JPH021460A - Sulfonylcyclopropane derivative, production thereof and herbicide containing the same derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R<1> is phenyl; R<2> and R<3> are cyano, COOR<5>, -COR<5> (R<5> is CH3, C2H5 or phenyl), etc.; R<2> and R<3> together may represent -CO-A-CO; A is (CH2)3, etc.; R<4> is H or CH3]. EXAMPLE:1-Diethylphosphino-1-ethoxycarbonyl-2-phenylsulfonylcyclopropane. USE:A herbicide capable of exhibiting herbicidal effects on various weed species except gramineous weeds and enhancing the effects by mixed use with other herbicides. PREPARATION:An alpha-bromovinylsulfonic acid derivative expressed by formula II or III is reacted with an active methylene compound expressed by formula IV in a solvent (e.g., THF) in the presence of a dehydrohalogenating agent (e.g., sodium hydride) at 0-100 deg.C temperature for 0.5-12hr to afford the compound expressed by formula I.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides novel sulfonylcyclopro/4 derivatives,
The present invention relates to a method for producing the same and a herbicide containing the same as an active ingredient.

<Prior art and its problems> The sulfonylcyclopropane derivative of the present invention is a new compound, but reports on the synthesis of compounds with similar structures to the compound of the present invention are published in Borland Patent No. 103194 and J. Chem. , Sac, Perkin Tran
s.

I Vol. 1985, p. 2785.

This is a reaction expressed by the following reaction formula.

Ar (Ar Niaryl Group) However, in this reaction, only a sulfonylcyclopropane derivative having an aryl group can be obtained.

Therefore, in order to obtain the derivative without an aryl group, chlorovinyl sulfone was used, but the desired general formula [ID
No compound of the present invention was obtained.

Furthermore, when looking at the uses of sulfonylcyclopropane derivatives themselves, there are extremely limited examples of their application in the agricultural field.
Regarding the insecticidal effect, European Patent No. 230863,
British Patent No. 2146981 and Pe5tic, S.
et., 11(2), pages 148-155, and the bactericidal effect is only described in Yotsu/4' Patent No. 180136 and West German Patent No. 3440116. Moreover, there is no mention of herbicidal effects in these. In addition, the chemical structure of these compounds can be expressed by the general formula [!] of the present invention. ] is different from the compound.

<Means for Solving the Problem> As a result of research into novel sulfonylcyclopropane derivatives, their production methods, and their uses, the present inventors found that - a series of new compounds represented by the formula (1) were obtained by the general formula (We have discovered that it can be produced by using the compound represented by ID and that the derivative is useful as a herbicide, and have completed the present invention.)

That is, the present invention provides a formula [ID] in which R1 represents a phenyl group, and R2 and R3 simultaneously or each independently represent a cyano group, -COOR group, -COR5
group, -PO(OR5) 2 groups, (where R" Vi-CH
3 group, -C2H5 group, or phenyl group.

R2 and R3 may also together represent a 100-A-Co- group. Here, A represents a -(CH2)3- group or a -CH2CH(CH3)CH2- group.

R4 represents hydrogen or a -CH3 group. However, R2R3
is simultaneously -C00C2I (except when it is 5 groups and R4 is hydrogen); a herbicide containing this as an active ingredient;
, RA represents the same meaning as above. ] α−
Bromovinyl Nurphone Conductor - Formula CI) / [In the formula, R2 and R5 represent the same meanings as above. The present invention provides a method for producing a sulfonylcyclopro-S1 conductor represented by the general formula (4), which is characterized by reacting the sulfonylcyclopro-S1 conductor with an active methylene compound represented by the formula (4).

Structure> Specific examples of the compound represented by general formula (1) include 1.
1-Jethoxycarbonyl-2-zenylsulfonylcycloderonone, 1-diethylphosphono-1-cyano-2-phenylsulfonylcycloprot'? N, 1-
Diethylphosphono-1-ethoxylic is nyl-2-phenylsulfonylcyclopropane, 1
,1-jethoxycarbini#-2-methyl-3-phenylsulfonylcycloprono! Examples include:

Specific examples of compounds represented by the general formula [■] are:

Phenyl-α-bromovinyl sulfone, phenyl-α-
Bromozolobenyl sulfone is the most common.

