acids (III) and their functional derivatives are described by Dole Gordon Brown (Denton, Texas), December 1974. Si's paper, "Study on the Structure-Activity of Halopyrethroids," and can be prepared in a manner similar to those described in this paper.

Of course, the ester (II) used at the beginning of the process α of the present invention is present in a number of isomers which are asymmetric carbon atoms and at least one asymmetric carbon atom, or E / Z isomerization at positions 1 and 3 of the cyclopropane ring. Formed by the presence of an alcohol moiety having one or more double bonds which causes

Similarly, acids (III) or functional derivatives thereof used at the beginning of the methods β and α of the present invention exist in various isomeric forms derived from asymmetric carbon atoms at positions 1 and 3 of the cyclopropane ring.

The compound represented by formula (I) has remarkable pesticidal properties, in particular very potent insecticidal effects and very good stability against atmospheric conditions (heat, light and humidity).

These compounds are particularly suitable for use in combating pests in the agricultural sector. For example, these compounds are effective in controlling aphids, Lepidoptera Larvae and Coleoptera.

These compounds are preferably used at a dosage between 1 and 100 g of active ingredient per hectare. Because of their rapid action they can also be used as household pesticides.

Insecticidal effects of the compounds according to the invention are particularly effective on housefly, Spodopters Littoralis, Epipilna varivestris larvae, Sitophilus Granarius and Tribolin castanium ( It is evident in the tests for Triboleun Castaneum and Blatella Germanica. These tests are described in more detail in the Examples.

The present invention also provides a pesticide containing at least one compound represented by the above general formula (I) as an active ingredient, more specifically, the presence of an asymmetric carbon atom in the 1 'position of the above general formula (I) as an active ingredient. A pesticide containing at least one compound consisting of isomers (A), isomers (B), or mixtures of these isomers attributable to, examples of the above isomers are as described above.

One or more other pesticides may be added to these active ingredients. These compounds may be prepared in powder, granules, suspensions, emulsions, solutions, solutions for aerosols, flammable flakes or pharmaceutical forms commonly used in the use of these kinds of compounds.

In addition to the active ingredients, these compositions generally contain a nonionic surfactant which makes the dispersion of the excipients and materials constituting these mixtures uniform. Examples of excipients to be used include liquids such as water, alcohols, hydrocarbons or other organic solvents, mineral oils, animal or vegetable oils, powders such as talc, clay silicates or Kieselguhr, or plate powder (or pyre). Combustible solids, such as trum mark).

In order to enhance the insecticidal effect of the compounds according to the present invention, 1- (2, 5, 8-trioxadodecyl 2-propyl 4, 5-methylenedioxy) benzene (or piperonyl butoxide),

N- (2-Epiheptyl-bicyclo [2, 2-1] -5-heptene-2, 3-dicarboximide, or piperonyl-bis-2- (2'-n-butoxy methoxy ) Synergists such as ethyl acetal (or trotal) may be added.

It is preferable that these pesticides contain 0.005-10 weight% of active ingredients.

The present invention therefore also relates to a pesticide as described above, characterized in that it contains a synergist, in particular piperonylbutoxide, which is added to the active ingredient.

In addition, the compounds of the general formula (I) have acarides and nematodes. Next, the insecticidal effect on the spot solution (Tetranychus Urticae) and Ditylenchus Myceliophagus was mentioned.

The present invention also relates to a nematode nematode containing at least one or more of all possible isomers of the compounds represented by the general formula (I) as defined above, and more specifically the compounds named as follows.

A and B isomers of-(S) α-cyano 3-phenoxybenzyl 1R, cis 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1 Carboxylates, and

A and B isomers of-(S) α-cyano 3-phenoxybenzyl 1R, cis 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane 1-carboxylate.

The present invention also relates to nematicides containing at least one or more of all possible isomers of the compound represented by the general formula (I) as defined above, more specifically, the compounds named as follows.

A and B isomers of-(S) α-cyano 3-phenoxybenzyl 1R, cis 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1 Carboxylates, and

A and B isomers of-(S) α-cyano 3-phenoxybenzyl 1R, 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1 -Carboxylates.

As with the former pesticides, one or more other pesticides may be added to the antacid insecticide and the insecticide. The nematicide nematode and nematicide are particularly preferably formulated as powders, granules, suspensions, emulsions and solutions.

In order to use as a nematicide insecticide, it is preferable to use it as a foliar spray wetting agent containing 1-80% weight% of an active ingredient, or a foliar spray solution containing 1-500 g / L of an active ingredient. Moreover, the powder for foliar dispersion containing 0.05-3 weight% of active ingredients can be used.

For use as a nematicide, it is suitable to use as a soil treatment containing 300-500 g / l of active ingredient.

It is preferable to use the nematode nematode compound and nematicide compound according to the present invention at a dosage of 1 to 100 g including an active ingredient per hectare.

The anti-improving properties of the compounds of formula (I) as described above can be added to control the parasites in which these compounds are parasitic in animals, in particular for the control of the parasitic ixodides and sarcoptides. It allows the use in form. The test described in detail in the Examples shows the effect of the compound of formula (I) on Lipicephalus Sanguineus in the system.

Compounds of formula (I) can be used in animals to control all kinds of tributaries, such as sarcoptic scabies, psorooptic scabies and chorioptic scabies.

Compounds of general formula (I) are all types of ticks, such as, for example, Boophilus species, Hyalommia species Am blyoma species, and Lipicephalus Species. To control.

The present invention therefore also relates to a method of eradicating nematode parasites in an animal by using it as a veterinary medicament containing at least one compound of formula (I) as an active ingredient.

The former composition may be used through an external route, but may also be used through parenteral or digestive organs.

It is beneficial to add Pyrethrinoides as synergists to the former composition. Such reagents are as defined above. These compositions are formulated by conventional methods.

Finally, in order to use the compound (I) for animals, it is convenient to use the mixture with a certain amount of animal feed.

For example, 0.002-0.4% by weight of α-cyano 3-phenoxybenzyl 1R cis 2,2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1- It is possible to use animal feed compounds containing carboxylates.

These compositions used for animal feed are characterized in that they consist of at least one of a certain amount of animal feed compound and a compound represented by formula (I).

The composition according to the invention also consists of at least one compound of the general formula (IA) corresponding to general formula (I).

Wherein X ₁ , X ₂ and X ₃ are the same as before.

Among these, (S) alpha -cyano 3-phenoxy benzyl 1R, cis 2, 2-dimethyl 3- (2 ', 2', 2 ', 1' (RS)-tetrabromoethyl) cyclopropane- 1-carboxylate and (S) α-cyano 3-phenoxybenzyl 1R, cis 2, 2-dimethyl 3- (2 ', 2'-dichloro 2', 1 '(RS) dibromoethyl cyclopropane -1-carboxylates have significant antifungal properties when used in the agricultural field to control plant pathogens.

The antifungal effect of these compounds, represented by the formula (IA), was investigated by experiments with Fusarium Roseuem, Botrytis Cinerea Bhoma specus, and Penicillium Roqueforti. It is described in detail later.

The present invention further relates to an antifungal agent containing at least one or more of the compounds represented by the above general formula (IA) as an active ingredient or at least one or more of the compounds as an active main ingredient.

In these antifungal agents, one or more other pesticides may be added to the active ingredient. These antifungal agents can be formulated as powders, granules, suspensions, emulsions, solutions, aerosol solutions or other pharmaceutical forms commonly used in the use of this type of compound.

In addition to the active main ingredients, these antifungal agents generally contain excipients and nonionic surfactants which uniformly disperse the materials constituting the compound. Excipients used include water, alcohols, hydrocarbons or other organic solvents, or liquids such as mineral fibers, animal fibers, or vegetable oils, or powders such as talc, clays, silicates and Kijelger.

It is preferable that these antifungal agents contain 25-95 weight% of active ingredients with respect to spray powder, and 10-30 weight% of active ingredients with respect to soil spray powder or liquid.

The present invention also provides a possible method for obtaining new acids of the structure (IV) and their derivatives. The following examples are intended to illustrate the present invention in detail, and are not intended to limit the present invention.

Example 1

(S) α-cyano 3-phenoxy benzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane-1-carboxylate Isomers A and Isomers B of

7.57 grams of (S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'- dibromovinyl) cyclopropane-1-carboxylate to 100 cc of carbon tetrachloride To this, a solution of 2.4 grams of bromine dissolved in 15 cc of carbon tetrachloride was added, stirred at 20 ° for 45 minutes, concentrated to dryness under reduced pressure, and the residue (10 grams) was purified by chromatography on silica gel. Separated and developed into a mixture with benzene and petroleum ether (B.pt 35-75 °) and initially (S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', Isomer (A) (4.12 grams) of 2 ', 2', 2'-tetrabromoethyl) cyclopropane-1-carboxylate was obtained followed by isomer (B) (4 grams).

Isomer A has the following properties.

[α] D = −53 ° (C = 0.5%, benzene).

Analysis: C ₂₂ H ₁₉ B ₁₄ NO ₃ (665, 037)

Calculated C 39.73% H 2.88% Br 48.06% N 2.11%

Found 39.9 2.9 48.2 2.1

IR spectrum (chloroform)

Absorption at 1740 cm ^-1 (ester); Absorption at 1615, 1588, 1573 and 1488 cm- ¹ is due to the aromatic ring.

NMR Spectrum

Peak at 1.25-1.33 p.p. (hydrogen atom of methyl group at 2-position of cyclopropane); Peak at 1.75-2.17 p.m (hydrogen at 1 and 3 positions of cyclopropane); Peak at 5.19-5.55 p.m (hydrogen at 1 'position of the layered chain); Peak (benzyl hydrogen) at 6.38 p. Peak at 6.91-77.5 p.p.m, corresponding to hydrogen in an aromatic ring.

Isomer (A) has the highest mobility in thin layer chromatography.

Isomer (B) has the following characteristics.

[α] _D = + 111 ° (C = 0.6%, benzene).

Assay: C ₂₂ H ₁₉ Br ₄ NO ₃ (665,037)

Calculated Value: C 39.73% H 2.88% Br 48.06% N 2.11%

Found: 39.8 3.0 48.1 2.0

I. R spectrum (chloroform)

Absorption (ester) at 1743 cm- ¹ : At 1615, 1588, 1573 and 1488 the absorption is due to the aromatic ring.

NMR Spectrum

Peak at 1.24-1.40 p.p. (hydrogen of methyl group at 2-position of cyclopropane): peak at 1.83-2.25 p.p.m (hydrogen at position 1 and 2 of cyclopropane); Peak at 3.93-5.20 p.m (hydrogen at 1 'position of the side chain); Peak (benzyl hydrogen) at 6.39 p. Peak at 6.92-7.52 p.p.m, corresponding to hydrogen in an aromatic nucleus.

Isomer (B) has the least mobility in thin layer chromatography.

Cyclic dichroic (dioxane)

+4.7 at Δε = 223 mm;

+4.2 at Δε = 247 mm.

Example 2

(S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Isomer A and Isomer B of Rate.

Dissolve 17.06 grams of (S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylate in 200 cc of carbon tetrachloride, To this was added 6.55 grams of bromine solution dissolved in 20 cc of carbon tetrachloride for at least 10 minutes, stirred at 20 ° for 48 hours, concentrated under distillation under reduced pressure, and concentrated with benzene and cyclohexane (7-3). Chromatography with silica gel developing into a mixture to separate crude residue (23.8 grams) was carried out to separate (S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'- Obtained 0.4 g of isomer A of dichloro 1 ', 2'-dibromoethyl) cyclopropane-1-carboxylate with the highest mobility in thin layer chromatography and 10 g of isomer (lowest mobility in thin layer chromatography) .

Isomer A has the following properties.

[alpha] _D = −61 ° (C = 0.5%, benzene).

Analysis: C ₂₂ H ₁₉ Br ₂ Cl ₂ NO ₃ (576,125)

Calculated Value: C 45.85% H 3.3% Br 27.44% Cl 12.3% N 2.4%

Found: 45.8 3.3 27.7 12.3 2.3

I. R spectrum (chloroform)

Absorption (ester) at 1738 cm- ¹ , absorption at 1485, 1585 and 1610 cm- ¹ is due to the aromatic ring.

NMR Spectrum

Peak (hydrogen in a pair of methyl groups of cyclopropane) at 1.29-1.37 p.p.m; Peak at about 2.05 p · m (hydrogen at positions 1 and 3 of cyclopropane); Peak at 5.20-5.29-5.37-5.15 p.m (hydrogen attached to the asymmetric carbon atom of the side chain); Peak (benzyl hydrogen) at 6.45 p.m; At 7.0–7.6 p.m, the peak is due to hydrogen in the aromatic nucleus.

Cyclic dichroic (dioxane)

-8 (refractive) at Δε = 221 mm;

+14 (maximum) at Δε = 289 mm.

Isomer B has the following properties.

[α] _D = + 119 ° (C = 1% benzene)

Analysis: C ₂₂ H ₁₉ Br ₂ Cl ₂ NO ₃ (576,125)

Calculated Value: C 45.86% H 3.3% Br 27.7% Cl 12.3% N 2.4%

Found: 46.2 3.4 27.6 12.2 2.3

I.R Spectrum

Absorption at 1740 cm ^-1 (ester); At 1610, 1585, 1485 cm- ¹ the absorption is due to aromatics.

NMR Spectrum

Peak (hydrogen in a pair of methyl groups of cyclopropane) at 1.25-1.38 p.p.m; Peak at 1.87-2.3 p.m (hydrogen at positions 2 and 3 of cyclopropane); Peak at 4.97-5.11-15.1-15.1 p.m (hydrogen attached to asymmetric carbon atoms of side chains); Peak (benzyl hydrogen) at 6.46 p. At 77.67 p.p.m, the peak is due to hydrogen in the aromatic nucleus.

Cyclic dichroic (dioxane)

+9 (maximum) at Δε = 220-221 mm.

+0.23 (max) at Δε = 289 mm.

Example 3

(S) α-cyano-3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane-1-carboxyl Rate:

Step A: (1R, cis) 2, 2-dimethyl 3- (1, 2 ', 2', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid:

10.4 grams of bromine dissolved in carbon tetrachloride 150 cc (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid and dissolved in 22 cc of carbon tetrachloride The solution was added, stirred at 20 ° C. for 1 hour, concentrated under distillation under reduced pressure to give 314 grams of crude product (melting point = 145 ° C.). This crude product was recrystallized from 110 cc of carbon tetrachloride to give (1R, cis) 2,2-dimethyl 3- (1, 2 ', 2', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid (melting point = 150). 22.12 grams) were obtained.

This product is a mixture of two isomers (A) and (B) which appear in bright colors by the N.M.R spectrum. In fact, NMR spectra correspond to peaks from 5.33–5.66 ppm corresponding to hydrogen attached to monobrominated asymmetric carbon atoms and peaks from 1.31 to 1.43 ppm corresponding to hydrogen in a pair of methyl groups (corresponding to almost two thirds of the mixture). ) And other compounds having a peak at 4.24-5.34 ppm corresponding to hydrogen attached to the monobrominated asymmetric carbon atom and a peak at 1.28-1.48 ppm corresponding to hydrogen in a pair of methyl groups (corresponding to about one third of the mixture). Indicates.

This mixture also showed peaks (movable hydrogen with acid function) at 1.67-2.17 p.p.m (hydrogen at positions 1 and 3 of cyclopropane) and about 11.25 p.p.m.

