JPS5951257A - Naphthylthiocarbamate derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:O-2-Naphthyl N-(3-methoxyphenyl)-N-methylthiocarbamate shown by the formula I . USE:A herbicide. Showing selectively high herbicidal effect on Echinochloa crus- galli Beauv. var. praticola Ohwi, and other common weeds, having no phytotoxicity to transplanted paddy-rice plant. PROCESS:A naphthol derivative shown by the formula II (X is H, halothiocarbonyl) is reacted with a 3-methoxy-N-methylaniline derivative shown by the formula III (Y is as shown for X but a different combination with it) in the presence of dehydrohalogenating agent such as sodium hydroxide, etc. in an organic solvent such as methanol, etc., to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to naphthylthiocarbamates and processes for their production.

It has been well known that arylthiocarbamate compounds have antibacterial and nematicidal properties as medicines. It has also been disclosed that a phenyl carbamate compound converted into a mackerel can be used as a herbicide.

The present inventors have conducted extensive research to develop naphthylthiocarbamate derivatives with sufficient herbicidal effects and a high degree of selectivity. We discovered a compound that has not been described in the literature that shows a selective high reservoir effect on other common weeds of No. rays.
The invention has been completed.

That is, 0-2-naphthyl N-(3-methoxyphenyl)-N-methylthiocarpame) (,
The present invention provides a compound of the present invention (LJT) and a method for producing the same.

Inventive formulation F1 has a high herbicidal effect. The herbicide containing the compound of the present invention as an active ingredient exhibits excellent selective herbicidal activity as a paddy herbicide, is harmless to transplanted paddy rice, and effectively controls many paddy weeds including field weeds. Take power.

The compound of the present invention can be produced according to the following reaction formula.

OCT is also used (in the formula, Had represents a halogen atom). The above reaction is carried out in the presence of a dehydrohalogenating agent and in the presence or absence of a reaction solvent, usually at a temperature of 0°C to 150°C. The reaction proceeds at the reaction temperature, and the reaction time is about several minutes to 48 hours.

As a dehydrohalogenating agent, earth, alkali hydroxide such as sodium hydroxide, potassium hydroxide, alkaline earth hydroxide such as calcium hydroxide, sodium charcoal No. 6, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. Examples include alkali carbonates, hydrogenated metals such as thorium, and tertiary amines such as triethylamine, dimethylaniline, and pyridine. In reaction formula (2), the Jjii material 3-methoxy-N-methylaniline can be used as the dehydrohalogenating agent.

As a reaction solvent, #': i, alcohols such as water and methanol, ethanol, and isopropanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, enal ether, and tetrahydrofuran' , ethers such as diokylene, halogenated hydrocarbons such as chlorobenzene, chloroporm, tetrahydrocarbon, dichloroethane, and polar solvents such as dimethylformamide and dimethyl sulfoxide.

Next, the method for producing the compound of the present invention will be explained in detail.

[Example 1] N-(s-methoxyphenyl)-N-methylthiocarbamoyl chloride 2.00 g, β-naphthol 1.4
49 and 1.66 g of anhydrous potassium carbonate were added to 50 mg of methyl ethyl ketone, and the mixture was heated under reflux for 15 hours. After the reaction mixture was cooled to room temperature, it was poured into water and the product was extracted with benzene.

After washing the benzene-resistant solution with water and a saturated aqueous solution of sodium chloride and drying over anhydrous magnesium sulfate, the benzene was distilled off under reduced pressure. The residue was purified by columnar mudgraphy (silica gel, developed with benzene) and purified with 0-2-
Crystals of naphthyl N-(5-methoxyphenyl)-N-methylthiocarbamate t 459 (yield 45 t)
It's a;t.

Melting point: 95-94°C (recrystallized from ethanol) Elemental analysis c (%) n Fs) N (h) Actual value
71125 519 4.72ir1f direct
70.57 5.30 4.33 Nuclear magnetic resonance spectrum (δ, CD(:1.)3,6
6 (All, 8), &75 (!1t(,8),
6.66-7.90 (1111, m) Infrared absorption spectrum (alt-', K'Br) 1595.158
0.1465,1425.1360if 1 Analysis spectrum Detection peak: 525 (molecule 1.+523), Fragmentation peak: i80,164 Example 6 - Medoxy N-medylaniline 157g and anhydrous charcoal paste) Potassium 1.669 20ml of acetone and tl (
Add [7. While stirring at room temperature for 12 minutes, add 2-naphthyl alcohol lactimepormate 2.259% analone 20 mL 1K
It was dissolved and dripped. After stirring for 15 hours, the reaction mixture was poured into cold water and extracted with ethyl ether. The ether solution was washed with dilute hydrochloric acid, 11+ of water, and dried over anhydrous magnesium chloride.

