WO1994002449A1 - Carbamate derivative and weedkiller containing the same as active ingredient - Google Patents

Abstract

A carbamate derivative having a phenyl skeleton and a carbamate group bonded thereto through carbon atoms, which has an excellent activity of killing lowland weeds, can eliminate lowland weeds efficiently even at a low dose, and is extremely reduced in the damage to paddy rice, thus being useful as a weedkiller.

Description

 Description Carbamate derivatives and herbicides containing them as active ingredients

 The present invention relates to a novel carbamate derivative and a herbicide containing the same as an active ingredient.

 Background

 Herbicides are extremely important for labor saving in weed control and for improving productivity of agricultural and horticultural crops.Therefore, research and development of herbicides have been actively conducted for many years, and a wide variety of chemicals are currently in practical use. Has been However, even today, there is a need for the development of new drugs with even more excellent herbicidal properties, especially those that can selectively control target weeds at low doses without causing phytotoxicity to cultivated crops. .

 In the paddy field, together with rice, various weeds, such as annual grasses such as Nobie, annual grasses such as evening larvae, annual weeds such as Magarii, oak, Kikasidasa, etc. It is known that perennial weeds such as Mizugayari, Krogwai, Omodaka and Seri grow, and these weeds can be efficiently weeded with a small amount of spraying without damaging the rice and environmental pollution. This is extremely important for rice cultivation. In particular, since Nobie is a grass weed, chemicals that have herbicidal activity against Nobie have a high herbicidal activity against Nobie due to their harm to rice. The development of highly selective drugs has become an important issue.

 Similar compounds having herbicidal activity include, for example, compounds represented by the formula described in JP-B-53-37409.

で表される化合物 [—般名： トリディファン （ t r i d i p h a n e ) ] や、 特 開平 1一 5◦ 8 7 3 6号公報に記載された式 … (I)

[—Generic name: tridiphane] or a compound described in Japanese Patent Publication No.

(Compound No. 1 in the publication) is known.

 The compound represented by the formula (I) described in JP-B-53-37409 is already practically used as a herbicide for controlling grass weeds in corn fields. However, when used as a rice herbicide, poor selectivity may cause harm to rice.

 Further, the compound represented by the formula (II) described in the above-mentioned Japanese Patent Application Laid-Open No. 1-5087336 is excellent against paddy field weeds such as nobie, evening magayari, mizugayari and annual broadleaf weeds. The herbicidal effect requires relatively high doses and is not always satisfactory for practical use.

 Disclosure of invention

 Accordingly, an object of the present invention is to provide a novel compound having excellent herbicidal activity against paddy weeds, capable of efficiently removing paddy weeds with a low dose, and capable of suppressing phytotoxicity to paddy rice extremely low. An object of the present invention is to provide a herbicide contained as an active ingredient.

 The present inventors have noted that the above-mentioned known compounds have herbicidal activity against grasses, and have excellent herbicidal activity and selectivity against other paddy weeds such as annual weeds such as grasshoppers. Devoted research has been conducted on derivatives having.

As a result, a novel derivative having a fuunil skeleton and a carbamate group bonded to this phenyl skeleton via a carbon atom is useful for waterweeds such as nobies, evening magallaris, mizugayari, and annual broadleaf weeds. Excellent herbicidal effect and high selectivity Based on this finding, it was found that it has excellent selectivity between genus of paddy rice and Nobie and can efficiently remove paddy weeds with a low dose and has little phytotoxicity to rice. The present invention has been completed.

 That is, the present invention relates to the general formula

(Where A is

O H

 ^ ^ Then H 2 \ I ΙΪ 2 C then I 2 ~ X

 Indicates Y C, B is

Is shown. X represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms; Y represents a halogen atom. R ¹ , R ⁴ , and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group or a methoxethyl group having 1 to 4 carbon atoms, and R ³ represents a carbon atom. Represents an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a methoxethyl group or a phenyl group, and R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. Represents an acyl group having 1 to 4 carbon atoms represented by the general formula: CO—R ⁷ (R ⁷ -hydrogen or an alkyl group having 1 to 3 carbon atoms) or a phenyl group, and m represents 1 to 4 Indicates an integer. ), And a herbicide containing the carbamate derivative as an active ingredient.

 BEST MODE FOR CARRYING OUT THE INVENTION

The carbamate derivative represented by the general formula () is a novel compound, and specifically, A, B, X, Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in} the formula The explanation is as follows.

 A is

CH ₂ , CH ₂ CC 12 -X

 \

OH

To CH I _X CH ₂ CC 1 ₂ -X

 Y C.

 X is a halogen atom or an alkyl group having 1 to 4 carbon atoms. Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the haloalkyl group having 1 to 4 carbon atoms include a group in which an alkyl group having 1 to 4 carbon atoms is substituted with one or two or more of the above halogen atoms, for example, a halomethyl group, a haloethyl group, a halopropyl group, a halobutyl group. Is mentioned.

Y is a halogen atom. Here, halogen atoms include fluorine, chlorine, bromine, iodine Prime _c

 B is

It is.

■ R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a methoxyl group. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ³ is an alkynole group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a methoxyethyl group or a phenyl group. Here, examples of the alkynole group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the haloalkyl group having 1 to 4 carbon atoms include a group in which an alkyl group having 1 to 4 carbon atoms is substituted with one or more of the above halogen atoms, for example, a halomethyl group, a haloethyl group, a halopropyl group, and a haloptyl group. 《No.

R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ° is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, Formula - is CO- R ⁷ having 1 4 Ashiru group atoms represented by (R ⁷ = zR containing or a C 1 3 alkyl group) or a phenyl group. Here carbon number :! Examples of the alkyl groups 6 to 6 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the haloalkyl group having 14 carbon atoms include a group in which an alkyl group having 1 to 4 carbon atoms is substituted with one or two or more of the above-described halogen atoms, for example, a halomethyl group, a haloethyl group, a halopropyl group, and a halobutyl group. Can be Examples of the C14 alkoxy group include a formyl group, an acetyl group, a propionyl group, and a butyrinole group.

 Hereinafter, the methyl group may be abbreviated as Me, the ethyl group may be abbreviated as Et-n-propyl group, the n-Pri-propyl group may be abbreviated as i-Prn-butyl group, and the n-But-butyl group may be abbreviated as t-Bu. is there.

 Representative examples of the carbamate derivative of the present invention represented by the general formula (Π1) include those listed in Tables 1 to 3.

 In the compound of the general formula (式), the formula A is

Are represented as Compounds (IVa), (IVb) and (IVc) in Table 1 below.

 Equation A

であるォキシラン誘導体を、 下表 2において化合物 （Wa) , (VEb) , ( c) と表示した。

Are shown as compounds (Wa), (VEb) and (c) in Table 2 below.

 Equation A

OH

CH-CH ₂ CC! X

 Y '

In Table 3 below, the halogenohydrin derivative is referred to as Compounds (a) and (Mb).

¾ JN.

(Hereinafter the margin)

Table 1 (Part 1)

CH; CH ₂ CC 1 -X

R ¹ Compound No. XR ¹ R ² R ³

 1 C 1 H H Me

2 C 1 Ho H E t

3 C 1 H H n -P r

 O

 4 C 1 H H i-P r

 〇

 5 C 1 H H

 6 C 1 H H i one B u

7 C 1 H H t -B u

 CO

 8 C 1 H H Ph

9 C 1 HH CH ₂ CH ₂ C 1

10 C 1 H H

^CH 2 ^{CC 1} 3

11 C 1 Me H Me

12 C 1 Me H E t

13 C 1 H Me Me

14 C 1 H Me E t

15 C 1 H E t Me

16 C 1 HE t 1 (Part 2)

CH; CH ₂ CC 12 1 X

R ¹ Compound No. XR ¹ R ² R ³

17 H H Me

^CF 3

 18 H H E t

^CF 3

 19 Me H E t

^CF 3

 20 H Me Me

^CF 3

21 CH ₂ C 1 HH Me

22 CH ₂ C 1 HHE to

23 CH ₂ CH CIHHE t

 O

 1 0 1 C 1 H Me i— P r

1 0 2 C 1 H H 〇

1 0 3 CH C 1 H Me Me

1 0 4 CH C 1 H Me E t

1 0 5 CH ₂ C 1 Me H Me

CH

化合物 No. X R⁴ R⁵ R⁶

Compound No. XR ⁴ R ⁵ R ⁶

 24 C 1 H H Me

25 C 1 H H E t

26 C 1 H H n-P r

27 C 1 H Hi 1 Pr

28 C 1 H H n -B u

29 C 1 H H t t B u

30 c] H H Ph

31 C 1 HH CH ₂ CH ₂ C 1

32 C 1 Me H E t

33 C 1 Me Hi-Pr

34 C 1 E t H Me

35 C 1 H Me Me

36 C 1 H E t E t

37 H H Me

^CF 3

 38 H H E t

^CF 3

 39 Me H E t

^CF 3

 40 Me Hi i Pr

^CF 3

Compound No. XR ⁴ R ⁵ R ⁶

1 0 6 C 1 H H H

1 0 7 C 1 Me H H

1 0 8 C 1 H Me E t

 0

1 0 9 C 1 H H II

-C-CH ₃

1 1 0 H H H

^CF 3

 1 1 1 H Me Me

^CF 3

 1 1 2 Me H Me

^CF 3

1 1 3 CH ₂ C 1 HHH

1 1 4 CH ₂ C 1 HHE t

1 1 5 CH ₂ C 1 H Me Me

(Part 5)

CH ₂ CC 1 -X

Compound No. X m R ⁴

1 1 6 C 1 2 H

Table 2 (Part 1)

R ¹

表 2 (その 2)

Table 2 (Part 2)

丫卜 物 Wn R² _R3

Object Wn R ² _R 3

 7 U u ivi c

^CF 3

 o Γ F p f

59 Me H E t

^CF 3

 60 H Me Me

^CF 3

61 CH ₂ C 1 HH Me

62 CH ₂ C 1 HHE t

63 CH ₂ CH ₂ C 1 HHE t

1 1 7 C 1 H Me i -P r

1 1 8 C 1 HH CH ₀ CH ₂ 0CH ₃

1 1 9 CH ₂ C 1 H Me Me

1 2 0 CH ₂ C 1 H Me E t

1 2 1 CH ₂ C 1 Me H Me

化合物 No X R⁴ R⁵ R⁶

Compound No XR ⁴ R ⁵ R ⁶

 C 1 H H M e

C 1 H HE T r I u n — P r 7 11 XI i _ p r Q r 1 H 11 U

7 o C 1 H H p h

71 C 1 HH CH ₂ CH ₂ C 1

72 C 1 Me H E t

73 C 1 Me Hi-Pr

74 C 1 E t H Me

75 C 1 H Me Me

76 C 1 H E t E t

77 H H Me

^CF 3

 78 H H E t

^CF 3

 79 Me H E t

^CF 3

 80 Me H

^CF 3 Table 2 (Part 4)

6 one Table 2 (Part 5)

(Part 1)

OH

CH; Z CH ₂ CC 12 X

 Y

R ¹ Compound No. XYR ¹ R ² R ³

 81 C 1 Br H H E t

82 C 1 B r H H n-P r

83 C 1 C 1 H H n-P r

84 C 1 Br H Hi iPr

85 C 1 Br HH CH ₂ CH ₂ C 1

1 3 3 C 1 C 1 HH CH ₀ CH ₂ OCH ₃

Table 3 (Part 2)

OH

CH ₂ CC 1 -X

Y

R ⁴

9 one In addition, the carbamate derivative of the present invention has an enantiomer based on a quaternary carbon of a benzyl moiety, an oxysilane moiety, and a 7K acid moiety, and is usually obtained as a racemic form, but is obtained by a known method such as asymmetric synthesis. It is also possible to obtain each enantiomer. The carnomate derivative of the present invention may be in a racemic form or in each enantiomer alone, each of which can be used as a herbicide.