The analysis of the obtained mixture (melting point = 150 ° C) is as follows.

Analysis: C ₈ H ₁₀ Br ₄ O ₂ (457,804)

Calculated: C% 20.99 H% 2.20 Br% 69.82

Found: 20.9 2.2 70.2

Step B: (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetra bromoethyl) cyclopropane-1-carboxylic acid chloride

0.2 cc of diethylformamide and 8.5 cc of thionyl chloride were introduced into 179 cc of petroleum ether (boiling point at 35-75 ° C.), and the mixture was refluxed and dissolved in 150 cc of methylene chloride (1R, cis) 2, 2-dimethyl. A 35.76 gram solution of 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid was introduced, refluxed for 2 hours, stirred, cooled, and concentrated in a distillation to dryness. After addition to toluene, the mixture was further concentrated by distillation to dryness under reduced pressure to obtain 38 grams of coarse acid chloride (melting point = 88 DEG C) used in the next step.

Step C: (S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1- Carboxylate

Into a solution of 18.4 grams of (S) α-cyano-3-phenoxybenzyl alcohol dissolved in 100 cc of benzene, 7.5 cc of pyridine was introduced at 10 DEG C under an inert atmosphere, followed by introducing 38 grams of the crude acid chloride obtained in step B. Stir at 20 ° C. for 15 minutes, then add water, stir, decanter to separate the organic phase, extract with benzene, wash the benzene phase with water, then sodium bicarbonate, water, normal hydrochloric acid, then Washed with water in order of water, concentrated under distillation to dryness under reduced pressure, and the residue was purified by chromatography on silica gel to form (S) α-cyano 3-pen in the form of a mixture of isomers (A) and isomers (B). Oxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylate was obtained.

In a similar manner to the foregoing examples, the compounds described in the examples described below were prepared.

Example 4

(RS) α-cyano-3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) -1-cyclopropane-1 Carboxylates;

This compound is (RS) alpha -cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'- dibromovinyl) which is a mixture of isomers (A) and (B). Obtained by the action of bromine on cyclopropane-1-carboxylate.

I.R spectrum (chloroform)

Absorbed at 1740, 1586 and 1485 cm- ¹ .

NMR Spectrum

Peak (hydrogen of methyl group at 2-position of cyclopropane) at 1.20-1.26-1.35 p.p.m; Peak at 4.3-4.48-4.67 p.m (hydrogen at 1 'of the ethyl side chain at 3-position of cyclopropane); Peak at 6.48 p.p.m (hydrogen attached to the same carbon atom as C = N); Peak at 6.97-7.17 p.m (hydrogen of an aromatic ring).

Example 5

(RS) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Rate

This compound is a mixture of isomers (A) and (B) (RS) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane It is obtained by bromination of -1-carboxylate.

I.R spectrum (chloroform)

1743cm ^-1, 1588cm ^-1, absorption at 1487cm ^-1.

NMR Spectrum

Peak at 1.20-1.26-1.35-1.35 p.m (hydrogen of methyl group at 2-position of cyclopropane): peak at 1.68-1.77 p.p.m (hydrogen at 1-position of cyclopropane); Peak (hydrogen at 3-position of cyclopropane) at 1.95-2.42 p.m; Peak at 4.23-4.25-4.40-4.4.5-4.57 p.m (hydrogen at 1 'above ethyl side chain at 3-position of cyclopropane); Peak at 6.48p.p.m (hydrogen attached to the same carbon atom as C≡N); Peak (hydrogen of an aromatic ring) at 7.0-1.67 p.m.

Example 6

(S) -1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromo Ethyl) cyclopropane-1-carboxylate

Step A: (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetraboromoethyl) cyclopropane-1-carboxylic acid

This compound is obtained by bromination of (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid, which is a mixture of isomers (A) and (B). Obtained.

NMR Spectrum

Peak at 1.30-1.40 p.m (hydrogen of a methyl group at the 2-position of cyclopropane); Peaks (hydrogen at positions 1 and 3 of cyclopropane) at 1.65-1.74 and 1.97-2.37 p.p.m; Peaks (hydrogen at the 1 'position of the ethyl group) at 4.30-4.76 and 4.47-4.65 p. Peak (hydrogen of carboxyl group) at 9.63 p.m.

Step 3: (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride

Action of thionyl chloride on (1R, trans) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid obtained in step A To obtain the acid chloride used in the next step.

I.R spectrum (chloroform)

Absorption at 1778cm- ¹ .

Step C: (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetra Bromoethyl) cyclopropane-1-carboxylate

(S) 1 in the form of a mixture of isomers (A) and (B) by the action of (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-ol in the presence of pyridine on said acid chloride. -Oxo 2-allyl 3-methyl cyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane Obtain 1-carboxylate.

I.R spectrum (chloroform)

Absorbed at 725cm ^{- 1} , 1710cm- ¹ , 1655cm- ¹ , 1638cm- ¹ , 995cm- ¹ , 918cm- ¹ .

NMR Spectrum

Peak (hydrogen of methyl group at 2-position of cyclopropane) at 1.30-1.32-1.36 p.m; Peak (hydrogen of methyl group at 3-position of allerrone) at 1.98-2.05 p.p.m; Peak at 4.83-5.25 p. P. (Hydrogen of allyl side chain terminal methylene group); Peaks at 4.30-4.48 and 4.48-4.67 p.m (hydrogen at 1 'position of the ethyl side chain at 3-position of cyclopropane): peaks at 5.33-6.11 p.m (hydrogen at 2' position in allyl side chain of allerrone).

Example 7

5-benzyl 3-furylmethyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylate isomer (A) and (B)

The following compound was obtained by esterification of the acid chloride obtained in step B of Example 3 with 5-benzyl 3-furylmethanol in the presence of pyridine.

a) 5-Benzyl 3-furylmethyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane- 1-carboxylate.

[alpha] _D = −104 ° (C = 0.5%, benzene). Isomer with the highest mobility in thin layer chromatography.

NMR Spectrum

Peak at 1.23-1.37 ppm (hydrogen of methyl group at 2-position of cyclopropane); Peak at 1.65-2.03 ppm (hydrogen at 1 and 3 positions of cyclopropane); Peak at 3.92 ppm (hydrogen of methylene group of benzyl); Peak at 4.92 ppm (hydrogen of methylene of CO ₂ —CH ₂ ); Peak at 5.27 to 5.67 ppm (hydrogen at 1 'position of the ethyl chain at the 3 position of cyclopropane); Peak at 5.96 ppm (hydrogen at 4 position of furyl); Peak at 7.25 ppm (hydrogen of phenyl); Peak at 7.33 ppm (hydrogen at position 2 in furyl).

Cyclic dichroic (dioxane)

-6.5 at Δε = 2.17 nm

b) 5-benzyl 3-furylmethyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane- 1-carboxylate.

[α] _D = + 84 ° (C = 0.5%, benzene).

NMR Spectrum

Peak at 1.20-1.42 ppm (hydrogen of methyl group at 2-position of cyclopropane); Peak at 1.67-2.17 ppm (hydrogen at 1 and 3 positions of cyclopropane); Peak at 3.92 ppm (hydrogen of methylene group of benzyl); Peak (hydrogen of methylene group of CO ₂ -CH ₂ ) at 4.95 ppm); Peak at 4.95-5.18 ppm (hydrogen at 1 'position of the ethyl side chain at the 3 position of cyclopropane); Peak at 7.25 ppm (hydrogen of the aromatic ring of benzyl); Peak at 7.33 ppm (hydrogen at position 2 in furyl).

Cyclic dichroic (dioxane)

+4.30 at Δε = 247 nm

Example 8

(S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl ) Cyclopropane-1-carboxylate (isomers A and B)

In the presence of pyridine, (S) 1-oxo 2-allyl 3-methyl cyclopent-2-ene 4-ol and (1R, cis) 2, 2-dimethyl 3- (1 ') obtained in step B of Example 3 , 2 ', 2', 2'-tetrabromoethyl) The following compounds were obtained by esterification with cyclopropane-1-carboxylic acid chloride.

a) (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabro Isoethyl) Cyclopropane-1-carboxylate (A).

[alpha] _D = −56 ° (C = 0.6%, benzene).

NMR Spectrum

Peak at 1.28-1.39 p.m (hydrogen of a methyl group at the 2-position of cyclopropane); Peak at 1.96 (hydrogen of methyl group at position 3 of alleletron); Peak at 4.83-5.16 p.m (hydrogen of allyl-chain terminal methylene group); Peak at 5.33-6.16 p.m (hydrogen at position 1 'of ethyl chain at position 3 of cyclopropane and hydrogen at position 2' of allyl chain).

Cyclic dichroic (dioxane)

+1.84 at Δε = 332 nm;

+2.06 at Δ3 = 20 nm;

-19 at Δε = 225 nm.

Isomer (A) has the highest mobility in thin layer chromatography.

b) (S) 1-oxo 2-allyl 3-methyl cyclopent-2-en 4-yl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabro Mother ethyl) cyclopropane-1-carboxylate (melting point = 110 ° C).

[alpha] _D = + 81 ° (C = 0.6%, benzene).

NMR Spectrum

Peak at 1.27-1.47 p.p. (hydrogen of a methyl group at 2-position of cyclopropane); Peak at 2.07p.p.m (hydrogen of methyl group at 3-position of alleletron); Peak at 4.83-5.33 p. P. (Hydrogen at 3 'position of cyclopropane, hydrogen at 1' position of the side chain and hydrogen of methylene group at 2 'position of allyl chain); Peak at 5.5-6.16 (Hydrogen at position 2 'of allyl chain; Peak at 5.15p.p.m (Hydrogen at position 4 of alletrone).

Cyclic, dichroic (dioxane)

Example 9

3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane-1-carboxylate (isomers A and B)

Ester with (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride 3-phenoxybenzyl alcohol in the presence of pyridine To give the following compounds.

a) Isomer of 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'.2'- tetrabromoethyl) cyclopropane- 1-carboxylate (A) (melting point = 90 ° C)

[alpha] _D = −106 ° (C = 0.5%, benzene).

NMR Spectrum

Peak at 0.92-1.37 ppm (hydrogen of methyl group at 2-position of cyclopropane); Peak at 1.67-0.08 ppm (hydrogen at positions 1 and 3 of cyclopropane); Peak at 5.08 ppm (hydrogen in methylene group of CO ₂ —CH ₂ ); Peak at 5.38 to 5.56 ppm (hydrogen at 1 position of ethyl group at 3 position of cyclopropane); Peak at 6.67-77.5 ppm (hydrogen of aromatic ring).

Cyclic dichroic (dioxane)

-10 at Δε = 218 mm

Isomer (A) has the highest mobility in thin layer chromatography.

b) Isomers of 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'.2'-tetrabromoethyl) cyclopropane-1-carboxylate (B).

[alpha] _D = + 61.5 ° (C = 2.3%, benzene).

NMR Spectrum

Peak at 1.22 to 1.42 ppm (hydrogen of methyl group at 2-position of cyclopropane); Peak at 1.67-0.08 ppm (hydrogen at positions 1 and 3 of cyclopropane); Peak at 4.93-5.33 ppm (hydrogen at 1 'position of the ethyl group at the 3 position of cyclopropane); Peak at 5.15 ppm (hydrogen of methylene group of CO ₂ CH ₂ ); Peak at 6.75 to 7.58 ppm (hydrogen of aromatic nucleus).

Cyclic dichroic (dioxane)

+4.6 at Δε = 247 mm

Example 10

(6) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (R, trans) 2, 2-dimethyl 3- (2 ', 2'- dichloro 1', 2'- dibromo Ethyl) cyclopropane-1-carboxylate

Step A: (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid

(1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid by minimal action on (1R, trans) 2,4-dimethyl 3- (2 A mixture of ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid, isomers (A) and (B) was obtained.

NMR Spectrum

Peak at 1.17-1.37 p. P. M (hydrogen of a methyl group at the 2-position of cyclopropane); Peak at 1.65-1.73 to 1.93-2.03 p.p. (peak at 1 position of cyclopropane); Peak from 4.23 to 4.45 to 4.45 to 4.62 p.m (hydrogen at the 1 'position of the ethyl group at the 3 position of cyclopropane).

Step B: (1R, trans 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride

By the action of thionyl chloride on the acid prepared in step A, (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane -1-carboxylic acid chloride was obtained.

I.R. Spectrum (chloroform)

Absorbed at 1777 cm ^-1

Step C: (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'- Dibromoethyl) cyclopropane-1-carboxylate

In the presence of pyridine, the chloride prepared in step (B) is esterified with (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-ol in the form of a mixture of isomers (A) and (B) ( S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl ) Cyclopropane-1-carboxylate was obtained.

NMR spectrum.

Peak at 1.30-1.34 p.m (hydrogen of a methyl group at 2-position of cyclopropane); Peak at 1.63-3.0 p.m (hydrogen at 1 and 3 positions of cyclopropane); Peak at 2.05p.p.m (hydrogen of methyl group at 3 position of alleletron); Peak (hydrogen of methylene group at 1'position of allyl body) at 1.95-3.03 p.p.m; Peak at 4.25 to 4.43 to 4.61 p. P. (Hydrogen at 1 'position of the ethyl group at the 3 position of the cyclopropane); Peak at 4.25 p.p. (hydrogen of methylene group at terminal position being allyl chain);

Peak at 4.83-5.41 p. P. (Hydrogen at 2 'position in the allyl chain); Peak at 5.83p.p.m (hydrogen at 4 position of alleletron).

Example 11

(RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxyl Rate

Step A: (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloromethyl) cyclopropane-1-carboxylic acid

11.8 grams of chlorine was introduced into 30 cc of carbon tetrachloride while bubbling at −15 ° C., and then dissolved in 37 cc of methylene chloride at −10 ° C. (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibro Solution of 24 grams of cyclopropane-1-carboxylic acid was added, stirred for 1 hour and a half at 0 ° C. and 2 hours at 25 ° C., concentrated under reduced pressure, and recrystallized with carbon tetrachloride (1R, cis). ) 7.4 grams of 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid were obtained (melting point = 134 ° C).

(Mixture of isomers (A) and (B)).

NMR Spectrum

Peaks (hydrogen of a methyl group at 2-position of cyclopropane) at 1.32-1.44 and 1.28-1.48 p.p.m; Peaks at 5.08-5.45 and 4.67-5.0 p.p.m (hydrogen at 1'position of the ethyl chain at 3-position of cyclopropane); Peak (hydrogen of carboxyl group) at 10.1 p.m.

Step B: (1R, cis) 2, 2-dimethyl 3- (2'2'-dibromo 1'-, 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride

By the action of thionyl chloride on the acid obtained in step A in the presence of pyridine, (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', used in the next step, 2'-dichloroethyl) cyclopropane-1-carboxylate was obtained.

Step C: (RS) -Cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1- Carboxylate

In the presence of pyridine, (RS) α-cyano 3-phenoxybenzyl alcohol is esterified with the acid chloride obtained in the above step to give (RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'- dibromo 1', 2'-dichloromethyl) cyclopropane-1-carboxylate (mixture of isomers (A) and (B)) was obtained.