In addition, as a specific example of the compound represented by the formula Cl),
Noethyl malonate, triethyl phosphonoacetate, diethyl cyanomethylphosphonate, ethyl benzoylacetate,
Methyl benzoyl acetate, benzoyl acetate, dipenzoylmethane, 1,3-cyclohexanedione, 1-methyl-
Examples include 3,5-cyclohexane dione.

This reaction is usually carried out in a solvent in the presence of a dehydrohalogenating agent, and the reaction temperature is 0 to 100°C and the reaction time is 0.5°C.
~12 hours, and the conditions for each compound to be subjected to the reaction are preferably: 1 part of α-bromovinylsulfone derivative [■], 1 part to 1 part of active methylene compound CI) and 1 to 1 part of dehydrohalogenating agent. 5 This is the bond.

As a solvent, soyisoprobyl ether, dioxane,
Ethers such as tetrahydrofuran and ethylene glycol methyl ether, nitriles such as acetonitrile and isobutyronitrile, acid amides such as formamide, N,N-trimethylformamide, N,N-dimethylacetamide, hexamethylphosphorintriamide, etc. kind,
Sulfur compounds such as dimethyl sulfoxide and sulfolane,
Alternatively, a mixture thereof may be mentioned.

Examples of dehydrohalogenation agents include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride, trialkylamines, pyridine and its homologs, quinoline and its homologs, N, N −
dialkylarylamine, N-alkylmorpholine,
Examples include organic bases such as N-alkylmorline and alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

Reaction 't1. after completion of reaction. After adding l-i water, the desired compound of the present invention can be obtained by performing usual post-treatments such as organic solvent extraction and concentration, and if necessary, purifying by operations such as recrystallization and chromatography. can.

The α-bromovinylsulfone derivative of the general formula [■], which is the raw material compound of the compound of the present invention, can be produced, for example, by the following route (Synthegta 1985 A
6/7, p. 676).

(In the formula, R1 and R4 have the same meanings as above.) When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, liquid carrier, surfactant, or other formulation auxiliary agent. , emulsions, wettable powders, granules, etc.

These preparations contain the general formula (1) of the present invention as an active ingredient.
of rust conductor in a weight ratio of 0.05 to 90%, preferably 0.
．． Contains 1 to 80%.

Examples of solid carriers include fine powders or granules such as kaolin clay, Attano-9-lugite clay bentonite, acid clay, pyrophyllite, Merck, diatomaceous earth, calcite, walnut powder, urine sludge, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as Impropatol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, trimethyl sulfoxide, N, N-
Examples include dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wetting, etc. include anionic surfactants such as alkyl sulfate entel salts, alkylaryl sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkylaryl ether phosphate ester salts. , polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers and sorbitan fatty acid esters. Adjuvants for formulation include lignin sulfonate, alginate, polyvinyl alcohol,
Gum arabic, CMC (carboxymethyl cellulose)
, PAP (impropyl acid phosphate), and the like.

The compound of formula CI] of the present invention is usually formulated and treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from above the plant body, as well as local treatment that treats only weeds so that they do not attach to crops.

When using the compound of the general formula of the present invention as an active ingredient of a herbicide, the amount to be treated will vary depending on weather conditions, formulation form, treatment time, method, location, target weeds, target crops, etc., but is usually 1. 0.029 to 100,9 per are,
Preferably, it is 0.05.9 to 50 g, and the predetermined amount of emulsions, wetting agents, suspending agents, etc. is usually 11 g per are.
It is treated by diluting it with 7 to 10 liters of water (adding an auxiliary agent such as a spreading agent if necessary), and granules and the like are usually treated as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agents include polyoxyethylene resin acid (ester), lignin sulfonate,
Abietate, dinaphthylmethane disulfonate, /
Examples include 4' rough-in.

