JPS5970696A - Novel methylphosphinic acid compound and herbicidal and miticidal agent - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R<1> is H; R<2> is (substituted) 1-4C alkyl, (substituted) 1-4C alkenyl or (substituted) aryl; M<1> and M<2> are H, metallic cation, (substituted) ammonium cation, or cation derived from choline molecule; m is reciprocal number of the ionic value of M<1> cation; n is reciprocal number of the ionic value of M<2> cation]. EXAMPLE:[(3-Phenylmethyleneamino-3-carboxy)-propyl-1]-methylphosphinic acid disodium salt. USE:A herbicidal and miticidal agent having low toxicity to man and cattle. PROCESS:For example, the carbonyl compound of formula III, pereferably an aldehyde, is condensed to the methylphosphine compound of formula II preferably at -10-+50 deg.C for 1-24hr is necessary in the presence of a solvent (preferably a lower alkanol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel methylphosphinic acid compound having herbicidal and acaricidal activity, and also to a herbicidal and acaricidal compound containing this as an active ingredient.
Regarding acaricides.

The compound represented by the following formula (commonly known as glufozonate) or a salt thereof is known, and among the optically convoluted forms of this compound, the L-unit can be produced (2-amino-4-methylphosphino-butyryl). - Acid hydrolysis method of alanylalanine (Japanese Patent Application Laid-open No. 85538/1985), Enzyme degradation method (
JP-A-49-31890), and the production of its DL form can be carried out, for example, by (% JP-A-49-31890).
No. 1019, No. 54-154715 and No. 55-2
This is possible by various methods shown in Japanese Patent No. 0714).

Glufosinate or its salt represented by the above formula is known to have a strong herbicidal effect on annual and perennial weeds when sprayed on foliage.
No. 7 and No. 54-92628).

As a result of research to develop a herbicidal compound superior to glufosinate, the present inventors discovered that it is a novel compound as a rust conductor of glufosinate, has low toxicity to humans and livestock, and is an extremely strong foliar weed killer. We have succeeded in creating a new methylphosphinic acid compound having active and acaricidal activity.

Therefore, the first invention provides the following formula (I):
R1 represents a hydrogen atom, R2 is an alkyl group with or without a substituent (C1 to C4), an alkenyl group with or without a substituent (C, to C4), or an alkenyl group with or without a substituent. M and M may be the same or different from each other and are hydrogen atoms, or metal cations, ammonium cations, [ammonium cations with substituents or cations derived from choline molecules]. and m is the reciprocal of the ionic valence of the M cation, and n times M is the reciprocal of the ionic valence of the cation.

Furthermore, the second invention is based on the following formula [wherein R represents a hydrogen atom, R is an alkyl group with or without a substituent (C-C), and a (C-C) with or without a substituent 4] -C) represents an alkenyl group, A4 or an aryl group with or without a substituent, M
and M may be the same or different from each other and represent a hydrogen atom or a metal cation, an ammonium cation, an ammonium cation with a substituent, or a cation derived from a purine molecule, and m is the M cation. The gist of this invention is a herbicide and acaricide characterized by containing a methylphosphinic acid compound represented by f, the reciprocal of the ionic valence, n is the reciprocal of the ionic valence of the M2 cation, as an active ingredient. be.

In the compound of general formula fI) above, when R is an alkyl group, an alkenyl group or an aryl group having a substituent, the substituent is one or more halo, nitro, hydroxyl groups.

(C-C)alkyl group, (01-C4)alkoxy+4 group, mono- or di(C,-C4)alkyl-substituted amino group, aryl group, especially phenyl group or aryloxy group, especially phenyloxy group or dichlorophenyloxy group can be a base.

Further, R can be a phenyl group or a naphthyl group with or without a substituent.

Preferred examples of R are methoxyphenyl group, di-methoxyphenyl group, dimethylaminophenyl group, hydroxyphenyl group, chlorophenyl group, dichlorophenyl group, fluorophenyl group or nitrophenyl group. Furthermore, R2 can be a group of the following formula or its sodium salt form.