NMR Spectrum

Peak at 1.23-1.52 p.m (hydrogen of a methyl group at 2-position of cyclopropane); Peak at 1.77-2.11 p.m (hydrogen at 1 and 3 positions of cyclopropane); 4.72-4.88 and 5.02-5.21 p.m peaks (hydrogen at the 1 'position of the ethyl side chain at the 3 position of cyclopropane); Peak at 6.40-6.43 p.m (hydrogen bond by the same carbon atom as C≡N); Peak (hydrogen in aromatic ring) at 6.94-77.6 p.p.m.

Example 12

(S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'- dibromo 1', 2'-dichloro Ethyl) cyclopropane-1-carboxylate

The acid chloride obtained in the step (B) of Example 11 was esterified with (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-ol, and (S) 1-oxo 2-allyl 3-tyl. Cyclopent-2-en-4-yl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate ( Mixtures of isomers (A) and (B)) were obtained.

NMR Spectrum

Peaks (hydrogen of a methyl group at 2-position of cyclopropane) at 1.25-1.45 and 1.29-1.40 p.p.m; Peak at 1.96p.p.m (hydrogen of the titanium group at the 3-position of the allertron); Peak (hydrogen of methylene group at 1'position of allyl chain) at 2.96-3.03 p.m; Peak at 4.83-5.16 p. P. (Hydrogen in terminal methylene group of allyl chain) peak at 5.25-5.36 p. P. M (hydrogen at 1 'position of ethyl chain at 3-position of cyclopropane); Peak at 5.5-6.9 p.m (hydrogen at 4 position of alleletron and hydrogen at 2 'position of allyl chain).

Example 13

(RS) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2'-2'-dibromo 1 ', 2'-dichloroethyl) cyclopropane-1-carboxyl Rate.

(1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-converted to an acid chloride by the action of thionyl chloride by the action of chlorine by carboxylic acid (1R , Trans) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid was obtained.

Subsequently, they were esterified with (RS) alpha -cyano 3-phenoxybenzyl alcohol as described above to obtain (RS) alpha -cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1 ', 2'-dichloroethyl) Cyclopropane- 1-carboxylate (a mixture of isomers (A) and (B)) was obtained.

NMR Spectrum

Peak at 1.22-1.27-1.37-1.4-1.45 p.m (hydrogen of methyl group at 2-position of cyclopropane); Peak at 1.67-2.5 p.m (hydrogen at positions 1 and 3 of cyclopropane); Peak at 2.67-4.5 p.m (hydrogen at the 1 'position of the ethyl chain at the 3-position of the cyclopropane); Peak at 6.52p.p.m (hydrogen bond by the same carbon atom as C≡N); Peak (hydrogen of aromatic ring) at 7.0-77.6 p.m.

Example 14

(S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-di Bromoethyl) cyclopropane-1-carboxylate.

Step A: (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid:

In a manner similar to that described above, by the action of cancellation on (1R, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane-1-carboxylic acid, but not -60. (1R, trans) 2, 2-dimethyl 3- (2 ', 2'- difluoro 1', 2'- dibromoethyl) cyclopropane- 1-carboxylic acid was obtained by operation at degreeC (melting point = 122 ° C.).

(Mixture of isomers (A) and (B)).

NMR Spectrum

Peak at 1.33-1.36 p. P. (Hydrogen of a methyl group at the 3-position of cyclopropane); Peak (hydrogen at 1 and 3 positions of cyclopropane) at 1.60-2.23 p.m; Peak at 3.75-4.37 p.p.m (hydrogen at 1 'position of the ethyl chain at the 3 position of cyclopropane); Peak (hydrogen of carboxyl groups) at 10.96 p.m.

Step B: (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid:

(1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'- used in the next step by the action of thionyl chloride on the acid obtained in step A above. Dibromoethyl) cyclopropane-1-carboxylic acid chloride was obtained.

Step C: (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-yl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2 '-Dibromoethyl) cyclopropane-1-carboxylate

The acid chloride obtained in the step (B) is esterified with (S) 1-oxo 2-allyl 3-methylcyclopent-2-ene 4-ol in the presence of pyridine to give (S) 1-oxo 2-allyl 3-methylcyclone. Pent-2-en-4-yl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'- difluoro 1', 2'- dibromoethyl) cyclopropane-1-carboxylate (A mixture of isomers (A) and (B)) was obtained.

NMR Spectrum

Peak at 1.32p.p.m (hydrogen of methyl group at 2-position of cyclopropane); Peaks at 3.26-1.68 and 1.73-2.19 p.m (peak at 1 position of cyclopropane); Peak (hydrogen of methyl group at position 3 of alleletron) at 1.20 p.m; Peak at 2.93 to 3.05 p.m (hydrogen of methylene group at 1'position of allyl chain); Peak (hydrogen of the terminal methylene group of allyl chain) at 4.83-5.25 p.m; Peak at 3.58 to 4.33 p. P. (Hydrogen at 1 'position of the ethyl chain at the 3 position of cyclopropane); Peak at 4.83-5.25 p.m (hydrogen at 2'position of the allyl chain); Peak at 5.83p.p.m (hydrogen at 4 position of alleletron).

Example 15

(RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Rate

Steps: (1R, cis) 2, 2-Dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid.

(1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane- 1-by act of cancellation of carboxylic acid (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid (a mixture of isomers (A) and (B)) was obtained.

NMR Spectrum

Peak at 1.26-1.30 and 1.41-1.42 p.p. (hydrogen of methyl group at 3-position of cyclopropane) peak at 1.83-2.17p.p.- (hydrogen at position 1 and 3 of cyclopropane); Peak at 4.83-5.58 p.m (hydrogen at 1'-position of ethyl group at 3-position of cyclopropane); Peak (hydrogen of carboxyl group) at 8.17 p.m.

Step B: (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride.

This was obtained by the action of thionyl chloride on the acid obtained in step A above.

Step C: (RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1 -Carboxylates.

The acid chloride obtained in step (B) above in the presence of pyridine was esterified with (RS) α-cyano 3-phenoxybenzyl alcohol (a mixture of isomers (A) and (B)) to obtain this.

Example 16

(RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- tetrabromoethyl) cyclopropane-1-carboxylate .

Step A: (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride.

(1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) in a mixture of 40 cc of petroleum ether (melting point, 35-70 ° C) and 10 cc of thionyl chloride 8.9 grams of cyclopropane-1-carboxylic acid was introduced and refluxed, the reflux was maintained for 3 hours, and petroleum ether and excess thionyl chloride were removed by distillation to give crude (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride was obtained.

Step B: (RS) 2-Cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1- Carboxylates.

7 g of α-cyano 3-phenoxybenzyl alcohol was introduced into a mixture of 5 cc of benzene and 10 cc of pyridine, and the crude acid chloride obtained in the above step A, dissolved in 40 cc of benzene at 0 ° C. for about 15 minutes, was added. After stirring for 16 hours at < RTI ID = 0.0 > C, < / RTI > acidified with dilute hydrochloric acid solution to pH 1, extracted with benzene, the organic phase was washed with water, dried over magnesium sulfate, concentrated to benzene solution until drying and the residue Chromatography with silica gel developing with benzene to give (RS) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl 7.33 grams of cyclopropane-1-carboxylate were obtained.

Analysis: C ₂₂ H ₁₉ O ₃ NBr ₄ (665.05)

Calculated Value: C 39.73% H 2.88% N 2.10% Br 48.06%

Found: 39.7 3 2.2 47.4

I.R spectrum (chloroform)

Absorption at 1743 cm ^-1 , characteristics of a carbonyl group; 1613, 1588, 1477cm- ¹ Absorption, the characteristic of the aromatic nucleus.

V. V spectrum (ethanol)

NMR Spectrum (Tuterochloroform)

Characteristic of hydrogen of a peak and a pair of methyl groups at 1.23-1.5 p.p.m; The properties of hydrogen in peaks and cyclopropyl at 1.83-2.16 p.m; The properties of hydrogen at the 1-position of the peak substituted ethyl side chain at 4.82-5.5 p. P.m; Peak at 6.37-6.42 p.m (characteristic of hydrogen attached to the same carbon atom as -C≡N group); Characteristics of sorghum of peaks and aromatic rings at 6.83-7.58 p.p.m.

(1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid used in step A can be prepared by the following method. have.

5 g of (1R, cis) 2,2-dimethyl 3- (2'2'-dibromovinyl) cyclopropane-1-carboxylic acid was introduced into 30 cc of carbon tetrachloride, and dissolved in 10 cc of carbon tetrachloride for about 30 minutes or more. A solution of 0.9 cc of bromine was introduced, stirred for 1 hour 30 minutes, concentrated to dryness under reduced pressure, and coarse (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- 8 and 9 grams of tetrabromoethyl) cyclopropane-1-carboxylic acid were obtained.

Example 17

3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- tetrabromoethyl) cyclopropane-1-carboxylate

To 20 cc of benzene (1R, trans) 2, 2-dimethyl 2- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride and 5 grams of 3-phenoxybenzyl 2.4 grams of alcohol was dissolved, cooled to 0 ° C., 4cc of pyridine was slowly introduced, stirred at 20 ° C. for 48 hours, the reaction mixture was decanted into aqueous hydrochloric acid solution, extracted with benzene and then sodium bicarbonate, followed by Washed with water, dried over sodium sulfate and concentrated to dryness under reduced pressure. Chromatography with silica gel developing with a mixture of petroleum ether (boiling point, 35-75 ° C.) and ethyl ether (9/1) yielded 6.2 grams of residue. 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3.68 grams of 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylate (mixture of isomers A and B) were recovered.

Analysis: C ₂₁ H ₂₀ Br ₄ O ₃ (640.03)

Calculated Value: C 39.41% H 3.15% Br 49.94%

Found: 39.9 3.2 50.2

I.V spectrum (chloroform)

Absorption at 1728cm- ¹ , the characteristic of a carbonyl group, absorption at 1615-159-1490cm- ¹ , and the characteristic of an aromatic nucleus.

NMR Spectrum (Duterochloroform)

Characteristics of hydrogen of a pair of methyl groups at 1.26-1.29-1.35 p.p.m; The hydrogen at the 1-position of the peak and cyclopropyl at 2.00-2.23 p.m; Hydrogen at the 3-position of the peak and cyclopropyl at 1.70-1.79 p.p.m; Peak at 4.31-4.48-4.50-4.67 p.m, and hydrogen properties at the 1 ′ position of the substituted ethyl side chain; Characteristic of hydrogen of methylene of peak and benzyl group at 5.17-5.20 p.m; Characteristics of hydrogen in peaks and aromatic rings at 6.92-77.5 p.p.m.

The (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride used at the beginning of this example is as follows. Can be obtained.

Step A: (1R, trans) 2, 2-Dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid.

Canceling was reacted with (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid in a similar manner to that described in Example 16 (1R, trans S) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetra bromoethyl) cyclopropane-1-carboxylic acid (mixture of isomers A and B) was obtained.

NMR Spectrum (Duterochloroform)

Peak at 1.30-1.40 p. P. M (hydrogen of a methyl group at 2-position of cyclopropyl);

Peaks (hydrogen at 1 and 3 positions of cyclopropyl) at 1.65-1.74 and 1.97-2.37 p.p.m;

Peaks (hydrogen at 1'position of ethyl) at 4.30-4.76 and 4.47-4.65 p.

Peak (hydrogen of carboxyl group) at 9.63 p.m.

Step B: (1R, trans) 2, 2-Dimethyl 3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylic acid chloride.

In a similar manner to that described in Example 16, thionyl chloride was reacted with the acid obtained in step A to (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrabro Mother ethyl) cyclopropane-1-carboxylic acid chloride was obtained.

Example 18

3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- tetrachloroethyl) cyclopropane-1-carboxylate

Step A: (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid

Foamed with chlorine until dissolved in 30 cc of carbon tetrachloride (dissolved 11.8 grams of chlorine) and dissolved in 40 cc of methylene chloride or the like at (1R, cis) 2,2-dimethyl 3- (2 ', 2) A solution of 16.7 grams of '-dichlorovinyl) cyclopropane-1-carboxylic acid was introduced for about 30 minutes or more, stirred at 0. C for 24 hours, and the temperature of the reaction mixture was increased to + 25 ° C. After stirring for 3 hours, foaming was carried out in the presence of nitrogen to remove excess chlorine, concentrated under distillation under reduced pressure, and then chromatographed with silica gel, which was developed with a mixture of cyclohexane and ethyl acetate (8/2). Water was purified and crystallized from petroleum ether (boiling point, 35-75 ° C.) to give (1R, cis) 2,2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane 3.14 grams of -1-carboxylic acid (melting point = 144 ° C.) were obtained.

Analysis: C ₈ Cl ₄ O ₂ (279.98)

Calculation: C 34.3% H 3.6% Cl 50.6%

Found: 34.4 3.7 50.3

NMR Spectrum (Duterochloroform)

Peaks at 1.26 to 1.42 and 1.30 to 1.42 p.m (characteristic of hydrogen of a pair of methyl groups);

Peak at 4.67-5.17 p.m and 5.08-5.43p.m, the nature of hydrogen at the 1 'position of the substituted ethyl side chain;

The characteristics of hydrogen of the peak and cyclopropyl at 1.67-2.0 p.p.m;

Characteristics of hydrogen in peaks and carboxyl at 10.2 p.m.

Step B: (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid chlorolide

(1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclo in a mixture of petroleum ether (boiling point, 35-70 ° C) 60 and thionyl chloride 8.6 cc 6.75 grams of propane-1-carboxylic acid was introduced and the reaction mixture was refluxed, left for 4 hours and 30 minutes, concentrated under distillation under reduced pressure, benzene was added and concentrated to dryness in the next step. Crude (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- tetrachloroethyl) cyclopropane-1-carboxylic acid chloride to be used was obtained.

Step C: 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate

The crude acid chloride was dissolved in 60 cc of benzene, a solution of 5.2 grams of 3-phenoxybenzyl alcohol dissolved in 50 cc of benzene at 75 ° C. was introduced, followed by 2.6 cc of pyridine, stirred at 20 cc for 16 hours and the reaction mixture was watered. After inclining to a mixture with hydrochloric acid, extracted with ethyl ether, the ethereal solution was concentrated to dryness, and then eleven grams of the residue was chromatographed with silica gel, which was developed with a mixture of benzene and cyclohexane (1/1). And ether were obtained to obtain 4.6 grams of the first fraction of 3-phenoxybenzyl (1R, cis) cyclopropane-1-carboxylate (melting point = 86 ° C).

＝－86.5°(C＝0.5%, 벤젠)

= -86.5 ° (C = 0.5%, benzene)

Analysis: C ₂₁ H ₂₀ Cl ₄ (462.20)

Calculation: C 54.56% H 4.36% Cl 30.68%

Found: 54.9 4.5 30.3

U.V spectrum (ethanol)

NMR Spectrum (Duterochloroform)

Peak at 1.27 to 1.4 p.m (characteristic of hydrogen of a pair of methyl groups of isomer A);

기의 수소의 특성);Peak at 5.13 ppm, of isomer A

The properties of hydrogen of the group);

Peak at 5.27-5.43 p. P., And characterization of hydrogen at the 1 'position of the ethyl side chain of isomer A;

The peak, the properties of hydrogen of a pair of methyl groups of isomer B at 1.23-1.40p.p.m,

기의 수소의 특성;Peak at 5.18 ppm, of isomer B

The nature of the hydrogen of the group;

The peak at 4.83-5.17 p.m, the properties of hydrogen at the 1 'position of the ether side chain of isomer B,

Characteristic of hydrogen of peak and cyclopropyl at 1.61-2.03p.p.m,

Characteristic of hydrogen of peak, aromatic nucleus at 6.92-77.5p.p.m,

This N.M.R spectrum shows that the compound contains about 9/10 isomers and 1/10 isomer B.