<Examples> Examples are shown below, but the present invention is not limited to the methods disclosed in the following examples.

1-diethylphosphono-1-ethoxycarbonyl-2
-Phenylsulfonylcyclopronoyan (Compound No. 3
) Preparation: 1.1 g of diethyl ethyl methyl phosphate in 1 Q ml of tetra-1 nitrofuran (THF)
(5+nmol 1 ) was dissolved in a bath at room temperature, and 0.1 g (6 mmol) of sodium hydride was dissolved in THF 10
Add t-7j to what was suspended in d. Next, phenyl-α
-bromovinylsulfone 1.24 g (5 mmol
) dissolved in 5 ml of THF was added, and the mixture was heated at room temperature for 12 hours.
After stirring for an hour, the mixture was extracted with nochloromethane to obtain 1.34 g (yield: 75.9%) of crude crystals of the target product. It was recrystallized from ether and petroleum ether and made into a tree product. Melting point of this compound, elemental analysis IL, ■R1'+(-NMR
The analysis results of 113C-NMR and MS are shown below.

m, p-63, 0 to 65.0°C Elemental analysis value C16H2307SP Calculated value C: 49.23 H: 5.94 Actual value C:
49.35 H: 5.90IR (KBr); 11
60,1250,1320.1740crR-''H-
NMR (CDCl2); w 1.22 (t,
3H, C02CH2CH3).

1.30 (t, 3H, PO-CHρ, 1.35
(t, 3H, PO-CH3).

1.82 (ddd+Jp++=15.6+JA1=5.
6+J, B=8.7I (z l IH+HB) 12.2
2(ddd IJ, H=13., LJAl=5.'6
+JxA=6.4H2IIH)H') + 3.14
(d d d * JpH=14.7 r JXA=6
．． 4 HJzB=8.7Hz 1IH2Hx), 3,
934.19 (m, 4H, PO-CH2), 4
．． 31 (dq, 2Hr C02CH2) + 7.55
7.98 (m + 5H1Ph).

X5C-NMR (CDCl2): wl 3.9
(8r C02CH2CH5) e 14.0(d
, CH2cyclopropane) + 16.2(
q, PO-CJ).

28.4+31.1 (d, Ccyclopropane
L42.3 (+LPhSO2-CI), 62.7
(a, C02CH2), 63.6 (q, PO
-CH2) -128,0, 129,3, 134,0,
1,39,9 (breath, Ph), 164.3 (d, Co
).

MS (75av), mlz (M++1)
391゜Example 2 ph Production of 1-noethoxycargonyl-2-phenylsulfonylcyclopropylene (compound number 41): THF
Noethyl malonate 1.6g (10mm01) in 30d
Dissolve this in sodium hydride 0.5N at room temperature.
(13 mmol) was added to the suspension in THF 30 d. Next, 2.5 g (10 mmol) of phenyl-α-bromovinyl sulfone dissolved in 10 m of THF was added, and after stirring at room temperature for 5 hours, extraction was performed with sochloromethane to obtain 1.34 g (1.34 g) of crude crystals of the target product ( A yield of 759% was obtained. It was recrystallized from ether and petroleum ether to obtain an rptw product. The analysis results of this compound are shown in the same manner as in Run f1''1.

m, p, 79.0-80.0°C Elemental analysis value: C15f (1606S Calculation Ii C: 55.37 I (+5.
56 Actual value C: 55.20 H: 5.53IR (K
Br): 1160, 1320.1740z-”1H
-NMR (CDC4): w 1.25 (t t
3) 1-C) (5) , 1.35 (t.

3H, CI(5), 1.71 (dd p Jia=
5A, JxA'=9. IHL, IFI.

H') + 2.23 (d d + JAB=5.1
t Jsx"7.1 Hz + IH+ H" C3
,35(dd,J,,=7.1,JxA=9.IH
l, IH, HX), 4.09-4.44 (m, 4H,
CH2), 7.54-7.71 and 7.88”7.97 (
m, 5H.

ph).

