DD251125A5 - PROCESS FOR PREPARING SUBSTITUTED PROPARGYLOXY ACETONITRILE DERIVATIVES - Google Patents

Abstract

The invention relates to a process for the preparation of substituted propargyloxyacetonitrile derivatives of the general formula (I) in which R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a methylenedioxy group, a nitro group or a cyano group, n is an integer of 1 to 5 and when n is an integer of 2 or more, R may be the same or different, R 1 is a hydrogen atom or a lower alkyl group, and R 2 is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a halogen atom, provided that that R1 and R2 are not simultaneously hydrogen atoms. The compounds have herbicidal and fungicidal activities. Formula (I)

Description

Field of application of the invention

The invention relates to substituted propargyloxyacetonitrile derivatives of the general formula (I)

(D, 1

OCH-CHC-R

wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a methylenedioxy group, a nitro group or a cyano group, η is an integer of 1 to 5, and when η is an integer of 2 or more, the radicals R may be the same or different, R ^{1 is} a hydrogen atom or a lower alkyl group, and R ^{2 is} a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a halogen atom, provided that R ¹ and R ^{2 are} not simultaneously hydrogen atoms; which are very useful as a rice or pipe herbalicide or a fungicide for agriculture and horticulture.

Characteristic of the known technical solutions

So far, much work has been invested in agriculture and horticultural amide derivatives, and numerous compounds having characteristic biological activities have been found and put to practical use. For example, with respect to substituted benzamide derivatives, ethyl-N-benzoyl-N- (3,4-dichlorophenyl) -2-aminopropionate (benzoylpropyl) is known as a herbicide and 2-methyl-N- (3-i-propoxylphenyl) -benzamide (mepronil) is known as a fungicide. GP Patents 2095237 and 2094786 describe herbicides and fungicides comprising amide-substituted acetonitrile derivatives. British Patent 2094786 describes allyloxyacetonitrile derivatives, but gives no indication of the substituted propargyloxyacetonitrile derivatives. Further, British Patent No. 2094786 relates to the use of allyloxyacetonitrile derivatives as fungicides and herbicides. In this patent, the herbicides are illustrated by pre-emergence and post-emergence applications, and their phytotoxicity is examined on sugar beets, cruciferous vegetables, cotton, soybean, corn, wheat and rice. As crops with selectivity, the sugarbeet, cruciferae, lettuce and peas are mentioned and it is clearly stated that these derivatives are valuable compounds for crops of the family Compositae and Legominose. However, no selectivity was found for rice and these compounds are considered inapplicable to rice. Numerous herbicides such as amide compounds, thiocarbamate compounds and diphenyl ether compounds have been developed and have been used in rice paddy practice, but their performance has been inadequate. Butachlor, an amide compound, is applied at about the time of seedling, but its phytotoxicity to rice is always a problem depending on temperature conditions and the like. Molinate, a thiolcarbamate compound, has fish toxicity and its use is limited. Benthiocarb causes phytotoxicity to rice under soil-depleting conditions.

The diphenyl ether compounds are used around the seedling time, such as butachlor, but if the treatment time is delayed, their activity is greatly diminished. Because of their excellent performance in many ways, these herbicides are currently gaining widespread recognition. However, their shortcomings and problems gradually became actual and there was a strong need for a rice herbicide which is easier to use and has excellent performance.

For the compounds described in GB-PS 2094786 efficacy against the downy mildew of the wine and against the late tomato rot fungicide is indicated. Captafol, TPN, captan and dithiocarbamate-type chemicals have generally become widely used against late rot and fluffy Mildew of various crops used and contributed to the increase in harvests. However, these compounds predominantly have a preventive effect against these plant diseases and one can not expect from them a healing effect. Thus, they are deficient in that their effects on crops already affected by these diseases can not be fully expected. Is the application of chemicals to

In fact, considering the control of plant diseases, the timing of application of these chemicals is more or less due to the onset of plant diseases, and it is difficult for these compounds to fully control the plant diseases. In an effort to remedy these deficiencies, intensive work has been devoted to new control agents, and N-phenylalanine ester derivatives such as metalaxyl [N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester], which have been disclosed also have excellent healing properties, and these have gradually gained practical recognition throughout the world. However, the problem with these N-phenylalanine ester derivatives is that there are already fungi strains that are resistant to these compounds.

Object of the invention

The object of the invention is to remedy the shortcomings of the prior art discussed above and to provide a process for the preparation of compounds having very good properties as a rice herbalicide and as a fungicide for agriculture and agriculture, in particular compounds having a wide range of applicability as a herbicide have a broad range as to the appropriate timing for application to rice fields having low phytotoxicity to rice and low fish toxicity, and as fungicide have both a preventative and a healing effect against late rot and downy mildew of various crops and an excellent control effect on soil diseases of various crops such as Possess rotting of the seedlings.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties and processes for their preparation.

The present inventors made extensive investigations on amide-substituted acetonitrile derivatives to achieve the above objects, and found that substituted propargyloxyacetonitrile derivatives possess biological properties which were unpredictable due to the compounds disclosed in the above-mentioned patent documents and a broad scope the appropriate time of application, combined with low phytotoxicity to rice and low fish toxicity as rice herbicide and both a preventive and curative effect on late blight and downy mildew in various crops and excellent control effect on soil diseases of various plants such as rotting the seedlings as Possess fungicide. Finding this fact led to the present invention.

The substituted propargyloxyacetonitrile derivatives of the invention are novel compounds of the following general formula (I)

XN

_{2 (l)}

T) CH-C = C-IT

A ¹

wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a methylenedioxy group, a nitro group or a cyano group, η is an integer of 1 to 5, and when η is an integer of 2 or more, the radicals R may be the same or different, R ^{1 represents} a hydrogen atom or a lower alkyl group, and R ^{2 represents} a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a halogen atom, provided that R ¹ and R ^{2 are} not simultaneously hydrogen atoms

 The present inventors continued to work extensively on a process for preparing the substituted propargyloxyacetonitrile derivatives of the general formula (I) to overcome the deficiencies of the prior art and accordingly found a method whereby the compounds can be produced in high yields by a considerably shorter process can be obtained.

Thus, according to the invention, a process is provided for the preparation of the substituted propargyloxyacetonitrile derivatives of the general formula (I) which comprises reacting an acid chloride of the general formula (II)

COCl _(I)

in which R and η are as defined above, with aminoacetonitrile to give an acylaminoacetonitrile of the general formula (III)

wherein R and η are as defined above, the treatment of the resulting compound with a halogenating agent to give an intermediate of the following general formula (IV)

^ CN

(IV) X

in which R are as defined above and X is a halogen atom, and the reaction of the intermediate with a substituted propargyl alcohol of the general formula (V)

R ² -C = C-CH-OH _(V)

wherein R ¹ and R ^{2 are} as defined above.

This process according to the invention is shown by the following reaction scheme.

^R NH ₉ CH-CN ^R r \ r-ν

- -) 03 VCONHCH ₂ CN

(ID (III)

X "" rK / -ν .CN I HO-CH-C = CR ² (V)

'2

CONHCH ^ _

^ OCH-C = C-R

I)

R ¹

This method will be described in more detail.

First, the acid chloride (II) is reacted with aminoacetonitrile to obtain the acylaminoacetonitrile (III). The acylaminoacetonitrile (III) is reacted with a halogenating agent in a suitable solvent to obtain the halogenated intermediate (IV). Examples of the solvent may include aliphatic halogen compounds such as methylene chloride, chloroform, carbon tetrachloride and 1,4-dichloroethane, aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate and ethyl propionate, and carbon disulfide. The use of aliphatic carboxylic acids, especially of ethyl acetate, gives good results. For example, bromine, chlorine, phosphorus oxychloride, sulfury chloride and phosphorus tribromide can be used as halogenating agents. The reaction temperature is 0 to 120 ⁰ C, preferably room temperature. This reaction can be carried out in an inert gas atmosphere. Since the halogenated intermediate (IV) is unstable, it is used immediately after the preparation. The halogenated compound (IV) is then reacted with the substituted propargyl alcohol (V). This reaction can be carried out in the presence of an acid acceptor. Examples of the acid acceptor include organic bases such as triethylamine, dimethylaniline and pyridine, and inorganic bases such as ammonia, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide and ammonium carbonate. This reaction is preferably carried out in a solvent or diluent. Pyridine can be used both as a solvent and as an acid acceptor. Since the intermediate does not have good heat stability, it is undesirable to carry out this reaction at too high temperatures. Since it is still an exothermic reaction, it is conveniently carried out with cooling. At low temperatures, the reaction intermediate tends to precipitate and the reaction rate becomes so slow that it is impractical. Suitably, the reaction at -30 to 50 ⁰ C, preferably at -20 to 20 ° C, performed. The desired substituted propargyloxyacetonitrile derivative (I) can be isolated and easily purified by a conventional method such as recrystallization and column chromatography.

