JPH04149177A - Dioxolan derivative - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel dioxolane derivatives useful as herbicides.

(Prior art and problems to be solved by the invention) One group of compounds conventionally used as herbicides include dichloro group-substituted diphenyl ether compounds 1, which are used as flooded soil treatment agents. There are trifluoro group-substituted diphenyl ether compounds that are used as foliage treatment agents.

However, although the latter's herbicidal activity was generally much higher than that of the former, its range of application was mainly limited to foliage treatments. The reason for this is that the latter group of compounds developed so far did not have selective herbicidal activity between control broad-leaved plants and gramineous plants.

(Means for Solving the Problem) Therefore, the present inventors searched for a compound that compensates for the above-mentioned drawbacks and has high herbicidal activity, particularly showing a high degree of selective herbicidal activity against broad-leaved weeds. As a result, it was discovered that a new dioxolane derivative exhibits high herbicidal activity against a wide variety of broad-leaved weeds, and has applicability in a wide range of weeding situations, leading to the completion of the present invention.

That is, the present invention is based on the general formula (1), y+ and X4 represent different or similar hydrogen atoms, halogen atoms, or substituted or unsubstituted alkyl groups, X3 represents a nitro group, cyano group, or hydrogen atom, and A represents R', R2 and R3 represent different or similar hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted thienyl groups, or substituted or unsubstituted furyl groups. . ) is a dioxolane derivative represented by

In the present invention, in the above-mentioned ritual (1), χ1. When x2 or X represents a halogen atom, the halogen atom is, for example, chlorine, bromine, fluorine, iodine, or the like.

Above - Ritual (in 1, X,, X2. X,, R',
When representing an R2 or R3 alkyl group, the alkyl group is not particularly limited, but a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. Specifically, methyl group, ethyl group, n-)'robyl group, 1so-propyl group,
Examples include n-butyl group, iso-butyl group, tert-butyl group, and cyclohexyl group. The alkyl group may be substituted with a substituent.

In the above-mentioned ceremony (1), when XI+×2 or X4 represents a substituted alkyl group, the substituted alkyl group is not particularly limited; suitable.

Specifically, chloromethyl group, bromomethyl group, fluoromethyl group, iodomethyl group, dichloromethyl group, chlorodifluoromethyl group, difluoromethyl group, trichloromethyl group, trifluoromethyl group, chloroethyl group, bromoethyl group, fluoroethyl group. group, dichloroethyl group,
Examples include dibromoethyl group, difluoroethyl group, trichloroethyl group, trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, and the like.

In the above-mentioned formula (1), when R1, RE or R3 represents a substituted alkyl group, the substituted alkyl group is not particularly limited, but all or part of the hydrogen atoms in the alkyl group are halogen atoms, alkoxy groups, alkylthio groups. , those substituted with a cyano group, etc. are preferred.

Specifically, chloromethyl group, bromomethyl group, fluoromethyl group, iodomethyl group, dichloromethyl group, chlorodifluoromethyl group, difluoroethyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group,
Ethoxymethyl group, methylthiomethyl group, cyanomethyl group, tetraloethyl group, bromoethyl group, fluoroethyl group, dichloroethyl group, dibromoethyl group, difluoroethyl group, trichloroethyl group, trifluoroethyl group, perfluoroethyl group, perfluoroethyl group, Examples include fluoropropyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, methylthioethyl group, ethylthioethyl group, cyanoethyl group, and cyanobrovir group.