In the compound of general formula (1), one or both of Ml and M2 can be an alkali metal cation, an alkaline earth metal cation, a copper cation, a zinc cation, a nickel cation or a manganese cation. Also, one or both of M and M is a mono-, di- or tri(C-C)4 alkyl-substituted ammonium cation, mono-.

Di or tri=(hydroxy(C-C) alkyl)
4 Substituted ammonium cation, or mono-.

It can be a di- or tri(C1-C4) alkenyl substituted ammonium cation. The metal compound of formula (1) can be in the form of either DL integral or L integral.

The present invention includes all possible isomers of the compound represented by formula (1). Among the isomers, DL-unit and L-unit are representative. In terms of herbicidal and acaricidal effects, the compound L is the most active.The compound TI of the present invention can be easily prepared by any method suitable for the formation of the groups or bonds contained therein. I can do it.

A preferred manufacturing method is as follows. That is,
Compound CI) of the present invention has the following formula [wherein M', M2. m
and n have the same meanings as shown in formula (I)] to a carbunyl compound represented by the following formula [wherein R1 and R2 have the same meanings as shown in formula (I)], preferably can be produced by condensing aldehyde compounds.

The condensation reaction with is preferably carried out without a solvent or in a water-organic solvent system or an organic solvent such as a lower alkanol such as methanol, ethanol, propatool, butanol and the like. The reaction temperature is -2
0°~200cc, preferably -10ec~50cc,
That's about it. The reaction time is about 1 to 24 hours. The number of moles used is preferably about 1 to 2 equivalents of the compound of formula (m) relative to the compound of formula (If).

Compound (1) of the present invention can be used as an active ingredient and mixed with a carrier to be used as a herbicidal or acaricide. When actually applying this, any conventional method can be used, but in many cases, it is combined with an appropriate diluent, solution, water conservancy, emulsion, powder, fine granule, etc. known in the field. The most commonly used formulations are When preparing these preparations, in order to improve spreadability, adhesion, dispersibility, etc.
Nonionic surfactants, cationic surfactants, and/or anionic surfactants such as octylphenyl polyoxic ethanol, dirioxoethylene dodecyl ether, yflJ oxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl allyl ether, etc. An appropriate amount of the agent can be added to ensure and improve the effect.

The amount of the compound of the present invention (CI) required for killing weeds and shrubs and suppressing their regeneration varies depending on weather conditions such as temperature and light intensity, as well as grass species. )
An example of this is the formula in Table 1.

Needless to say, the amount of the compound of the present invention to be used as an acaricide varies depending on the conditions of use, but is in the range of 0.05 to IO.
O,! It is preferable to use i'/l Oa.

Next, a synthesis example for producing compound (I) of the present invention will be described.

Synthesis Example 1 Synthesis of [(3-phenylmethyleneamino-3-cardoxy)-propyl-1]methylphosphinic acid disodium salt [(3-amino-3-carboxy)-propyl-1]methylphosphinic acid 5.00 g (27.6 mmol) of I N -NaOH ss, 2i (ss, 2 mmol)
and 20 d of ethanol were added, and the solution was distilled off under reduced pressure.

The residue was dissolved in 20 ml of ethanol, and then 3.239 (30.4 mmol) of ginsaldehyde was added to carry out a condensation reaction. This solution was distilled off under reduced pressure, and 40% of ethanol was added to the resulting powder, which was filtered with suction, washed with 20 mg of ether, and then dried under reduced pressure.

8 of the title target compound (referred to as compound mud 1) shown by the following formula
．． 259 (yield 95.5%) was obtained. This compound melts at 225-228°C with decomposition.

nrnr (CD OD, δ)', 20 (3Hd
Jp Hl 3Hz )1.25~2.40 (4H
m) 3.80 (IHt) 7-25~7.90 (
5I(m) 8.26 (IHs) [(3-amino-
3-Carboxy)-propyl-1]methylphosphinic acid is subjected to a condensation reaction in the same manner as in Synthesis Example 1, but instead of benzaldehyde in Synthesis Example 1, an appropriate raw material aldehyde compound shown in the following table is subjected to a condensation reaction. As a result, the compound of the present invention of formula (I') shown in the following table was obtained.