Chromatography was continued, and after recrystallization with ether, 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1- 3.3 grams of carboxylate (melting point = 62 ° C) were obtained.

＝－9°(C＝1%, 벤젠).

= -9 degrees (C = 1%, benzene).

I.R spectrum (chloroform)

Absorption at 1725 cm- ¹ , properties of carbonyl group, absorption at 1615-1590-1490 cm- ¹ , and properties of hydrogen in aromatic nuclei.

N.M.R spectrum (deuterochloroform)

Peak at 1.23-1.41 p. P.m (peak at 4.83-5.17 p.p.m of hydrogen in a pair of methyl groups of isomer A (characteristic of hydrogen at the 1 'position of the ethyl side chain of isomer B));

기의 수소의 특성);Peak at 5.2 ppm (of isomer B

The properties of hydrogen of the group);

Peak at 1.22 to 1.4 p.m (characteristic of hydrogen in a pair of methyl groups of isomer A);

Peak at 5.27 to 5.4 p.m (characteristic of the hydrogen at the 1 'position of the ethyl side chain of isomer A);

기의 수소의 특성);Peak at 5.13 ppm (of isomer A

The properties of hydrogen of the group);

Peak (characteristic of hydrogen in cyclopropyl) at 1.58 to 2.08 p.p.m;

Peak at 6.9–7.16 p.m (characteristic of hydrogen in aromatic nucleus).

This N.M.R spectrum shows that the compound contains about 3/5 isomers B and 2/5 isomers A.

Example 19

(RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- tetrachloroethyl) cyclopropane-1-carboxylate

Step A: (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid chloride

5.4 grams of the corresponding (1R, cis) acid were used and operated in a similar manner as used in step B of Example 18.

Step B: (RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-cara Carboxylate

The acid chloride obtained in step A of this example was dissolved in 50 cc of benzyl, a solution of 4.6 grams of (RS) α-cyano 3-phenoxybenzyl alcohol dissolved in 30 cc of benzyl at + 5 ° C was introduced, followed by 2.2 cc of pyridine. Introduced, stirred at ambient temperature for 48 hours, the reaction mixture was inclined to a mixture of water and hydrochloric acid, extracted with ether, the ethereal solution was concentrated to dryness, and the residue was purified from benzyl and cyclo nucleic acid ( Chromatographic purification with silica gel developing with a mixture of 1/2), (RS) alpha -cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 4.7 grams of 1'-tetrachloroethyl) cyclopropane-1-carboxylate was obtained.

＝－56.5°(C＝0.4%, 벤젠).

= -56.5 ° (C = 0.4%, benzene).

Assay: C ₂₂ H ₁₉ Cl ₄ NO ₃ (487.22)

Calculated Value: C% 54.23 H% 3.93 Cl% 29.11 N% 2.87

Found 54.3 3.8 29.0 2.8

U.V spectrum (ethanol)

N.M.R spectrum (deuterochloroform)

Peak at 1.22-1.43 p.p.m (characteristic of hydrogen in a pair of methyl groups);

Peak at 1.67 to 2.08 p.m (characteristic of hydrogen of cyclopropyl group);

Peak at 4.83-66.4 p.m (characteristic of hydrogen at 1 ′ position of the substituted ethyl side chain);

Peak at 6.32-66.4 p.m (characteristic of hydrogen bound to the same carbon atom as the CN group);

Peak at 6.92-77.5 p.p.m (characteristic of hydrogen in aromatic nuclei).

Example 20

(RS) Alleletron (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate

Step A: (1R, Cis) 2, 2-Dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid chloride.

It was prepared as in step 18, starting with 7 grams of the corresponding (1R, cis) acid.

Step B: (RS) Alleletron (1R, cis) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate.

＝－54.7°(C＝0.5%, 클로로포름).The acid chloride obtained in step A of this example was dissolved in 20 cc of benzene, a solution of 4 grams of alleletron dissolved in 15 cc of benzene at + 5 ° C was introduced, followed by the introduction of 2.5 cc of pyridine and stirred at 20 ° C for 18 hours. It was then inclined to a mixture of water and hydrochloric acid, extracted with ether, the ethereal solution was concentrated to dryness, and the chromatography of silica gel developed as a mixture with cyclohexane and ethyl acetate (9/1). This purification gave 8 grams of (RS) alleletron (1R, cis) 2,2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate. did.

= -54.7 ° (C = 0.5%, chloroform).

Analysis: C ₁₇ H ₂₀ Cl ₄ O ₃ (414.15)

Divided Value: C% 49.30 H% 4.87 Cl% 34.24

Found: 49.5 4.9 34.1

U.V spectrum (ethanol)

.Up to 227mm

.

N.M.R spectrum (deuterochloroform)

Peak at 1.31 to 1.42 p.m (characteristic of hydrogen of a pair of methyl groups);

Peak at 1.67-2.17 p.m (characteristic of hydrogen in cyclopropyl group);

Peak at 4.83-6.17 p.m (characteristic of hydrogen at 1 'position of the substituted ethyl side chain).

Example 21

(RS) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'- tetrachloroethyl) cyclopropane-1-carboxylate

Step A: (1R, trans) 2,2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid

13.25 grams of chlorine was dissolved in 30 cc of carbon tetrachloride at -10 ° C and dissolved in 30 cc of methylene chloride (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid 18.8 grams of the dissolved solution is added to the reaction vessel for at least 15 minutes, and the reaction vessel is equipped with a cooling capacitor (circulating liquid at -60 ° C) to concentrate unreacted chlorine, and then -10 ° C for 1 hour 30 minutes. The mixture was stirred at 0 ° C. for 1 hour 30 minutes, foamed in the presence of nitrogen to remove excess chlorine at 20 ° C., concentrated to dryness under reduced pressure, and the residue was concentrated with cyclohexane / ethyl acetate (7/3). Chromatographic purification with silica gel developing with a mixture of (1R, trans) to give 23 grams of 2,2-dimethyl 3- (2'2'2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid And use it in the next step.

Step B: (1R, trans) 2, 2-Dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylic acid chloride.

12.276 grams of the acid obtained in step A was introduced into a mixture of 30 cc of petroleum ether (boiling point 35-75 °) and 16 cc of thionyl chloride, and refluxed, and the reflux was maintained for 4 hours 30 minutes, and then distilled to dryness under reduced pressure. Concentrated, benzene was added, and then concentrated to the next drying (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-cara An acid chloride is obtained, which is used in the next step.

Step C: (RS) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-cara Carboxylate.

25 cc of benzene was added to the acid chloride obtained in step B of this example, and a solution of 10.5 grams of (RS) α-cyano 3-phenoxybenzyl alcohol dissolved in 20 cc of benzene was quickly added at + 5 ° C, and pyridine 4.5 was added. After rapid introduction of cc and stirring at 20 ° C. for 16 hours, the reaction mixture was decanted into a mixture of water and hydrochloric acid, extracted with ethyl ether, the ether phase was washed with water, dried and distilled under reduced pressure. It was concentrated to dryness and dried (RS) alpha -cyano 3-phenoxybenzyl (1R, trans) 2, 2- dimethyl 3- (2 ', 2', 2 ', 1'- tetrachloroethyl) cyclopropane- 14.18 grams of 1-carboxylate were obtained.

＝－22.5°(C＝0.5%, 벤젠)

= -22.5 ° (C = 0.5%, benzene)

Analysis: C ₂₂ H ₁₉ Cl ₄ NO ₃ (487.21)

Calculation: C 54.2% H 3.9% N 2.9% Cl 29.1%

Found: 54.0 4.0 2.7 29.0

R I. Spectrum (Chloroform)

Absorption at 1742 cm ^-1 , characteristics of a carbonyl group; 1610, 1584, 1484 cm ^-1 Absorption, characteristic of aromatic nucleus.

U.V spectrum (ethanol)

NMR Spectrum (Duterochloroform)

The characteristics of hydrogen in the peak and methyl groups at 1.22-1.42 p.m;

The characteristics of hydrogen of a peak and a cyclopropyl group at 1.50-2.50 p.m;

Peak at 3.66-4.11 p. P.m, characteristic of hydrogen at the 1 'position of the side chain;

Characteristics of hydrogen bonded by carbon at 2-position of peak, -C≡N at 6.5p.p.m

Characteristics of peak and aromatic nucleus at 7.00-77.6 p.p.m.

Example 22

3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate

Step A: (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetra chloroethyl) cyclopropane-1-carboxylic acid chloride

Starting with 10.4 grams of acid and operating in the same manner as described in Example 21, a solution of the acid chloride dissolved in 30 cc of benzene was added to obtain 37.2 cc of a benzene solution of acid chloride.

Step B: 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate

A solution of 4 grams of 3-phenoxybenzyl alcohol dissolved in 15 cc of benzene in 18.6 cc of the acid chloride solution obtained in step A was added at 0 ° C, and 2 cc of pyridine was added, followed by stirring at 20 ° C for 18 hours. The reaction mixture was inclined to a mixture of water, ice and hydrochloric acid, then washed with ethyl ether, the organic phase was washed with water, dried over magnesium sulfate, filtered and concentrated to distillation under reduced pressure to give a residue (8.6). Gram) was purified by chromatography on silica gel which developed with a mixture of cyclohexane and ethyl acetate (95/5) and then a mixture of cyclohexane and benzene (5/5).

Analysis: C ₂₁ H ₂₀ Cl ₄ O ₃ (462.20)

Calculation: C 54.6% H 4.4% Cl 30.7%

Found: 55.2 4.5 29.4

I. R spectrum (chloroform)

Absorption at 1728cm- ¹ , characteristics of C = 0, absorption at 1615-1587cm- ¹ , and characteristics of hydrogen in the aromatic nucleus;

U.V spectrum (ethanol)

N.M.R Spectrum (Tuterochloroform)

Peaks at 1.19-1.33 p.p.m and properties of hydrogen in a pair of methyl groups;

The characteristics of the hydrogen of the peak and cyclopropyl group at 1.66-2.25 p.p.m;

Peak at 4.0-4.41 p. P. M, hydrogen character at 1 'position of the substituted ethyl side chain;

Characteristic of the methylene group of the peak, benzyl group at 5.18 p.m;

Characteristics of hydrogen in peaks and aromatic nuclei at 6.83-77.6 p.p.m.

Example 23

(S) Alleletron (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate

Step A: (1R, trans) 2, 2-Dimethyl 3- (2 ', 2', 2 ', 1'-tetra chloroethyl) cyclopropane-1-carboxylic acid chloride.

It was prepared in the same manner as described in step B of Example 21, starting with 10.4 grams of the corresponding (1R, trans) acid.

Step B: (S) Alleletron (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane-1-carboxylate

The acid chloride obtained in step A of this example was dissolved in 30 cc of benzene to obtain 37.2 cc of acid chloride (solution A).

After cooling 18.6 cc of solution, a solution of 3.2 grams of (S) alleletron dissolved in 15 cc of benzene was added thereto (+ 5 ° C.), stirred, and 2 cc of pyridine was added, followed by stirring at 20 ° C. for 16 hours. The reaction mixture was decanted onto a mixture with water, ice and hydrochloric acid, extracted with ether, concentrated under distillation under reduced pressure, and chromatographed with silica gel developed into a mixture with cyclohexane and ethyl acetate (80/10). (S) Alleletron (1R, trans) 2, 2-dimethyl 3- (2 ', 2', 2 ', 1'-tetrachloroethyl) cyclopropane- 1-carboxylate (melting point = 85 degreeC) 4.56 grams were obtained.

Analysis: C ₁₇ H ₂₀ Cl ₄ O ₃ (414.16)

Calculation: C 49.3% H 4.8% Cl 34.2%

Found: 49.0 4.8 35.5

I.R spectrum (chloroform)

Absorption at 1710 cm ^-1 and 1730 cm ^-1 , characteristics of the C = 0 group; Absorption at 1655 and 1538 cm ^-1 , characteristics of C = C group, absorption at 918, 922 cm ^-1 , characteristics of -C = CH ₂ group.

U.V spectrum (ethanol)

＝357);Maximum at 227-228 mm

= 357);

＝8).At 278 mm (

= 8).

N.M.R spectrum (Tuteros spectrum).

Peak at 1.32-1.37 p.p.m, and the properties of hydrogen in a pair of methyl groups;

Peak at 2.08 p.

The characteristics of hydrogen in the methylene group of the allyl chain of the alleletron adjacent to the peak and the ring at 2.98-3.08 p.p.m;

The peaks at 4.12-4.23 and 4.28-4.39 p.p.m, and the properties of hydrogen at the 1 'position of the substituted ethyl side chain;

Characteristics of terminal methylene of allyl chain of peak and alleletron at 4.83-5.25 p.m;

Peak to 5.5-16.1p.p.m, hydrogen attached to carbon atoms at 1 'position of alleletron and hydrogen in carbon at position A of the allyl chain of alleletron.

Example 24

3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2'- dibromo 2', 2'-dichloroethyl) cyclopropane-1-carboxylate

4.65 grams and 3- of 2-, 2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane-1-carboxylic acid dissolved in 20 cc of benzene Pyridine 4cc was slowly added to a solution of 2.40 grams of phenoxybenzyl alcohol at 0 ° C., stirred for 17 hours, the reaction mixture was inclined to an aqueous solution of hydrochloric acid, extracted with benzene, and the organic phase was saturated with a saturated solution of sodium bicarbonate. Washed, then washed with water, dried over magnesium sulfate, concentrated to distillation under reduced pressure, and then the residue was mixed with petroleum ether (boiling point 35-75 ° C.) and ethyl ether (9/1). Chromatography with developing silica gel 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane-1-carboxyl The rate (mixture of the isomers A and B) (melting point = 75 degreeC) was obtained.

Analysis: C ₂₁ H ₂₀ B ₁₂ Cl ₂ O ₃ (551.11)

Calculated Value: C 45.76% H 3.65% Br 29.0% Cl 12.86%

Found: 45.8 3.6 28.5 12.9

I.R spectrum (chloroform)

Absorption at 1725 cm ^-1 and characteristics of a carbonyl group; Absorption and characteristic of an aromatic nucleus at 1615-1590-1942cm- ¹ .

N.M.R Spectrum (Tuterochloroform)

Characteristics of peaks and hydrogen in a pair of methyl groups at 1.25-1.37 and 1.22-1.39 p.p.m.

The characteristics of the hydrogen of the peak and cyclopropyl at 1.75-2.17 p.p.m;

The properties of hydrogen in methylene of the peak and benzyl groups at 5.1-5.14 p.p.m;

Characteristics of hydrogen at the 1 'position of the peak, substituted ethyl side chain at 5.0-5.22 and 5.35-5.23 p.m

Characteristics of hydrogen in peaks and aromatic nuclei at 6.83 to 7.59 p.p.m.

N.M.R spectrum shows that this compound consists of 2/3 isomer A and 1/3 isomer B.

In addition to those described in Example 15 (1R, cis) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride ( 1R, cis) 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid, starting with the method described in Example 16, can be prepared.