A substituted propargyloxyacetonitrile derivative of the general formula (I) prepared by the method of the present invention is very useful as a rice herbicide and a fungicide for agriculture and horticulture. For use as a rice herbicide, the appropriate application rate of the compound prepared by the method of the present invention is usually 0.1 to 100 g, preferably 0.5 to 25 g per Ar, although depending on the type of weeds to be controlled, it is the stage Growth, the type of formulation to be applied, the method of application and various environmental conditions. The herbicidal activity of the compound produced by the method of the present invention is characteristically strong against grassy weeds, but it also shows a strong suppressive effect on other weeds, although it varies in extent depending on the types of the weeds. It shows a particularly strong inhibiting effect on weeds of the family Cyperaceae (Umbrella plants), such as Cyperus difformis Linnaeus (small-flowered umbrella plant). This property is advantageously taken into account when considering the use of this compound as a mixture with a conventional chemical which has poor activity in grassy weeds, or in a mixed application, e.g. B. in a tank mix.

The appropriate time of application of the compounds produced by methods of the invention extends within a wide range from the pre-emergence period of the weeds to their growth stage. The compounds prepared by the process of the invention have a much broader range of suitable application timing than the known amide-type compounds such as butachlor or thioicarbamate compounds such as benthiocarb and can become herbicides which are little limited in the time of application and easy to use are. The practical doses of the compounds prepared by the method according to the invention, which show a herbicidal activity in millet millet, are of course different depending on the time of application. However, while benthiocarb or butachlor merely provides inadequate action in millet bulls in the 3.5-leaf stage at practical dosages, the compounds prepared by the method of the present invention show complete practical activity at lower doses than those used in practice. The compounds produced by the method of the present invention cause very little phytotoxicity to transplanted rice after application at any stage of growth.

When used as a fungicide for agriculture and horticulture, the compounds prepared by the process of the present invention are effective not only against late blight and downy mildew of various crops caused by phycomycetes, but also against various diseases caused by various phytopathogenic fungi be brought about. Examples of the most important diseases in which the compounds according to the invention prepared by the process according to the invention can be used include the late rotting of the potato (Phytophthora infestans), the late rotting of the tomato (Phytophthora infestans), the black stem of the tobacco (Phytophthora parasitica var. nicotianae), the leather rot of the strawberry (Phytophthora cactorum), the phytophthora rotting of the adzuki bean, the downy mildew of the wine (Plasmopara viticola), the downy mildew of the cucumber (Pseudoperonospora cubensis), the downy mildew of the hop (Pseudoperonspora humuli ), the downy mildew of the garland chrysanthemum (Peronospora chrysanthemi) or the rotting of the seedling of various crops caused by fungi of the genus Aphanomyces and Pythium.

The method of applying the compounds prepared by the process according to the invention consists, for. B. in the seed preparation, in the application to the foliage, in the soaking of the soil or in the introduction into the soil. They have sufficient efficacy in any application method that would be normally used by the skilled person. The rate of application and the concentration of use will vary depending on the crop in which it is applied, the type of disease being controlled, the type of formulation, the method of application, and various environmental conditions. In spraying, the suitable application rate is 5 to 200 g, preferably 10 to 10 g of SeAr, and the suitable spray concentration is 20 to 1000 ppm, and preferably 50 to 500 ppm. The herbicide and fungicide of the present invention containing compounds produced by the process of the present invention may be used in admixture with compounds having other biological activities, e.g. As agricultural chemicals such as another fungicide, an insecticide, another herbicide or a plant growth regulator, a soil conditioner or a fertilizer material can be used. Alternatively, mixed formulations of both may be prepared.

The compounds prepared by the method of the invention may be applied directly, but preferably in the form of a composition in which the active ingredient is mixed with a carrier comprising a solid or liquid diluent. The carrier as used herein refers to a synthetic or natural inorganic or organic material which aids in the delivery of the active ingredient to the site to be treated and facilitates the storage, transport and handling of the active ingredient.

Examples of suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic materials such as diatomaceous earth, terra alba, talc, vermiculite, gypsum, calcium carbonate, silica gel and ammonium sulfate, organic substances of vegetable origin such as soybean meal, sawdust and wheat flour and urea.

Examples of suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oils, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, alcohols such as methanol, propanol and ethylene glycol , Dimethylformamide, dimethyl sulfoxide and water.

To increase the efficacy of the compounds prepared by the process of the invention, various adjuvants can be used singly or in combination according to various purposes such as emulsification, dispersion, spreading, wetting, binding and stabilization, by determining the type of formulation and the application situation Consider pulling. Examples of such adjuvants include water-soluble bases such as lignosulfonates, nonionic surfactants such as alkylbenzenesulfonates and alkyl sulfate esters, lubricants such as calcium stearate and waxes, stabilizers such as isopropyl hydrogen phosphate, methyl cellulose, carboxymethyl cellulose, casein and gum arabic. The amount of the active ingredient prepared by the method of the present invention in the composition is usually 0.5 to 20 wt% for a dust, 10 to 90 wt% for a wettable powder, CT, 1 to 20 wt% for granules, 5 to 50 wt. % for an emulsifiable concentrate, and 10 to 90% by weight for a flowable composition. Typical examples of the substituted propargyloxyacetonitrile derivatives prepared by the process of the present invention of the general formula (I) are shown in Table 1 below.

Table 1

-CONHCH.

, CN

"OCH-GeC-R" R ¹

(D

Verbinduncr

Property (Fp ⁰ C)

NMR (100 MHz, δ)

84-85.5

, .CDCl -.- DMSO-d.

^δ _ΤΜς 3 6 (ppm):

1.82 (3H, t), 4.30 (2H, q), 6.40 (IH, d), 7.2-8.1 (5H, m), 9.37 (IH, d)

71-72

1.80 (3H, t), 4.37 (2H, q), 6.42 (IH, d), 7.1-7.9 (5H, in)

86-87

(ppm): 1.85 (3H, t), 4.32 (2H, q),

6.40 (IH, d), 7.2-7.9 (5H, m)

93-94

CDCl-j-DMSO-d,

⁶ _TMq 3 6 (ppm):

1.80 (3H, t), 4.35 (2H, q), 6.38 (IH, d), 7.3-8.2 (3H, m), 9.92 (IH, d)

Table 1 (continued)

Connection no.

Property (Fp ° CJ

NMR (100 MHz, δ)

Cl

Cl

124-128

1.85 (3H, t), 4.30 (2H, q), 6.38 (IH, d), 7.3-8.0 (3H, πι), 9.50 (IH, d)

54.5-55.5

(ppm): 1.87 (3H, t), 4.38 (2H, q),

6.48 (IH, d), 7.0-8.2 (5H, m)

54.5-55

«.CDCl ^ -DMSC-d, ⁶ TMS ^{3 6}

1.85 (3H, t), 4.35 (2H, q), 6.45 (IH, d), 7.0-7.9 (4H, m), 9.67 (IH, d)

mn

63.5-64.5

(ppm): 1.88 (3H, t), 4.50 (2H, q),

6.42 (IH, d), 6.9-8.0 (5H, in)

br

62-63

(ppm): 1.88 (3H, t), 4.38 (2H, q),

6.42 (IH, d), 7.2-8.1 (5H, m)

Table 1 (cont.)

Connection no. η R ¹ R ² Property (Fp ⁰ C) NMR (100 MHz, , t), q) (5H, δ) (3H, (IH, s), d), 10 "% H CH ₃ 63.5-64.5 δ JrJ ^ ¹ S (ppm): 1.83 (3H ^inb 4.40 (2H 7.2-7.8 , t), q) (5H, , 2.37, 6.42 m) (3H, (IH, s), d), 11 H CH ₃ 105-106 δ 3 (ppm): 1.85 (3H ^b 4.38 (2H 7.1-7.9 , t) , q) (4H, , 2.42, 6.43 ra) (6H, (IH, s), d), 12 ^H 3 ^C H ₃ C H CH ₃ 117-119 ⁶ SSq ¹³ (PPm): 1-82 (3H ™ ^S 4.31 (2H 7.1-7.5 , t) r q) (5H, , 2.38, 6.43 m) (3H, (IH, s), d), 13 H ₃ CO H CH ₃ 60.5-62 ⁶ VM? ³ (PP ^m): i- ^{82 (3H inb} 4.35 (2H 6.9-7.7 , t), q) (5H, , 3.82, 6.45 m) (3H, (IH, s), d), 14 H CH ₃ 73-74 CDCl% mq ³ (PP ¹ ") ^{: 1} x 82 (3Η ^inb 4.32 (2H 6.8-8.0 , 3.87, 6.37 m)

Table 1 (Ports.)