 In addition, when the chiral bamate derivative of the present invention has two asymmetric carbons, diastereomers are present, and each diastereomer can be obtained by a known method such as column chromatography. The compounds of the present invention may be a mixture of diastereomers or each diastereomer alone, each of which can be used as a herbicide. ,

 Among the carbamate derivatives (Ι) of the present invention, polyhaloalkene derivatives (IV) (compounds (IVa), (IVb) and (IVc) in Table 1) are represented by the following formula: It can be produced using the propene derivative (V) as a raw material.

CH _2. CH ₃

すなわち、 塩化第一銅などの触媒及びピぺリジンゃシクロへキシルァミンなど のァミン類の存在下、 プロペン誘導体 （V) とポリハロアルカン （CC 1₂ XX ' ) とを、 通常 0°Cないしポリハロアルカンの沸点の範囲の温度において 1~2 〇時間程度反応させることにより、 所望のポリハロアルケン誘導体 （IV)又はポ リハロアルカン誘導体 （VI)力《得られる。 この場合、 反応条件を適当に選ぶこと によりポリハロアルケン誘導体 （IV) に直接導いてもよいし、 ポリハロアルカン 誘導体 （VI) に導いてもよい。 ポリハロアルカン誘導体 （VI) を得た場台には、 このものを、 例えば 0—ジクロ口ベンゼン、 1， 2—ジクロロェタンなどの溶媒 中において塩化第一銅、 塩化第二鉄などの触媒の存在下に適当な温度に加熱する ことにより、 所望のポリハロアルケン誘導体 （IV) に導くことができる。

That is, the presence of Amin such as catalyst and Kishiruamin to piperidine Ya cycloalkyl such as cuprous chloride, propene derivative (V) and poly haloalkane (CC 1 ₂ XX ') and, usually 0 ° C to poly haloalkane The desired polyhaloalkene derivative (IV) or polyhaloalkane derivative (VI) is obtained by reacting at a temperature in the range of the boiling point for 1 to 2 hours. In this case, the reaction may be led directly to the polyhaloalkene derivative (IV) or to the polyhaloalkane derivative (VI) by appropriately selecting the reaction conditions. When the polyhaloalkane derivative (VI) is obtained, it is placed in a solvent such as 0-dichlorobenzene, 1,2-dichloroethane in the presence of a catalyst such as cuprous chloride or ferric chloride. By heating to an appropriate temperature, a desired polyhaloalkene derivative (IV) can be obtained.

 Further, among the carbamate derivatives (IH) of the present invention, the oxosilane derivative (VII) (compound (Vila), compound (Vllb) and compound (Vile) in Table 2) is a polyhaloalkene as shown in the following formula. The derivative (IV) can be produced by epoxidation using a peroxide.

 F, C H; CC 1 -X (X = halogen atom or C 1-4

 Kill group)

 C

この反応において用いられる過酸化物については特に制限はなく、 通常ェチレ ン性二重結合のエポキシ化に用いられるもの、 例えばクメンハイ ドロパーォキシ ド、 t—プチルーハイ ドロパーォキシド、 シクロへキシルハイ ドロパーォキシド や過酢酸、 α—ハイ ドロパーォキシイソ酪酸、 過安息香酸、 m—クロ口過安息香 酸などの過有機力ルポン酸および過酸化水素、 ォキソン （ペルォキシ—硫酸力リ ゥム） などを使用することができる力 これらの中で過有機カルボン酸、 特に過 酢酸及び m—クロ口過安息香酸が好適である。 この反応は通常、 不活性溶媒中に おいて、 好ましくは 0〜8 0。Cの範囲の温度において実施される。 不活性溶媒と しては、 例えば塩化メチレン、 クロ口ホルム、 四塩化炭素、 ジクロロメタン、 1 , 1 , 1 一トリクロロェタン、 o—ジクロ口ベンゼンなどのハロゲン化炭化水素類 カ《好ましく用いられる。 また、 所望により、 この反応系に酢酸ナトリウム、 安息 香酸ナトリウム、 りん酸水素ニナトリウム、 炭酸リチウムなどの緩衝剤を添加し て反応を行ってもよい。 前記アルゲン誘導体 （IV) と過酸化物との使用割合につ いては、 過酸化物をアルゲン誘導体 （IV) に対して 1〜4倍当量の割合で用いる ことカ望ましい。 反応時間は、 反応温度や使用する過酸化物の種類などによって 異なり、 一義的に決めることができないが、 通常 1 ~ 5 0時間程度である。

There is no particular limitation on the peroxide used in this reaction, and those usually used for the epoxidation of ethylenic double bonds, such as cumene-hyperoperoxide, t-butyl-hy-dropperoxide, cyclohexyl-hydroperoxide, peracetic acid, α- Perorganic powers such as hydroperoxyisobutyric acid, perbenzoic acid, m-chloroperbenzoic acid, and other powers that can use ruponic acid, hydrogen peroxide, and oxone (peroxy-sulfuric acid). Among them, perorganic carboxylic acids, particularly peracetic acid and m-chloroperbenzoic acid are preferred. The reaction is usually carried out in an inert solvent, preferably from 0 to 80. Performed at temperatures in the range of C. As the inert solvent, for example, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloromethane, 1,1,1-trichloroethane and o-dichlorobenzene are preferably used. If desired, a buffer such as sodium acetate, sodium benzoate, disodium hydrogenphosphate, lithium carbonate or the like may be added to the reaction system to carry out the reaction. Regarding the use ratio of the above-mentioned argen derivative (IV) and peroxide, it is preferable to use the peroxide in a ratio of 1 to 4 equivalents to the argen derivative (IV). The reaction time varies depending on the reaction temperature, the type of peroxide used, and the like, and cannot be determined uniquely, but is usually about 1 to 50 hours.

 In addition, among the carbamate derivatives (1) of the present invention, the halogenohydrin derivative (VIII) (compound (ViIla) and compound (VIlib) in Table 3; ne))) can be produced using a polyhaloalkene derivative (IV) as a raw material, as shown by the following formula.

(Hereinafter the margin)

_{CH 2 CH 2 CC 12 -X (} X = halogen atom orヽhaloalkyl group having 1 to 4 carbon atoms)

'CH ¹丄

すなわち、 水の存在下、 テトラヒドロフラン、 ジメチルスルホキシドなどの不 活性溶媒中でポリハロアルカン誘導体 （IV) に N—ブロモこはく酸イミ ドあるい は N—クロ口こはく酸イミ ドを通常 0°C〜80°Cの範囲の温度において 3〜20 時間程度反応させることにより、 所望のハロゲノヒドリン誘導体 （VIII) を得る こと力 きる。

That is, N-bromosuccinic acid imide or N-chloro succinic acid imid is usually added to polyhaloalkane derivative (IV) in an inert solvent such as tetrahydrofuran or dimethylsulfoxide in the presence of water at 0 ° C to 80 ° C. By reacting at a temperature in the range of ° C for about 3 to 20 hours, the desired halogenohydrin derivative (VIII) can be obtained.

 The propene derivative (V) used as a raw material in the production of the carbamate derivative () of the present invention can be produced by an ordinary method using readily available raw materials. The representative examples are shown below.

(Hereinafter the margin)

0. CH ₃

Lid '

CH _2. CH _:

(K)

 : Ν

 RMgB KOH

G Η \ C CH ₂ , CH:

 \

L i A 1 Η ₄ -A 1 C 1

(X) (K), C0 2 H

1) NH ₂ OH N a BH ₄

, 2) L i A 1 -A 1 C 1 L i A 1 H ₄ -A 1 C 1

CH ₂ , CH, CH _2. CH

(式中の B、 R¹、 R²、 R³、 R⁴、 R⁵、 R⁶ および R⁷ は前記と同じ意 味を有し、 Rは R¹、 R⁴ を示す。 ）

(In the formula, B, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as described above, and R represents R ¹ and R ^4. )

 The carbamate derivative of the present invention has excellent herbicidal activity against annual rice weeds such as Nobie which is a paddy weed; It also has herbicidal activity against perennial weeds. In addition, it has high selectivity and can effectively control these weeds at a dose of, for example, about 50 g per 10 ares, and does not cause harm to paddy rice at the above dose.

 The herbicide of the present invention contains the above-mentioned carbamate derivative, that is, the novel carbamate derivative of the present invention represented by the general formula (III) as an active ingredient. It can be mixed with a solid carrier such as mineral fine powder and formulated into wettable powders, emulsions, powders, granules and the like. A surfactant may be added to impart emulsifiability, dispersibility, spreadability and the like during formulation.

 When the herbicide of the present invention is used in the form of a wettable powder, it is usually used in a proportion of 10 to 55% by weight of the carbamate derivative of the present invention, 4 ° to 88% by weight of the solid carrier and 2 to 5% by weight of the surfactant. The composition may be prepared by blending on a table and used. When the emulsion is used in the form of an emulsion, it is usually compounded in a proportion of 20 to 50% by weight of the power bamate derivative of the present invention, 35 to 75% by weight of a solvent and 5 to 15% by weight of a surfactant. L,

 On the other hand, when used in the form of a powder, the carbamate derivative of the present invention is usually blended at a ratio of 0.5 to 16% by weight, a solid carrier at 80 to 97.5% by weight, and a surfactant at a ratio of 2 to 5% by weight. It may be prepared by adjusting. Further, when used in the form of granules, the carbamate derivative of the present invention is in a ratio of 0.5 to 16% by weight, a solid carrier is 80 to 97.5% by weight, and a surfactant is 2 to 5% by weight. What is necessary is just to mix and prepare. Here, fine powder of a mineral substance is used as the solid carrier. Examples of the fine powder of the mineral substance include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as Secco, talc and pie. Mouth ferrite, clay, violin, bentonite, acid clay, white carbon, quartz powder, gay stone powder and the like can be mentioned.

As a solvent, organic solvent power is used. Specifically, benzene, toluene, Aromatic hydrocarbons such as silene, chlorinated hydrocarbons such as o-chlorotoluene, trichloromethane, trifluoroethylene, alcohols such as cyclohexanol, amyl alcohol and ethylene glycol, isophorone, cyclohexanone, cyclohexenyl-cyclo Examples include ketones such as xanone, ethers such as butyl ether, dimethyl ether and methyl ethyl ether, esters such as isopropyl acid, benzyl acetate and methyl phthalate, amides such as dimethylformamide and mixtures thereof. Power <Can.

 Further, as the surfactant, any of an anionic type, a nonionic type, a cationic type and a zwitterionic type (amino acid, betaine, etc.) can be used.