In the above-mentioned ceremony (1), when R1, R2 or R3 represents a substituted phenyl group, a substituted thienyl group or a substituted furyl group, the substituted phenyl group, substituted thienyl group or substituted furyl group is not particularly limited, but It is preferable that one or more hydrogen atoms in the above are substituted with different or similar halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, cyano groups, alkoxycarbonyl groups, etc. Specific examples of the substituted phenyl group include chlorophenyl group, bromophenyl group, fluorophenyl group, iodophenyl group, dichlorophenyl group, trichlorophenyl group, chloro-methylphenyl group, bromo-fluorophenyl group,
Chloro-ethylphenyl group, chloro-cyanophenyl group, chloro-methoxycarbonylphenyl group, methyl-ethylphenyl group, trimethylphenyl group, cyanotril group, methylthiotril group, trimethoxyphenyl group, tetrachlorophenyl group, chloro-dimethylphenyl group ,
Examples include methoxyphenyl group, ethoxyphenyl group, isopropoxyphenyl group, ethylthiophenyl group, dichloro-cyanophenyl group, dichloro-ethoxycarbonylphenyl group.

Specific examples of the substituted thienyl group include chlorothienyl group, bromothienyl group, fluorothienyl group, iodothienyl group, dichlorothienyl group, trichlorothienyl group, chloromethylthienyl group, bromofluorothienyl group, and chloroethylthienyl group. group, chloro-cyanothienyl group, chloro-methoxycarbonylthienyl group, methylethylthienyl group, trimethylthienyl group, cyanotril group, methylthiotril group, trimethoxy-f-enyl group, tetrachlorothienyl group, chloro-dimethylthienyl group, methoxy thienyl group, ethoxythienyl group,
Examples include isopropoxythienyl group, ethylthiothienyl group, dichlorocyanochenyl n'M, and cycloethoxycarbonylthienyl group.

Further, specific examples of the substituted furyl group include chlorofuryl group, bromofuryl group, fluorofuryl group, iodofuryl group, dichlorofuryl group, trichlorofuryl group, chloro-methylfuryl group, bromo-fluorofuryl group, chloro-ethylfuryl group. group, chloro-cyanofuryl group, chloro-methoxycarbonylfuryl group, methyl-ethylfuryl group, trimethylfuryl group, cyanotril group, methylthiotril group, trimethoxyfuryl group, tetrachlorofuryl group, chloro-dimethylfuryl group, methoxyfuryl group , ethoxyfuryl group, isopropoxyfuryl group, ethylthiofuryl group, dichloro-cyanofuryl group, dichloro-ethoxycarbonylfuryl group, and the like.

The dioxolane derivative shown in the above-mentioned ritual (1) of the present invention has an infrared absorption spectrum (IR), a mass spectrum (
MS) and 1H-nuclear magnetic resonance spectra ('H-N?I
The structure can be confirmed by measurement of R) and elemental analysis.

When the above IR measurement is performed on the dioxolane derivative of the present invention, characteristic absorption based on carbonyl group at 1780-1850c+n-', 1200-1250cm-'d:
Characteristic absorption based on the f−7− bond can be observed. As a representative example, JR of 2-[5+-(2'', 4''-dichlorothienyl group)-2-nitrophenyl 1-5-isopropyl-1,3-dioxolan-4-one is shown in FIG.

Furthermore, when the above MS measurement is performed on the dioxolane derivative of the present invention, the following characteristic peaks are observed in addition to the molecular ion peak (hereinafter abbreviated as "H"). That is, the following general formula (where Z, XI+ X2.
3. R', R2 and R3 are as shown in general formula (1). ) On the other hand, the following general formula (however, Z, XI+ X2. L, R', R"
and R3 are as shown in general formula (1). , ) etc. are observed. From this observation result, it is possible to know the bonding mode of each atomic group within the molecule.

Furthermore, when the above 'H-NMR measurement is performed on the dioxolane derivative of the present invention, ZL in the above-mentioned ritual (1),
Xz, X:1. X4. R', R'' and R3f7
) Regardless of the type, the proton on the Hensen ring is 6.0
It generally appears as a multiplet around ~8.5 ppWl. As a representative example of the above 'I(-NMR measurement), 2-
[5-(2″,4″dichlorophenoxy)-2-nitrophenyl]5-isopropyl-1,3-dioxolane-
The '11-NMR diagram of 4-on is shown in FIG.