Connection no. H ₃ CO (O) - H ₃ CO R ¹ R ² Property (Pp ⁰ C) NMR (100 MHz, 6) 15 H CH ₃ 110-111 ⁶ SSq ¹³ (PPm): 1.85 (3H, t), 3.90 (6H, s), ^nb 4.31 (2H, q), 6.43 (IH, d), 6.8-7.6 (4H, m) 16 F C 'es- H CH ₃ 111-113 ⁶ SSo ¹ S (ppm): 1.85 (3H, t), 4.34 (2H, q), ⁱⁿ 6.04 (2H, s), 6.42 (IH, d), 6.8-7.7 (4H, "m) 17 F ₃ C- {Ö) - H CH ₃ 83-83.5 PTVl ⁶ τις 3 (ppm): 1.87 (3H, t), 4.37 (2H, q), ^ni> 6.48 (IH, d), 7.1-8.2 (5H, m) 18 O ₀ N H CH ₃ 94-96 mn% mo 3 (PP ^ra > ^: 1-84 (3H, t), 4.38 (2H, q), ^iWb 6.45 (IH, d), 7.3-8.1 (5H, m) 19 H CH ₃ 90-92 ⁶ SSo ¹ S (ppm): 1.82 (3H, t), 4.40 (2H, q), ^b 6.46 (IH, d), 7.5-8.8 (5H, m)

Table 1 (cont.)

connection

Property (Fp ⁰ C)

NMR (100 MHz, 6)

20

NC

125-129

(ppm): 1.85 (3H, d), 4.37 (2H, q),

6.42 (IH, d), 7.5-8.3 (5H, m)

21

111-113

.CDCl ^ DMSO-d. ,

⁶ m _Mq 3 6 (ppm):

4.48 (2H, s), 6.37 (IH, d), 7.4-8.2 (5H, m), 9.70 (IH, d)

22

Cl

91-93

cCDCl 2 -DMSO-d,.

^δ _ΤΜς 3 6 (ppm):

^{in u} A.52 (2H, s), 6.38 (IH, d),

7.2-8.1 (4H, m), 9.10 (IH, d)

23

88-90

/.CDCl^-DMSO-d,,

^Ö _TMS 3 6 (ppm):

4.52 (2H, s), 6.40 (IH, d), 7.3-8.1 (4H, m), 9.10 (IH, d)

24

Cl

102-104

: 4.54 (2H, s), 6.43 (IH, d), 7.4-8.0 (4H, m)

25

Cl

Cl '

128-130

4.50 (2H, s), 6.30 (IH, d), 7.2-8.1 (3H, m), 9.25 (IH, d)

Table 1 (cont.)

connection

Property (Fp ⁰ C)

NMR (100 MHz, δ)

26

114-115

(ppm): 4.52 (2H, s), 6.42 (IH, dd), 6.9-8.3 (5H, m)

27

99-100

, .CDCU-DMSO-d _,,, ^δ _ΤΜς 3 6 (ppm):

ⁱⁿⁱ³ 4.50 (2H, s), 6.32 (IH, d),

7.0-7.9 (4H, m), 9.95 (IH, d)

¹ Ko

118-119

_Λ CDCU-DMSOd,.

⁶ _ΦΜς 3 6 (ppm):

4.50 (2H, s), 6.38 (IH, d), 6.9-8.1 (4H, m), 9.62 (IH, d)

br

108-110

CDCl ₃ -DMSOd _{6 (ppm):}

6.54 (2H, s), 6.42 (IH, d), 7.2-8.3 (4H, m), 9.38 (IH, d)

30

H ₃ C

87-88

-CDCU-DMSO ,. , _v ⁶ _TM o 3 6 (ppm):

2.36 (3H, s), 4.50 (2H, s), 6.38 (IH, d), 7.1-7.9 (4H, d), 8.70 (IH, d)

Table 1 (cont.)

Connection no. H ₃ C ^ O) - R ¹ R ² Property (Fp ⁰ C) NMR (100 MHz, δ) 31 ^H 3 ^C (oy H ₃ (Z H I 104-106 .CDCl ^ -DMSO-d,,. 6 _TMS 3 6 (ppm): ^{ni 3} 2.40 (3H, s), 4.50 (2H, s), 6.38 (IH, d), 7.0-8.0 (4H, m), 8.80 (IH, d) 32 ^H 3 ^C0 (oy H I 113-114 mn ^δ ™ ς 3 (ppm): 2.37 (6H, s), 4.52 (2H, s), ^lPlt3 6.40 (IH, d), 7.1-7.6 (4H, m) 33 H ₃ CO - (^ o) - H I 82-84 mn ⁶ ΦΜς 3 (ppm): 3.87 (3H, s), 4.52 (2H, s), ^xnb 6.38 (IH, d), 6.9-7.9 (5H, m) 34 ^H 3 ^C0 H ₃ CO H I 96-98 mn ^{δ ΦΜς} 3 (ppm): 3.88 (3H, s), 4:46 (2H, s), ^ü 6:32 (IH, d), 6.7-8.0 (4H, m), 8.25 (IH, d) 35 H I 118-119 .CDCI-DMSO-d .. ,. ^δ Φ _Μς 3 6 (ppm): ^1nö 3.82 (6H, s), 4.48 (2H, s), 6.37 (IH, d), 6.5-7.3 (3H, m), 9.90 (IH, d)

Table 1 (cont.)

connection

Property (Fp ⁰ C)

NMR (100 MHz, 6)

36

150-152

4.52 (2H, s), 6.05 (2H, s), 6.38 (IH, d), 6.7-7.7 (3H, m), 9.48 (IH, d)

CTiC 1

67-69

(ppm): 4.57 (2H, s), 6.42 (IH, d), 7.4-8.2 (5H, .m)

125-127

_A CDCl 3 -DMSO-d _i -. ,

^ö _TM o 3 6 (ppm):

ⁱⁿⁱ³ 4.53 (2H, s), 6.34 (IH, d),

7.5-9.0 (4H, m), 10.40 (IH, d)

NC

134-135

.CDCl-j-DMSO-d,.

 6 (ppm):

4.50 (2H, s), 6.38 (IH, d), 7.3-8.5 (4H, m), 10.10 (IH, d)

99-100

CDCl 3 -DMSO-d,

> _ΤΜς 3 6 (ppm):

ⁱⁿ 4.37 (2H, s), 6.37 (IH, d),

7.2-8.1 (5H, m), 9.52 (IH, d)

Table 1 (cont.)

Verbindunc

rr

R "

Property (Fp ⁰ C)

NMR (100 Hz, δ)

Cl

mn

86-88

; 4.4O (2H, s), 6.38 (IH, d), 7.2-7.9 (5H, m)

ΓΠΠ

81-83

3 (ppm): 4.40 (2H, s), 6.38 (IH, d), 7.2-7.9 (5H, m)

Cl

Cl

128-130

 , CDCl ^ -MSO-d,

^δ _ΦΜς 3 6 (ppm):

¹ . 4.37 (2H, s), 6.30 (IH, d),

7.4-8.0 (3H, m), 10.06 (IH, d)

H ₃ C

85-86

mn% "c3 (ppm): 2.38 (3H, s), 4.36 (2H, s),

^Xn 6.37 (IH, d), 7.1-7.9 (5H, m)

115-117

: 2.41 (3H, s), 4.38 (2H, s), 6.34 (IH, d), 7.0-7.8 (5H, m)

Table 1 (cont.)

Connection no.

Property (Fp ⁰ C)

NMR (100 MHz, 6)

46

CDCl

br

98-100

(ppm): 4.42 (2H, s), 6.43 (IH, dd), 7.0-8.3 (5H, m)

47

CDCl

br

77-78

(ppm): 4.42 (2H, s), 6.41 (IH, d),

7.0-7.8 (4H, m), 8.03 (IH, d)

48

Cl

br

107-108

.CDCl ^ DMSO-d. .

 δ 3 6 (ppm):

4.38 (2H, s), 6.33 (IH, d), 7.3-8.2 (3H, m), 9.94 (IH, d)

49

H ₃ C

H ₃ C

br

112-114

-CDCl- ⁶ TMS ³

2.38 (6H, s), 4.40 (2H, s), 6.40 (IH, d), 7.1-7.5 (4H, m)

50

CH ₂ Cl

88-89

.CDCI ₀ ,

6 _TMS 3 (ppm)

4.10 (2H, t), 4.42 (2H, t), 6.36 (IH, d), 7.1-8.0 (5H, m)

Table 1 (cont.)