 The herbicide of the present invention may contain other herbicidally active ingredients, if necessary, together with the carbamate derivative represented by the general formula (III) as an active ingredient. Examples of such other herbicidally active ingredients include known herbicides such as phenoxy, diphenyl ether, triazine, urea, carbamate, thiol carbamate, acid anilide, and pyrazole. , Phosphate, sulfonylprea, oxadiazone, etc., and can be used by appropriately selecting from these herbicides.

 Further, the herbicide of the present invention can be mixed with an insecticide, a fungicide, a plant growth regulator, a fertilizer, and the like, if necessary.

 Next, the present invention will be described in more detail by way of production examples and test examples, but the present invention is not limited to these examples.

 (Production Example of Compound (IVa), Compound (IVb) and Compound (IVc) in Table 1) Production Example 1

 Production of methyl N— [3 -— (1,1,1,1-trichloro-3-butene-1--3-yl) benzyl] carbamate (Compound No. 1)

 Dissolve 1.0 g (4.8 mmol) of methyl N- (3-isopropenylbenzyl) carbamate in 30 ml of bromotrichloromethane, and add 0.01 g of cuprous chloride and 0,7 of piperidine. ml (7.1 mmol) were added sequentially, and the mixture was heated at 70 ° C. for 30 minutes. Next, 5% by weight of hydrochloric acid was added, and the mixture was extracted with chloroform. The extract was dried over anhydrous sodium sulfate. Column chromatography of the crude product (silica gel, ethyl acetate

- twenty one - L: hexane = 1: 3) and purified with methyl N— [3--1,1,1-trichloro-1,3-butene-3-yl) benzyl] carbamate 1.30 g (83% yield). Obtained. The analytical values of this are shown in Table 4 (Part 1).

Production Example 2

 Production of methyl N— [3- (2,2-dichloro-1,1,1-trifluoro-1-pentene-4-yl) benzyl] carbamate (Compound No. 17)

 Methyl N— (3- ^ f-sopropenylbenzyl) carbamate 3.81 (18.6 mimol) was dissolved in 1,1,1-trichloro-2,2,2-trifluoroethane 14 Om 1 0.03 g of cuprous copper and 2.5 ml of piperidine (25.3 mmol) were sequentially added, and the mixture was heated under reflux for 1 hour. Next, 5% by weight of hydrochloric acid was added, and the mixture was extracted with chloroform. The extract was dried over anhydrous sodium sulfate. The chloroform was distilled off under reduced pressure to obtain methyl N— [3- (2,2,4-trichloro-1,1,1,1-trifluoropentane-14-yl) benzyl] carbamate as an intermediate. . This intermediate was dissolved in 120 ml of 1,2-dichloroethane, and 1.〇 g (6.2 mmol) of anhydrous ferric chloride was added, followed by heating at 70 ° C. for 30 minutes. Next, 5% by weight hydrochloric acid was added, and the mixture was extracted with chloroform. The extract was dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl citrate: hexane = 1: 3), and methyl Ν- [3- (2,2-dichloro-1,1,1-trifluoro-4-pentene-1) was obtained. 4.13) Benzyl] carbamate 5.13 g (78% yield) was obtained. The analytical values of this are shown in Table 4 (Part 4).

 Similarly, other compounds described in Table 1 were produced according to the methods described in Production Examples 1 and 2. The analytical values of these are shown in Tables 4 (1) to (13).

(Hereinafter the margin) Table 4 (Part 1) Analysis results

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3370, 2990, 1720 3.70 (s, 3H), 3.87 (d, 2H), 4.38 (d, 2Η)

1 1540, 1260, 1050 5.09 (b s, 1 Η), 5.52 (d, Η), 5.63 (d, 1 Η)

 815, 715 7.10 ~ 7.54 (m, 4Η)

 3350, 2995, 1715 1.28 (t, 3Η), 3.88 (d.2Η), 4.15 (q, 2Η)

2 1535, 1260, 1040 4.38 (d, 2Η), 4.99 (b s, 1Η), 5.50 (d, 1Η)

 805, 715 5.61 (d, 1Η) .7.12 to 7.50 (m, 4Η)

t

 0.93 (t, 3Η), 1.41— 1.87 (m, 2 Η)

 3310, 2950, 16 5

 3.87 (α, 2Η), 4.04 (t, 2Η), 4.38 (α, 2Η)

3 1520, 1245, 950

 5.00 (bs, 1), 5.50 (d, 1Η), 5.61 (d. 1Η) 780, 700

 7.12 to 7.48 (m, 4 Η)

 3350, 2990, 1710 1.25 (d, 6Η), 3.88 (d, 2Η), 4.37 (d, 2Η)

4 1535, 1250, 1015 4.80 to 5.21 (m, 2Η) .5.51 (d, 1Η)

 800, 720 5.63 (d, 1Η), 7.13—7.51 (m, 4Η)

 0.91 (t, 3Η), 1.12-1.76 (m, 4Η)

 3325, 2990, 1705

 3.87 (d, 2Η), 4.07 (t, 2Η), 4.37 (d, 2Η)

5 1540, 1260, 1020

 4.87 (bs, 1H), 5.50 (d, 1H), 5.62 (d, 1H) 810, 720

7.12 to 7.51 (m, 4H)

Table 4 (Part 2) Analysis results

 Compound No.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 0.92 (d, 6 H), 1.72 ~ 2.1 2 (m, 1 H)

 3375, 29 0, 17 1 0

 3.82-3.98 (m, 4H), 4.37 (d, 2H)

 6 1 545, 1 245, 1 000

 4.95 (bs, 1H), 5.51 (d1H), 5.61 (d, 1H) 795, 715

 7.14 to 7.53 (m, 4 H)

 3360, 2975, 1 705 1.48 (s, 9 H), 3.89 (d, 2 H), 4.32 (d, 2 H)

7 1 530, 1 250, 10 1 5 4.90 (bs, 1 H), 5.50 (d, 1 H), 5.62 (d, 1 H)

 805.7 1 5 7.18 to 7.54 (m.4H)

ο

 3400, 3090, 1 730 3.90 (d, 2H), 4.43 (d, 2 H), 5.38 (bs, 1 H)

8 1 545, 1 5 1 0, 1235 5.52 (d, l H), 5.65 (d, 1 H)

 1 025, 775, 705 6.97-7.74 (m, 9H)

 3.70 (d d, 2 H), 3.88 (d, 2 H)

 3360, 2995, 1 7 1 5

 4.28 to 4.48 (m, 4H), 5.20 (b s, 1 H)

 9 1 540, 1455, 1 260

 5.5 1 (d, 1 H), 5.63 (d, 1 H)

 1 1 55, 8 1 0, 710

 7.14 to 7.50 (m, 4H)

 3350, 2975, 1735 3.87 (d, 2H), 4.43 (d, 2H), 4.76 (s, 2H)

1 0 1 540, 1 250, 1 1 60 5.38 (b s, 1 H), 5.5 1 (d, 1 H), 5.62 (d, 1 H)

1 1 10, 8 10, 7 1 5 7.13 to 7.5 1 (m, 4 H)

Table 4 (Part 3) Analysis results

Compound NO.

Infrared absorption spectrum (cm ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3370, 2990, 1720 1.45 (d, 3H), 3.63 (s, 3H), 3.87 (d, 2H)

1 1 1540, 1450, 1225 4.69 5.04 (m, 1H), 5.18 (bs, 1H)

 1 195. 1050, 725 5.49 (d, 1 H), 5.62 (d, 1 H)

 7.09 7.49 (m, 4H)

 3375 Q 95 1 715 1.22 (, 3H), 1.45 (d, 3H), 3.87 (d, 2H)

12 1530, 1435, 1235 4.13 (q, 2H), 4.67 5.05 (m, 2H)

 1205, 715 5.50 (d, 1 H), 5.63 (d, 1 H)

 7.1 to 7.51 (m, 4H)

 2990, 1705, 1505 2.87 (s, 3H), 3.77 (s, 3H), 3.89 (d, 2H)

13 1420, 1225, 1 150 4.49 (s, 2H), 5.51 (d, 1H), 5.62 (d, 1H)

 815.710 7.10 7.52 (m, 4H)

 2990, 1700, 1490 1.29 (t, 3H) 2.84 (s, 3H), 3.88 (d, 2H)

14 1405, 1230, 1 145 4.21 (q, 2H), 4.48 (s, 2H), 5.50 (d.1H)

800, 705 5.62 (d, 1 H), 7.09 7.48 (m. 4 H)

Table 4 (Part 4) Analysis results

 Compound NO.

Infrared absorption scan Bae spectrum (c ΠΤ ¹⁾ Nuclear magnetic co eggplant Bae click preparative Le (P Pm)

 1.06 (t, 3H), 3.10 to 3.42 (m, 2H)

 2970, 1705, 1500

 3.75 (s, 3H), 3.88 (d, 2H), 4.49 (s, 2H)

15 1410, 1230, 1160

 o 1 π 7 1 n 5.50 (d, 1 H), 5.61 (d, 1 H)

 7.08-7.46 (m, 4H)

 2995, 2950, 1705 1.27 (t, 3H), 3.31 (s, 3H). 3.88 (d, 2H)

16 1475, 1425, 1240 4.18 (q, 2H), 4.57 (s, 2H), 5.50 (d, 1H)

 1125, 790, 715 5.61 (d, 1 H), 7.10 to 7.39 (m, 4 H)

o

 3375, 2 95, 1725 3.48 (d, 2H), 3.70 (S, 3H), 4.38 (d, 2 H)

17 1545, 1275, 1195 5.06 (b s, 1 H), 5.48 (d, 1 H), 5.60 (d, 1 H)

 1 160, 990, 785 7.17 to 7.50 (m, 4H)

 3390.3000.1720 1.27 (t, 3H), 3.48 (d, 2H), 4.10 (q, 2H)

18 1540, 1275, 1190 4.40 (d, 2H), 5.15 (b s, 1H), 5.47 (d. 1H)

 1 150. 995, 765 5.61 <d, 1 H), 7.16 to 7.48 (m, 4 H)

 1.26 (t, 3H), 1.46 (d, 3H), 3.48 (d, 2H)

3370, 2990, 1710

 4.09 (q, 2H), 4.69—5.19 (m, 2H)

 1 1525, 1270, 1 195

 5.48 (d, l H), 5.60 (d, l H)

 1 175, 980, 725

7.13〜7.51 (m, 4H)

Table 4 (Part 5) Analysis results

Compound No.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (PPm)

2980, 17 U, 154 U. ¾ (s, 3,, 3.4 ο (α,,, 3.1 ί \ s, Δ Π 12 U 1275, 1 190, 1 145 4.48 (s , 2Η), 5.47 (d, 1 Η), 5.60 (d, 1 Η)

 995, 775 7.07 to 7.50 (m, 4Η)

 3370, 2990, 1735 3.54 (s, 2Η), 3.70 (s, 3Η), 3.86 (s, 2Η)

21 1545, 1440, 1270 4 39 39 (α, 2 τΗ τ) \, f 5.. 1 1 (レ b s, 1 Η \, r 5r. 44 (α, 1 Η)

 1215, 710 5.53 (d, 1Η), 7.12 to 7.46 (m, 4Η)

 1.23 (, 3Η), 3.55 (s, 2Η), 3.85 (s, 2Η)

