JPH03206070A - Phenoxyalkyne carbamate derivative and herbicide containing same derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R1 is aryl; R2 is H or lower alkyl; R3 and R4 are lower alkyl, aryl or nitrogen containing heterocycle). EXAMPLE:Phenoxy-2-butyne-N,N-diethylcarbamate. USE:A herbicide having extremely low phytotoxicity especially on gramineous crops and excellent herbicidal effects on cockspur-grass, bulrush, umbrella sedge, broad-leaved weeds, etc. PREPARATION:A phenoxy-2-butyn-1-ol shown by formula II is reacted with an N,N-diethylcarbamoyl chloride shown by formula II in a solvent such as TFH in the presence of a deoxidizer (e.g. sodium hydride) at -10 to 40 deg.C to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a new compound, a phenoxyalkyne carbamate derivative, and a herbicide containing the same.

[Prior art and its problems] Many herbicides containing carbamate compounds as active ingredients have been known for a long time, and a considerable number of these compounds have been put into practical use. For example, S-(4-chlorohexyl-4)N
,N
arb>, S-ethyl 6-height lower acetyl thioate (++olinate>,
Methyl 4N-(4-aminophenyl sulfate) has 20 carbon atoms.

Although these carbamate compounds have the property of selectively controlling grass and Cyperaceae weeds,
It has the disadvantage of low herbicidal efficacy against broad-leaved and perennial weeds. [Problems to be Solved by the Invention] The present invention solves the above-mentioned problems and provides a novel compound that has excellent herbicidal activity and does not cause any chemical damage to crops, especially Afu f4 crops. and to provide a herbicide containing the same as an active ingredient.

[Means for Solving the Problems] The present inventors have conducted intensive research to find a compound that has excellent herbicidal activity among carbamate compounds and does not cause phytotoxicity to crops, and as a result has achieved the present invention. Reached. That is, the present invention is based on the general formula (wherein R1 represents Zll! or an unsubstituted aryl group, R represents a hydrogen atom or a lower alkyl group, and Rs and R. are independently lower alkyl groups or substituted or The present invention provides a novel phenoxyalkyne carbamate derivative represented by an unsubstituted aryl group or a nitrogen-containing polycyclic group, and a herbicide containing the compound.

In the present invention, the nitrogen-containing heterocyclic group may be either aromatic or aliphatic.

The compound of the present invention can be synthesized, for example, by the following reaction.

(However, R + . R 2 . R s in the formula,
R< is the same as above. ) The above reaction is carried out in a suitable solvent, such as benzene, toluene, xylene, dichloromethane, chloroform, acetic acid ethyl ester, dioxane, tetrahydrofuran, diethyl ether, dimethylformamide, dimethyl sulfoxide, etc., a suitable deoxidizing agent,
For example, this is suitably carried out by adding triethylamine, pyridine, potassium hydroxide, caustic soda, sodium hydride, and the like.

The reaction temperature is usually -10°C to 40°C, but it can be further heated depending on the degree of progress of the reaction.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example ■ Sodium hydride 0. 34g (8.41g IIol
) was suspended in 50+mI of THF, and 1.50 g (92
5 mmol) of THF10++1g solution was added dropwise. 7 barley that was stirred for 1 hour, N,N-
Luhamoyl chlorite 1.25g (925mmol1
) was added dropwise to the mixture and stirred for 15 hours.

THF was removed under reduced pressure, diluted with ether 450+*l, washed with dilute hydrochloric acid, dilute caustic acid, and water in this order, and then dehydrated with anhydrous macrosulfate. The ether was removed under reduced pressure, and the crude bottom material was purified by kerosene column chromatography to obtain an oily product of phenoquino-2-futin-N. 53 g of N-ethyl carbonate 1 was obtained.

Example 2 Sodium hydride 0. 28g (7. Low garden o1)
was suspended in 50 ml of THF, and (4-methodoxyphenol)-2-7'tin-1 was added with stirring at 0°C.
50g (7.80mmol) of T}IF10m
l solution was added dropwise. After stirring for 1 hour,
N, N->'Engine f4 Calha'moyl chlorite゛1.
06 g (7.80 layer weight 1) of T}IF 10 ml was added dropwise and stirred for 15 hours. The procedure of Example 1 was followed to obtain 200 g of (4-methoxyphenono)-2-phytyne-N,N-thiamine carhamate as a yellow oil.

Table 1 shows the novel phenoxyalkyne carbamate derivatives of the present invention obtained according to the above examples.

Table 2 shows the 'H-NMR absorption spectrum values of the compounds of the present invention that were obtained as wave-like products using conventional separation and purification methods.