Ver ηγ R ¹ J R ² H property CDCl-C (Ppm) NMR (100 MHz, 6 (2H, (2H, t), ) 4:46 (2H, t), binding 1Mb (IH, .7 ( d) 7.4-8 .0 ( 4H, m) No. Cl (Mp ⁰ C) : 4.15 < H CH ₂ Cl .CDCl. O j (Ppm) 6:40 (3H, t), 2.20 (2H, m), 51 C ^ 98-99 TMS (2H, (3H, t), 6:41 (IH, d) Cl : 1.12 .0 ( (IH, 4H, m) < H C ₀ H 4:32 -2 ( 52 100-101 7.3-8 Cl ' ö 3 (Ppm) (3H, m), 1:54 (2H, m), Cl TMS (2H, m), 4:36 (2H, t), : 0.92 (IH, d) 7.3-7 • 9 ( 4H, m) < H nC _o H ^ 2.18 53 j / 85-86 .CDCL ⁶ m _MQ 3 (Ppm) 6:40 : 0.65-1.65 (7H , m), 2:32 (2H, m), ci ^; IHO 4.30 t), 6:32 (IH, d) Cl 7.3-7 4H, m) < H nC.H _Q 54 4 9 89-90 Cl 6 3 (Ppm) : 1.48 dd) , 2.60 (IH , t), Cl 4:58 m), 6:47 (IH, dd) 7.4-8 4H, m) < CH 55 118-120 Cl ' f- \ ) -Ν ° y > - \ oV o> oV Oh

IS) UI

IS) (Jl

 Ρ V-I O

Xi Ε-ι

+ J I ι | τ? 33 r- 33 * · 33 CN CQ in ε I in TD 33 ν ft » 33 CC vo I Γ- to - ~ -. Γ- » HH rü »- * CN rH CO r \ CO 33 CN O cn CO 33 W 33 33 CN rH ΓΟ cn TD 33 ·· ro i- \ rt I O Ε TJ O jr. , CJ 33 - · I in "· - in W · I O CN rH - · ro CN ^ - · - * - ~ - · CO rh 33 ^ ν rh O ° ι-Ι CO co co cn 33 U ε oo S I in CN 33 33 I vo S fa ¹ · - ' O I OO O I cn in CQ co ι cn Quvo vo I QI rh * "-" Ή · - { O · <* Cn U ro  - · · 33 ro co Cbco ro co ro rh rh • Η W VD ^ * vo CQ • ca _o λ • · V ro vo Γ-- ,H co U CN ro 33 VO - 33 O I rf VO> - CJ CO CQ ro vo "T CQ • ·· ε ·· YES) «A · cn ε Q S 33 • · in 33 VD ~ » "i "ε t · CJ i- < ^ s * vo · (k ε Qu Cu Qu <· VD O O ro ro * - * Cu Cu co ro 33 33 <o C 1θ 33 in 33 to t) - ^ CJ CJ α; in ro vo ro CO TJ Ό CJ ε N rh in rh cn 33 33 «· O 33 ,1 CJ co U CO 33 33 33 in from 33 vo fl) -S U Q S D S CO rH rH «- '" - CN O > yes 2; U Eh CJ B ^ • w ^ - - · O <o <o O O I-I cn co in co "tj> cn co ro o \ ro vo a ro vo r S .. Z ·· 's Ή α. cb cb * ~ " ro ro rh rh U CO CJ CO Q S Q S U Eh CJ ζ-ι <o <o

Table 1 (cont.)

Verbindunc

Property (Fp ⁰ C)

NMR (100 MHz, 6)

138-140

CDCl -.- DMSO-d,

 3 6 (ppm):

4.40 (2H, s), 6.02 (2H, s), 6.37 (IH, d), 6.8 (IH, m), 7.5 (2H, m), 9.58 (IH, d)

CF.

cnn

86-90

(ppm): 4.42 (2H, s)> 6.40 (IH, d), 7.3-8.2 (5H, m)

109-111

(ppm): 4.45 (2H, s), 6.38 (IH, d), 7.5-8.1 (5H, m)

NO,

131-132

.CDCI-j-DMSO-d,, __

^{(3 6 ppm):}

4.42 (2H, s), 6.37 (IH, d), 7.5-9.0 (4H, m), 10.35 (IH, d)

NC

120-124

.CDCl-j-DMSO-d, - _{lnn λ} δ _ΤΜς 3 6 (ppm):

^b 4.40 (2H, s), 6.34 (IH, d),

7.4-8.5 (4H, m), 10.18 (IH, d)

Table 1 (cont.)

VerbinduTK

R.

rr

Property (Fp ⁰ C)

NMR (100 MHz, δ)

CH-

81-83

(ppm): 2.28 (6H, s), 4.35 (2H, s),

6.40 (IH, d), 7.1-7.9 (4H, m)

Cl

67-68

CDCl-j-DMSO-d... ^ 6 (ppm):

4.40 (2H, s), 6.31 (IH, d), 7.3-8.1 (4H, m), 10.10 (IH, d)

Cl

Cl

123-125

, CDCl.- DMSO-d, -, _n , ⁶ _{ΤΜ s} 3 6 (ppm):

4.38 (2H, s), 6.28 (IH, d), 7.5-8.1 (3H, m), 10.23 (IH, d)

CH.

CH

90-91

.CDCl ^ -DMSC-d,.

δ _φΜς 3 6 (ppm):

2.43 (6H, s), 4.38 (2H, s), 6.30 (IH, d), 7.1-7.5 (3H, ra), 10.15 (IH, d)

CH.

95-97

(ppm): 1.47 (3H, dd), 2.60 (1H, t), 4.55 (IH, m), 6.54 (IH, dd), 7.2-8.0 (6H, m)

Table 1 (cont.)

connection

Property (Fp ⁰ C)

NMR (100 MHz, δ)

71

Cl

CH.

72-73

(ppm): 1.52 (3H, dd), 2.62 (IH, t), 4.58 (IH, m), 6.50 (IH, dd), 7.0-8.0 (5H, m)

72

CH.

68-69

_c CDCl _o ,. ⁶ TMS ^{3 (ppm)}

1.62 (3H, dd), 2.58 (IH, t), 4.53 (IH, m), 6.48 (IH, dd), 7.1-8.0 (5H, m)

73

CH.

70-71

(ppm): 1.47 (3H, dd), 2.64 (IH, t), 4.58 (IH, m), 6.55 (IH, m), 6.9-8.3 (5H, m)

74

CH.

64-65

(ppm): 1.58 (3H, dd), 2.70 (IH, t), 4.58 (IH, m), 6.53 (IH, dd), 7.1-8.0 (5H, m)

75

CH.

79-81

: 1.48 (3H, dd), 2.62 (IH, t), 4.58 (IH, m), 6.49 (IH, dd), 6.9-8.1 (5H, m)

76

br

CH.

79-82

(ppm): 1.48 (3H, dd), 2.59 (IH, t), 4.52 (IH, m), 6.47 (IH, dd), 7.1-8.2 (5H, m)

Table 1 (cont.)

Ver ^CH 3x R ¹ R ² property NMR (100 MHz (3H, , δ) 2.37 (3H , s) I m) binding (O) - (IH, 4.56 (IH, πι), No. (Mp ⁰ C) Οφμο ^ (ppm): 1.48 (IH, dd) 7.2-7.8 (5H, CH ₀ H 2.60 (3H, t) 2.37 (3H , s) m) 77 Ch _7- ZoV ό 70-71 6:52 (IH, dd) 4.54 (IH, m), δ _φΜ _ 3 (ppm): 1.48 (IH, dd) 6.9-8.0 (5H, CH ₁ CH ₀ H 2:59 t), 78 100-101 6:45 (3H, dd) 2.28 (6H , s) m) (IH, 4.54 (IH, m), ⁶ TMq ³ (PP ^m ) ^{: 1} ^ ⁵⁴ (IH, dd) 7.1-7.7 (4H, CH ₃ CH ₀ H 2 .62 t), 79 CH, O 83-85 6:50 dd) ^J \ (3H, 2.5 8 (IH , t) m) (O)- (3H, 4.54 (IH, m), δ3 (ppm): 1.47 (IH, dd) 6.9-8.0 (5H, CH. H 3.80 (3H, s), 2.60 (IH , t) m) 80 CH ₃ O-ZoV j 84-85 6:50 (3H, dd) 4.60 (IH, m), j \ / ⁶ TMs ^{13 (} PP ^{m): 1} ^ ⁵⁰ (IH, dd) 6.8-8.0 (5H, CH ₀ H 3.82 s), 81 j 86-87 6:45 dd)

UO Cn

Q) H rH

+ j OS he· ε CO "i VO co  , *. CN rr 4Y Xi I O in 4J XJ E E CO VD m Connection no. E - CN jj - E Xi O JJ X! in co XJ vo "Z co X5 ΓΟ (H [- » I CO (H E rh W ro O t-i Xi I E - r- E «. co CN υ ο "- (H I E - co I E ^ (H (H E rH E in co ι CO CN VO H E Γ- Σ a r " (H E in *-' (H - ^ (H ro in ^ S Cn D "- ' in o CN - * CN I ro O - Ή CN ro • · · •H • VO rh CO I (H CJ CO (H in in front" e VO CO rH ^ J ¹ r * ^ W CN · VO CN VO Q S in σ • in ro • * 3 e (N "3 · ^ s • O · CJ Eh • in e CN · e CN · ro OS ε e CN · VO <o e CN · ro VO - U vo - (UI e (H χι - ^ «. ro VO ro VO - » e ε (P) ε CU U OS. XJ ω Ε e e ε CJ χΤ ~ - xT-, «. Bi Ia) <o CJ Xi ^^ XJ - * U χ? -. ". xi ε ε χι ε ε ro cj ^ - ^ ·, ·. ·. --- xj ε χ; χι fo} χι ε ε ro ^ "^" ^ in in CJ co 2 N E E ro ro O T ^ in Cu ·. ". · - Q ε e C ro vo cn E E ·. ". · - CJ E E CJ Eh Σ r- υ cj EEEE E E ro (H o <o cri in I ·· rO (H rH (H ro rH vo cn O «F CO tf CN ε ro co r ~ (N I (H t »· CO Roι ro ο co in co VO «3 · I «3> vo in • ~ " (H ro vo Cu rf in ro "3 · in r • d • * ^ · · «t · • »« rH "3 * Γ- OS ·· (H "3 ¹ vo σ> S (UI ·· ou ·· (UI CU (Ul CU ro Cu CU CJ CO Q Σ Cu ro CJ Eh ro rH U CO <o rH CJ CO Q S Q E CJ Eh CJ Eh <o •O

Table 1 (cont.)