3350, 2995, 1715

Λ 1 ^ Λ (V Δ ΧΛ \ \) _r 4 Λ. QJ? (U Λ „Δ W ri \), C. OU Ό VD ο S, 1 丄 1 Μ, /

22 1535, 1430, 1260

 5.44 (d, 1 Η), 5.51 (d, 1 Η)

 1045, 700

 7.14〜7.45 (m, 4 Η)

 1.23 (t, 3Η), 3.18 (d d d, 4Η), 3.50 (d, 2Η)

3360, 3005, 1715

 4.16 (q, 2Η). 4.33 (d. 2Η), 5.08 (bs, 1 H)

23 1540, 1450, 1260

 5.39 (d, 1 H), 5.52 (d, 1 H)

 1 150, 1055, 805

 7.13 to 7.47 (m, 4H)

 3350, 2995, 1715 2.80 (d, 3H), 390 (d, 2H), 4.85 (bs, 1H)

24 1530, 1260, 1025 5.13 (s, 2H), 5.52 (d, 1H), 5.64 (d, 1H)

815.715 7.18 ~ 7.58 (m, 4H)

Table 4 (Part 6) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 1.13 (t.3H), 3.07 to 3.43 (m, 2H)

 3360, 3000, 1710

 3.90 (d, 2H), 4.78 (b s, 1 H), 5.1 1 (s, 2H)

25 1540, 1260, 1035

 5.51 (d, 1 H), 5.64 (d, 1 H)

 805, 720

 7.20-7.58 (m, 4H)

 0.1 (t, 3H), 1.30—1.73 (m, 2 H)

 3350, 2 90, 1725

 2.95-3.30 (m, 2H) .3-90 (d, 2H)

 26 1545.1250, 1030

 4.92 (bs, 1H), 5.10 (s, 2H), 5.50 (d, 1H) 81 5,710

 5.62 (d, 1H), 7.19—7.57 (m, 4H)

 3375, 3000, 171 5 1.15 (d, 6H), 3.61 to 4.06 (m, 1 H)

 27 1535, 1255, 1030 3.90 (d, 2H), 5.1 1 (s, 2H), 5.51 (d, 1H)

 820.71 5 5.64 (d, 1 H), 7.18-- 7.57 (m, 4 H)

 0.91 (t, 3H), 1.12 ~ 73 (m, 4H)

 3345, 2995, 1720

 3.01-3.32 (m, 2H), 3.90 (d, 2H)

 28 1520, 1260, 1010

 4.95 (bs, 1H), 5.11 (s, 2H), 5.50 (d, 1H) 825, 710

5.63 (d, 1H), 7.19 to 7.58 (m, 4H)

4 (Part 7) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3375, 3005, 1730 1.33 (s.9H) .3.90 (d, 2H), 4.72 (bs, 1H)

29 1525, 1265, 1050 5.07 (s, 2H), 5.52 (d, 1H) 5.65 (d, 1H)

 795, 705 7.21 to 7.60 (m, 4H)

 3390, 3025, 1725 3.88 (d, 2H), 5.17 (s, 2H), 5.49 (d, 1H)

30 1615, 1540, 1475 5.60 (d, 1 H), 6.89 to 7.68 (m, 1 OH)

 1240, 1060, 710

 3350, 2995, 1720 3.37-3.76 (m, 4H), 3.89 (d, 2H)

 31 1530, 1245, 1025 5.11 (s, 2H), 5.30 (bs, 1H), 5.51 (d, 1H)

 800, 730, 695 5.63 (d, 1H), 7.19-7.58 (m, 4H)

 1.12 (t, 3H), 1.50 (d, 3H)

 3365, 3010. 1715

 3.05 to 3.40 (tn, 2H), 3.90 (d, 2H)

 32 1540, 1260, 1025

 4.83 (bs, 1H), 5.50 (d, 1H). 5.63 (d, 1H) 810, 715

 5.80 (q, 1H), 7.18-7.55 (m, 4H)

 1.13 (d, 6H), 1.50 (d, 3H)

 3375, 3000, 1725

 3.61 to 4.00 (m, 3H), 4.78 (bs, lH)

 33 1525, 1210, 1045

 5.52 (d, 1 H), 5.62 (d, 1 H)

 820, 725

7.19 ~ 7.58 (m, 4H)

Table 4 (Part 8) Analysis results

Compound No.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (P Pm)

 0.87 (t, 3H), 1.67-2.03 (m, 2H)

 3350, 2970, 1 720

 2.76 (s, 3H), 3.88 (d, 2Η), 4.63 (bs, 1H)

34 1 525, 1260. 1 1 35

 5.5 1 (d, 1 H), 5.57 to 5.72 (m, 2 H)

 800, 705

 7.18 to 7.5 1 (m, 4 H)

 2950, 1 705, 1 500 2.92 (s, 6H), 3.89 (d, 2H), 5.13 (s, 2H)

35 1405, 1 360, 1 1 90 5.5 1 (d, 1 H), 5.64 (d, 1 H)

 1 060, 705 7.21 ~ 7.57 (m, 4H)

 3000, 1 7 10, 1485 1.12 (t, 6H), 3.30 (q, 4H), 3-90 <d, 2 H)

36 1435, 1285, 1 1 75 5.14 (s, 2 H), 5.52 (d, 1 H), 5.63 (d ₍ 1 H)

 1 075, 7 10 7.20-- 7.58 (m, 4 H)

 3375, 3000, 1 7 1 5 2.82 (d, 3H), 3.47 (d, 2H), 4.72 (bs, 1H)

37 1 540, 1265.1 1 90 5.13 (s, 2H), 5.49 (d, 1H), 5.64 (d, 1H)

 1 1 55, 975. 770 7.17 to 7.54 (m, 4 H)

 1.13 (t, 3H) .3.02 to 3.34 (m, 2H)

 3390, 2995, 1 720

 3.48 (d, 2H), 4.68 (bs, 1H), 5.12 (s, 2H)

38 1 545, 1280, 1 1 95

 5.47 (d, l H), 5.61 (d, 1 H)

 1 1 60, 990, 755

7.19 ~ 7.57 <m, 4 H)

Table 4 (Part 9) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 1 1 3 (t, 3 H), 1.52 (d, 3 H)

 3400, 3005, 1705

 3. 04

 39 1 550, 1275, 1 190 to 337 (m, 2 H), 3.47 (d, 2 H)

 4.82 (bs, 1H), 5.48 (d, 1H), 5.63 (d, 1H) 1 160, 985, 790

 5.80 (q. 1 H), 7.17 to 7.53 (m, 4H)

 1.12 (d, 6 H), 1.62 (d, 3 H), 3.48 (d, 2 H)

3370, 3000, 1 7 1 5

 3.57-3.98 (m, 1 H), 4.61 (b s, 1 H)

 40 1 545, 1 270, 1 1 95

 5.47 (d, 1H), 5.62 (d, 1H), 5.80 (q, 1H) 1165, 980.775

7.20 to 7.59 (m, 4H)

4 (Part 10)

Table 4 (Part 11) Analysis results

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 《<< 4 U, J5 r no, _7 O V · = »Δ f, J?. O f,))

3350, 1710, 1540

 3-85 (s, 2H), 4.60—5.20 (m, 1 H)

 1 0 5 1260, 1070, 790

 5.45 (m, 1H), 5.63 (m, 1H)

 700

(. U / O O vj V Hi _f ^ i tl ノ

 3450, 1720, 1610

 3.90 (s, 2H), 5.10 (b s, 4H), 5.50 (m, 1 H)

1 0 6 1450, 1400, 1300

 5.63 (m, 1H), 7.15 7.75 (m, 4H)

) 1050, 710

 -¾ 400 1 600 1 400 1 4 Q (H H) 3 «(s 2 H) 5 2 '? (H ς H)

1 0 7 1320, 1080, 800 5.49 (m, 1 H), 5.61 (m, 1 H), 5.78 (q, 1 H)

 720 7.10 7.60 (m, 4H)

 2900, 1700, 1480 1.09 (t, 3H), 2.91 (s, 3H), 3.32 (q, 2H)

1 0 8 1400, 1180, 770 3.88 (s, 2H), 5.15 (s, 2H), 5.49 (m1H)

 700 5.62 (m, 1H), 7.15 7.75 (m, 4H)

 3300, 1780, 1720

 2.39 (s, 3H), 3.85 (s, 2H), 5.15 (s, 2H) 1500, 1390, 1300

 1 0 9 5.50 (m, 1 H), 5.62 (m. 1 H)

 1200, 1080, 780

 7.10-7.60 (m.4H), 8.25 (bs, 1H)

720

Four

4 (Part 12)

4 (part 1 3)

(Compound (Vila), Compound (VI lb) and Compound (Production Example of VI IO) in Table 2) Production Example 3

 Production of methyl N— [3 -— (1,1,1-trichloro-1,3,4-epoxybutane-3-yl) benzyl] carbamate (Compound No. 41)

 Methyl N— [3- (1,1,1-trichloro-3-butene-3-yl) benzyl] carbamate 1. Dissolve 30 g (4. mmol) of carbamate in 30 ml of methylene chloride and add hydrogen phosphate Disodium (0.01 g) and 70% m-chloroperbenzoic acid (1.50 g, 6.1 mmol) were sequentially added, and the mixture was stirred at room temperature for 36 hours. Next, the methylene chloride layer was washed with a saturated aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane == 1: 3), and methyl N— [3 -— (1,1,1-trichloro-3,4-epoxybutane-1-) Benzyl) carbamate 1.12 g (82% yield) was obtained. The analytical values of this are shown in Table 5 (Part 1).

 Similarly, other compounds described in Table 2 were produced according to the method described in Production Example 3. The analytical values of these are shown in Table 5 (Part 1) to (Part 12).