However, in the production of compound &17, aqueous ammonia was used instead of NaOH.

Examples of formulations of the herbicide and acaricide of the present invention are shown below.

In the following formulation examples and test examples, the compounds in Table 2 of Synthesis Examples 1 and 2 to 1g are used as substitutes for compound groups.

Formulation example 1 (liquid) (1t% by weight) Compound washing + (L form) 20.0 octylphenyl? Lioxoethanol 15.0 methylz
4-hydroxypenzoate 0.15 water
64
．． Mix and dissolve 85 or more, dilute with water before use, and spray on foliage.

Formulation example 2 (powder) (wt%) Compound A6 (DL form) 10.0 l
Ruri
89.0 Silicic anhydride fine powder
Uniformly mix and grind 1.0 or more. When using, sprinkle the leaves with powder.

Formulation example 3 (hydrating powder) (wt%) Compound 111+ o (L form) 45.0
Diatom ± 50.0 Polyoxyethylene alkyl ether 5.0
Mix the above ingredients uniformly and grind finely. To use: Dilute with water 7 and spray on leaves and foliage.

The herbicidal and acaricidal activities of the compounds of the present invention will be explained using the following test examples.

Test Example 1 A pot with a diameter of 6 crn was filled with field soil, and Novie seeds were sown in 8 to 9 pots. The indicated doses of each of the compounds of the present invention (L-form and DL-form) and control drugs were
0 are portrait + 00 was sprayed on the entire stem and leaves at the appropriate amount of water. As a developing agent, 0.1% octylphenyl polyoxyethanol was added. Investigation after processing 1
I went there on the 0th month and showed the staff that it was dead. The results are shown in Table 3 (0: harmless to 100: completely dead).

Table 3 Table 3 (Continued) Test Example 2 Compound M1 of the present invention (see Synthesis Example 1; the distinction between L and DL forms is indicated in Table 4) and a control drug were administered to native weeds during the growing season. A predetermined amount of the chemical was sprayed over the entire stems and leaves using a spraying water amount of 10 ares and btooz. As a spreading agent, octylphenylpolyoxy7ethanol was added at a concentration of 0.1%. The investigation was conducted on the killing effect (Ol: harmless to 100%: complete death) on the 21st day after treatment, and on the regeneration suppressing effect (Oe16: no effect ~ 100 %: complete inhibition of regeneration). The results are shown in Table 4. Table 4 As shown in Table 4, Compound Black 1 of the present invention was obtained by combining glyphosate (the free acid form of raw material compound (2)), or glyphosate. Comparison shows that the herbicidal effect is strong at equimolar application amounts.

Test Example 3 Effect of the compound of the present invention on the pseudonymph spider mite parasitic on young potted plants of Rinko and Himikan.

After dissolving the compound slo of the present invention in water to a concentration of 50 ppm, a spreading agent W-150 (Toho Chemical Co., Ltd.) was added to 0.
- Added 1% and sprayed with a small sprayer until the entire apple and ε-can trees where each stage of the false apple mite was grown were sufficiently wet. Thereafter, the plants were placed in a greenhouse at 230C and after 7 and 14 days, the presence or absence of female adults and chemical damage were examined, and the results are shown in Table 5.

Table 5 Test example 4 Effects of the compounds of the present invention on the black spider mite.

Compound A1-ya16 of the present invention was dissolved in water to a predetermined concentration, and then 2 g of Tween 80 was added to prepare an aqueous solvent for spraying. False spider mites were raised in Indan and used as parasitizers on watercress plants with 4 to 6 leaves planted in 6-diameter glass pots.