Ver ^R Rin ZJ 1 R ² property ₆ CDC1 CT ¹ MC 3 NMR (100 MHz (3H, (3H, , 6) 2.28 (6H r S) t m) binding ) - \ R ¹ Irlo (IH, (IH, 4.50 ( IH, m), No. οΥ (Mp ⁰ C) (ppm): 1.44 (IH, (IH, dd) 7.0-8 .0 (4H, CH H ₆ CDC1 T ¹ MC 3 2:57 (3H, I (IH, t), 1.78 ( 2H, m), m) 87 CH. ) - \ CH ₀ 84-85 IrI ο 6:52 (IH, dd) 4.41 ( IH, m), j Oh ο (ppm): 1.06 (IH, (3H, q) 7.0-8. 2 ( 5H, F V H ₆ CDC1 TMC! 3 2.62 (3H, (IH, t), 1.80 ( 2H, m), m) 88 / - \ C _? H 74-75 6:53 (IH, (IH, d) 4.37 ( IH, m), Τ)> - (ppm): 1.07 (IH, q) 7.1-8. 3 ( 511 H ₆ CDC1 ΦΜς 3 2:58 - ^DMS ° - ^d 6 (ppm): t), 89 ³ VX > - \ C ₉ H 61-62 6:45 0.98 d) 1.72 ( 2H, m), m), oV 2.80 4.37 ( IH, m), H 6:32 q) R 7.4-8. 1 ( 3H, 90 - \ ^C 2 ^H 5 128-129 10.U t), d) V: _β CDCl 3 (ppm): 1.06 d) 1.78 ( 2H, m), m) Cl TMS 2.62 4.38 ( IH, m), < 6:52 q) 7.3-8. 5 ( 5H, H t), 91 Cl C ₉ H, - 50-52 d) < Cl ' CF, -Λ <

Table 1 (cont.)

! ver CH, 0 ) - \ R ¹ R ² property NMR (100 MHz, 6 (3H / q) , ) 1.78 (2H, m), binding no. ) - \ (Mp ⁰ C) (IH , t), 3.85 (3H, s). \ OV y ' ⁶ TMQ 3 (ppm): 1.02 (IH , m), 6:47 (IH, d) \ - ' CH ₃ H ^inb 2.58 .5 (4H, m), 8 .20 ( IH, d) 92 Z oo 62-64 4:38 CH ₃ 6.9-7 (3H f q) / 1.78 (2H, m), (6H / S), 2:57 (IH, t), 6 3 (ppm): 1.05 (IH , m), 6:52 (IH, d) C ₀ H, H ^1Mb 2.33 .9 (4H, m) 93 λ o 82 4.30 7.0-7

Embodiment:

The invention is explained in more detail below with reference to some examples.

The process according to the invention for the preparation of the compounds of formula (I) is further illustrated by the synthesis examples

explained.

Synthetic Example 1 Synthesis of alpha-benzoylamino- (2-butynyloxy) -acetonitrile (Compound No. 1)

Benzoylaminoacetonitrile was synthesized conventionally from benzoyl chloride and aminoacetonitrile. 40 g of bromine were added all at once to a solution of 4.0 g of benzoylaminoacetonitrile in 200 ml of ethyl acetate at room temperature. When the color of the bromine in the reaction solution disappeared, the reaction solution was cooled to 0 to 5 ^° C. 2.1 g of 2-butyn-1-ol and 5.6 g of triethylamine were dissolved in 10 ml of ethyl acetate, and the solution was added dropwise to the previously cooled ethyl acetate solution. After addition, the reaction was continued for 30 minutes at room temperature. Triethylamine hydrobromide was separated by filtration and the filtrate was distilled under reduced pressure to evaporate the solvent. The residue was purified by silica gel column chromatography. Elution with hexane-ethyl acetate gave 3.8 g of alpha-benzoylamino- (2-butynyloxy) -acetonitrile as a solid. The yield was 65.5%, and the melting point of the product was 84 to 85.5 ° C.

NMRS CDCl ₃ -DMSO-d _{6 (ppm)} . TMS

1.82 (3H, t), 4.30 (2H, q), 6.40 (1H, d), 7.2-8.1 (5H, m), 9.37 (1H , d).

The starting acylaminonitrile can be easily prepared by reacting an acyl halide with aminoacetonitrile in a conventional manner, for example, according to the following procedure.

For example, a 10% aqueous solution of sodium hydroxide in ice water is cooled, and with stirring, sulfuric acid and aminoacetonitrile are added to form a solution. A toluene solution of an acid halide is added dropwise with ice cooling, and after the addition, the mixture is stirred at the same temperature. The precipitated crystals are collected by suction filtration, washed first with toluene and then with water, and then dried.

Synthesis Example 2 Synthesis of alpha- (2-butynyloxy) -3,5-dichlorobenzoylaminoacetonitrile (Compound No. 5)

2.8 g of bromine were added all at once to a solution of 4.0 g of 3,5-dichlorobenzoyl-aminoacetonitrile in 100 ml of ethyl acetate at room temperature. The mixture was stirred until the color of the bromine of the reaction solution disappeared. The reaction solution was then cooled to 0 to 5 ⁰ C. A mixture of 1.5 g of 2-butyn-1-ol, 3.5 g of triethylamine and 30 ml of tetrahydrofuran was cooled to 0 to 5 ⁰ C on an ice bath and added dropwise with stirring, the ethyl acetate solution of the bromine compound prepared above. After the addition, the reaction was continued for 30 minutes under cooling. 100 ml of water were added to dissolve the precipitated triethylamine hydrobromide. The oil layer was separated, washed with water and dried. The solvent was then distilled off under reduced pressure, the solid remaining as a residue was suspended in ethyl ether, filtered, washed and dried to give 4.2 g of the desired alpha- (2-butynyloxy) -3,5-dichlorobenzoylaminoacetonitrile as a white solid. The yield was 79.9% and the melting point of the product was 124 to 128 ° C.

NMRS CDCl ₃ -DMSO-d _{6 (ppm)} . TMS

1.85 (3H, t), 4.30 (2H, q), 6.38 (1H, d), 7.3-8.0 (3H, m), 9.50 (1H, d) ,

Synthesis Example 3 Synthesis of alpha-pi-dichlorobenzoylaminoMS-iodopropargyloxyacetonitrile (Compound No. 25)

2.8 g of bromine were added all at once to a solution of 4.0 g of S-dichlorobenzoylaminoacetonitrile in 100 mL of ethyl acetate at room temperature. The mixture was stirred until the color of the bromine in the reaction solution disappeared. After that, the reaction solution was cooled to 0 to 5 ° C. A mixture of 3.8 g of 3-iodopropargyl alcohol, 3.5 g of triethylamine and 30 ml of tetrahydrofuran was cooled to 0 to 5 ° C over an ice bath. The above-prepared ethyl acetate solution of the bromine compound was added dropwise to this mixture without stirring. After the addition, the reaction was continued for 30 minutes under ice-cooling. 100 ml of water were added to dissolve the precipitated Triäthylaminhydrobromid. The oily layer was separated, washed with water and dried. The solvent was then evaporated under reduced pressure. Addition of ethyl ether to the residue gave 5.3 g of the desired alpha-P 1 -dichlorobenzoylaminoMS-iodopropargyloxy J-acetonitrile as a white solid. The yield was 71.1% and the melting point of the product was 128 to 130 ^° C.

NMRS CDCI ₃ -DMSOd _{6 (ppm)} . TMS

4.50 (2H, s), 6.30 (1H, d), 7.2-8.1 (3H, m), 9.25 (1H, d).

The above 3-iodopropargyl alcohol was prepared according to the method described in Bull. Chem. Soc. Jpn., 45, 2611 (1972).