(Hereinafter the margin)

3 ^

Table 5 (Part 1) Analysis results

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3350, 2975, 1715 2.95 (d, 1H), 3.22 (d, 1H), 3.38 (d, 2H)

41 1520, 1250, 1120 3.70 (s, 3H), 4.38 (d, 2H), 5.02 (bs, 1 H)

 1020, 725 7.13 to 7.62 (m, 4H)

 3345, 2970, 1700 1.23 (t, 3H), 2.96 (d, 1H), 3.22 (d, 1H)

42 1520, 1245, 1135 3.38 (d, 2H), 4.16 (q, 2H), 4.36 (d, 2H)

 1035, 770, 695 5.15 (b s, 1 H), 7.12 to 7.59 (m, 4H)

 0.93 (t, 3H), 1.41—1.87 (m, 2H)

 3375, 2995, 1720

 2.97 (d, 1H), 3.22 (d, 1H), 3.40 (d, 2H)

43 1540, 1270, 1150

 4.04 (t, 2H), 4.37 (d, 2H), 5.06 (bs, 1H) 1055. 715

 7.12 to 7.60 (m, 4H)

 3350, 2800, 1700 1.25 (d, 6H), 2.98 (d, 1H), 3.24 (d, 1H)

44 1540. 1270, 1 150 3.40 (d, 2H), 4.36 (d, 2H)

 1035, 725 4.79 to 5.18 (m, 2H), 7.11 7.61 (m. 4H)

 0.91 (t, 3H), 1.13—1.78 (m, 4H)

 3375, 2800, 1725

 2.96 (d, 1H), 3.21 (d, 1H), 3.38 (d, 2H)

45 1550, 1270, 1 155

 4.06 (t, 2H), 4.34 (d, 2H), 5.18 (bs, 1H) 1060, 725

7.13 to 7.62 (m, 4H)

Table 5 (Part 2) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 0.92 (d, 6H), 1.71 to 2.09 (m, 1 H)

 3390, 3000, 1740

 2.98 (d, 1H), 3.22 (d, 1H), 3.38 (d, 2H)

46 1540, 1265, 1160

 3.88 (d, 2H), 4.37 (d, 2H), 5.12 (bs. 1H) 7.11 7.57 (m, 4H)

 3360, 2975, 1705 1.47 (s, 9H), 2.97 (d, 1H), 3.21 (d, 1H)

47 1515, 1365, 1045 3.38 (d, 2H), 4.30 (d, 2H), 4.94 (bs, 1H)

 1 165, 705 7.18 ~ 7.63 (m, 4H)

 3390, 3095, 1735 2.97 (d, 1H), 3.21 (d, 1H), 3.39 (d, 2H)

48 1540, 1505, 1225 4.42 (d, 2H), 5.50 (b s, 1 H)

 1050, 780, 715 6.98-7.64 (m, 9H)

 3345, 2 60, 1720 2.98 (d, 1 H), 3.24 (d, 1 H), 3.40 (d, 2H)

49 1525, 1430, 1240 3.69 (dd, 2H) .4.28 to 4.48 (m, 4H)

 1 135, 1040, 700 5.20 (b s, 1 H), 7.12 to 7.55 (m, 4H)

 3350, 2950, 1740 2.95 (d, 1H), 3.23 (d, 1H), 3.38 (d, 2H)

50 1535, 1240, 1 150 4.42 (d, 2H), 4.74 (s, 2H), 5.56 (bs, 1H)

1035, 820, 710 7.15 to 7.56 (m, 4H)

Table 5 (Part 3) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3355, 3000, 1715 1.46 (d, 3H), 2.98 (d, 1 H), 3.23 (d, 1 H)

51 1540, 1460, 1260 3.40 (d, 2H), 4.65 (s, 3H),

 1205, 1080, 715 4.68 to 5.14 (m, 2H), 7.14-7.53 (m, 4H)

3390, 3030, 1735 1.21 (t, 3H), 1.46 (d, 3H). 2.98 (d, 1 H)

52 1550, 1355, 1270 3.23 (d, 1H), 3.40 (d, 2H), 4.08 (q.2H)

 1085, 725 4.67-5.12 (m, 2H), 7.18-7.57 (m.4H)

2960, 1710, 1480 2.84 (s, 3H), 2.99 (d, 1H), 3.23 (d, 1H)

53 1295, 1240, 1 145 3.40 (d, 2H), 3.78 (s, 3H), 4.49 (s, 2H)

 770, 705 7.12 ~ 7.58 (m, 4H)

 2995, 1700, 1485 1.29 (t, 3H), 2.83 (s, 3H), 2.98 (d, 1H)

54 1415, 1240.1 150 3.23 (d, 1H), 3.39 (d, 2H), 4.20 (q, 2H)

 775, 715 4.48 (s, 2H), 7.08—7.50 (m, 4 H)

 1.05 (t, 3H), 2.99 (d, 1H), 3.21 (d, 1H)

2800, 1715, 1485

 3.09-3.40 (m, 2H), 3.39 (d, 2H)

 55 1450, 1420, 1265

 3.76 (s, 3H), 4.49 (s, 2H)

 1155.780, 715

7.13〜7.53 (m, 4H)

Table 5 (Part 4) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 2995, 2945, 1700 1.28 (t.3H), 2.98 (d, 1H), 3.19 (d, 1H)

56 1 4 7 ^ 1420J% 1 2 ^ 0 "3 Q 1 la" J3 u ΓΙ \ / -a .- Da 71 ί HU, Uilno, A

 1120, 775, 710 4.56 (s, 2H), 7.09 7.52 (m, 4H)

 3360, 2985, 1715 2.93 (d 2H), 2.98 (d, 1 H), 3.16 (d, 1 H)

57 1535, 1260, 1200 3.70 (s, 3H), 4.37 (d, 2H), 5.04 (bs1H)

 1065, 710 7.17 7.52 (m, 4 H)

 3375, 3010, 1725 1.26 (t, 3H), 2.93 (d, 2H), 3.00 (d, 1H)

58 1540, 1275, 1220 3.18 (d, 1H), 4.16 (q, 2H), 4.39 (d, 2H)

 1200, 1160, 715 4.98 (b s, 1H), 7.18 7.52 (m, 4H)

 3350, 2995, 1715 1.22 (t, 3H), 1.47 (d, 3H), 2.93 (d.2H)

59 1535, 1260. 1205 3.01 (d, 1 H), 3.18 (d, 1 H), 4.09 (q. 2H)

 1180, 1065, 710 4.71 5.18 (m, 2H) .7.15 7.53 (m, 4H)

2990, 1715, 1495 2.83 (s, 3H) .2.93 (d, 2H), 3.00 (d, 1H)

60 1405.1270, 1200 3.17 (d, 1H), 3.76 (s, 3H), 4.48 (s, 2H)

1 160.960, 775 7.12 7.52 (m, 4H)

7

Table 5 (Part 5) Analysis results

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (P Pm)

 2.84 (d, 1H), 3.02 to 3.31 <m, 3Η)

 3360, 2980, 1 730

 3.70 (s, 3Η), 3.78 (d, 1Η), 3.95 (d, 1Η)

6 1 1 535, 1440, 1 260

 4.38 (d. 2 Η), 5.00 (b s, 1 Η)

 1 200, 7 1 0

 7.19 to 7.5 1 (m, 4 Η)

 1.24 (t, 3 3), 2.82 (d. 1Η)

 3345, 2985, 1705

 2.98-3.28 (m, 3Η), 3.76 (d, 1Η)

 62 1 520, 1425, 1 250

 3.94 (d, 1Η), 4.15 (q, 2Η), 4.36 (d, 2Η) 1035, 700

 5.01 (b s, 1Η), 7.19 to 7.50 (m, 4Η)

 3350, 2980, 1705 l. 25 (t, 3H), 2.49 to 3.86 (m, 8H)

 D 3 1 525, 1 250, 1 140 4.I 5 (q, 2H), 4.36 (d, 2H), 5.05 (b s, l H)

 1 040.780, 700 7.I 8-7.49 (m, 4H)

 3400, 2990, 1730 2.81 (d, 3 H), 2.98 (d, 1 H), 3.23 (d, 1 H)

64 1 540, 1 270, 1 145 3.38 (d, 2H), 4.80 (bs, 1H), 5.10 (s, 2H)

 990, 785, 7 1 5 7.19 to 7.60 (m, 4 H)

 l. l l (t. 3 H), 2.97 (d, l H)

 3370, 2995, 1 7 1 0

 3.06-3.32 (m, 3H), 3.38 (d.2H)

 65 1 535, 1 260, 1 030

 4.88 (bs, 1H) .5.10 (s.2H)

 785, 7 1 0

7.19 ~ 7.58 (m, 4H)

5 (Part 6) Analysis results

Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 0.91 (t, 3H), 1.30—1.74 (m, 2H)

 3375, 2985, 1720

 2.98 (d, 1H), 3.04 to 3.31 (m, 3H)

 66 1535, 1265, 1145

 3.38 (d, 2H), 4.90 (bs, 1H), 5.10 (s, 2H) 1055, 780, 710

 7.20〜7.61 (m, 4H)

 1.17 (d, 6H), 2.98 (d, 1H), 3.24 (d, 1H)

3360, 2995, 1715

 3.39 (d, 2H), 3.60 to 4.05 (m, 1H)

 67 1535, 1330, 1250

 4.68 (b s, 1 H), 5.10 (s, 2 H)

 1085.710

 7.2 7.60 (m, 4H)

 0.91 (t, 3H), 1.12-1.75 (m, 4H)

 3355, 2980, 1715

 2.98 (d, 1 H), 3.06 to 3.32 (m, 3 H)

 68 1535, 1470, 1250

 3.38 (d, 2H), 4.90 (bs, 1H) 5.10 (s, 2H) 1 145, 780, 710

 7.20— 7.62 (m, 4H)

 3390, 3000, 1735 1.32 (s, 9H), 2.98 (d, 1H), 3.23 (d, 1H)

69 1520, 1280, 1220 3.38 (d, 2H), 4.76 (bs, 1H), 5.06 (s, 2H)

1085, 785, 715 7.2 2 7.63 (m, 4H)

9

(Part 7) Analysis results

 No.1

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3350, 3070, 1725 2.98 (d, 1H), 3.21 (d, 1Η), 3.39 (d, 2Η)

70 1610, 1535, 1450 5.15 (s, 2H), 6.85 (b s, l Η)

 1225, 1060, 705 6.92 to 7.64 (m, 9Η)

 3375, 29 0, 1735 2.98 (d, 1Η), 3.22 (d, 1Η), 3-39 (d, 2Η)

71 1540, 1260, 1205 3.4 4 3.72 (m, 4Η), 5.1 1 (s, 2Η)

 790, 745, 715 5.32 (b s, 1 H), 7.22 to 7.63 (m, 4 H)

 1.12 (t, 3H), 1.51 (d, 3H)

 3400, 3025, 1725

 2.94—3.35 (m, 4H), 3.40 (d, 2H)

 72 1550, 1265. 1215

 4.72 (bs, 1H), 5.79 (q, 1H)

 1085, 1020, 720

 7.20 to 7.61 (m, 4H)

 1.12 (d d, 6H), 1.50 (d, 3H), 2.98 (d, 1 H)

3380, 3005, 1725

 3.23 (d, lH), 3.40 (d, 2H)

 73 1540, 1365, 1335

 3.96 3.98 (m, 1 H), 4.60 (b s, 1 H)

 1260, 1090, 720

 5.80 (q, 1H), 7.19 to 7.62 (m, 4H)

 0.85 (t, 3H), 1.66-2.01 (m.2H)

 3375, 2990, 1735

 2.77 (d, 3H), 2.98 (d, 1H), 3.23 (d, 1H)

74 1535, 1260, 1 145

 3.38 (d, 2H), 4.71 (b s, 1H), 5.59 (t, 1H) 985, 800, 715

7.19 ~ 7.54 (m, 4H)

(Part 8)

 result of analysis

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 2945, 1710, 1495 2.93 (s, 6H), 2.98 (d, 1H), 3.22 (d, 1Η)

75 1400, 1335, 1 185 3.39 (d, 2H), 5.12 (s, 2H)

 1050, 770, 705 7.20 to 7.54 (m, 4Η)

 3000, 1710, 1575 1.12 (t d, 6H) .2.99 (d, l H)

 76 1490. 1435, 1280 3.12 to 3.48 (m, 5H), 5.16 (d, 2H)

 1 180, 775, 710 7.24 to 7.66 (m, 4H)

 3390, 2970. 171 5 2.82 (d, 3H), 3.01 (d, 2H), 3.08 (d, 1H)

77 1 535. 1260, 1 190 3.17 (d, 1 H), 4. 73 (b s, 1 H), 5.12 (s, 2 H) ο

 1 145, 995, 705 7.2 2 7.58 (m, 4H)