The dioxolane derivative of the present invention is generally a yellow-white or yellow-brown solid at room temperature and pressure.

The dioxolane derivatives of the present invention include benzene, ether, alcohol, acetone, N,N-dimethylformamide,
It dissolves well in organic solvents such as dimethyl sulfoxide, but
Insoluble or sparingly soluble in water.

The method for producing the dioxolane derivative shown in the above-mentioned ritual (1) of the present invention is not particularly limited, and any production method may be used.

A representative manufacturing method that is generally suitably used will be explained below.

(a) Method for producing a dioxolane derivative in which A is 8 - Ritual (4) (However, Z, X, , X2, X3. and R1 are as shown in general formula (1).) The carbonyl compound expressed by the general formula (5)% formula% (5
) (However, X has a halogen atom or a hydroxy group,
R2 and R3 are as shown in general formula (1). The dioxolane derivative of the present invention is produced by reacting the carboxylic acid derivative represented by ) in the presence of a solvent.

(a) Process for producing dioxolane derivatives in which A is A2 - Ritual (6), Y+ (However, X represents a halogen atom or a hydroxy group,
Z, X,, X,, X3+ and R2 are represented by the general formula (1
) Exactly as shown. ) The carboxylic acid derivative represented by the general formula (7) (however, R
1 and R3 are as shown in general formula (1). ) and the presence of a solvent to produce the dioxolane derivative of the present invention.

In the reaction of the above production method (a), the molar ratio of the carbonyl compound represented by -ritual (4) and the carboxylic acid derivative represented by general formula (5) may be determined as necessary, but usually Use equimolar or a slight excess of the carboxylic acid derivative. In addition, in the reaction of the above production method (b), the molar ratio of the carboxylic acid derivative represented by -ritual (6) and the carbonyl compound represented by general formula (7) may be appropriately determined as necessary. , usually equimolar or a slight excess of the carbonyl compound is used.

The solvent used in the reaction of the above production method (a) or [with]) generally includes benzene, toluene, xylene,
Methylene chloride, chloroform, etc. are used.

In addition, in the reaction of the above production method (a) or (b), when x is a halogen atom, a hydrogen halide scavenger is usually allowed to coexist in the reaction system in order to capture the by-produced hydrogen halide. preferable. The hydrogen halide scavenger is not particularly limited and any publicly known hydrogen halide scavenger may be used; however, the hydrogen halide scavenger that is generally preferably used includes trialkylamines such as triethylamine, trimethylamine, and tripropylamine; pyridine; sodium alcoholade; Sodium carbonate; potassium carbonate heptahydroxide;
Examples include potassium hydroxide; sodium hydride. In the reaction of the above production method (a) or (b), when χ is a hydroxy group, it is usually preferable to coexist a dehydration catalyst in the reaction system in order to remove by-produced water. The dehydration catalyst is not particularly limited and any known catalyst can be used, but examples of dehydration catalysts that are generally preferably used include P-toluenesulfonic acid and boron trifluoride ethyl ether.

The reaction temperature in the above-mentioned production methods (a) and (b) is usually carried out in the range of room temperature to 200°C, but preferably in the range of room temperature to 150'C. Further, the reaction time is carried out in the range of 0.5 to 40 hours, preferably 8 to 40 hours.
It is best to do this in 15 hours.

As a method for isolating and purifying the dioxolane derivative, which is the desired product, from the reaction system, known methods can be employed without limitation. For example, when X is a hydroxy group, the reaction solution is concentrated and the resulting residue is purified by recrystallization or chromatography; when X is a halogen atom, the reaction solution is added to water, Examples include a method of extracting with an organic solvent, distilling off the solvent, and then purifying the residue by recrystallization or column chromatography.

When the dioxolane derivative of the present invention is used as a herbicide, its usage form is not particularly limited, and it can be used in any known form. For example, use inert solid carriers, liquid carriers, emulsifying dispersants, etc. to formulate any dosage form such as granules, powders, emulsions, wettable powders, flowables, tablets, aerosols, smokers, etc. can do. In the above formulation, auxiliary agents such as a spreading agent, a diluent, and a surfactant may be appropriately mixed and used.