Synthesis Example 4 Synthesis of alpha-IS-bromopropargyloxyl-S 1 -dichlorobenzoylaminoacetonitrile (Compound No. 43)

2.8 g of bromine were added all at once to a solution of 4.0 g of 3,5-dichlorobenzoylaminoacetonitrile in 100 ml of ethyl acetate at room temperature. The mixture was stirred until the color of the bromine in the reaction solution disappeared. The reaction solution was cooled to 0 to 5 ° C. 2.8 g of 3-bromopropargyl alcohol and 3.5 g of triethylamine were dissolved in 10 ml of ethyl acetate. The solution was added dropwise to the above-prepared ethyl acetate solution of the bromine compound under ice-cooling. After the addition, the reaction was continued at room temperature for 30 minutes. The triethylamine hydrobromide was separated by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography. Elution with hexane-ethyl acetate afforded 4.5 g of alpha- (3-bromopropargyloxy) -3,5-dichlorobenzoylaminoacetonitrile as a white solid. The yield was 71.2% and the melting point of the product was 128 to 130 ^° C.

NMR S CDCIs-DMSO-ds _<ppm): TMS

4.37 (2H, s), 6.30 (1H, d), 7.4-8.0 (3H, m), 10.06 (1H, d).

The above 3-bromopropargyl alcohol was prepared according to the method described in Bull. Chem. Soc. Jpn., 45, 2611 (1972).

Synthesis Example 5 Synthesis of alpha- (1-methylpropargyloxyl-S) -dimethylbenzoylaminoacetonitrile (Compound No. 79)

3.2 g of bromine were added all at once to a solution of 3.8 g of 3,5-dimethylbenzoylaminoacetonitrile in 100 ml of ethyl acetate at room temperature. The mixture was stirred until the color of the bromine in the reaction solution disappeared. The reaction solution was cooled to 0 to 5 ° C. 1.7 g of 1-butyn-3-ol and 4.1 g of triethylamine were dissolved in 10 ml of ethyl acetate. The solution was added dropwise to the above-prepared ethyl acetate solution of the bromine compound under ice-cooling. After the addition, the reaction was continued for 30 minutes at room temperature. After the reaction, triethylamine hydrobromide was separated from the reaction mixture by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography. Elution with hexane ethyl acetate gave 3.6 g of alpha- (1-methylpropargyloxy) -3,5-dimethylbenzoylaminoacetonitrile as a white solid from the eluate. The yield was 69.6% and the melting point of the product was 83 to 85 ° C.

NMR (100MHz, 5): 6 ^{CDC |} 3 (ppm): TMS

1.54 (3H, dd), 2.28 (6H, s), 2.62 (1H, t), 4.54 (1H, m), 6.50 (1H, dd), 7 , 1-7,7 (4H, m)

The following formulation examples illustrate the formulation of the rice herbicide or fungicide for agriculture and horticulture containing compounds prepared by the process of the present invention.

The active compounds in these examples are designated by the numbers of the compounds given in Table 1. All parts are by weight.

Formulation Example 1 Dust

Three parts of compound No. 1.20 parts of diatomaceous earth, 30 parts of terra alba and 47 parts of talc were uniformly pulverized and mixed to obtain 100 parts of a dust.

Formulation Example 2 Wettable powder

30 parts of compound No. 10.44 parts of diatomaceous earth, 20 parts of terra alba, 1 part of sodium lignosulfonate and 2 parts of sodium alkylbenzenesulfonate were uniformly pulverized and mixed to give 100 parts of a wettable powder.

Formulation Example 3 Emulsifiable concentrate

40 parts of Compound No. 13.10 parts of cyclohexanone, 30 parts of xylene and 20 parts of Sorpol (trade name for a surfactant) were mixed uniformly to give 100 parts of an emulsifiable concentrate.

Formulation Example 4 Granules

One part of Compound No. 25.78 parts of bentonite, 20 parts of TEU TEAIK and 1 part of sodium lignosulfonate were mixed and kneaded with a moderate amount of water. The mixture was granulated usually in an extrusion granulator and dried to give 100 parts of granules.

Formulation Example 5 Granules

7 parts of compound No. 59.1 parts of polyethylene glycol nonylphenyl ether, 3 parts of polyvinyl alcohol and 89 parts of clay were uniformly mixed. Water was added and the mixture was granulated and dried to give 100 parts of granules.

Formulation Example 6 Dust

2 parts of compound No. 71.40 parts of calcium carbonate and 58 parts of clay were uniformly pulverized and mixed to give 100 parts of a dust.

Formulation Example 7

Wettable powder

50 parts of Compound No.77.40 parts of talc, 5 parts of sodium lauryl phosphate and 5 parts of sodium alkylnaphthalenesulfonate were mixed uniformly to give 100 parts of a wettable powder.

Formulation Example 8

Fifty parts of compound No.79.10 parts of sodium lignosulfonate, 5 parts of sodium alkylnaphthalenesulfonate, 10 parts of white carbon and 25 parts of diatomaceous earth were mixed and pulverized to give 100 parts of a wettable powder.

Formulation Example 9 Flowable composition

40 parts of Compound No. 88.3 parts of carboxymethyl cellulose, 2 parts of sodium lignosulfonate, 1 part of sodium dioctylsulfosuccinate and 54 parts of water were wet pulverized by means of a sand mill to add 100 parts of a flowable composition

result.

The following test examples illustrate the herbicidal activity of the compounds obtained by the invention

Procedures were made.

Test Example 1 Test before emergence in a paddy field

One filled soil in Wagner pots (1 / 5000Ar) and sowed seeds of mealgrass (Echinochloa crus-galli), broad-leaved weeds (Rotala indica, Lindemia procumbens pyxidaria, Monochoria vaginalis, etc.), Scirpus juncoides, Alisma canaliculatum and Cyperus difformis. The soil in the pots was kept in a flooded condition. Previously grown rice seedlings (2- to 3-leaf stage) were placed in each consisting of two seedlings plantings. Two plantings were transplanted into each pot and grown in a greenhouse. One day after the transplanting, when the weeds were not yet aground, a granule composition prepared according to Formulation Example 5 using a predetermined amount of each of the test compounds was applied to the pots in a flooded state. Thirty days after the application, the condition of the occurrence of weeds and phytotoxicity to rice was examined. The results are shown in Table 2. The degree of phytotoxicity to the crops and the herbicidal activity against weeds in Table 2 were determined by comparing the air-dried weight of the crop or weed to the air-dried weight of the crop or weed in an untreated area and the state of appearance or evaluated the growth of the crop or weed on the scale 0 to 5, below. The test compounds are given by the numbers of the compounds given in Table 1 (this also applies to the following test examples)

rating scale

Evaluation survival rate expressed as a ratio

of the air-dried weight to that of the non-treated area

0 91-100%

1 71-90%

2 41-70%

3 11-40%

4 6-10%

5 0-5% control compounds

A: alpa-allyloxy-3-chlorobenzoylaminoacetonitrile (described in British Pat. No. 2,094,786) B: alpha-allyloxy-S 1 -dichlorobenzoylaminoacetonitrile (described in British Pat. No. 2,094,786) C: butachloro [2-chloro-2 ', 6'-diethyl -N- (butoxymethyl) acetonitrile] The weeds in Table 2 are designated by the following abbreviations.

Ec: Echinochloa crus-galli Mv: Monochoria vaginalis Cd: Cyperus difformis Sj: Scirpus juncoides Ac: Alisma canaliculatum

test compound application rate ec mv Herbicidal action sj ac phytotoxicity (G / a) 5 5 CD 5 5 rice 2 50 5 3 5 5 5 0 4 50 5 5 5 3 5 0 5 50 5 2 5 5 5 0 7 50 5 4 5 5 5 0 9 50 5 3 5 5 5 0 10 50 5 4 5 5 5 0 12 50 5 5 5 5 5 0 21 50 5 5 5 5 5 1 22 50 5 5 5 5 5 0 24 50 5 5 5 5 5 0 25 50 5 5 OI 5 4 1 27 50 5 4 4 5 5 1 28 50 5 5 5 5 4 0 29 50 5 5 5 5 5 0 32 50 5 5 5 5 4 1 35 50 5 Oil 5 OI 4 0 37 50 5 5 5 5 5 1 40 50 5 5 5 5 5 0 41 50 3 3 5 5 5 0 42 50 5 5 4 5 5 0 43 50 5 5 5 5 5 0 44 50 5 5 5 5 5 0 47 50 5 5 4 5 5 1 48 50 5 5 5 5 5 0 51 50 5 5 5 3 5 0 53 50 2 5 5 5 5 0 55 50 5 5 5 5 5 0 56 50 5 5 5 5 5 1 57 50 5 OI 5 5 OI 1 58 50 5 5 5 5 5 1 62 50 5 5 5 5 5 1 67 50 5 5 5 5 5 1 68 50 5 5 5 5 5 0 69 50 5 5 5 5 5 0 70 50 5 5 5 5 5 0 71 50 5 5 5 5 5 0 74 50 5 5 5 5 5 1 75 50 5 5 5 5 5 0 76 50 5 5 5 5 5 0 77 50 5 5 5 5 5 0 79 50 5 5 5 5 4 1 80 50 5 5 5 5 4 0 84 50 5 5 5 5 5 1 90 50 3 3 5 3 3 0 A 50 3 5 5 4 3 2 B 50 4 5 5 5 4 2 C 50 3 2