Example 25

(S) Alleletron (1R, cis) 2, 2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane-1-carboxylate

Step A: (1R, cis) 2, 2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride

(1R, cis) 2, 2-dimethyl 3- (1 ', 2'-dibromo-2', 2'-dichloroethyl) cyclopropane-1-carboxylic acid starting from 3.6 grams and used in Example 24 In a similar manner to the above, 4 grams of acid chloride was obtained.

Step (B): (S) alleletron (1R, cis) 2, 2-dimethyl 3- (1 ', 2'-dibromo-2', 2'-dichloroethyl) cyclopropane-1-carboxyl Rate

4 grams of the acid chloride obtained in the previous step (A) of benzene 40 cc and 1.75 grams of (S) alleletron were dissolved, a mixture of 2 cc pyridine and 2 cc benzene was introduced at 0 ° C., and stirred at 20 ° C. for 24 hours. The reaction mixture was decanted into a mixture with water, ice and hydrochloric acid and then extracted with benzene, the organic phase was washed with saturated aqueous sodium bicarbonate solution and then with water, dried over sodium sulfate and then distilled off under reduced pressure. Concentrate and chromatograph this residue (5.1 grams) with silica gel, which is developed with a mixture of benzene and ethyl acetate (97/3) to give (S) alleletron (1R, cis) 2, 2-dimethyl 3- (1 4.25 (gram) of ', 2'- dibromo 2', 2'- dichloroethyl) cyclopropane- carboxylate were obtained.

Analysis: C ₁₇ H ₂₀ Br ₂ Cl ₂ O ₃ (503.07)

Calculated Value: C 40.58% H 4.0% Br 31.76% Cl 14.09%

Found: 41.3 4.1 31.0 14.2

I.R spectrum (chloroform)

Absorption at 1718 cm- ¹ , characteristics of C = 0 groups; 1655, absorption at 1638 cm ^-1 , characteristics of the C = C group; Absorption at 918-997 cm ^-1 , characteristics of -CH = CH ₂ group.

N.M.R spectrum (tuterochloroform)

The characteristics of the peak, hydrogen of a pair of methyl groups at 1.25-1.28 and 1.39-1.42 p.p.m;

Peak at 1.95 to 2.07 ppm, and the properties of hydrogen in the methyl group at the 3 ¹ position of alleletron;

The properties of hydrogen in the terminal methylene group of the allyl side chain of the peak and alleletron at 4.83-66.1 p.m;

Peak at 4.83-6.17p.p.m, characteristic of hydrogen at 1'position of the substituted ethyl side chain;

Peak at 5.75 p.m, characteristic of hydrogen at 4 'position of alleletron.

Example 26

5-Benzyl 3-furylmethyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'- dibromoethyl) cyclopropane-1-carboxylate.

Step A: (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromo ethyl) cyclopropane-1-carboxylic acid chloride.

This was used in Example 24 starting with (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromo ethyl) cyclopropane-1-carboxylic acid Prepared in a similar reaction to that.

Step B: 5-Benzyl 3-furylmethyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromo ethyl) cyclopropane-1-carboxylate.

The acid chloride obtained in step A was dissolved in benzene to obtain 27 cc of acid chloride solution (solution A).

To a solution of 2.9 grams of 5-benzyl 3-furylmethyl alcohol dissolved in 15 cc of benzene, 12 cc of acid solution A was introduced into the solution, cooled to 0 ° C., then 3 cc of pyridine was introduced and stirred at 20 ° C. for 48 hours. The reaction mixture was inclined to a mixture of hydrochloric acid and ice, extracted with benzene, treated in a conventional manner, and then distilled and concentrated to dryness. Chromatography of silica gel that develops the residue into a mixture of petroleum ether (boiling point, 35-75 °) and ether (95/5), followed by a mixture of petroleum ether (boiling point, 35-75 ° C.) and ether (9/1). Purified with 5-benzyl 3-furylmethyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate 2.2 Gram was obtained.

＝－57.5°(C＝0.4%, 벤젠)

－-57.5 ° (C = 0.4%, benzene)

Analysis: C ₂₀ H ₂₀ Br ₂ Cl ₂ O ₃ (539.104)

Calculated Value: C 44.56 H 3.74 Br 29.04 Cl 13.15

Found: 44.9 3.8 29.1 13.3

U.V spectrum (ethanol)

＝20); 264mm에서 굴절(

＝11);Refraction at 252 mm (

= 20); Refraction at 264 mm (

= 11);

＝15); 268mm에서 굴절(

＝9).Refraction at 258 mm (

= 15); Refraction at 268 mm (

= 9).

IR spectrum (chloroform)

Absorption at 1720 cm- ¹ , characteristics of carbonyl group, absorption at 1100, 1522, 1493 cm- ¹ , characteristics of aromatic nucleus and -C = C- group.

NMR Spectrum (Duterochloroform)

The properties of hydrogen in the methyl group at the 2-position of the peak and cyclopropyl at 1.23-1.35 and 1.20-1.38 p.p.m;

The properties of hydrogen in the peak and cyclopropyl groups at 1.67-2.17 p.p.m;

The properties of hydrogen in methylene of the peak, benzyl group at 3.93 p.m;

The nature of hydrogen bound by carbon adjacent to the peak, carboxyl group at 4.93-5.0 p.p.m;

Peak at 6.02-6.1 p.m, and hydrogen properties at the 3-position of the furan core;

The peaks at 4.83-5.16-55.33-p8m, and the properties of hydrogen at the 1 'position of the ethyl side chain;

Characteristic of the hydrogen in the peak, phenyl group at 7.3 p.m;

Peak at 7.37 p.m and characteristics of hydrogen at position 5 of the furan core.

Example 27

3, 4, 5, 6-tetrahydrophthalideidomethyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'- dibromoethyl) cyclopropane-kaa Carboxylate.

Step A: (1R, cis) 2, 2-Dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-carboxylic acid chloride.

This is similar to that used in Example 24, starting with 10 grams of (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-carboxylic acid. Prepared by the method.

Step B: 3, 4, 5, 6-tetrahydrophthalimidomethyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro-1', 2'-dibromoethyl) cyclo Propane-carboxylate.

The acid chloride obtained in the above step A was dissolved in benzene to obtain 27 cc of a benzene solution (solution A), and in a solution in which 1.4 g of benzene 15 cc -3, 4, 5, 6-tetrahydrophthalimido and 1.4 grams of methyl alcohol were dissolved. 7.5 cc of acid chloride solution A was introduced, followed by 2 cc of pyridine at 0 ° C., stirred at 20 ° C. for 36 hours, the reaction mixture was inclined to a mixture with water, ice and hydrochloric acid, extracted with benzene, and then the organic phase was extracted. Washed with a saturated aqueous solution of sodium bicarbonate, followed by water, dried over sodium sulfate, distilled under reduced pressure, concentrated to dryness and the residue was evaporated into a mixture of benzene and ethyl acetate (9/1). Purification by chromatography. Thus, 3, 4, 5, 6-tetrahydrophthalimidomethyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-kaa 1.89 grams of carboxylate were obtained.

＝－53.5°(C＝0.98%, 벤젠).

= -53.5 ° (C = 0.98%, benzene).

Analysis: C ₁₇ H ₁₉ Br ₂ Cl ₂ NO ₄ (532.07)

Calculated Value: C 38.37 H 3.6 N 2.63 Br 30.03 Cl 13.32

Found: 39.0 3.6 2.6 28.3 12.7

IR spectrum (chloroform)

Absorption at 1778-1735-1723 cm ^-1 and characteristics of carbonyl group;

Absorption at -1665cm ^-1 , Characteristics of -C = C group

NMR Spectrum (Duterochloroform)

Peaks at 1.21-1.22-1.39 p.m and characteristics of hydrogen in a pair of methyl groups,

Characteristics of the hydrogen in the methyl group at the α position of the peak and the cyclopropyl group at 1.67-1.83 p.p.m and the -C = C group;

Peak at 2.37 p.p.m, and the characteristics of the methylene group at the α position of the —C═C— group;

Peak at 5.0-5.5 p.m, and hydrogen properties at the 1 ′ position of the ethyl side chain;

Characteristics of hydrogen in methylene groups at the α position of the peak and carboxyl groups at 5.5-5.75 p.m

Example 28

(RS) α-cyano 3-phenoxybenzyl α1-cis-trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Rate.

(RS) α-cyano 3-phenoxybenzyl α1-cis-trans 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate having the following characteristic values is used. do.

U.V spectrum (ethanol)

＝522); 272mm에서 굴절(

＝47);Refraction at 226 mm (

522; Refraction at 272 mm (

= 47);

＝43); 278mm에서 최대(

＝52).Refraction at 267 mm (

= 43); At 278 mm (

= 52).

NMR Spectrum (Duterochloroform)

The characteristics of the hydrogen in the peak and methyl groups at 1.20-1.30 p.p.m;

The properties of hydrogen at the 1 'position of the dichlorovinyl chain corresponding to the peak, trans isomer at 5.60-5.75 p.m;

The properties of hydrogen at the 1 'position of the dichlorovinyl chain corresponding to the peak, cis isomer at 6.20-6.31 p.m;

The properties of hydrogen bonded by carbon at the α-position of the -C≡N group, at a peak at 6.41-66.4 p.m;

Characteristics of hydrogen of peak and aromatic nucleus at 7.0-77.66 p.p.m.

(RS) α-cyano 3-phenoxybenzyl α1-cis-trans 2,2-medityl 3- (2 ', 2' dichlorovinyl) cyclopropane-1-carboxyl having 30 cc of carbon tetrachloride as described above. 6.7 grams of rate were introduced, and a clear 0.85 cc solution dissolved in 10 cc of carbon tetrachloride was introduced for about 1 hour or more, stirred at 20 ° C. for 2 hours, and concentrated to dryness under reduced pressure to obtain 10 grams of crude product. This was purified by chromatography on silica gel which was developed with a mixture of cyclohexane and ethyl acetate (9/1), to give (RS) α-cyano 3-phenoxybenzyl α1-cis-trans 2,2-dimethyl 3- ( 7.5 grams of 2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate were obtained.

Analysis: C ₂₂ H ₁₉ O ₃ NCl ₂ Br ₂

Calculated Value: C 45.86 H 3.32 N 2.43 Cl 12.30 Br 27.74

Found: 46.2 3.6 2.4 12.5 27.05

U.V spectrum (ethanol)

＝34); 277mm에서 최대(

＝38);Refraction at 267 mm (

= 34); Max at 277 mm (

= 38);

＝35);Refraction at 272 mm (

= 35);

N.M.R spectrum (deuterochloroform)

Characteristics of the hydrogen in the peak and methyl groups at 1.20-1.44 p.p.m;

Hydrogen at 1 and 3 positions of the peak, cyclopropane ring at 1.54-2.40 p.m;

The properties of hydrogen at the 1 'position of the diclovinyl chain corresponding to the peak, trans isomer at 4.21-4.11 p.m;

The properties of hydrogen at the 1 'position of the dichlorovinyl chain corresponding to the peak, cis isomer at 4.97-5.50 p.

The properties of hydrogen bonded by carbon at the position of the peak, -C≡N group at 6.42-6.50 p.m;

Characteristics of hydrogen of peak and aromatic nucleus at 7.0-7.75 p.p.m.

Example 29

5-benzyl-3-furylmethyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'- dibromoethyl) cyclopropane-1-carboxylate

To benzene 30 cc (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl chloride 7.6 grams and 5-benzyl 3- 3.2 cc of furylmethyl alcohol was introduced, 5 cc of pyridine was added dropwise, stirred at 20 ° C. for 48 hours, the organic phase was decanted and separated, the aqueous layer was extracted with benzene, the organic phase was combined, and dried, Concentrated to dryness under distillation, and then chromatographed with silica gel developing with a mixture of benzene and cyclohexane (7: 3) to 5-benzyl 3-furylmethyl (1R, trans) 2,2-dimethyl 3- (2 '. , 2'-dichloro-1 ', 2'-dibromoethyl) Cyclopropane-1-carboxylate 6.1 grams were obtained.

＝－19°(C＝0.5%, 벤젠).

=-19 degrees (C = 0.5%, benzene).

Analysis: C ₂₀ H ₂₀ Br ₂ Cl ₂ O ₃ (539.09)

Calculated Value: C 44.56 H 3.74 Br 29.65 Cl 13.15

Found: 44.2 3.7 29.4 13.5

I.R Spectrum

Absorption at 1725 cm ^-1 and characteristics of a carbonyl group; Absorption at 1555, 1540, 1498, 1496 cm ^-1 , and -C = C- and the characteristic of an aromatic nucleus.

U. V spectrum (methanol)

＝265); 621mm에서 굴절(

＝7)Refraction at 216 mm (

= 265); Refraction at 621 mm (

＝ 7)

＝10.5); 263mm에서 굴절(

＝6)Refraction at 251 mm (

= 10.5); Refraction at 263 mm (

＝ 6)

＝8.5); 268mm에서 최대(

＝4.5)Max at 257 mm

= 8.5); At 268 mm (

= 4.5)

NMR Spectrum (Duterochloroform)

Characteristics of hydrogen in a peak 'pair of methyl groups at 1.22-1.25-1.28 p.p.m;

The properties of hydrogen in the peak and cyclopropyl groups at 1.62-2.32 p.m;

Characteristic of hydrogen of methylene of peak, benzyl group at 3.93p.p.m;

4.25-4.37-44.5 p.m peak, characteristic of hydrogen at 1 'position of the substituted ethyl side chain;

The properties of hydrogen in methylene groups adjacent to the peak and carboxyl groups at 4.95-4.97p.p.m and 6.0-6.05p.p.m;

Peak at 7.23 p.m, and hydrogen properties at position 4 of the furyl nucleus;

Characteristics of hydrogen of the peak, phenyl group at 7.25p.p.m.

In addition to those described in Example 10, the acid chlorides used in the beginning of this example were carried out starting with (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid. Prepared in the same manner as described in Example 16.

Example 30

3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (1 ', 2'- dibromo 2', 2'-dichloroethyl) cyclopropane- 1-carboxylate

To a 9-gram solution of 3-phenoxybenzyl alcohol dissolved in a mixture of 50 cc of benzene and 10 cc of pyridine, (1R, trans) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl A solution of 19.35 grams of cyclopropane-1-carboxylic acid chloride was added dropwise and stirred at 20 ° C. for 18 hours, after which the reaction mixture was decanted into water, extracted with benzene, dried over magnesium sulfate, and distilled off. Concentrate to dryness. The residue was chromatographed with silica gel developed with a mixture of petroleum ether (boiling point 35-75 ° C.) and ethyl ether (95/5) to give 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (1 '. 8.1 grams of 2'-dibromo-dichloroethyl) cyclopropane-1-carboxylate were obtained.

＝－20.5°(C＝0.6%, 벤젠).

= -20.5 ° (C = 0.6%, benzene).

Analysis: C ₂₁ H ₂₀ Br ₂ Cl ₂ O ₃ (551.11)

Calculated Value: C 45.17% H 3.66% Br 29.0% Cl 12.87%

Found: 45.7 3.7 28.5 12.0

I.R spectrum (chloroform)

Absorption at 1730 cm ^-1 , characteristics of a carbonyl group; Absorption at 1618 and 1590 cm ^-1 , Properties of hydrogen in aromatic ring.