The ether was distilled off, and the resulting solid was recrystallized from ethanol to obtain +M+Si2'''9 (yield 91%). This was the same as the crystals obtained in Example 1.

The herbicidal spectrum of the compound of the present invention shows excellent efficacy against the major green grasses of rice fields, such as grasshopper and cypress, and also shows a strong effect against broad-leaved weeds such as Japanese grasshopper and grasshopper.

The safety for paddy rice transplanted from young seedlings is extremely high, and 1,000
No effect was observed even with R/10a, and extremely excellent selective herbicidal activity was obtained.

Next, the herbicidal effect of the compound of the present invention will be explained using Example 3.

[Example 3] Put paddy soil in a 1644, 9-on porcelain pot,
Two paddy rice seedlings (variety: Nipponbare) were planted at a depth of 1 t:nr during the watering period. The next day, 12 arr of water was flooded.
10 parts of the compound of the present invention as a carrier, 873 parts of Zikrite [trade name, manufactured by Kunimine Kogyo ■], and 1.3 parts of Neoperex [trade name, manufactured by Kao Atlas TL13] as a surfactant.
5 parts and 1.35 parts of Tsurubaichiru 800 A (trade name: manufactured by Toho Chemical Industries, Ltd.) were mixed and ground, and the predetermined amount of the resulting wettable powder was diluted in 10 ml of water per pot and dropped onto the water surface. Processed.

Thereafter, the mixture was allowed to stand at room temperature, and after 20 days of treatment, the herbicidal effect and the effect on paddy rice were investigated.

The evaluation was displayed on a 6-level scale, and specifically, V1 was rated 9 below. The results are shown in Tables 1 and 2.

Display Paddy rice damage weeding effect 5
100% control of withering (residual amount of weeds: 0) 4
Severe damage 80 inches control (residual grass needles 20%) 5
Medium damage 60 inches control (residual grass amount 40 inches) 2
Minor damage 40 inches control (residual grass amount 60 inches) 1
Slight damage 20% control (residual grass 11 80chi) 0
Non-hazardous 0% control (residual grass 11,100 yen) Table 1 Table 2 Patent applicant Toyo Soda Kogyo Co., Ltd. Tōzoku Amended April 15, 1981 lit, ・i'1 catty Shin Wakasugi Kazuo 1' Indication of Old No. 1 Patent Application No. 122921 filed in 1982, Name of Invention Naphthylthiocarbamate Derivatives and Method for Producing the Same Relationship with Person Who Noted 3 Amendments !II BoF Applicant Telephone Number (5
85) 3311 4th day of 11th order f-1 Voluntary Number of inventions increased from 5th supplementary 111c 0゜6 Subject of amendment [column of application (patent application pursuant to the proviso to Article 38 of the Patent Act)] [Column for the number of inventions stated in the claims of the application,” “Column for the scope of claims in the specification,” and “Column for the detailed description of the invention in specification 1.” 7. Contents of amendment (1) Application , To the right of the patent application, write "(A patent application pursuant to the provisions of Article 38 of the Patent Law)" between the column for the name of the joined invention and the column for the inventor (1-7l) - Scope of Claims Added 24 inventions described in (2) Specification and claims "as attached" (3) Specification, page 4, page 5, line 12 [recirculated]. ] is corrected to "refluxed."

2. Claims (+) 0-2-naphthyl N-(3-methoxyphenyl)-N-methylthiocarbamate (2) General formula (in the formula, Xi is represented by hydrogen or a halothiocarbonyl group) Naphthol visit The conductor is 3-methoxy-N represented by the general formula (wherein, Y is a halothiocarbonyl group when X in the preceding formula is hydrogen, and is hydrogen when X in the preceding formula is a halothiocarbonyl group). - A method for producing 0-2-naphthyl N-(3-methoxyphenyl)-N-methylthiocarbamate, which comprises reacting it with a methylaniline derivative. -1

Claims (1)

[Scope of Claims] +110-2-naphthyl N-(5-methoxyphenyk
)-N-metal □ meocarbame-) (2) General formula (wherein, When X in both formulas is hydrogen, it is a halotiosulfonyl group, and when X75Z in both formulas is an ocarbonyl group, it is hydrogen.
0 characterized by reacting with a methylaniline derivative
-2-naphthyl N-(5-methoxyphenyl)-N-
Method for producing methylthiocarbamate.