In addition, compound numbers are also applied to the following Examples and Test Examples.

(hereinafter 4th 1st 1tll Table 1 (2) Table i (31 (hereinafter 4th a-1 Table 2 < 1st Table 2 (2) 15 ].. 10ft..J:7.011z.6H )2.
18 (s. 3H) 2. 22fs, 3}1) 3. 30 (q.J=7 0Hz Table 2 (3) 26 1.40-1..80fb.8}1). 3.40 (
t. J++5.0}1z. 2}1) 4.75 (s.4H
l. 6.75-7.40(c3Hl346(+..
J.5. OH7. ．． 281 (IuTI??e>-, When the compound of the present invention is used as a herbicide, inert solid carriers, liquid carriers, emulsifying dispersants, etc., which are used in the formulation of general agricultural chemicals, etc., are used to make it more convenient to use. It can be used in any form such as a permanent agent, an emulsion, a powder, a granule, a flowable agent, etc.These inert carriers include, for example, talc, kush, bentonite, kaolin, Examples include diatomaceous earth 5 calcium carbonate, wood flour, corn flour, gum arabic, water, alcohol, kerosene, benzene, xylene, n-hexane, acetone, dimethylformamide, glycol, ether, N-methylpyrrolidone, etc. The above-mentioned auxiliary agents, such as spreading agent diluents, surfactants, and solvents, can be appropriately blended.

Furthermore, by mixing with fungicides, insecticides, other agricultural chemicals, fertilizers, soil conditioners, etc., a wider range of effects can be expected.

When actually using the compound of the present invention, the amount of the compound used (the compound of the present invention) is generally 1. 1-500g per are, preferably 5-1
00g.

Next, examples of the herbicide of the present invention will be given, but the compounds, carriers, adjuvants and usage ratios are not limited to these examples.

It should be noted that the 1'lli ratio of components in this example indicates parts by weight.

Example 3 (hydrating powder) Compound No. 310 parts Sodium liquninsulfonate
1 5 parts
．． 5th part clay
87 parts A portion of each of these is mixed until homogeneous and pulverized to obtain a permanent agent.

Example 4 (emulsion) Compound No. 720 parts Albenzene a salt
Part 5 Hon゜Rio A Sietylenoa K Kill Aryl Ete 4 Part 10 Kiren
65 parts These ingredients are mixed until homogeneous and dissolved to obtain an emulsion.

Example 5 (granules)> To compound number 237 parts'notonite
30 parts aluminum sulfuric acid sorter'
Part 2 clay

61 parts of these ingredients were mixed until homogeneous, kneaded, and granulated using a conventional granulation method to obtain granules.

Next, the herbicidal effects of the compounds of the present invention will be explained using test examples. In addition, the test compound number in each test example is the same as the compound number in Table 1.

Test example 1. / Fill a 15,500 are bonoto with paddy soil (clay loam), and sow a uniform mixture of various weed seeds such as field weeds, broad-leaved weeds, firefly, cypress, and Japanese cypress on the surface layer, and sow them at the 2- to 3-leaf stage. Rice seedlings were transplanted to a depth of 2 cm and flooded to a depth of 3 cm. After 3 days, at the beginning of the appearance of wild flies, a predetermined amount of a diluted hydrating agent solution of each compound was dropped onto the water surface. After that, it is grown in a glass chamber and treated with 4
After a week, the herbicidal effect and paddy rice damage were investigated. The results are shown in Table 3. In addition, the numerical values in the table indicate paddy rice phytotoxicity and herbicidal effects, and are specifically as follows.

5. Complete withering; 4. Major harm, 3: Chusho, 2, Minor harm, ■: Slight harm, 01 Harmless (normal development) 1'! Table 3: Herbicidal effect by waterlogged soil treatment [Effects of the invention] The herbicide containing the phenoxyalkyne carbamate derivative, which is a new compound of the present invention, as an effective ingredient has very little phytotoxicity on various crops, especially gramineous crops, and is effective against various weeds. It has excellent herbicidal activity and is useful as a herbicide.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents a substituted or unsubstituted aryl group, R_2 represents a hydrogen atom or a lower alkyl group, and R
A phenoxyalkyne carbamate derivative represented by _3 and R_4 each independently representing a lower alkyl group, a substituted or unsubstituted aryl group, or a nitrogen-containing heterocyclic group. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents a substituted or unsubstituted aryl group, R_2 represents a hydrogen atom or a lower alkyl group, and R
A herbicide characterized by containing a phenoxyalkyne carbamate derivative represented by _3 and R_4 each independently representing a lower alkyl group, a substituted or unsubstituted aryl group, or a nitrogen-containing heterocyclic group.