The sprayed chemical solution was sprayed at 2 d of each concentration onto 2 pots of watercress from 40 crnO on a small Turncheagle.

After the treatment, each pot was placed under a fluorescent light for plant cultivation in a constant temperature room at 24°C, and the acaricidal effect of the test compound was examined. The investigation was carried out after 3 days, and evaluation was given as + if there were no living insects, - if there were a mixture of living and dead insects, and - if there were no dead insects. The results were as shown in Table 6.

Table 6 Procedural Amendment (Voluntary) March 28, 1980 Director General of the Japan Patent Office 1 Indication of the case 1982 Patent Application No. 179800 2 Title of the invention 3 Relationship with the person making the amendment Patent application Jinbashira Address: Bussan Building Annex, 2-4-16 Kyobashi, Chuo-ku, Tokyo Telephone: (591) 02615, 4. Detailed explanation of the invention by specification subject to amendment A. 6. Contents of amendment (1) Details 2-15 Correct the formula in line 4 of the page.

(2) r 7.21 (3 rows from the bottom of Table 19, page 1)
Insert a closing parenthesis ")" next to IHddJ9HzJ.

(3) r, r2Hz in the second row from the bottom of the 19th shale)
Insert r 7.57 (IHdJ before J.

Claims (1)

[Claims] 1. The following formula [wherein R1 represents a hydrogen atom, R2 represents a (C-C') alkyl group with or without a substituent, and substituent 4 has or does not have a substituent] (C1 to C4) represents a Kenyl group or an aryl group with or without a substituent, M and M may be the same or different, and are hydrogen atoms or metal cations, 7' Ammonium cation, indicates an ammonium cation with a substituent or a cation derived from the choline molecule, 1~, m is M
A methylphosphinic acid compound represented by the reciprocal of the ionic valence of the cation, where n is the reciprocal of the ionic valence of the cation. 2. When R2 is an alkyl group, an alkenyl group, or an aryl group having a substituent, the substituent is one or more -4 groups, a nitro group, a hydroxyl group,
(C-C) alkyl group, (4 C-C) alkoxy7. ? :, mono- or di-(C.4-C4)alkyl-substituted amine group, aryl group. 2. A compound according to claim 1 which is in particular a phenyl group or an aryloxy group, in particular a phenyloxy group or a dichlorophenyloxy group. 8. The compound according to claim 1, wherein R is a phenyl group or a naphthyl group with or without a substituent. 4. R is a methoxyphenyl group, a di-methoxyphenyl group, or a dimethylaminophenyl group. Hydroxyphenyl group, chlorophenyl group. The compound according to claim 1, which is a dichlorophenyl group, a fluorophenyl group, or a hanitrophenyl group. 5. Claims vJ in which R2 is a group of the following formula 0 or a group of its sodium salt
3. The compound according to item 1. 6. The compound according to claim 1, wherein one or both of M and M is an alkali metal cation, an alkaline earth metal cation, a copper cation, a zinc cation, a nickel cation or a manganese cation. 7. One or both of M and M is mono-1S)
- or tri(C,~C4)alkyl-substituted ammonium cations, mono-, di- or tri(hydroxy(
C-C) alkyl) substituted ammonium 4° cation, or mono-, C- or tri-(C-
C) A compound according to claim 1 which is an alkenyl-substituted ammonium cation. 8. The compound according to claim 1, wherein the compound of formula (1) is DL-integrated or L-integrated. 9. The following formula [wherein R represents a hydrogen atom, R is a (C=-C) alkyl group with or without a substituent, a (C-C) alkenyl with or without a substituent 4 group, A4 or an aryl group with or without a substituent7,
Ml and M2 may be the same or different from each other and represent a hydrogen atom, a metal cation, an ammonium cation, an ammonium cation with a substituent, or a cation derived from a choline molecule, and m is the M cation. A herbicide and acaricide characterized by containing a methylphosphinic acid compound represented by the inverse ionic valence fi, nFiM, which is the reciprocal of the ionic valence of a cation] as an active ingredient.