U.V spectrum (ethanol)

NMR Spectrum (Duterochloroform)

Characteristic of hydrogen in a peak and a pair of methyl groups at 1.22-1.27-1.29 p.p.m;

Characteristics of hydrogen at the 1-position of peak and cyclopropyl at 1.66-1.75 p.m and 1.92-2.13 p.p.m;

The hydrogen at the 3-position of the peak and cyclopropyl at 1.92-2.23 p.m;

Peaks at 4.22-4.38 and 34.38-4.57 p.m, the nature of hydrogen at the 1 'position of the substituted ethyl side chain;

The properties of hydrogen in the methylene group of the peak and benzyl groups at 5.12-5.13 p.m;

Characteristics of hydrogen in peaks and aromatic nuclei at 6.83 to 7.53 p.p.m.

Example 31

3, 4, 5, 6-tetrahydrophthalimidomethyl (1R, trans) 2, 2-dimethyl 3- (1 ', 2'- dibromo 2', 2'- dichloroethyl) cyclopropane- carboxyl Rate

To 200 cc of benzene (1R, trans) 2, 2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) 2 g of cyclopropane-carboxylic acid chloride and 3, 4, 5, 6 -0.930 g of tetrahydrophthalimidomethanol was dissolved, 2.5 cc of pyridine was added dropwise, followed by dropwise addition at 20 DEG C for 48 hours, washed with water, then decanted, extracted with benzene and concentrated to dryness, The residue was chromatographed with silica gel which developed with a mixture of benzene and ethyl acetate (9/1) to give 3, 4, 5, 6-tetrahydrophthalimidomethyl (1R, trans) 2, 2-dimethyl 3- (1 2.17 grams of ', 2'-dibromo 2' and 2'-dichloroethyl) cyclopropane-carboxylate (melting point = 117 ° C) were obtained.

＝－6.5°(C＝0.9%, 벤젠).

= -6.5 ° (C = 0.9%, benzene).

Analysis: C ₁₇ H ₁₉ Br ₂ Cl ₂ NO ₄ (532.066)

Calculated Value: C 38.38% H 3.60% Br 30.04% Cl 13.32% N 2.63%

Found: 38.5 3.5 29.9 13.4 2.5

I.R spectrum (chloroform)

The characteristics of the absorption C = 0 group at 1783 cm- ¹ ;

Absorption at 1728 and 1750 cm- ¹ , characterizing C = 0 and ester groups;

Absorption at 1669 cm- ¹ , characteristics of C = 0 group

U.V spectrum (ethanol)

＝301)Max at 223 mm (

301)

＝172)Refraction at 236 mm (

= 172)

＝293)229-230 mm maximum

＝ 293)

＝8)Refraction at 272 mm (

＝ 8)

Example 32

3-phenoxybenzene (1R, trans) 2, 2-dimethyl 3- (2 ', 2-dibromo 1', 2'- dichloroethyl cyclopropane- carboxylate.

Step A: (1R, trans) 2, 2-Dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl cyclopropane-1-carboxylic acid chloride.

(1R, trans) 2, 2-Dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) Similar to Example 16 starting with 4.5 grams of cyclopropane-1-carboxylic acid Manipulated with; (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride was obtained.

Step B: 3-Phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate.

To a solution of 2.7 grams of 3-phenoxybenzyl alcohol dissolved in 7 cc of benzene, the acid chloride obtained in the previous step A was dissolved in 7 cc of benzene, and the resulting solution was introduced at 0 ° C., and 1.5 cc of pyridine was added to the solution at 20 ° C. After stirring for 16 hours, the reaction mixture was inclined to a mixture of water, ice and hydrochloric acid, extracted with ethyl ether, the organic phase was washed with water, dried over magnesium sulfate and concentrated to distillation under reduced pressure to dryness. I was. The residue (6.37 grams) was chromatographed and purified by silica gel developing with a mixture of cyclohexane and ethyl acetate (90/10) to give 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 '. , 2'-dibromo 1 ', 20.9-dichloroethyl) 20.9 grams of cyclopropane-1-carboxylate were obtained.

Analysis: C ₂₁ H ₂₀ Br ₂ Cl ₂ O ₃ (551.13).

Calculated Value: C 45.7% H 3.6% Br 29% Cl 12.8%

Found: 46.0 3.8 29.4 12.6

I.R spectrum (chloroform)

Absorption at 1930 cm ^-1 , characteristics of group C = 0, absorption at 1615-1590 cm- ¹ , characteristics of an aromatic ring.

U. V. Spectrum (ethanol)

＝205)Refraction at 220mm (

= 205)

＝36)271-272 mm maximum

＝ 36)

＝33)Refraction at 266 mm (

＝ 33)

＝34)Refractive maximum at 278 mm (

＝ 34)

NMR Spectrum (Duterochloroform)

Characteristic of hydrogen in a peak and a pair of methyl groups at 1.25-1.28-1.33 p.p.m;

The properties of hydrogen in the peak and cyclopropyl groups at 1.7-2.42 p.m;

Peak at 3.98-3.45 p.m, the nature of hydrogen at the 1 'position of the substituted ethyl side chain;

The properties of peaks and hydrogens of aromatic nuclei at 6.85 to 7.5 p.m;

The properties of hydrogen in methylene of the peak benzyl group at 5.13 p.m;

(1R, trans) 2, 2-dimethyl- 3- (2 ', 2'- dibromo 1', 2'- dichloroethyl) cyclopropane- 1-carboxylic acid can be manufactured by the following method.

Into a mixture of 20 cc of carbon tetrachloride and 20 cc of methylene chloride, 24 g of (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid was introduced, and -10 ° C. After introducing chlorine into the reaction solution of a reaction vessel equipped with a cooling condenser in a bubble, methanol is circulated at -60 ° C for 2 hours and 30 minutes at + 10 ° C, and at + 10 ° C. Stir for 1 hour 30 minutes, evaporate excess chlorine, remove solvent by distillation under reduced pressure, cyclohexane, ethyl acetate and acetic acid (75/25/1), then cyclohexane, ethyl acetate and Chromatographic purification of the residue with silica gel developed in a mixture with acetic acid (80/20/1) (1R, trans) 2, 2-dimethyl 3- (2 ', 2', dibromo 1 ', 2'- 16.3 grams of dichloroethyl) cyclopropane-1-carboxylic acid was obtained.

N.M.R spectrum (deuterochloroform)

Peaks at 1.33-1.65 p.p.m and properties of hydrogen in a pair of methyl groups;

The properties of hydrogen in the peak and cyclopropyl groups at 1.7-12.25 p.p.m;

Peak at 4.11-4.37 p.p.m., hydrogen character at 1'position of the substituted ethyl side chain;

Characteristics of hydrogen in peak and carboxyl groups at 10.8 p.p.m.

Example 33

(S) Alleletron (1R, trans) 2, 2-dimethyl 3- (2 ', 2'- dibromo 1', 2'- dichloroethyl) cyclopropane- 1-carboxylate.

Step A: (1R, trans 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride.

(1R, trans) 2, 2-dimethyl-3- (2 ', 2'-dibromo 1', 2'-dichloroethylcyclopropane-1-carboxic acid, starting with 4.5 grams, Operation in a manner similar to that described (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride did.

Step B: (S) Alleletron (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate.

To a solution of 2.05 grams of S-Allerrone dissolved in 7 cc of benzene, the solution obtained by dissolving the acid chloride obtained in the previous step (A) in 7 cc of benzene was added to 0 deg. C, and pyridine 1.5 cc was added, followed by 20 deg. After stirring for 16 hours, the reaction mixture was inclined to a mixture with water, ice and hydrochloric acid, washed with ether, the organic layer was washed with water, dried over magnesium sulfate and concentrated to dryness by distillation.

The residue (5.15 grams) was chromatographed purified by silica gel developing with a mixture of cyclohexane and ethyl acetate (80/20), and crystallized from isopropyl ether to give S-allerrone (1R, trans) 2, 2-dimethyl. 1.86 grams of 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate (melting point = 120 ° C) were obtained.

I.R spectrum (chloroform)

Absorption at 1713-1730 cm ^-1 , Absorption at group C = 0, Absorption at 1658 -1642 cm ^-1 , Properties of -C = C-group, Absorption at 923 -995 cm ^-1 , Properties of -CH = CH ₂ group.

U.V spectrum (ethanol)

＝315호)Max at 229 mm (

315)

＝1)Deflection at 300mm (

= 1)

NMR spectrum (deuterochloroform).

Characteristics of hydrogen in a peak and a pair of methyl groups at 1.32-1.35-1.38 ppm;

Peak at 4.23-4.4 ppm, 4.1-4.27 ppm, and hydrogen at 1 ′ position of the substituted ethyl side chain;

Peak at 2.08-2.15 ppm, methyl at 3-position of alleletron, peak at 2.98-3.08 ppm, and methylene at 5-position of alleletron;

The characteristics of hydrogen in the peak methylene group of the peak and alleletron at 4.83-5.25 ppm;

The characteristic of hydrogen at the position of the allyl group of the peak, alleletron at 5.5-66.1 ppm;

Peak at 5.83ppm, characteristic of hydrogen at 4 'position of alleletron.

Example 34

3-phenoxybenzyl (1R, cis) 2, 2-dimethyl) 3- (2 ', 2'- dibromo 1', 2'- dichloroethyl) cyclopropane- 1-carboxylate.

Step A: (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride.

(1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclo in a mixture of 30 cc of petroleum ether (boiling point 35-70 ° C.) and 10 cc of thionyl chloride After introducing 5 grams of propane-1-carboxylic acid and refluxing the reaction mixture, the mixture was kept in this state for 4 hours, concentrated from distillation to distillation to dryness, and benzene was added thereto, followed by distillation under reduced pressure. The mixture was concentrated to dryness to obtain 5.4 g of (1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid chloride. .

Step B: 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylate.

To 3.2 g of 3-phenoxybenzyl alcohol, 5.4 g of the acid chloride obtained in the above step A was added, followed by the slow addition of 38 cc of benzene at about + 80 ° C, followed by the addition of a solution of 4.5 g of pyridine dissolved in 10 cc of benzene, After stirring for 17 hours at 20 ° C., the mixture was inclined to a mixture of water and ice, extracted with benzene, dried over magnesium sulfate, the benzene solution was concentrated to dryness, and the residue was dried with benzene and ethyl acetate (7/3 Chromatographed and purified by silica gel developed into a mixture of a) and then determined by petroleum ether (boiling point 35-70 ° C.) to 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2' -Dibromo 1 ', 2'-dichloroethyl) 4.7g of cyclopropane- 1-carboxylates were obtained (melting point = 68 degreeC).

＝－34°(C＝1%, 클로로포름)

= -34 ° (C = 1%, chloroform)

Analysis: C ₂₁ H ₂₀ Cl ₂ B ₂₂ O ₃ (551.20)

Calculated Value: C 45.76% H 3.66% B _L 29.00 Cl 12.86%

Found: 46.0 3.6 29.3 12.7

I.R spectrum (chloroform)

Absorption at 1725 cm ^-1 , characteristics of carbonyl group: Absorption at 1615-1588 cm- ¹ and 1490 cm- ¹ , characteristics of aromatic nucleus

U.V spectrum (ethanol)

＝214)Refractive at 227 mm (

214)

＝35)At 272 mm (

＝ 35)

＝33)Refraction at 266 mm (

＝ 33)

＝36)Refractive maximum at 278 mm (

＝ 36)

NMR Spectrum (Duterochloroform)

Peak at 1.22-1.39 ppm and 1.26-142 ppm, and the properties of hydrogen in a pair of methyl groups;

Characteristics of hydrogen in peak and cyclopropyl groups at 1.66 to 2.08 ppm;

기의 수소의 특성;Peak at 4.8-5.37 ppm

The nature of the hydrogen of the group;

Characteristics of hydrogen at peak and aromatic nucleus at 6.83-77.5 ppm.

(1R, cis) 2,2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-carboxylic acid used in the steps of the present example is A of Example 11. Prepared in step.

Example 35

(S) Alleletron (1R, cis) 2, 2-dimethyl 3- (2 ', 2'- difluoro 1', 2'- dibromoethyl) cyclopropane- 1-carboxylate.

Step A: (1R, Cis) 2, 2-Dimethyl 3- (2'2-difluoro 1,2-dibromoethyl) cyclopropane-1-carboxylic acid.

15.2 g of bromine dissolved in 120 cc of (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane-1-carboxylic acid and then dissolved in 40 cc of carbon tetrachloride The solution of was introduced at −65 ° C. for at least about 2 hours, stirred at −65 ° C. for 2 hours 30 minutes, and then heated up to 20 ° C., concentrated to distillation to dryness under reduced pressure, and heated to a residue. Dissolved in 50 cc, cooled to 0 ° C., stirred at this temperature for 45 minutes, the insoluble material was filtered off, the filtrate was concentrated by distillation under reduced pressure, and the residue dissolved in 40 cc of carbon tetrachloride, then −10 Stir at 30 ° C. for 30 minutes, filter off the insoluble material, distill the filtrate under reduced pressure and concentrate to dryness and chromatograph of silica gel which develops the residue into a mixture of cyclohexane and ethyl acetate (75/25). Graffiro It was determined by petroleum ether (boiling point 35-75 ° C), and (1R, cis) 2,2-dimethyl 3- (2,2-difluoro 1,2-dibromoethyl) cyclopropane-1-cara 1.465 g of acids (melting point = 124 ° C) was obtained.

N.M.R spectrum (deuterochloroform)

Peaks at 1.28-1.38 p.p.m and properties of hydrogen in a pair of methyl groups;

The characteristics of hydrogen in the peak and cyclopropyl groups at 1.6-2.0 p.m;

Characteristics of hydrogen of the peak, substituted ethyl side chain at 4.67-5.33 p.p.m.

Step B: (1R, Cis) 2, 2-Dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride.

Petroleum ether (boiling point, 35-75 ° C.) to 15 cc (1R, cis) 2,2-dimethyl 3- (2,2-difluoro-1,2-dibromoethyl) cyclopropane-1-carboxylic acid 1.43 g were introduced, 2.5 cc of thionyl chloride was added, and the mixture was refluxed. The reflux was maintained for 4 hours and 30 minutes. The excess thionyl chloride and the solvent were distilled off under reduced pressure, and benzene was added to the residue. Distilled under reduced pressure, concentrated to dryness and coarse (1R, cis) 2,2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-cara Acid chlorides are obtained and used in the next step.

Step C: (S) Alleletron (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate .

A solution of 0.7 g of (S) alleletron dissolved in 5 cc of benzene was introduced at a solution of (1R, cis) acid chloride obtained in the above step B in 10 cc of benzene at + 2 ° C, and 0.5 cc of pyridine was introduced. After stirring for 16 hours at 占 폚, the reaction mixture was inclined to a mixture of water, ice and hydrochloric acid, extracted with ethyl ether, and then the organic layer was washed with water, dried over magnesium sulfate, and concentrated to dryness. It contains 2.02 g of crude ester, which is purified by chromatography to develop with a mixture of cyclohexane and ethyl acetate (80/20) to alleletron (R, cis) 2, 2-dimethyl 3- (2 ', 2). 1.224 g of '-difluoro 1' and 2'-dibromoethyl) cyclopropane-1-carboxylate were obtained.