Test Example 2 Test after emergence in a paddy field

The soil was placed in Wagner pots (1 / 5000Ar) and sowed seeds of barnyardgrass (Echinochloa crus-galli), broad-leaved weeds (Rotala indica, Lindernia procumbens pyxidaria, Monochoria vaginalis, etc.), Scirpus juncoides, Alisma canaliculatum and Cyperus difformis and kept the soil in the pots in a flooded condition. Previously grown rice seedlings (2- to 3-leaf stage) were placed in each consisting of two seedlings plantings. Two plantings were transplanted into each pot and grown in a greenhouse. Twelve days after the transplanting, when the weeds were in the growth stage, a granular composition prepared according to Formulation Example 4 using a predetermined amount of each of the test compounds was applied to the pots in the flooded state. Thirty days after the application, the condition of the occurrence of roughage and phytotoxicity to rice was examined. The results are shown in Table 3. The phytotoxicity degree to the crops and the herbicidal activity against the weeds in Table 3 were examined according to the method shown in Test Example 1. The control compounds used were as follows:

A: as in Test Example 1 B: as in Test Example 1 D: Benthiocarb (S-p-chlorobenzyl-diethylthiocarbamate)

The weeds in Table 3 are given the same abbreviations as in Test Example 1.

Table 3

test compound application rate ec mv Herbicidal action sj ac phytotoxicity (G / a) 5 4 CD 3 3 rice 2 50 3 5 3 3 5 0 3 50 4 4 5 3 4 0 9 50 5 3 4 4 5 0 10 50 5 4 5 3 4 0 12 50 5 5 3 2 3 0, 21 50 5 5 4 2 3 0 22 50 5 5 5 2 2 0 25 50 5 4 3 3 4 0 27 50 5 4 4 3 4 0 30 50 5 4 4 3 4 0 32 50 5 5 4 3 4 0 33 50 5 5 4 3 4 0 37 50 5 5 4 3 4 0 41 50 5 5 4 3 4 0 43 50 5 5 4 3 4 0 55 50 5 5 4 3 3 0 56 50 5 4 3 1 2 0 57 50 5 5 4 2 4 0 62 50 5 4 3 3 4 0 70 50 5 5 4 3 4 0 71 50 5 4 4 4 4 0 74 50 5 4 4 4 4 0 75 50 5 5 4 3 4 0 76 50 5 5 3 3 4 0 77 50 5 5 3 3 4 0 79 50 3 CN 3 1 1 0 A 50 3 CM 3 1 1 0 B 50 4 5 3 3 3 0 D 50 4 0

The results shown in Tables 2 and 3 show that the group of compounds prepared by the method of the present invention, a broad range of herbicidal activity in various rice field damaging weeds not only in the treatment before emergence, but also in the treatment during the Growth period, show in which the conventional herbicides have no significant herbicidal activity and that these compounds hardly lead to a phytotoxicity to rice.

Control Compounds A and B, d. H. Alpha-allyloxy-3-chlorobenzoylaminoacetonitrile and alpha-allyloxy-3,5-dichlorobenzoylaminoacetonitrile, disclosed in British Patent No. 2094786, exhibited phytotoxicity to rice in the pre-emergence rice field test and therefore lacked selectivity as a rice herbicide the compounds prepared by the method of the invention exhibited excellent selectivity without phytotoxicity to rice.

The following test examples show the fungicidal activity of the compounds prepared by the process according to the invention, with regard to late rotting and downy mildew, the compounds prepared by the process according to the invention were compared with amide-substituted allyloxyacetonitrile derivatives (control compounds A and B), which appear to have a structure which, among the compounds disclosed in GB-PS 2094786, is relatively close to that of the compounds prepared by the process according to the invention.

Test Example 3 Test to control the late rotting of the potato (preventive effect)

The potato (variety "Danshaku", height about 25 cm) was grown in a greenhouse in pots.When using each of the test compounds according to the method of Formulation Example 2, a wettable powder was prepared and diluted with water to a predetermined concentration was sprayed with a spray gun (1.0 kg / cm ² ) at a rate of 50 ml per three pots and then air dried A zoospore suspension of Phytophthora infestans was prepared previously cultivated on potato chips for seven days. The suspension was inoculated into the potato plants by spraying The plants were kept at a temperature of 17 to 19 ° C and a humidity of more than 95% for six days and then the degree of injury formation was examined.

One observed the ratio of the area of injuries and rated it for each leaf and determined the morbidity rate. For each area, the disease index was calculated according to the following equation.

Disease index

4n ₄ + 2n ₃ + 2n ₂ + 1n, + On ₀

ΣΝ

The rating scale was as follows: Morbidity rate

Ratio of the area of the injuries

0%

1-5%

6-25% 26-50% 51% or more

n ₀ : number of leaves with a disease rate of 0 Πτ: number of leaves with a disease rate of 1 n ₂ : number of leaves with a disease rate of 2 n ₃ : number of leaves with a disease rate of 3 n ₄ : number of leaves with a morbidity rate of 4

The results are shown in Table 4

 The control compounds were as follows.

A: the same as in Test Example 1

B: the same as in Test Example 1

E: zinc ethylenebis (dithiocarbamate)

F: tetrachloroisophthalonitrile

E and F are commercially available chemicals for controlling late potato rotting and cucumber downy mildew.

Table 4

test compound

Concentration of the active substance (ppm) disease index

phytotoxicity

4 5 12 21 22 23 24 25 26 27 31 32 34 35 36 37 39 43 49 51 52 53 55 62 67 68 69 71 72 74 75 76 77

200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200

0.55

0.50

0.42

0.31

0.25

0.56

0.35

0.20

none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none

test compound Kor 78 200 79 200 80 200 81 200 83 200 84 200 85 200 86 200 87 200 89 200 90 200 A 200 B 200 e 200 F 200

Concentration of the active substance (ppm) disease index

phytotoxicity

untreated area -

0.12

0.60

0.43

2.02

1.75

3.65

none none none none none none none none none none none none none none none none

Test Example 4 Test to control the late rotting of the potato (curative effect)

By spraying, a zoospore suspension of Phytophthora infestans prepared as described in Test Example 3 was inoculated into potatoes (variety "Danshaku", height about 25 cm) grown in pots in a greenhouse Thereafter, a chemical at a predetermined concentration (obtained by preparing a wettable powder of each of the test compounds according to Formulation Example 2 and diluting it to a predetermined concentration) was maintained at a temperature of 17 to 19 ° C and a humidity of 95% spray dried (1.0 kg / cm ² ) After drying in air, the plants were again held for five days at a temperature of 17 ° C to 19 ° C and a humidity of more than 95% and the degree the formation of the injuries was investigated.

The rating scale and the disease index are the same as in Test Example 3. The results are shown in Table.

The control compounds used were A, B, E and F, which were the same as in Test Example

Table 5

test compound Concentration of the active substance (ppm) Erkrankungs phyto index toxicity 2 200 0.58 none 4 200 0.42 none 5 200 0 none 12 200 0.45 none 22 200 0.12 none 23 200 0.05 none 24 200 0.24 none 25 , 200 0 none 27 200 0 none 28 200 0.05 none 29 200 0 none 30 200 0 none 32 200 0 none 33 200 0.13 none 34 200 0 none 35 200 0.10 none 36 200 0.12 none 37 200 0 none 43 200 0 none 51 200 0 none 52 200 0 none 53 200 0.08 none 54 200 0.14 none 55 200 0 none 62 200 0.40 none 67 200 0.64 none 68 200 0 none 69 200 0.13 none 71 200 0 none 72 200 0.36 none

test compound

Concentration of the active substance (ppm) disease index

phytotoxicity

74 200

75 "" 200

76 200

77 200

78,200

79 200

80 200

81 200

83 200

84,200

85 200

86 200

87,200

89 200

90 200 A 200 B 200 E. 200 F 200 untreated area -

none none none none none none none none none none none none none none none none none none none none

Test Example 5 Test for the control of downy mildew in cucumber (preventive effect)

A chemical was prepared in a predetermined concentration (obtained by preparing a wettable powder of each of the test compounds according to the method of Formulation Example 2 and diluting it with water to a predetermined concentration) on cucumbers (variety: "Sagami Hanshiro", at the stage where two Main leaves were sprayed and air-dried at a rate of 30 ml per three pots. "" Pseudoperonospora cubensis was collected from the injuries of the cucumber leaves infected with downy mildew and transferred to a spore suspension using deionized water. The suspension was inoculated into the cucumber plants in the pots by spraying The pots were immediately kept at a temperature of 18 to 20 ^° C. and at a humidity of more than 95% for 24 hours and then placed in a greenhouse (room temperature 18 to 27 ^° C.) Seven days later, the degree became investigated the formation of the injuries. The rating scale and the disease index were the same as in Test Example 3. The results obtained are shown in Table 6

 The control compounds used were A, B, E and F, which were the same as in Test Example 3.