(Effect) The dioxolane derivative represented by the above-mentioned formula (1) of the present invention is effective against compounds conventionally used as herbicides, such as dichloro group-substituted diphenyl ether compounds, trifluoro group-substituted diphenyl ether compounds, etc. Compared to,
This compound has the property of highly selective weeding against broad-leaved weeds.

Therefore, it has become possible to apply it to a wider range of crops than ever before. Furthermore, there is less chemical damage to transplanted rice than ever before.

[Examples] In order to explain the present invention more specifically, Examples will be described below, but the present invention is not limited to these Examples at all. In the table, Et represents an ethyl group, n-Pr represents a normal propyl group, 1so-Pr represents an isopropyl group, and ter-Bu represents a tertiary-butyl group.

Production Example 1 2-[5-(2',4'-dichlorophenoxy)-2
Preparation of nitrophenyl]-5-isopropyl-1,3 dioxolan-4-one (compound number 1) 3-methyl-2
-Hydroxybutyric acid2. Og, 5-(2",4"-dichlorophenoxy)-2-nitrobenzaldehyde 5.23
g was dissolved in 60n+42 of benzene, 0.3- of boron trifluoride/diethyl ether was added, and the mixture was heated under reflux for 10 hours while removing the produced water.

The solvent was distilled off, and the residue was purified by silica gel chromatography and mud (benzene) to obtain 6.65 g of a pale yellow solid.

The results of measuring the infrared absorption spectrum of this product are as shown in Figure 1, with absorption based on nitro groups at 1552 and 1350ci-', and an ether bond (at 1250cm-').
C-0-C), and an absorption based on carbonyl group at 1805 cm-'. Its elemental analysis value is
C53.41, N3.59%, N3.33%,
It matched well with the calculated values of C52.45%, N3.67%, and N3.40% corresponding to the composition formula Cl8H15N106C12. Also, when MS was measured, m/e412
shows the peak corresponding to M''', and CHff ■ m/e312 shows the peak of OC)N3 corresponding to [M'-C-CHC)I].
m: Tetramethylsilane standard, deuterium chloroform solvent)
The results of the measurements are shown in Figure 2. The analysis results were as follows.

A multiplet corresponding to six protons was observed at 0.70 to 1.40 ppm, and could be attributed to methyl proton (a). A broad singlet corresponding to one proton was observed at 1.90 to 2.60 ppm, and could be attributed to proton H1. 4.20-4.50
A multiplet corresponding to one proton was observed at ppm+, and could be attributed to protonation.

A multiplet corresponding to 6 protons was observed at 6.80 to 7.80 ppm, and the protons Ha, Ht, 11
9. Hh.

It could be attributed to H,,H,.

A double line corresponding to one proton was observed at 8.21 ppm, and could be attributed to proton Hp.

From the above results, it can be seen that the isolated product is 2-[5-(2',
4'-dichlorophenoxy)-2-nitrophenyl 1-
It became clear that it was 5-isopropyl-1,3-dioxolan-4-one. The yield was 96.0%.

Production Example 2 5-(2',4'-dichlorophenoxy)- as a raw material
2 was prepared in the same manner as in Production Example 1 except that 2-nitrobenzaldehyde and 3,3.3-trichlorolactic acid were used.
-[5-(2',4'-dichlorophenoxy)2-nitrophenyl] -5-(LLI -trichloromethyl)
-1,3-dioxolan-4-one (compound number 2) was synthesized. The analysis results of this compound were as follows.

IR (cm-'): 1345.1515. (NO2
), 1205 (C-0-C), 1.808 (C=
O); MS (M”): 487; Properties: pale yellow solid; 'H-N gate R (δppm): 5.0
5 (s, IH), 6.30 (s, 1) 1)
.