Analysis: Cl ₁₇ H ₂₀ Br ₂ F ₂ O ₃ (470.162)

Calculation: C 43.4% H 4.3% Br 34.0% F 8.1%

Found: 43.2 4.4 33.7 8.1

U.V spectrum (ethanol)

＝348)Maximum at 227-228 mm

= 348)

N.M.R spectrum (deuterochloroform)

Peak at 1.25-1.36 p.p.m, and the properties of hydrogen in a pair of methyl groups;

Peaks at 2.0 to 2.06 p.m, and hydrogen in methyl at the 2-position of alleletron;

The properties of hydrogen in the terminal methylene of the side chain of the peak, alleletron at 4.83-5.25 p.m;

The peaks at 5.5-6.11 p.m, the hydrogen at the β position of the side chain of the alleletron and the hydrogen bonded by carbon at the 1 position of the alleletron;

Peak at 4.83-6.17p.p.m, characterization of hydrogen at position 1 of the substituted ethyl side chain;

Characteristics of hydrogen in the peak and cyclopro group at 1.67-2.16 p.p.m,

Peaks at 2.95 to 3.05 p.m and characteristics of hydrogen in the methylene group at the α-position of the side chain of alleletron;

Characteristics of methylene in the peak and allerrone ring at 1.67-3.17 p.m;

Example 36

(RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1- Carboxylate

Step A: (1R, Cis) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride.

2.5 g of (1R, cis) acid obtained in the step A of Example 35 was introduced into 15 cc of petroleum ether (boiling point 35-75 ° C), 7 cc of thionyl chloride was added thereto, and the mixture was refluxed. Hold for minutes, distilled under reduced pressure, concentrated to dryness, benzene was added, concentrated to dryness and coarse (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1 ', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride is obtained and used in the next step.

Step B: (RS) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2,2-difluoro 1,2-dibromoethyl) cyclopropane-1-cara Carboxylate

The acid chloride obtained in the above step A was dissolved in 15 cc of benzene, and a solution of 1.995 g of (RS) alpha -cyano 3-phenoxybenzene alcohol dissolved in 10 cc of benzene was added at +2 占 폚, followed by 1 cc of pyridine. The mixture was added and stirred at 20 ° C. for 15 hours, the reaction mixture was decanted into a mixture of water, ice and hydrochloric acid, extracted with ether and then concentrated by distillation to dryness.

NMR Spectrum (Duterochloroform)

Peaks at 1.03-1.45p.p.m. And hydrogen in a pair of methyl groups;

The characteristics of hydrogen in the peak and cyclopropyl groups at 1.75-2.0 p.m;

Peak at 4.42-5.17 p.m, and hydrogen at position 1 of the ethyl side chain;

Peak at 6.4-66.4 p.m, and hydrogen properties at the α position of C≡N;

Example 37

3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'- difluoro 1', 2'- dibromoethyl) cyclopropane- 1-carboxylate

Step A: (1R, trans) 2,2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride

To 40 cc of petroleum ether (boiling point, 35-75 ° C.), (1R, trans) 2,2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane 11 g of 1-carboxylic acid was introduced, 10 cc of thionyl chloride was added, the reaction mixture was refluxed, the reflux was maintained for 4 hours, distilled under reduced pressure to remove excess thionyl chloride and solvent, and benzene was removed. And further concentrated to dryness (1R, trans) 2,2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid chloride Is obtained and used in the next step.

Step B: 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate

The acid chloride obtained in the previous step A was dissolved in 50 cc of benzene to obtain 56 cc of solution (solution A).

A solution of 2.4 g of 3-phenoxybenzene alcohol dissolved in 2.5 cc of benzene in 18.5 cc of Solution A was introduced at + 2 ° C, 1cc of pyridine was added and stirred at 20 ° C for 16 hours, after which the reaction mixture was mixed with water. , Inclined to a mixture with ice and hydrochloric acid, washed with ether and then the organic layer was washed with water, dried over magnesium sulfate, concentrated to dryness and remained as silica gel developed with a mixture of cyclohexane and benzene (95.5) Water was chromatographed to purify 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-cara 3.204 g of carboxylate were obtained.

Analysis: C ₂₁ H ₂₀ Br ₂ F ₂ O ₃ (518.206)

Calculation: C 48.7% H 3.9% Br 30.9% F 7.3%

Found: 48.9 3.9 31.0 7.1

U. V. Spectrum (ethanol)

＝225)Refraction at 225 mm (

225)

＝37)Up to 271 mm (

＝ 37)

＝33) 277mm에서 최대(

＝36)Refraction at 265 mm (

33 = maximum at 277 mm (

＝ 36)

NMR Spectrum (Duterochloroform)

Peak at 1.27p.p.m, the properties of hydrogen in a pair of methyl groups;

The properties of hydrogen in the peak and cyclopropyl groups at 1.58-2.17 p.m;

Peak at 3.67-3.43 p.m, the nature of hydrogen at the 1-position of the substituted ethyl side chain;

The nature of the methylene group at the position of the peak, carboxyl group at 5.13 p.m;

Characteristics of hydrogen in peaks and aromatic nuclei at 7.58 to 7.75 p.m.

The (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl cyclopropane-1-carboxylic acid used in step A of this example is as follows. It can manufacture by a method.

26.4 g of (1R, trans) 2,2-dimethyl 3- (2 ', 2'-difluorovinyl) cyclopropane-1-carboxylic acid was dissolved in 150 cc of methylene chloride and dissolved in 50 cc of carbon tetrachloride in the resulting solution. A solution of 24 g bromine was introduced at −60 ° C. for at least about 1 hour 30 minutes, stirred at −60 ° C. for 3 hours, the temperature of the reaction medium was raised to 20 ° C., distilled under reduced pressure and concentrated to dryness. , Petroleum ether (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid (melting point = 116 ° C.) 14.09 g was obtained.

Analysis: C ₈ H ₁₀ Br ₂ F ₂ O ₂ (335.98)

Calculated Value: C 28.6% H 3.0% Br 47.6% F 11.3%

Found: 28.8 3.1 47.7 11.5

NMR Spectrum (Duterochloroform)

Peak at 1.33p.p.m, the properties of hydrogen in a pair of methyl groups;

The properties of hydrogen in the peak and cyclopropyl groups at 1.5-2.23 p.m;

Peak at 3.67-4.4 p.m, the nature of hydrogen at the 1-position of the substituted ethyl side chain;

Characteristics of hydrogen of peak and carboxyl groups at 10.9p.p.m.

Example 38

(RS) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1- Carboxylate

Starting with 11 g of acid as in Example 37 (1R, trans) 2, 2-methyl 3- (2 ', 2'-difluoro 1', 2'-dibromoethyl) cyclopropane-1-cara The acid chloride produced by preparing the acid chloride was dissolved in 50 cc of benzene to obtain 56 cc of an acid chloride solution (solution A).

A solution of 5.4 g of α-cyano 3-phenoxybenzyl alcohol dissolved in 5 cc of benzene in Solution A was introduced at 0 ° C, 2 cc of pyridine was added and stirred at 20 ° C for 16 hours, followed by reaction. The mixture was inclined to a mixture of water, ice and hydrochloric acid, extracted with ethyl ether, treated in a conventional manner, then distilled under reduced pressure and concentrated to dryness, and the residue was cyclohexane and ethyl acetate (90/10) Chromatography was purified by silica gel developed into a mixture of (RS) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (2 ', 2'-difluoro 1', 2 '. -Dibromoethyl) 5,46 g of cyclopropane-1-carboxylate was obtained.

Analysis: C ₂₂ H ₁₉ Br ₂ F ₂ NO ₃ (543.22)

Calculation: C 48.6% H 3.5% Br 29.4% N 2.6% F 7%

Found: 49.1 3.5 28.8 2.5 6.7

I.R. Spectrum (chloroform)

Absorption at 1745 cm ^-1 , characteristics of a carbonyl group; Absorption at 1615-1590 cm- ¹ , and characteristics of hydrogen in aromatic nuclei.

U.V spectrum (ethanol)

＝192)Deflection at 230mm (

192)

＝39)Maximum deflection at 278 mm (

＝ 39)

＝34)Refraction at 269 mm (

＝ 34)

＝1)Refraction at 305 mm (

= 1)

＝36)Refraction at 273 mm (

＝ 36)

N.M.R spectrum (deuterochloroform)

Peak-characteristics of hydrogen in a pair of methyl groups at 1.3-1.33 p.p.m;

The characteristics of hydrogen in the peak and cyclopropyl groups at 1.9-2.25 p.p.m;

Peak at 3.66-3.43 p.m, the nature of hydrogen at the 1-position of the substituted ethyl side chain;

The nature of hydrogen bound by the same carbon atom as the peak, C≡N group at 6.45 p.m;

Characteristics of hydrogen in peaks and aromatic nuclei at 6.91 to 7.78 p.p.m.

Example 39

3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 '(RS) -fluoro 2-chloro 1', 2'- dibromoethyl) cyclopropane-1-carboxylate (isomer) A and isomer B).

Step A: (1R, cis) 2, 2-dimethyl 3- (2 '(RS) -fluoro 2-chloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid

Dissolve 8.9 g of (R, cis) 2,2-dimethyl 3- (2-chloro 2'-fluorovinyl) cyclopropane-1-carboxylic acid (a mixture of isomers E + X) in 100 cc of carbon tetrachloride, and 20 cc of carbon tetrachloride. A solution of bromine 2.4 dissolved in the solution was added at −10 ° C. for at least about 30 minutes, stirred at + 10 ° C. for 4 hours, distilled under reduced pressure, concentrated to dryness, and the residue was purified by silica gel with ethyl acetate. Chromatography (1R, cis) gave 13.7 g of 2, 2-dimethyl 3- (2 '(RS) -fluoro 2-chloro 1, 2-dibromoethyl) cyclopropane-1-carboxylic acid.

I.R spectrum (chloroform)

Absorption at 1710 cm ^-1 , characteristic of group C = 0; Absorption at 3510 cm- ¹ , group properties.

NMR Spectrum (Duterochloroform)

Characteristics of hydrogen in a peak and a pair of methyl groups at 1.30-1.32-1.42 p.m;

The characteristics of hydrogen in the peak and cyclopropyl groups at 1.75 to 2.08 p.p.m;

Peak at 4.67-5.50 p.m, the nature of hydrogen at the 1-position of the substituted ethyl side chain;

Characteristics of hydrogen of peak, carboxyl group at 10.75p.p.m:

Step B: 3-Phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 '(RS) -fluoro 2-chloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Rate

3.5 g of (1R, cis) 2, 2-dimethyl 3- (2 '(RS) -fluoro 2-chloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylic acid obtained in step A , 3.5 g of 3-phenoxybenzyl alcohol, 3.5 g of dimethylformamide neopentyl acetal, and 35 cc of benzene were mixed, and the reaction mixture was kept at 50 ° C, held at this temperature for 17 hours, cooled, and then under reduced pressure. The residue was chromatographed with silica gel, which was distilled and concentrated to dryness and developed with a mixture of benzene and cyclohexane (1/1). 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ' 10.5 g of (RS) -fluoro 2-chloro 1 ', 2'-dibromoethyl) cyclopropane-1-carboxylate was obtained (melting point = 50 ° C).

Analysis: C ₂₁ H ₂₀ Br ₂ ClFO ₃ (534.65)

Calculated Value: C 47.17% H 3.77% Cl 6.63% F 3.55% Br 29.89%

Found: 47.4 3.8 7.2 3.7 29.4

I.R. Spectrum (chloroform)

Absorption at 1735 cm ^-1 , characteristics of C = 0 group; Absorption and characteristic of an aromatic nucleus at 1675-1590-1490cm- ¹ .

N.M.R spectrum (deuterochloroform)

Peak characteristics at 1.23 to 2.01 p. P.m, and the properties of hydrogen in a pair of methyl groups;

The characteristics of hydrogen in the peak and cyclopropyl groups at 1.75 to 2.01 p.p.m;

The properties of hydrogen in methylene of the peak, benzyl group at 5.08p.p.m;

Peak at 5.08-5.50 p.m, the nature of hydrogen at the 1 'position of the substituted ethyl side chain;

Characteristics of hydrogen in peaks and aromatic nuclei at 6.83 to 7.58 p.p.m.

On the other hand, 0.62 g of isomers (B) were obtained.

analysis :

Calculated Value: C 47.17% H 3.77% Cl 6.03% F 3.55% Br 29.89%

Found: 47.5 3.8 6.2 3.6 29.6

I.R. Spectrum (chloroform)

Same as that of isomer A.

N.M.R spectrum (deuterochloroform)

Peak at 1.22-1.34 p.m, the properties of hydrogen in a pair of methyl groups;

The characteristics of hydrogen in the peak and cyclopropyl groups at 1.75-2.0 p.m;

The properties of hydrogen in methylene of the peak, benzyl group at 5.12 p.m;

Peak at 4.83-5.33 p.m, and hydrogen at position 1 of the substituted ethyl side chain;

Characteristics of hydrogen in peaks and aromatic nuclei at 5.83 to 7.5 p.m.

The (1R, cis) 2,2-dimethyl 3- (2'-chloro 2-fluorovinyl) cyclopropane-1-carboxylic acid used in step A was prepared in brown (D. Brown's 1974 paper, similar to that used for "Structural Activity Studies of Halopyrethroids," published in 1976 by "Xerox University Microtfilms Ann Abor", Michigan, USA, but with t-butyl 2, 2- Instead of dimethyl 3RS-formylcyclopropane-1RS-carboxylate, t-butyl 2 and 2-dimethyl 3S-formylcyclopropane-1-carboxylate were produced.

Example 40

(S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane-1-carboxylate

Insecticidal properties of isomers (A) and (B) of (compounds Y ₁ and Y ₂ ) and (S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2 Tests for the pesticidal properties of isomers (A) and (B) of '-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxylate (compounds Y ₃ and Y ₄ );

(RS) α-cyano 3-phenoxybenzyl α1-cis-trans 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1-carboxyl Rate (Compound Y ₅ );

(S) α-cyano 3-phenoxybenzyl (1R, trans) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2'- tetrabromoethyl) cyclopropane-1-carboxylate (Compound Y ₆ ); (RS) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dibromo 1', 2'-dichloroethyl) cyclopropane-1-cara Carboxylate (compound Y ₇ ); (R, S) α-cyano 3-phenoxybenzyl (1R, trans) 2,2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-dibromoethyl) cyclopropane-1- Carboxylate (Compound Y ₈ ) and 5-benzyl 3-furylmethyl (1R, cis) 2,2-dimethyl 3- (1 ', 2', 2 ', 2'-tetrabromoethyl) cyclopropane-1 Carboxylates (Y ₉ ).

Test of lethal effect on housefly

1) Test of the effect of compounds Y ₁ , Y ₂ , Y ₃ , and Y ₄ .

As a test insect, the female of the housefly which is 4 days old is used. Using Arnold's micromanipulator, 1 μl of acetone solution was applied locally to the dorsal rib of the test insect. 50 animals were used for treatment.

Mortality was measured 24 hours after treatment.

This test was performed using piperonylbutoxide (10 parts synergist per part of the compound to be tested) without or as a synergist.

The experimental results summarized in the following table are shown as LD50 (nanograms) required to kill 50% of the test insects.

conclusion :

Y ₁ , Y ₂ , Y ₃ and Y ₄ compounds of the present invention have a very high lethal effect on houseflies. This effect is increased by adding piperonylbutoxide.