 3375, 3000, 1735 1.13 (t, 3H), 2.94 (d, 2H), 3.01 (d, 1 H)

78 1540, 1270, 1200 3.06 to 3.36 (m, 3H), 4.75 (bs.1H)

 1095, 1010, 715 5.1 1 1 (s, 2H), 7.22 to 7.60 (m, 4H)

1. 1 1 (t, 3H) , 1. 51 (d, 3H). 2. 93 (d F 2 H)

3375, 3000, 1720

 3.02 (d, 1H), 3.09-3.38 (m, 3H)

 79 1 535, 1270, 1200

 4.67 (bs, lH), 5.79 (q, lH)

 1070, 101 5, 710

 7.18 to 7.60 (m, 4 H)

 1.12 (d d, 6H), 1.50 (d, 3H), 2.95 (d, 2H)

3375, 3005, 1720

 3.02 (d, 1 H), 3.18 (d, 1 H)

 80 1 540, 1270, 1210

 3.59-3.98 (m, 1 H), 4.56 (b s, 1 H),

 1090, 965, 715

 5.81 (q, H), 7.19 to 7.61 (m, 4H)

1

(Part 9)

5 (part 10)

 result of analysis

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 3450, 1720, 1610 2.96 (d, 1 H), 3.21 (d, 1 Η), 3.41 (s, 2 H)

1 2 2 1450, 1400, 1320 4.98 (b s, 2H), 5.1 1 (s, 2 H)

 1050, 710 7.20 to 7.65 (m, 4H)

 3400, 1600, 1400 1.52 (d, 3H), 2.97 (d, 1H), 3.22 (d, 1H)

1 2 3 1320, 1080, 800 3.40 (s, 2H), 5.05 (bs, 2H), 5.76 (q, 1H)

 720 7.21 to 7.65 (m, 4H)

 2900, 1710, 1490 1.22 (t, 3H), 2.95 (s, 3H), 3.01 (d, 1H)

1 2 4 1410, 1180, 770 3.20-3.50 (m, 5H), 5.15 (s, 2H)

t

 710 7.20 to 7.70 (m, 4H)

 3300, 1770, 1720 2.40 (s, 3H), 2.95 (d, 1H), 3.22 (d, 1H) 1500, 1390.1300

 1 2 5 3.40 (s, 2H), 5.18 (s, 2H)

 1200, 1090, 780 7.18 to 7.70 (m, 4H), 8.00 (b s, 1 H)

 720

 3450, 1720, 1610

 1450, 1400, 1340 2.95 (s, 2H), 3.00 (d, 1H), 3.16 (d, 1H)

1 2 6 1260, 1200, 1050 4.90 (b s, 2H), 5.10 (s, 2H)

 1000.800, 7507.22 to 7.60 (m, 4H)

700, 530

(Part 1 1)

o

 Bird

 C

 U

 t ε Ε

t • to υ 5 (Part 12) Min Xin Result

 1 mouth J I υ ·

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

2950.1710, 1400 2.85 (d, 1Η), 2.95 (s, 6Η)

 1 3 1 1 160, 1200, 760 3.05 to 3.40 (m, 3Η), 3.86 (d, 2Η)

 700 5.15 (s, 2 Η), 7.10 to 7.70 (m, 4 Η)

1750, 1590, 1450

 1 280, 1200, 1040

 1 3 2

 1000, 990, 800

 700, 620

〇 m

 〇〇 LTi

In Ι>

.

C W (Production Example of Compound (Villa) and Compound (VI lib) in Table 3) Production Example 4

 Preparation of ethyl N— [3- (1-promo 4,4,4-trichloro-2-hydroxybutane-1--3-yl) benzyl] carbamate (Compound No. 81) ethyl N— [3 -— (1,1,1 —Trichloro-3-butene-3-yl) benzyl] 1.30 g (4.0 mimol) of carbamate was dissolved in 20 ml of tetrahydrofuran and 10 ml of water, and 0.85 g of N-bromosuccinic acid imide was dissolved. 4.8 ml) was added at 0 ° C, and the mixture was stirred for 1 hour. Next, after the temperature was raised to room temperature, the mixture was stirred for 5 hours, water and a saturated aqueous solution of sodium carbonate were sequentially added, and the mixture was extracted with getyl ether. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 3), and ethyl N- [3- (1-promo 4,4,4-trichloro-2-hydroxybutane 1-3-) was purified. Benzyl) carbamate 0.78 g (46% yield) was obtained. The analytical values of this are shown in Table 6 (Part 1).

 Similarly, other compounds described in Table 3 were produced according to the method described in Production Example 4. The analytical values of these are shown in Tables 6 (1) to (4).

(Hereinafter the margin)

Table 6 (Part 1) Analysis results

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 1.25 (t, 3H), 3.10 (s, 1H), 3.47 (d, 1H)

3450, 3360, 2995

 3.63 (d, 1 H), 3.77 (d, 1 H), 3.96 (d, 1 H)

81 1715, 1545, 1235

 4.15 (q, 2H), 4.38 (d, 2H), 5.18 (bs, 1H) 1080, 780, 710

 7.17 to 7.59 (m, 4 H)

 0.92 (t, 3H), 1.42—1.85 (m, 2H)

 3375, 2995, 1720 3.12 (s, 1 H), 3.47 (d, 1 H), 3.62 (d, 1 H)

1J1 82 1535, 1265, 1070 3.77 (d, 1H), 3.96 (d, 1H), 4.05 (t, 2H)

 785, 720 4.38 (d, 2H), 5.06 (bs, 1 H),

 7.15 to 7.61 (m, 4H)

 0.92 (t, 3H). 1.41— 1.83 (m, 2H)

 3370, 2985, 1710 3.15 (s, 1H), 3.42 (d, 1H), 3.67 (d, 1H)

83 1535, 1265, 1030 3.86 (d, 1 H), 4.03 (d, 1 H), 4.07 (t, 2H)

 780, 705 4.38 (d, 2H), 5.15 (b s, 1 H)

 7.13 ~ 7.58 (m, 4H)

 1.25 (d, 6H), 3.14 (s, 1 H), 3.47 (d, 1 H)

3460, 3375, 2980

 3.63 (d, 1 H). 3.78 (d, 1 H), 3.98 (d, 1 H)

84 1710. 1530, 1245

 4.37 (d, 1H), 4.78 to 5.19 (m, 3H)

 1095, 770, 715

7.15 to 7.59 (m, 4 H)

6 (Part 2) Analysis results

 Compound NO.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (Ppm)

 3435, 3350.2960 3.10 (s, 1H), 3.32 to 4.01 (m, 6H)

 85 1705, 1520, 1245 4.28 to 4.48 (m, 4H), 5.23 (bs, 1H)

 1 135, 765, 700 7.20 to 7.61 (m, 4H)

 1.14 (t, 3H), 3.08-3.39 (m, 3H)

 3375, 2995, 1710

3.46 (d, 1 H), 3.62 (d, 1 H), 3.76 (d ₍ 1 H)

86 1 530, 1255, 1 155

 3.96 (d, 1H), 4.75 (bs, 1H), 5.11 <s, 2H) 1090, 1030, 710

 IJ1 7.19 to 7.61 (m, 4H)

 1.13 (t, 3H). 3.08 to 3.36 (m. 3H)

 3360, 2980, 1705

 3.42 (d, 1 H), 3.68 (d, 1 H), 3.86 (d, 1 H)

87 1525, 1255, 1025

 4.02 (d, 1H), 4.78 (bs, 1H), 5.11 (s, 2H) 775, 700

 7.23 to 7.61 (m, 4 H)

 0.91 (t, 3H), 1.29-1.74 (m, 2H)

 3390, 29 0, 17 15 3.02 to 3.30 (m, 3H), 3.47 (d, 1H)

 88 1 525, 1230, 1075 3.63 (d, 1H), 3.77 (d, 1H), 3.97 (d, 1H)

 790, 71 5 4.69 (b s, l H), 5.1 1 (b s, l H)

7.22 ~ 7.58 (m, 4H)

6 (Part 3) Analysis results

 Compound No.

Infrared absorption spectrum (cm- ¹ ) Nuclear magnetic resonance spectrum (ppm)

 1.15 (d, 6H), 3.21 (s, 1Η), 3.48 (d, 1H)

3450, 3355, 2990

 89 1710, 1520, 1245 3.64 (d, 1 H), 3.68 to 4.03 (m, 3H)

 1085, 780, 710 4.69 (b s, 1H), 5.10 (s, 2H)

 7.24 to 7.60 (m, 4H)

 3475, 3345, 2980 1.15 (d, 6H), 3.17 (s, 1H), 3.41 (d, 1H)

90 1705, 1515, 1245 3-54-4.06 (m, 6H), 4.77 (bs, 1 H)

00 1025, 795, 720 5.10 (s, 2H), 7.23 to 7.60 (m, 4H)

6 (Part 4)

IJ1

Manufacturing implementation

 Preparation of 3-Isopropenyl benzonitrile (Compound IX)

 Dissolve 26.0 g (72.8 mimol) of methyltriphenylphosphonium bromide in 100 ml of tetrahydrofuran, and at room temperature under a nitrogen stream at room temperature 46.0 ml of a hexane solution of normal butyllithium (1.60 molno 1) (73.6 mmol) was added dropwise, and the mixture was stirred for 5 minutes. Next, a solution prepared by dissolving 1.0 g (68.9 mimol) of 3-cyanoacetophenone in 100 ml of tetrahydrofuran was added dropwise and stirred for 12 hours. Next, a saturated aqueous solution of ammonium chloride and water were added, and the mixture was extracted with ether. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 30) to obtain 8.92 g (yield 90%) of 3-isopropenylbenzonitrile. Table 7 shows the analysis value of this compound (K).

Production Example 6

Preparation of 3-Isopropenylbenzylamine (Compound X1I.R ¹ = H)

Under a nitrogen stream, to 50 ml of tetrahydrofuran at room temperature, 96 g (25.3 mmol) of lithium aluminum hydride and 1.1 g (8.2 mmol) of aluminum chloride were added in succession around JI. After stirring for 10 minutes, 3-isopro A solution of 3.0 g (21.0 mmol) of benzylbenzonitrile in 25 ml of tetrahydrofuran was added dropwise. After stirring for 1 hour at room temperature, 25 ml of water and 20 ml of a 10% aqueous sodium hydroxide solution were sequentially dropped at 0 ° C. Next, the reaction solution was filtered through celite, extracted with ether, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.78 g (yield: 90%) of 3-isopropenylbenzylamine. Table 7 shows the diffraction values of this compound (XII, R ¹ = H). Production Example 7

Step 1 of ¹ -Methyl-3-isopropenylbenzylamine (Compound XI1.R ¹ = Me)

1.4 g (9.8 mmol) of 3-isopropenylbenzonitrile were dissolved in 30 ml of benzene, and 5 ml of an ether solution of methylmagnesium bromide (3 molno 1) was added at 〇 ° C, and the temperature was returned to room temperature. Thereafter, the mixture was heated under reflux for 5 hours. Then at 0 ° C saturated ammonium chloride After adding 20 ml of a pharmacological solution and returning to room temperature, the mixture was stirred for 30 minutes. The reaction solution was extracted with ether, and the organic layer was washed successively with 5% by weight hydrochloric acid and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.5 g (yield: 96%) of 3-isopropenylacetophenone (compound X, R = Me).