6.60-7.80 (m, 5H), 8.12 (d, IH
); Elemental analysis value (%): C3B, 90. Hl
, 56. N2.66 (calculated value C39,42H,1,6
5, N2.87) Production Example 3 5-(2',4'-dichlorophenoxy)- as a raw material
2-[5(2',4'-dichlorophenoxy)-2-nitrophenyl]-5-methyl-1,3-dioxolane- was prepared in the same manner as in Production Example 1 except that 2-nitrobenzaldehyde and lactic acid were used. 4-one (compound number 3) was synthesized. The analysis results of this compound were as follows.

IR (C1-'): 1.340.1520 (NO
ri, 1210 (C-0-C), 1803 (C=0);
MS (M”): 384; Properties: yellow solid; 'H-NMR (δppm): 1.58 (d,
38), 4.62(q, IH).

6.62-7.63 (m, 6)1), 8.10
(d, IH); Elemental analysis value (%): C50
, 51, N2.94. N3.53 (calculated value C50,
02, N2.89. N3.65) Production Example 4 5-(2',4'-dichlorophenoxy)- as a raw material
2-nitrobenzaldehyde and 2-hydroxy-4-
2-[5-(2',4'-dichlorophenoxy) was prepared in the same manner as in Production Example 1 except that methylpentanoic acid was used.
-2-nitrophenyl] -5-isobutyl-1,3-
Dioxolan-4-one (compound number 4) was synthesized.

The analysis results of this compound were as follows.

JR (ci-1): 1338.1523 (NO□)
, 1209(C-0-C), 1807cc=o) ;M
S (M゛): 426; Properties: Yellow solid; 'H
-NMR (δppm”) 71.00 (d, 6H
), 1.40-2.20(m, 3)l), 4
．． 20-4.70 (m, IH), 6.80-7
．． 70 (m, 6H), 8.09 (d, IH)
; Elemental analysis value (%): C53,14, H4,19
, N3.40 (calculated value C53,54°H4,02N3
．． 29) Production Example 5 Same as Production Example 1 except that 5-[2-(3'-chloro-5'trifluoromethyl-2-pyridyloxy)]-]2-nitrobenzaldehyde and 2-methyllactic acid were used as raw materials. 2-[5-(3'-chloro-5
'-trifluoromethyl-2-pyridyloxy)-2-
Nitrophenyl]5,5-dimethyl-1,3,-dioxolan-4-one (Compound No. 5) was synthesized. The analysis results of this compound were as follows.

IR (C1-'): 1335, 1510 (NOz
), 1215 (C-0-C), 1800 (C=0);
MS (M”): 430; Properties: yellowish brown solid;) 1-NMR (δppm): 1.52
(s, 6H), 7.0-8.60 (m
, 6) 1) ; Elemental analysis value (%): C47,9
2, H3, 23° H7, 19 (calculated value C4B, 14.
H3,03,H7,02) Production Example 6 5-[2-(3'-chloro-5'trifluoromethyl-2-pyridyloxy)]-]2-nitrobenzaldehyde and 2-hydroxy-4-methyl as raw materials 2-[
5-(3'-chloro-5'-trifluoromethyl-2-
Pyridyloxy)-2-nitrophenyl]-5-isobutyl-1,3°-dioxolan-4-one (Compound No. 6) was synthesized. The analysis results of this compound were as follows.

IR(C1l-'): 1340.1510(N
Ox), 1215 (C-0-C), 1799 (C=O)
;MS (M'') 7458iProperty: Yellowish white solid;'H-NMR (δppm): 0.8B (
d, 6B), 1.40-2.05 (m, 3B)
;4.10-4.60 (BS, IH), 6.90
~8.40 (m, 6H); Elemental analysis value (%): C
49,01,H3,41°N6.29 (calculated value C49
, 52, H3, 50, N6.0B) Production Example 7 Compounds Nos. 7 to 72 shown in the following formula were synthesized in the same manner as in Production Example 1.