2) Test of the Effect of Compound Y ₇

The conditions of this test are the same as described above.

the results are as follow.

medium).

Mortality was measured 48 hours after treatment.

The experimental results are summarized in the following table.

conclusion :

Y ₁ and Y ₂ compounds of the present invention show a very high lethal effect on the larvae of Spodora teratolis.

2) Insecticidal effect test of the compound molecule of compounds Y ₁ and Y ₂ , the compound mixture of compound Y ₃ , and Y ₄ , and the caterpillars of spodotera littoralis of compound Y ₇ and compound Y ₉ .

This test was done for local use. One liter of the acetone solution of the compound to be tested was treated in the dorsal rib of each moth.

For each dose used, fifteen moths of Spodora terratrilis in the fourth larva stage were used. After treatment, individual moths were placed on Poitoit medium.

Conclusion: Compound Y ₇ has a potent insecticidal effect on housefly.

B) Test of lethal effect on larvae of Spodotera Littoralis

1) This test was carried out using an acetone solution locally on the thorax abdomen using an Arnold micromanipulator. 10-15 larvae were used per dose of the product to be tested.

The larva used was in the fourth larva stage and was grown for about 10 days at 24 ° C and 65% relative humidity.

After treatment, individual insects were subjected to artificial culture (Potite medium (24 hours after poitoit treatment, then 48 hours efficacy check (percentage of death compared to untreated control)) to lethal dose 50 (LD ₅₀₎ (ng) was measured.

The experimental results are summarized in the following table.

Control: No mortality.

CONCLUSIONS: The compounds tested show very high insecticidal effects against Spodorateratolis.

C) Test of impact effect on housefly

The insect to be tested is a female flyfly at 4 days of age. An equal volume mixture of acetone and kerosene (the amount of solution is 2 × 0.2 cm ₃ ) was used as a solvent to sort directly in the Cairns & Mark chanber.

About 50 insects were used per treatment. KT ₅₀ was measured by the usual method by checking it about 10 minutes at a distribution interval, and then about 15 minutes. The experimental results obtained are summarized in the following table.

K.T 50 or eradication time 50 refers to the time required to eradicate 50% of the congestion at a predetermined dose of the product to be tested.

This period is inversely proportional to the rate of action of the product.

Conclusions: Y ₁ , Y ₂ , Y ₃ and Y ₄ compounds of the present invention showed interesting lethal effects on housefly.

D) Testing insecticidal effects of compounds Y ₃ (isomer A) and Y ₄ (isomer B), Y ₅ , Y ₆ , Y ₇ and Y ₈ against larvae of ladybugs.

This test was used topically in a similar manner to that used for the larvae of Spodotera. The larvae of the penulti mafe laral stege were used, and larvae were fed to the larvae after treatment.

Mortality was checked 72 hours after treatment. The experimental results are summarized in the following table.

E) A mixture of equimolar ratios of compound Y ₁ (isomer A) and compound Y ₂ (isomer B), cytophilus granarius and tree of compound Y ₃ (isomer A) and compound Y ₄ (isomer B) Testing of Insecticidal Effects on Triboleum Castaneum.

This test was done by spraying directly on wheat that was prevalent as pests.

To 1000 g of wheat to be placed in a 1 L flask of a rotary evaporator, 5 ml of acetone solution and 0.1 cc of water were sprayed.

50 mice (Sitophilus or Tribolium) were artificially infected.

For each dose the percent mortality was measured after 7 days compared to the untreated control, averaged for 100 animals and lethality 50 (LC50) was measured. The experimental results are shown in the following table.

Control natural mortality rate: Cytophilus 1.0%

Tribolium 4.0%

CONCLUSIONS: The tested mixture showed a strong pesticidal effect against tribolium castanium.

The effect on cytophilus granarius was slightly small.

F) A mixture of equimolecular ratios of compound Y ₁ (isomer A) and compound Y ₂ (isomer B), and a mixture of equimolecular ratios of compound Y ₃ (isomer A) and compound Y ₄ (isomer B) is obtained by blatella Test for insecticidal effects of Blatella germanica (male adult).

The film was placed on glass and tested.

2 cc of acetone solution contained in 10 mg / l of the product to be tested was placed in a 154 cm 2 quail dish and the acetone was evaporated:

The formed film corresponds to 1.3 mg of active ingredient per m 2. Insects were placed on the film. Insects killed after 5, 10, 15, 20, 25, 30, 40, 50 and 60 minutes were counted.

Insects were removed from the quail dishes and transferred to clean necked jars. Mortality was checked after 24 hours, 48 hours and 72 hours (percentage of exterminated and dead insects measured in comparison to untreated controls).

The experimental results are summarized in the following table.

CONCLUSIONS: Mixtures of equimolecular ratios of Compound Y ₁ and Compound Y ₂ , and mixtures of equimolecular ratios of Compound Y ₃ and Compound Y ₄ have a significant pesticidal effect against blatellagermanica.

Example 41

Test of the scattering effect of a mixture of compound Y ₁ (isomer A) and compound Y ₂ (isomer B), mixture of compound Y ₃ (isomer A) and compound Y ₄ (isomer B)

A) Effects on spotted solution (Tefranychus urticae) Sallan test and larvae test.

Ten female spot solution per leaf were painted with birdlime on the edges using infected soybean leaves.

They were left for 24 hours, removed again, and divided into two groups of soybean-infected beans.

a) Group 1 was treated with the compound under test:

0.5 cc of an aqueous solution was sprayed onto the individual soybean leaves using concentrations of 50 and 25 g of the test compound per hectare.

b) Soybean leaves of the second group were treated without a treatment.

Numbers of live eggs and larvae were calculated 9 days after treatment.

The results, expressed as% mortality of eggs and larvae, are shown in the following table with regard to untreated controls.

The experimental results are summarized in the following table.

Control: The treated mixture of Compounds Y ₁ and Y _{2 and} the treated mixture of Compounds Y ₃ and Y ₄ have a scattering and insecticidal effect on the spot solution.

B) Effect of panonychus ulmi: This test was carried out with compound Y ₂ against the vine strain "SIRAH". Four replicates were made for each dose by the “block” method. Untreated controls were introduced in each block. Ten vines were used for each basic medium.

Using a constant pressure Vande weiz sprager, the process was performed in a single treatment based on 1000 liters of wash in hectares.

Shanks 7, 16 and 26 days after treatment. These were washed by brushing to calculate the 15 leaf presenting larvae (larvae and adults) and the results expressed in relation to the untreated control.

The experimental results obtained are summarized in the following table.

Number of herds moving in 15 leaves

Control: Compound Y ₁ has a clear scattering effect on adult and larvae of Pannature Woolmi.

Example 42

Ditilen chus mycelio phagus of a mixture of compound Y ₁ (isomer A) and compound Y ₂ (isomer B) and a mixture of compound Y ₃ (isomer A) and compound Y ₄ (isomer B) Test for Nematode Effect

0.5 ml of water containing about 2000 nematodes was placed in a pill-box containing 10 ml of an aqueous solution of scattering agent to be tested.

About 24 hours after the treatment, the mortality was checked with an enlarged binocular and repeated three times with 1 ml of the test sample.

The experimental results obtained are summarized in relation to the untreated control in the following table (results are expressed as percentage mortality).

CONCLUSIONS: The tested mixtures showed an interesting nematode effect against Dtilencher myceliopargus.

Example 43

Test of the ixodicidalactivity of an equimolecular mixture of compound Y ₁ and compound Y ₂ .

The solution prepared in Example 52 was used to carry out this test.

This solution, containing 0.5% of the active ingredient, was diluted with 50 times the water at the time of use.

A) In vitro test

A tick of Lipicephalus Sanguineus species was removed from the dog and contacted with a drug containing an active principal ingredient at a concentration of 1 / 10,000 for 30 minutes.

After 30 minutes the ixodes moved differently and after 4 hours they were lethal (on the other hand the control extremities were not injured).

B) testing in dogs

Two dogs were infected with the lipiceparus Sanguinea species and the ticks were attached to the head, ears, neck and chest.

The dog's body was moistened with a solution containing 1 / 10,000 active principal ingredients (2.5 per piece).

Areas with these animals were sprayed with residues of the solution under test.

Around 24 hours, the ticks were still attached and still moving.

Around 72 hours, the ticks were still attached, but all died.

Both local and total administration were good and the animals were observed 8 days after treatment.

Example 44

(S) α-cyano 3-phenoxybenzyl (R, cis) 2, 2-dimethyl 3- (1, 2, 2, 2-RS)-tetrabromoethyl) cyclopropane-1-carboxylate ( Compound Y ₁ + Y ₂ or A) and (S) α-cyano 3-phenoxybenzyl (1R, cis) 2,2-dimethyl 3- (2,2-dichloro 1,2- (RS) dibromo- Test of antifungal effect of ethyl) cyclopropane-1-carboxylate (Compound Y ₃ + Y ₄ or B)

The antimicrobial effect of the compound under test was tested by the introduction of 0.5 cc of the spore suspension of fungi to be eliminated by adjusting to about 100,000 spores per cc in 0.5 cc of the solution of the compound and 4 cc of the STARON nutrient medium. After 7 days of culture, the growth of fungi was visually inspected for the presence or absence of growth (0% or 100% effect).

Staron nutrient medium in the past has the following composition:

-20 g of glucose

-0.5 g of sodium chloride

-6 g of peptone

1 g of monopotassium phosphate

-1 g of yeast extract

-0.5 g of magnesium sulfate

-4 g of coon steaks

-Ferrous sulfate 10 mg

-Water (amount sufficient to make 1 liter)

A) Test for Fusarium Roseum

Using the above operation, the antifungal thresholds of Compounds A and B were found to be 25-50p.p.m.

B) Test for Gray Mold Disease (Botrychuc Cinerea)

Antifungal thresholds for compounds A and B were 25-50 p.m.

C) Testing for Phoma Species

The antifungal threshold of Compound A was between 25-50 p.p.m and that of Compound B was 10-25p.p.m.

D) Test of Penicillium Roguetorti

The antifungal threshold of Compound B was 150 to 200 p.p.m.

E) Conclusion:

Compounds A and B showed interesting antifungal effects on the fungi under test.

Example 45

Formulation of Emulsifiers

Make a uniform mixture with the following ingredients:

Isomer of-(S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1, 2, 2, 2-tetrabromoethyl) cyclopropane-1-carboxylate ( A) 0.25g

1 g of piperonyl butoxide

－Tween 80 0.25g

-Topanol A 0.1g

-98.4 g of water

Example 46

Formulation of Emulsifiers

The following ingredients were mixed:

Isomer of-(S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1, 2, 2, 2-tetrabromo ethyl) cyclopropane-1-carboxylate ( A) 0.015 g

0.5 g of piperonyl butoxide

-Brilliant green 0.5;

-P-nitrophenol 0.5

Example 47

Pesticides Containing Compounds of Formula (I)

Make the following mixture.

1 g of -α1 cistran (R, S) α-cyano 3-phenoxybenzyl 2,2-dimethyl 3- (2,2-dichloro 1,2-dibromoethyl) cyclopropane-1-carboxylate

-Piperonyl butoxide 8 g

－Tween 80 1

-Topanol A 0.1

-89.9 water

Example 48

Salases Containing Compounds of Formula (I)

Emulsifier (S) alpha -cyano 3-phenoxybenzyl (1R, cis) 2, 2- dimethyl 3- (2, 2, 2, 1- tetrabromo ethyl) cyclopropane- 1- carboxylate 20 weight %, Atlox 4851 (ethylene oxide triglyceride compounded with sulfonate, acid index 1.5) 6.5 weight%, Atlox 4855 (ethylene oxide triglyceride compounded with sulfonate, acid index: 3) 3, 3 weight% and key It was made to contain 70.2 weight% of styrene.

Example 49

Nematicides Containing Compounds of Formula (I)

The emulsifier for soil treatment is (S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2, 2, 2, 1- tetrabromo ethyl) cyclopropane-1-carboxyl The mixture was prepared by containing a rate of 45% by weight, 6.4% by weight of Atlox 4851, 3.2% by weight of Atlox 4855 and 45.4% by weight of xylene.

Example 50

Ixodicidal Agents Containing Compounds of Formula (I)

The solution was made with the following composition.

0.5 g of an equimolecular mixture of compounds Y ₁ and Y ₂

Polysorbate 80 10g

Triton X 100 25g

1 g Tocophenol Acetate

Ethanol, 100 mg dose

This solution was used diluted to 50 times water.

Example 51

₂ g of an injection solution prepared by containing a mixture of the oxoxide compound Y ₁ and Y ₂ containing the compound of formula (I)

Piperonyl Butoxide 6.65g

Tocopherol Acetate 0.33g

Paid Excipient 100cc

This oily excipient is prepared by mixing 29 g of benzyl acetate with enough arachis to make a total volume of 100 cc.

Example 52

Animal feed composition containing a compound of formula (I)

Corn, dehydrated alfalfa, straw, molasses-soft cabbage-palm cake, urine, and vitaminized minerals were used as basic feed.

This feed contains at least 11% or more water soluble protein (28% of which is taken from urine); It contains 2.5% fat and 15% cellulose, 6% mineral and 13% humectant.

The feed used corresponds to 82 kg of forage per 100 kg, with 100 kg of feed containing 910,000 IV vitamin A, 910,000 IV vitamin D ₃ , 156 mg vitamin E and 150 mg vitamin C.

Α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2, 2, 2, 1-tetrabromoethyl) cyclopropane-1-carboxylate (Compound A and Mixture with B) 0.04 kg.

Example 53

Antifungal agents

The solution was prepared as follows.

(S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (1 ', 2', 2 ', 2', (RS)-tetrabromoethyl) cyclopropane-1 -50 g of carboxylates

EmCo1 H 300B 80g

Xylene 870 g

Note: EmCo1 300B is a mixture of calcium salt of alkylbenzenesulfonate (anionic moiety) and polyoxyethylene ether (nonionic moiety).

Example 54

Antifungal agents

A hydrating agent was formulated in the following composition.

(S) α-cyano 3-phenoxybenzyl (1R, cis) 2, 2-dimethyl 3- (2 ', 2'-dichloro 1', 2'-RS dibromoethyl) cyclopropane-1-cara 20 g of carboxylate

－Ekapersol "S" (1) 15 g

0.5 g of BreCoane NVA (2)

-Zoosil 39 (3) 39.5 g

-Vercosyls (4) 25 g

Note: (1) Concentrate of Sodium Naphthalene Sulfonate

(2) sodium alkyl naphthalenesulfonate

(3) synthetic hydration silica obtained by precipitation

(4) colloidal kaolin

Claims (1)

The following general formula characterized by reacting a compound of formula (II) with a halogenating agent to obtain a compound of formula (III) and reacting an acid or a derivative thereof with an alcohol or a functional derivative of the formula R-OH Process for the preparation of phthalimidomethyl cyclopropanecarboxylic acid ester of formula (I).

In the above structural formula: X ₁ is selected from the group consisting of hydrogen, fluorine, chlorine and bromine, X ₂ is the same as or different from X ₁ and is selected from fluorine, chlorine or bromine, X ₃ is selected from chlorine, bromine and iodine, R is

Wherein R ₆ , R ₇ , R ₈ , R ₉ are each selected from the group consisting of hydrogen, chlorine and methyl, and S / I means an aromatic ring or a dihydro and tetrahydro ring.