13C-NMIζ (CDC45): w 13.8
'(s, CHρ, 13.9(s, CH2cyc16
propane) + 17.8 (s, CH3), 37.
0(s+CcyclopropaneL44.6(s
+CHcyclopropane) 62.5, 62
．． 8 (s, CH2CH3), 128.0-129.
4, 134.1.

139.9 (s, Ph), 164.3, 167.6
(s, Co).

MS (75ev), mlz (M”+1) 327
゜Example 3 H' 502-Pb\/ 1.1- ,)ethoxycarbonyl-2-methyl-3-
Production of phenylsulfonylcyclopropane (compound number 5): 0.80 g of diethyl malate in THF 10 + 11j
T)IF
Added to the suspension for 5 d. Next, HMPA
A solution of O,91 (5 mmol) in THF 5 ml and a solution of phenyl-α-bromoproynyl sulfone 1.31 JF (5 mmol) in THF 5- were added, and the mixture was stirred at room temperature for 1 hour. After 9 days, extraction with dichloromethane yielded 1.73M of the target substance in the form of a slag.
(yield 100%).

It was recrystallized from ethanol and made into a purified product. The analysis results of this compound are shown in the same manner as in Example 1.

IR (KBr): 1150, 1330, 173
0cm-''H-NMR (CDC4); w 1.1
0 (d e JA B= 6.1 )1z 13H*
C1(3) -1,15(t, 3Ht LH5)
+ 1.22 (L, JED=JGF=7.IHz
.

3H+ LH5) + 2.61 (m r LH, H
') + 3.20 (de JAC=7.4HE
, IHpHc)t 4.04-4.28 (m p 4
Hp CH2X2) , 7.457.92 (m, 5H,
Ph).

"C-NMR (CDC15): w9.83 (g,
LH5), 13.03.

12.79 (sec) (3 n, 23.78 (s, C2)
, 41.86 (a, CI).

48.73 (s, 03), 61.36, 61.52 (
a, CH2), 126.63128.30,132
．． 91,139.08 (s, Ph), 163.58°1
64.38 (s, Co).

Example 4 Preparation of (Compound No. 6): 0.56 1,3-cyclohexanedione in 5 THF
, f (5 mmol) and added 0.241! of sodium hydride at room temperature. (6 mmol) in THF 10-
was added to the suspension. Next, phenyl-α-gprovinyl sulfone 1.24. P (5rnmol) in TH
A solution of F 5 m was added thereto, and the mixture was stirred at room temperature for 1.5 hours, followed by extraction with dichloromethane to obtain a sill-like crude product. Purified by column chromatography using activated silica gel and benzene to obtain the desired product, 0.41
1! I got it. The analysis results are shown below.

m, p, 160.8-163.3℃ Elemental analysis value C14Hj4043 Calculated value C: 60.42 H: 5.07 fruit + ltl
Ik C: 60.17 H: 5.0? IR
(KBr) :1140,1320.1630m-''
H-NMR (CDCl2): wl, 98-2.27
(m, 2H+CH2).

2.11 (dd IJAj=4.71J,,=9.3
HzllHIH”)l 2.49(d d, JAI
l=4.7, JxA=7.6Hz, IH,)I
”), 2.56-2.85(m*4 H+C
H2x2) + 3.20 (d d + JXA=7
．． 6, JzB =9.3.

IH, Hx), 7.55-7.89 (m, 5H, Ph)
.

"C-NMR (CDCl2): wl7.38 (@tC
5), 1.844 (a, C2).

39.31, 39.95 (s, C4 or C6), 46.
61 (Cao, C3).

55.88 (lI, CI), 128.05, 129.3
6,134.15°139.58 (s, pH), 199
．． 53,203.44 (s, Co).