(However, χI ~X3+z, R' ~R3c first
The IR2 properties and elemental analysis values of the synthesized compounds are shown in Table 1.

Production Example 8 Production of 2-methyl-5-[5-(2′,4″-dichlorophenoxy)-2-nitrophenyl]-1,3,-dioxolan-4-one (Compound No. 73) 2-[5 −
(2',4'-Dichlorophenoxy)2-nitrophenyl-2-hydroxyacetic acid (3.58g) and acetaldehyde (0.66g) are dissolved in benzene (60af), and boron trifluoride/diethyl ether (0.3yxl) is added to produce. The mixture was heated to reflux for 6 hours while removing water.

The solvent is distilled off and the residual aroma is chromatographed on silica gel (benzene).
Purification was performed to obtain 2.63 g of a yellowish white solid.

The results of measuring the infrared absorption spectrum of this product are as shown in Figure 3, with absorptions based on nitro groups at 1515 and 1365CII-', strong absorption based on ether bonds (C-0-C) at 1220cm-', Absorption based on carbonyl group was shown at 1805as-'. Its elemental analysis values are C50.02%, H2, 89%, N3.65%, which are calculated values corresponding to the composition formula C16H11N106C12.
There was good agreement. Furthermore, when MS was measured, m/e3
84 shows a peak corresponding to M, and m/e ratio. In addition, the results of 'H-NMR (δppm: tetramethylsilane standard, deuterated chloroform solvent) are shown in FIG. The analysis results were as follows.

A double line corresponding to three protons was observed at 1.53 ppm of CHs (a), and could be attributed to methyl proton (a). A multiplet corresponding to one proton was observed at 4.20 to 4.90 pp-, and could be attributed to proton H5. A multiplet corresponding to six protons was observed at 6.40 to 7.80 ppm, and protons Hc,
It could be attributed to H,,H,,H,,H,,H4.

A double line corresponding to one proton was observed at 8.14 pps+, and could be attributed to proton H4.

From the above results, it can be seen that the isolated product is 2-methyl-5-[5
The product was found to be -(2',4''-dichlorophenoxy)-2nitrophenyl]-1,3-dioxolan-4-one. The yield was 68.5%.

Production Example 9 2-ethyl was prepared in the same manner as Production Example 8 except that 2-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-2-hydroxyacetic acid and propionaldehyde were used as raw materials. -5-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-1,3-
Dioxolan-4-one (compound number 74) was synthesized. The analysis results of this compound were as follows.

TR (C11-'): 1340.1522 (NOx
), 1211 (C-0-C), 1803 (C=O);
MS (M”): 398; Properties: yellowish brown solid; 'H-
NMR (δppm): 0.95 (d, 3 days), 1.
80-2.20 (s+, 2H), 5.60 (bs, IH
), 6.40 (s, IH), 6.62-7.80 (
m, 5H), 8.09 (d, 11); elemental analysis value (
%): C51.07, H3.42, N3.40 (
Calculated values C51,28, H3,29, N3.52) Production example 10 2-[5-(2',4'~dichlorophenoxy)-2-nitrophenyl]-2-hydroxyacetic acid and benzaldehyde as raw materials 2-phenyl-5-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-1,3-dioxolan-4-one (compound number 75) was synthesized.

The analysis results of this compound were as follows.

iR(C1+-'): 1342.1525(Non
), 1210 (C-0-C), 1802 (C・0):
MS (M”): 446. Properties: Yellow solid; 'H-N
MR (δppm): 6.12 (s, IH), 6.5
0-7.80 (m, 11H), 8.09 (d, IH);
Elemental analysis value (%”): C56,1B, H2,79
, N3.08 (calculated value C56, 52, H2, 94, N
3.14) Production Example 11 Same method as Production Example 8 except that 2-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-2-hydroxyacetic acid and isobutyraldehyde were used as raw materials. 2-isopropyl-5-[5-(2゛,4
'-dichlorophenoxy)-2nitrophenyl]-C3
-Dioxolan-4-one (Compound No. 76) was synthesized. The analysis results of this compound were as follows.