Step 2

 1.5 g (9.4 mmol) of 3-isopropenylacetophenone, 0.8 g (11.5 mmol) of hydroxylamine hydrochloride, 1.5 ml (18.5 mmol) of pyridine in 3 Oml of ethanol Dissolve and heat to reflux for 2 hours. Then, after returning to room temperature, water and 5% by weight of hydrochloric acid were added, the reaction solution was extracted with ether, and the organic layer was washed with 5% by weight of hydrochloric acid and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.46 g (89% yield) of 3-isopropenylacetophenone oxime. Step three

The same operation as in Production Example 6 was carried out except that 3-isopropynylacetophenone oxime was used in place of 3-isopropenylbenzonitrile in Production Example 6, to give 3-methyl-3-isopropenylbenzylamide. (Yield 94%). Table 7 shows the analytical values of the compound (XII.R ¹ = Me).

Production Example 8

 Production of methyl N- (3-isopropenylbenzyl) carbamate (raw material for compounds No. 1, 17, 21)

 3-isopropenylbenzylamine 2.78 g (18.9 mimol), pyridin 3.2 ml (39.6 mimol), N, N-dimethylaminopyridine 0.03 g in methylene chloride 5 ml The mixture was dissolved, and 2.3 ml (29.8 mmol) of methyl carbonate was added at 〇 ° C, followed by stirring for 2 hours. Next, water and 5% by weight hydrochloric acid were sequentially added, and the mixture was extracted with methylene chloride. The organic layer was washed with a saturated aqueous solution of sodium carbonate and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3.78 g (yield 98%) of methyl N- (3-isopropenylbenzyl) carbamate. Table 7 shows the analysis values of this compound (the raw materials of compound Nos. 1, 17, and 21).

Similarly, the raw materials of Compound Nos. 2 to 12, 18, 19, 22, 23, 102, and 105 shown in Table 1 were produced according to the method described in Production Example 8. Of these things The structure was confirmed by NMR.

Production Example 9

 Production of methyl N-methyl-N- (3-isopropenylbenzyl) carbamate (raw material for compound No. 13, 20, 103)

 0.82 g (4.0 mmol) of methyl N- (3-isopropenylbenzyl) carbamate, 1.0 ml (16.1 mmol) of methyl iodide, 20 ml of tetrahydrofuran and N, N-dimethylformamide It was dissolved in 2 ml of a mixed solvent, 0.25 g (6.3 mmol) of 60% sodium hydride was added, and the mixture was heated under reflux for 1 hour. Next, water and a saturated aqueous solution of sodium carbonate were successively added dropwise at °° C, and the mixture was extracted with ether. The organic layer was washed successively with a saturated aqueous solution of sodium carbonate and a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.90 g (yield quantitative) of methyl N-methyl-N- (3-isopropenylbenzyl) carbamate. Table 7 shows the determination values of this compound (the starting materials for compound Nos. 13, 20, and 103).

 Similarly, the starting materials of compound Nos. 14 to 16, 101 and 104 shown in Table 1 were produced according to the method described in Production Example 9. The structures of these were confirmed by NMR. Production Example 10

Preparation of 3-Isopropenylbenzyl alcohol (Compound XI R, R ⁴ = H) Step 1

 2.0 g (14.0 millimoles) of 3-isopropenylbenzonitrile was dissolved in 3 ml of ethanol, 15 ml of a 2% aqueous hydroxide solution was added, and the mixture was heated under reflux for 8 hours. Next, 2 °% by weight hydrochloric acid was added dropwise at 0 ° C. to adjust the pH to 1, followed by extraction with chloroform and drying over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3-isobutπ-benzyloxybenzoic acid (Compound XI) 2.01 (89% yield).

Step 2

The same operation as in Preparation Example 6 was carried out except that 3-isopropenylbenzoic acid was used in place of 3-isopropenylbenzonitrile in Preparation Example 6, to give 3-isopropenylbenzyl alcohol (yield 98%). Table 7 shows the analysis value of this compound (ΧΠΙ, R ⁴ -H).

Production Example 11 ' Preparation of monomethyl- ³ -isopropenylbenzyl alcohol (Compound ΧΠΙ, R ⁴ = Me)

Dissolve 1.5 g (9.4 mmol) of 3-isopropenylacetophenone in 3 ml of ethanol, add 0.4 g (10.6 mmol) of sodium borohydride at 0 ° C, and stir for 1 hour did. Next, water and 5% by weight of hydrochloric acid were added successively, and the mixture was extracted with chloroform. The extract was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.51 (99% yield) of methyl 3-isopropenylbenzyl alcohol. Table 7 shows the analysis values of this compound (XIII, R ⁴ Me).

Production Example 12

 Production of 3-isopropenylbenzyl N-methylcarbamate (raw material for compounds No. 24 and 37)

 Dissolve 0.86 g (5.8 mmol) of 3-isopropenylbenzyl alcohol and 1.6 g (ll. 6 mmol) of potassium carbonate in 15 ml of tetrahydrofuran, add 6 ml of methyl isocyanate at room temperature, and stir for 20 hours did. Then, water and a saturated aqueous solution of sodium carbonate were sequentially added, and the mixture was extracted with ether. The extract was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure to give 3-isopropenylbenzyl

1.08 g (yield 91%) of N-methyl carbamate was obtained. Table 7 shows the analysis values of this compound (the raw materials of compound Nos. 24 and 37).

 Similarly, starting materials for Compound Nos. 25-34, 38 to 40, 107, 112 and 114 shown in Table 1 were produced according to the method described in Production Example 12. The structures of these were confirmed by NMR.

Production Example 13

 Production of 3-isopropenylbenzyl N, N-getyl carbamate (raw material for compound No. 36)

3-isopropenylbenzyl alcohol 0.60 g (4.0 mmol), potassium carbonate 1.lg (8.0 mmol), N, N-dimethylaminopyridine 0.02 g _s 18-crown-6. 02 g was dissolved in 25 ml of acetone, 1.0 ml (7.9 mmol) of N, N-ethylcarbamic acid chloride was added, and the mixture was refluxed for 20 hours. Next, water and a saturated aqueous solution of sodium carbonate were sequentially added and extracted with ether.

- Tsu- The extract was washed with a weight% hydrochloric acid, a saturated aqueous solution of sodium carbonate and a saturated saline solution in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 98 g (yield: 98%) of 3-isopropenylbenzyl N, N-getylkabamate. Table 7 shows the analysis values of this compound (the raw material of the compound N 0.36).

 Similarly, the starting materials of compound No. 35 111 115 shown in Table 1 were produced according to the method described in Production Example 13. Its structure was confirmed by NMR.

 Table 7

製造実施例 14

Production Example 14

Production of 3-isopropenylbenzyl chloride (XIV, R ⁴ = H)

2.6 g (17.6 mmol) of 3-isopropenylbenzyl alcohol and 4.4 ml (35.2 mmol) of triethylamine are dissolved in 25 ml of methylene chloride, and methanesulfonyl chloride (2.6 ml) is dissolved at 〇 ° C. l (35.2 mmol) was added dropwise, the mixture was stirred at room temperature for 30 hours, water was added, the mixture was extracted with methylene chloride, and the organic layer was washed with saturated sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. Dried. The solvent was distilled off under reduced pressure to obtain 3.4 g (yield: 85%) of 3-isopropenylbenzyl chloride. Table 8 shows the analysis value of this compound (XIV, R ⁴ = H).

Production Example 15

 Production of N- (3-isopropenylbenzyl) oxazolidone (raw material for compound No. 116)

 0.63 g (3.3 mmol) of 3-isopropenylbenzyl chloride and 58 g (6.7 mmol) of 2-oxazolidone were mixed with 20 ml of tetrahydrofuran and 2 ml of N, N-dimethylformamide. Then, 33 g (8.3 mmol) of 6% sodium iodide was added, and the mixture was refluxed for 12 hours. Next, at 0, water and a saturated aqueous sodium carbonate solution were sequentially added dropwise, followed by extraction with ether. The organic layer was washed with a saturated aqueous sodium carbonate solution and a saturated saline solution in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.93 g of N- (3-isopropenylbenzyl) oxazolidone (yield 98%). Table 8 shows the analysis value of this compound (the raw material of No. 116).

Production Example 16

 Production of 3-isopropenylbenzyl N, N-ethylmethylcarbamate (raw material for compound No. 108)

0.5 g (2.4 mmol) of 3-isopropenylbenzyl N-methylcarbamate, 0.3 ml (4.7 mmol) of iodide thiol, 10 ml of tetrahydrofuran and N, N-dimethylformamide lm 1 Was dissolved in a mixed solvent of above, 0.12 g (2.9 mmol) of 60% sodium hydride was added, and the mixture was refluxed for 1 hour. Next, water and a saturated aqueous solution of sodium carbonate were successively added dropwise, followed by extraction with ether. The extract was washed successively with an aqueous sodium acid solution and a saturated saline solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.7 g of 3-isopropenylbenzyl N, N-ethylmethylcarbamate (yield: 56%). Table 8 shows the analysis value of this compound (the raw material of compound No. 108).

Production Example 17

 Production of 3-isopropenylbenzylcarbamate (raw material for compounds No. 106, 110 and 113)

 Dissolve 2.0 g (13.6 mmol) of 3-isopropenylbenzyl alcohol in 40 ml of benzene, and add 1.96 g (27.2 mmol) of sodium isocyanate and 2 ml (27.2 mmol) of trifluoroacetic acid. They were added sequentially and stirred at room temperature for 8 hours. Next, water was added, the mixture was extracted with ethyl acetate, and the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.25 g (89% yield) of 3-isopropenylbenzylcarbamate. Table 8 shows the analysis values of this compound (raw materials for compound N 0.106, 110, and 113).

Production Example 18

 Production of 3-isopropenylbenzyl N-acetyl carbamate (raw material for compound No. 109)

1.0 g (5.2 mmol) of 3-isopropenylbenzylcarbamate was dissolved in 1.9 ml (26 mmol) of acetyl chloride and stirred at 65 ° C for 3 hours. Then, after returning to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated sodium hydrogen carbonate and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 0.33 g (yield 27%) of 3-isopropenylbenzyl N-acetylcarbamate. Table 8 shows the analysis value of this compound (the raw material of compound No. 109). 8 Analytical result Compound II

 Nuclear magnetic resonance spectrum (P P m)

 2.14 (s, 3H), 4.56 (s, 2H),

 5. 01-5. 42 (m 2Η),

 7.13 7.54 (m, 4 H)

 Raw material for 2.1 (s, 3H), 3.46 (dd, 2H), compound No. 1 16 4.35 (dd, 2H), 4.45 (s, 2H), _5. · Γ1, J. Δ Ό ΙΠ ίΐ

 7.1 1 ~ 7.58 (m, 4 Η)

 1.10 (t, 3Η), 2.12 (s, 3Η), Compound No. 108 2 90 (s, 3Η), 332 (q, 2Η), raw material 5.05-5. 20 (m, 3 H) 5.38 (m, 1 H),

 7.10-7.55 (m, 4 H)

Compound No. 106, 2.15 (s, 3H), 5.08 (bs, 4H),

1 10, 1 13 of 5.02-5.44 (m, 2H)

Raw material 7.07-7.53 (m, 4 H)

 2.15 (s, 3H), 2.39 (s, 3H), Compound No. 109

4.90-5.20 (m, 3H) 5.35 (m, 1H) raw material 7.05 7.58 (m, 4H), 8.62 (bs, 1H)

Test Example 88

 (1) Preparation of herbicide

 97 parts by weight of talc (trade name: di-cryt) as a carrier, and alkyl sulfonic acid salt (trade name: neopellets, manufactured by Kao Atlas Co., Ltd.) · 1.5 parts by weight and nonionic type and anion Type surfactant (trade name: Solbol 8 O0A, manufactured by Toho Chemical Industry Co., Ltd.) 1.5 parts by weight were uniformly ground and mixed to obtain a carrier for a wettable powder.