Table 6

test compound

Concentration of the active substance (ppm) disease index

phytotoxicity

12 22 23 24 25 26 27 28 29 30 32 33 34 35 36 37 39 43 49 51 52 53 57 62 65

200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200

none none none none none none none none none none none none none none none none none none none none none none none none none none none none none

test compound Kor 67 200 68 200 69 200 71 200 72 200 74 200 75 200 76 200 77 200 78 200 79 200 80 200 81 200 83 200 84 200 85 200 86 200 87 200 89 200 90 200 A 200 B 200 e 200 F 200

Concentration of the active substance (ppm) disease index

phytotoxicity

untreated area

none none none none none none none none none none none none none none none none none none none none none none none none none

Test Example 6 Test for the control of the downy mildew of the cucumber (healing effect)

A zoospore suspension of Pseudoperonospora cubensis was prepared and sprayed on the same cucumber plants as used in Test Example 5 to inoculate the fungus. The plants were kept for 24 h at a temperature of 18 to 2O ⁰ C and at a humidity of more than 95%. A chemical was prepared at a predetermined concentration (obtained by preparing a wettable powder of each of the test compounds by the same method as in Formulation Example 2 and diluting it with water to a predetermined concentration) on the plants by means of a spray gun (1.0 kg / cm ² ). sprayed at a rate of 30 ml per three pots. The pots were then transferred to a greenhouse (temperature 18 to 27 ° C) and six days later, the degree of injury formation was examined.

The rating scale and the disease index were the same as in Test Example 3. The results are shown in Table 7.

The control compounds used were A, B, E and F, which were the same as in Test Example 3.

Table 7

test compound

Concentration of the active substance (ppm) disease index

phytotoxicity

4 5 7 9 12 22 24 25 27 28 29 30 32 33 34 36 43 44 51 52

200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200

none none none none none none none none none none none none none none none none none none none none none none

test compound Kon 53 200 54 200 55 200 65 200 67 200 68 200 69 200 71 200 72 200 74 200 75 200 76 200 77 200 78 200 79 200 80 200 81 200 83 200 84 200 85 200 86 200 87 200 89 200 90 200 A 200 B 200 e 200 F 200

Concentration of the active substance (ppm) disease index

phytotoxicity

untreated area

none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none

The results given in Tables 4, 5, 6 and 7 show that the compounds prepared by the process according to the invention have a preventive effect at very low dosages in late potato rotting and in cucumber downy mildew, which is superior to that of ethylene bis (dithiocarbamate) or tetrachloroisophthalonitrile, which are now commercially available and widely used, and also had a curative effect not possessed by the above two commercially available chemicals. It is thus clear that the compounds prepared by the process of the present invention have an excellent control effect which is not foreseeable due to the compounds disclosed in British Pat. No. 2,092,786, namely alpha-allyloxy-3-chlorobenzoylaminoacetonitrile and alpha-allyloxy-S-dichlorobenzoylaminoacetonitrile were.

Test Example 7 Test for controlling the fouling of seedlings of sugar beet

A dust of each of the test compounds prepared according to the method of Formulation Example 1 was well mixed with 1 kg of steam-sterilized soil such that the content of the active ingredient reached a predetermined value. The mixture was placed in a non-vitrified pot with a diameter of 18 cm and 20 sugar beet seeds (variety: "Monomidori") were sown.The pots were placed in a greenhouse (18 to 28 ° C) for three days and a zoospore suspension (approx 5 × 10 ⁴ cells / ml) of Aphanomyces cochlioides, which had been cultured separately, was inoculated at a rate of 50 ml per pot into the surface of the soil in the pot in which the beet seeds had been seeded The rape of the beet seedlings was examined for seeding, the test was carried out with three repetitions and the results are given in Table 8 as averages.

., ,, .... Number of healthy seedlings in each treated area

Control rate (%) = χ 100

Number of examined seedlings in each treated area

The control compounds were as follows: A: as in Test Example 3 B: as in Test Example 3 G: 3-hydroxy-5-methylisoxazole (commercially available beet-raking control agent)

Table 8

test compound

Application rate (g / a)

Control Rate (%) phytotoxicity 94 none 100 none 91 none 100 none 100 none 100 none 83 none 97 none 100 none 88 none ioo none 100 none 87 none 92 none 100 none 100 none 96 none 100 none 100 none 95 none 100 none 90 none 98 none 100 none 100 none 100 none 100 none 100 none 100 none 100 none 100 none 98 none 94 none 28 none 45 none 86 none 0 _

4 30

5 30 12 30

23 30

24 30

25 30 28 30

31 30

32 30

35 30

36 30 43 30

48 30

49 30

51 30

52 30

53 30

55 30

56 30 58 30 60 30 62 30 66 30

68 30

69 30

71 30

72 30 74 30

76 30

77 30 79 30 82 30 86 30 A 30 B 30 G 30 Untreated surface -

The results given in Table 8 show that the compounds prepared by the process of the invention had an obviously higher control of the beet fermentation caused by Aphanomyces cochlioides than the now commercially available 3-hydroxy-5-methylisoxazole (hymexazole). Furthermore, it is clear that the compounds prepared by the process according to the invention have an excellent control effect, which was not foreseen by the compounds disclosed in GBPS 2094786, namely alpha-allyloxy-S-chlorobenzoylaminoacetonitrile and alpha-allyloxy-3,5-dichlorobenzoylaminoacetonitrile could be.

As can be clearly understood from the foregoing description, the substituted propargyloxyacetonitrile derivatives produced by the method of the present invention, when used as a herbicide in paddy fields, exhibit an excellent herbicidal activity with a broad range at the appropriate time of application due to the conventional herbicides could not be expected, and when used as a fungicide for agriculture and horticulture, both preventive and curative at very low doses and concentrations, which would not be expected to be effective for conventional commercial chemicals. Therefore, agricultural chemicals comprising the substituted propargyloxyacetonitrile derivatives of the present invention are highly valuable as hficides and fungicides for agriculture and horticulture.

In the methods hitherto recommended for the preparation of acetonitrile derivatives, the hydrolysis reaction of the nitrile group occurs at the halogenation stage to form carbamoyl derivatives. Therefore, these methods must include stages such. Example, an alkoxylation of the halogen and then the dehydration of the Carbomoylgruppe to obtain the desired acetonitrile derivatives and the yields of desired compound are low. In contrast, in the process of the present invention for forming the substituted propargyloxy-acetonitrile derivatives of the present invention, the nitrile group undergoes no hydrolysis at the halogenation stage, and by simply adding the reaction material to the obtained halogenated intermediate, the end product can be easily produced in a high yield with the aid of a be obtained considerably shorter procedure.

Claims (7)

TL Process for the preparation of substituted porpargyloxyacetonitrile derivatives of the general formula ^ CH CONHCH ^ (D. ^^ OCH-C = CR ² wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a methylenedioxy group, a nitro group or a cyano group, η is an integer of 1 to 5, and when η is an integer of 2 or more, the radicals R may be the same or different, R ^{1 is} a hydrogen atom or a lower alkyl group, and R ^{2 is} a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a halogen atom, provided that R ¹ and R ^{2 are} not simultaneously hydrogen atoms; characterized in that it comprises the steps of: reacting an acid chloride of the following general formula (II) COCl _{(l |)} wherein R and η are as defined above, with aminoacetonitrile to form an acylaminoacetonitrile of the general formula (III) wherein R and η are as defined above, the treatment of the resulting compound with a halogenating agent to give an intermediate of the following general formula (IV) COHHCH (IV) in which R and η are as defined above and X is a halogen atom, and the reaction of the intermediate with a substituted propargyl alcohol of the general formula (V) R ² -C = C-CH-0H j (V). R ¹ wherein R ¹ and R ^{2 are} as defined above. 2. The method according to item 1, characterized in that in the compounds of formula 1, R ^{1 is} a hydrogen atom and R ^{2 is} a halogen atom. 3. The method according to item 1, characterized in that in the compounds of formula 1, R ^{1 is} a hydrogen atom and R ^{2 is} a methyl group. 4. The method according to item 1, characterized in that in the compounds of formula 1 R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom off. 5. The method according to item 1, characterized in that in the compounds of formula 1 R is a halogen atom or a methyl group, η is 1 to 4, R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom. 6. The method according to item 1, characterized in that in the compounds of formula 1 R is a halogen atom or a methyl group, η is 1 to 4, R ^{1 is} a hydrogen atom and R ^{2 is} a halogen atom or a methyl group. 7. The method according to item 1, characterized in that in the compounds of formula 1 R is a halogen atom or a methyl group, η is 1 to 4, R ^{1 is} a hydrogen atom and R ^{2 is} a methyl group.