IR (am-1): 1344, 1520 (Not),
1212 (C-0-C), 1800 (C=0); MS
(?I”): 412; Properties: pale yellow solid, ')I-N
IR (δppm): 1.0 (cl, 6H), 1
．． 80 ~ 2.43 (Kaku, IH), 5.50 (d, IN
), 6.32(s, II(), 6.80-7.75(
*, 5H), 8.10 (d, IH); elemental analysis value (%
) : C52,02, H3,58, N3.43 (
Calculated values C52,45, H3,67, N3.40) Production example 12 2-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-2-hydroxyacetic acid and chloral (CCIlffcHo) as raw materials 2-(1,1,1-trichloromethyl-5-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-1,3 -Dioxolan-4-one (compound number 77) was synthesized.The analysis results of this compound were as follows.

JR (cm-'): 134C1,1525 (NOx
), 1205 (C-0-C), 1803 (C・0);
MS (?I”): 487; Properties: yellow solid; II-
NMR (δppia): 5.05 (s, LH), 6
．． 10 (s, IH), 8.11 (d, IH).

6.50-7.95 (w, 5 [1); Elemental analysis value (%
): C39, 78°Hl, 79. N2.98 (
Calculated value C39, 42, Hl, 65. N2.87) Production Example 13 Same as Production Example 8 except that 2-[5-(2",4'-dichlorophenoxy)-2-nitrophenyl]-2-hydroxyacetic acid and isovaleric aldehyde were used as raw materials. 2-inbutyl-5-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl]-1,
3-dioxolan-4-one (compound number 78) was synthesized. The analysis results of this compound were as follows.

IR (Ca+-'): 1342,151B (No□
), 1209(C-0-C), 1B02(C・O
); MS (M''): 426; Properties: yellow solid; '
H-NMI? (δppm): 0.50 to 1.52 (
d, 6H), 1.50-2.45 (m, 3H).

5.80(d, 1)i), 6.15(s, LH
), 6.60-7.65 (m, 5H), 8
．． 05 (d, IH); Elemental analysis value (%): C53
,79,H4,11,N3.19 (calculated value C53,5
4,H4,02,N3.29) Production Example 14 Production example except that 2-[5-(2',4'-dichlorophenoxy)-2-nitrophenyl-2-hydroxyacetic acid and cyclohexylaldehyde were used as raw materials. 2-cyclohexyl-5-[5-(2
',4''-dichlorophenoxy)=2-nitrophenyl]-1,3-dioxolan-4-one (Compound No. 79
) was synthesized. The analysis results of this compound were as follows.

JR (cm-'): 1340, 1520 (NOx)
, 1212 (C-0-C), 1809 (C=O); M
S(M”): 452; Properties: yellowish brown solid, 'H-N
MR (δppmong): 0.80 to 3.00 (bmong,
11 fl), 5.50 (bJ) I), 6.25 (d, I
H), 6.70-7.80 (+w, 5H), 8.10
(d, 1B); Elemental analysis value (%): C55,26,
H4, 19, N3.0B (calculated value C55,77, H4
, 23, N3.10) Production Example 15 Compounds with compound numbers 80 to 145 shown in the following formula were synthesized in the same manner as in Production Example 8.

Y+ (However, x, ~χ, , Z, and R'-R3 are listed in Table 2.) The IR, properties, and elemental analysis values of the synthesized compound are shown in Table 2.
Shown in the table.

Formulation Example 1 Dioxolane derivative 1 synthesized in Production Examples 1 to 15
0 parts by weight, 2 parts by weight of polyoxyethylene nonylphenyl ether, 40 parts by weight of fine clay, and 4 parts by weight of gicrite.
A wettable powder was prepared by pulverizing and mixing 8 parts by weight.