 90 parts by weight of this carrier for wettable powders and 10 parts by weight of the carbamate derivatives shown in Tables 1 to 3 were uniformly ground and mixed to obtain a herbicide.

 (2) Biological test (submerged soil treatment test)

 Paddy field soil was filled in a porcelain pot of 1/15500 are, and seeds of nobies, evening magallari, and broadleaf weeds (Kikasigusa, Konagi) were uniformly sown on the surface layer, and rice plants in the second leaf stage were transplanted.

 Thereafter, when the weeds germinated, a predetermined amount of the herbicide diluent obtained in (1) above was uniformly dropped on the water surface and treated, and then the pot was left at room temperature and sprinkled appropriately.

 Tables 9 (1) to (7) show the results of investigations on the herbicide effect and rice crop damage 20 days after chemical treatment. The dose was expressed in terms of the amount of active ingredient per 1 are. The phytotoxicity of rice and the herbicidal effect were measured by air-dry weight, and indicated as follows.

()

 Paddy rice damage (compared to untreated area)

 0 100%

 95-99%

 2 90-94%

 3 80- 89%

 4 60-79%

5 50-59% Degree of weeding effect Weeding effect (compared to untreated area)

 0 100%

 1 61-99%

 2 21-60%

 11-20%

 4% to 1%

 0%

Test Comparative Example 1

 In Test Example 1, the structural formula was used instead of No. 2

2- (3,5-dichloromouth phenyl) -2- (2,2,2-trichloroethyl) oxylan [A] (generic name: tridiphane, Japanese Patent Publication No. 53-3749) The same operation as in Test Example 1 was performed except for using the same. The results are shown in Table 9 (Part 4).

(Hereinafter the margin)

9 (Part 1) Herbicidal effect Herbicide dosage

 Tama Gaya

 Active ingredient Nobie

 [? / 10 are]

Test Example 1 Compound No. 2 50 550 Test Example 2 Compound No. 3 50 550 Test Example 3 Compound No. 9 50 550 Test Example 4 Compound No. 1 150 550 Test Example 5 Compound No. 14 50 55 0 Test Example 6 Compound No. 17 50 55 0 Test Example 7 Compound No. 22 50 55 0 Test Example 8 Compound No. 23 50 55 0 Test Example 9 Compound No. 25 50 55 0 Test example 10 Compound No. 27 5〇550 Test example 11 Compound No. 35 50 55 0 Test example 12 Compound No. 36 50 55 0 Test example 13 Compound No. 37 50 55 0 Test example 14 Compound No. 41 50 55 0 Test example 15 Compound No. 42 50 55 1 Test example 16 Compound No. 43 50 55 0 Test example 17 Compound No .44 50 55 1 Test Example 18 Compound No. 45 50 55 0 Test Example 19 Compound No. 47 50 55 5 〇 Test Example 20 Compound No. 49 50 55 0 Test Example 21 Compound No. 50 50 55 0 Test Example 22 Compound No. 51 50 55 0 Test Example 23 Compound No. 52 5 0 5.5 0 Test example 24 Compound No. 53 50 55 0 Test example 25 Compound No. 54 50 55 0 Test example 26 Compound No. 55 50 55 0 Test example 27 Compound No. 57 5 〇 55 1 Test example 28 Compound No. 58 50 55 0 Test example 29 Compound No. 59 50 55 0 Test example 30 Compound No. 60 50 55 0 (Part 2) Herbicidal effect Herbicide dosage

 Tama Gaya

 Active ingredient Nobie

 [g / 10

Test Example 31 50 5 5 0

= -Ρ

 夹 夹-. O U cr

 D L) Yuya Fufu 1 A Jt

irf UDD u liquor bottle rf4 1L 0. D 4 U 1 compound o. D 5 DU 5 5 0 Test example 36 compound No. 66 50 5 5 0 Test example 37 compound No. 67 50 5 5 0 Test Example 38 Compound No. 69 50 55 0 Test Example 39 Compound No. 71 50 55 0 Test Example 40 Compound No. 72 50 55 0 Test Example 41 Compound No. 73 50 55 0 Test performed Example 42 Compound No. 74 50 55 0 Test Example 43 Compound No. 75 50 55 0 Test Example 44 Compound No. 76 50 55 0 Test Example 45 Compound No. 77 50 55 1 Test Example 46 Compound No. 78 50 550 Test conducted 47 Compound N 0.79 5 U 55 1 Test conducted 48 Compound No. 80 50 550 Test conducted 49 Compound No. 82 50 550 Test conducted 50 Compound No .84 50 550 Test example 5 Chemical compound No. 85 50 5 5 〇 Test example 52 compound No. 86 50 550 Test example 53 compound No. 87 50 550 Test example 54 compound No.89 50 5 5 0 9 (Part 3) Herbicidal effects

 "Ma Gaya

 Active Ingredients Novier Paddy Rice Injury lg / 10

 Test Example ί ·· ίθ.10 丄 550 Test Example 56 Compound No. 102 50 55 0 Test Example Compound No. 103 50 55 0 Test Example Compound No. 0

 ρ

Test Example Compound No. 1 05 50 5 50 Test Example 60 Compound No. 106 50 55 0 Test Example 6i Chemical compound No. 107 50 55 0 Test Example 62 Compound No. 108 50 55 0 Test Example 63 Compound No. 109 50 55 0 Test Example 64 Compound No. 1 10 50 55 0 Test Example 65 Compound No. Ill ■ 50 55 0 Test Example 66 Compound No. 1 12 50 5 5 0 Test Example 67 Compound No., 1 13 50 5 5 0 Test Example 68 Compound No. 1 14 50 5 5 0 Test Example 69 Compound No. 1 15 50 5 5 0 Test Example 70 Compound No. 1 16 50 5 5 0 1.

Test Example 71 ί ^ · 4ο l ο. L 丄 7 50 5 5 0 Test Example 72 Compound No. 1 18 5 U 550 Test Example 73 73 ί ί¾ ^ ο 丄. 95 5 5 5 5 ϋ

Si test 浏 74 Chemical compound J 1 UDU 550 Test example 75 Compound No. 121 50 55 0 Test example 76 Compound No. 122 50 55 1 Test example 77 Compound No. 123 50 55 0 Test Example 78 Compound No. 124 50 5 5 0 Test Example 79 Compound No. 125 50 5 5 0 Test Example 80 Compound No. 126 50 5 5 〇 Test Example 81 Compound No. 127 50 5 5 Table 9 (Part 4)

[A]: Tridi fan (Japanese Patent Publication No. 53-3749)

Test Examples 89 to 102

Biological test (tube test)

 Press the Nobie in water for 30 minutes. C, incubated for 24 hours. After that, when the seeds germinated from the seeds until the buds became 1 mm, the diluted solution of the herbicide obtained in (1) was dispensed into a sample tube bottle (capacity: 50 rnl), and 10 seeds of the germinated seeds were added. Incubation was performed in an artificial weather vessel (temperature of 25, every 12 hours light and dark). A control containing only ion-exchanged water was also included as a control. One week later, the length of the stem and leaf portion of the Nobie (the first leaf) was measured, and the elongation disorder rate ((1) the average value of each drug, the average value of the no control) × 10 ° was determined.

 The results are shown in Table 10 at a 50% elongation inhibitory concentration.

Test Comparative Example 2

 In Test Example 89, Compound No. 17 was replaced with a structural formula

[3- (5-Tolufluoromethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxysilane [B] (Japanese Patent Application Laid-Open No. Hei 11-518736) Except that Compound No. 1) was used, the same operation as in Test Example 84 was performed. The results are shown in Table 10 at a 50% elongation inhibitory concentration.

(Hereinafter the margin) Table 10

CB]: Oxysilane compound described in JP-A-11-508736

As is clear from Tables 9 (Part 1) to (Part 4) and Table 10, the compounds of the present invention are superior to the comparative compounds in the selectivity of the genus of paddy rice and Nobies, and are superior in remarkably low leaf volume. It exerts the effect of inhibiting the growth of nobies.

 The compounds used in Test Examples 1 to 88 exhibit herbicidal effects on annual broadleaf weeds. When the above was similarly evaluated, Test Examples 9, 10, 13, 16, 17, 19, 24, 25, 27, 28, 30, 31, 32, 34 to 41, 43, 45, 71, 81, 85 The degree of herbicidal effect of the compound used in 5 was 5. As described in detail above, the novel carbamate derivative of the present invention has excellent herbicidal activity against paddy weeds, and is excellent in selectivity, particularly, selectivity between paddy rice and Nobie. In addition, weeds can be effectively removed from paddy field weeds at a low dose, and the dose does not cause harm to rice. Therefore, the carbamate derivative of the present invention is extremely useful as a rice herbicide.

Claims

1. General formula

(Where A is  Contract CH: CH ₂ CC 12 -X  The surrounding H ₂ CC 12 1 X

OH  -C H2 \ I, C H: CC 1 X  Indicates Y C, B is 0 0 0

Is shown. X represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, and Y represents a halogen atom. R ¹ , R ⁴ , and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group or methoxethyl group having 1 to 4 carbon atoms, and R ³ represents a carbon atom. Alkyl group having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms ;: Represents a methoxyl group or a phenyl group; Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a general formula: CO—R ⁷ (R ⁷ = hydrogen, generally RH c ) An acyl group having 1 to 4 carbon atoms represented by A phenyl group N; m represents an integer of 1 to 4; ) A carbamate derivative represented by the formula: 2. The carbamate derivative according to claim 1, wherein the alkyl group having 1 to 3 carbon atoms as R ⁷ is a methyl group, an ethyl group, or a propyl group.

(Where A is CH ₂ CC 1 X

OH

And B is  0  'C, OR:

Is shown. X represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, and Y represents a halogen atom. R ¹ , R ⁴ , and R ° represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a methoxyethyl group, and R ³ represents a 1 carbon atom. 6 alkyl group, a haloalkyl group having 1 to 4 carbon atoms, indicates main Tokishechiru group or phenylene Le group, R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Haroarukinore group having 1 to 4 carbon atoms, CO—R ⁷ (R ⁷ = hydrogen or an alkyl group having 1 to 3 carbon atoms) represents an acyl group or a phenyl group having 1 to 4 carbon atoms, where m is an integer of 1 to 4 Is shown. ) A herbicide containing a carbamate derivative represented by the formula (1) as an active ingredient. 4. The herbicide according to claim 9, wherein the alkyl group having 1 to 3 carbon atoms as R ⁷ is a methyl group, an ethyl group or a propyl group.