MS (75ev), m/z (M++1) 279° Comparative Example 1 Reaction example using phenyl-α-chlorovinyl sulfone: 1.6.9 (1
0 mmol) was dissolved at room temperature, and 0.51 (13 mmol) of sodium hydride was dissolved in THF 30 r.
It was added to the suspension in at. Next, phenyl-α-
Chlorovinyl sulfone 2.09 (I Ommol)
was dissolved in 10 ml of THF, stirred at room temperature for 5 hours, and then extracted with nochloromethane.
The product was Harz (a black polymeric substance), and the desired sulfonylcyclopro-yane derivative could not be obtained.

Formulation Example The compound of the present invention was thoroughly ground and mixed in the proportions shown below, and then water was added and kneaded thoroughly to prepare a 10% wettable powder.

This agent 100
0 Fusanomi M clay 760
．． 5-inch ball 8070 27.0 Sunextract 27.0 Carplex
72.0 New Call 566
13.5 Test Example A cylindrical glass pot with a diameter of 12 crn and a depth of 6 m was filled with sterilized soil and used to grow millet, Japanese radish, Japanese cypress, Japanese knotweed, Japanese cypress, Japanese cypress, rice, indane, cucumber, wheat, radish, lettuce, and tomato. The seeds were sown and covered with soil. The test compound was made into a wettable powder according to the formulation example, a predetermined amount of the wettable powder was diluted with water equivalent to 150 liters per are, and the solution was applied to the soil surface using a spray gun connected to a compression pump.

After treatment, the plants were grown in a greenhouse (approximately 20 to 25°C) for 4 weeks to establish herbicidal efficacy. The results are shown in Table 2.

The evaluation method of the results is 1: 0-49% weeding, 2: 50-74%
% weeding, 3: 5-89% weeding, 4: 90-99% weeding, 5: complete weeding.

As shown above, the compound of general formula [l] of the present invention has a weak effect on grasses in soil treatment, but
It has herbicidal activity against various other grass species.

In addition to farmland, the compound of the present invention is also expected to be applied to rice fields, orchards, pastures, lawns, forests, non-agricultural lands, etc., and can also be used in combination with other herbicides to enhance herbicidal effects. You can expect it.

Claims (1)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 represents a phenyl group, R^2 and R^5
are simultaneously or each independently a cyano group, -COOR^5 group,
-COR^5 groups, -PO(OR^5)_2 groups (here R
^5 represents a -CH_3 group, a -C_2H_5 group, or a phenyl group. ) is shown. R^2 and R^3 can also be taken together to form -CO-A-CO
- may also represent a group. Here, A is -(CH_2)_3
- group, or -CH_2CH(CH_3)CH_2- group. R^4 represents hydrogen or a -CH_3 group. ] A sulfonylcyclopropane derivative represented by 2. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] [In the formula, R^1 represents a phenyl group, R^4 represents hydrogen , or represents a -CH_3 group. [III] [In the formula, R^2 and R^3 are simultaneously or independently cyano group, -COOR^5 group, -COR^5 group, -PO(O
R^5)_2 groups, (here R^5 is -CH_3 groups, -C
Indicates a _2H_5 group or a phenyl group. R^2 and R^3 can also be taken together to form -CO-A-CO
- may also represent a group. Here, A is -(CH_2)_3
- group, or -CH_2CH(CH_3)CH_2- group. ] General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 to R^4 are the same as above express meaning. ]
A method for producing a sulfonylcyclopropane derivative represented by 3. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[I] [In the formula, R^1 represents a phenyl group, R^2 and R^3
are simultaneously or each independently a cyano group, -COOR^5 group,
-COR^5 group, -PO(OR^5)_2 group, (where R^5 represents -CH_3 group, -C_2H_5 group, or phenyl group. R^2 and R^3 can also be taken together Te-CO-A-CO
- may also represent a group. Here, A is -(CH_2)_3
- group, or -CH_2CH(CH_3)CH_2- group. R^4 represents hydrogen or a -CH_3 group. ] A herbicide characterized by containing a sulfonylcyclopropane derivative represented by the following as an active ingredient.