Application example 1 Fill a 1/8850 are magnetic pot with paddy soil (alluvial loam) well mixed with water, sow paddy weeds, and then transplant 3-leaf stage rice seedlings (variety: Akinishiki) to a depth of 21. Then, water was added to bring the temperature to 21. Next, a predetermined amount of the 10% water diluted solution of the hydrating powder produced in Preparation Example 1 was dropped onto the weeds when they germinated.

After treatment, the plants were grown in a greenhouse at an average temperature of 25°C, and after 3 weeks, the herbicidal effects of each test compound were investigated. The results are shown in Table 3.

However, the broad-leaved plants shown in the table refer to azaena, japonica, red pepper, etc. The evaluation was on a 6-level scale, and the herbicidal effect was expressed as a number from 0 to 5 as shown below.

0...Weed suppression rate 0-9% 1...Weed suppression rate 10-29% 2...Weed suppression rate 30-49% 3...Weed suppression rate 50-69% 4. ...Weed suppression rate 70-89% 5...Weed suppression rate 90-100% Regarding chemical damage to transplanted rice, calculate the ratio of plant height, tiller number, and total weight (air dry amount) to the untreated plot, and The worst factor was set as 5, and evaluation was made on the following 6-level scale from 0 to 5.

0...Ratio to untreated area 100%1...
・Ratio to non-treated area 90-99%2...Ratio to non-treated area 80-89%3...Ratio to non-treated area 6
0 to 79% 4...Ratio to untreated area 40 to 59%
5... Ratio to untreated area O ~ 39% Table 1 (Continued) Application example 2 Fill a 1/8850 are magnetic pot with field soil (clay loam) and grow barnyard grass, radish, Japanese radish, and Japanese radish. Seeds of various plants such as Aobiyu were sown at a depth of 0.5 to 1 m (1 m,
When the radish had grown to the second-leaf stage, a spreading agent was added to a 10% water dilution of each hydrating powder prepared in Formulation Example 1, and a predetermined amount of the mixture was sprayed onto the foliage. After treatment, the plants were grown in a greenhouse at an average temperature of 25°C, and the herbicidal effects of each test compound were investigated two weeks later.

The survey results are shown in Table 4. Note that the evaluation of the herbicidal effect in Table 4 is the same as in Application Example 1.

Table 1 (Continued) Application example 3 A 1/8850 are magnetic pot is filled with field soil (clay loam), and seeds of various plants such as barnyard grass, radish, Japanese radish, Japanese radish, Japanese radish, and Japanese blueberry are placed at a depth of 0.5 to 1 cm. Then, a predetermined amount of a 10% water diluted solution of each hydrating powder prepared in Formulation Example 1 was sprayed onto the soil. After treatment, the plants were grown in a greenhouse at an average temperature of 25°C, and the herbicidal effects of each test compound were investigated two weeks later. The survey results are shown in Table 5. Note that the evaluation of the herbicidal effect in Table 5 is the same as in Application Example 1.

No. table No. Table (continued)

[Brief explanation of the drawing]

Figure 1 shows the compound obtained in Production Example 1 (compound number (1)
), Figure 2 is the 'I(-NMR spectrum) of the compound obtained in Production Example 1 (compound number (1)), and Figure 3 is the 'I(-NMR spectrum) of the compound obtained in Production Example 8 (compound number 7).
3), and FIG. 4 shows the 'H-NMR spectrum of the compound obtained in Production Example 8 (Compound No. 73).

Claims (1)

[Claims] (1) General formulas, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, Z indicates ▲Mathematical formulas, chemical formulas, tables, etc.▼ or a nitrogen atom, and X_1, X_2, and X_4 are different or similar hydrogen atoms, It represents a halogen atom or a substituted or unsubstituted alkyl group, X_3 represents a nitro group, cyano group, or hydrogen atom, and A represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and R^1, R^2 and R^3 are different or similar hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted thienyl groups, or substituted or unsubstituted thienyl groups. Dioxolane derivatives represented by (indicates a furyl group)