JPS62111941A - Aromatic alkene derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:An aromatic alkene derivative shown by formula I(X and Y are H or F). EXAMPLE:1-(4-Fluoro-3-phenoxyphenyl)-3-(2,2,3,3-tetramethylcyclopropyl )propene. USE:Effective as a synthetic intermediate for producing an aromatic alkane derivative useful for various industrial fields, especially insecticide in an agricultural field. PREPARATION:An aldehyde shown by formula II and a phosphorus compound shown by formula III (R is group shown by formula IV or -P<+>(Ph)3Z<->;R1 is lower alkyl; Z is halogen] are subjected to so-called Witting reaction to give a compound shown by formula I. Sodium hydroxide, etc., may be used as a base. The reaction temperature is preferably 0-100 deg.C. The amount of the phosphorus compound shown by the formula III is preferably 1.0-1.2 as mush as that of the aldehyde.

Description

[Detailed description of the invention] [Industrial application field] The present invention is based on the general formula (1) CH3CH.

(In the formula, X and Y represent a hydrogen atom or a fluorine atom.

) and a method for producing the same.

The compounds of the present invention are useful in various industrial fields, particularly in the agricultural field as synthetic intermediates for insecticides.

[Prior Art and Problems to be Solved by the Invention] In developing a new drug with outstanding insecticidal properties, the present inventors discovered the general formula (M (where X and Y are hydrogen atoms or fluorine atoms). shows.

We have discovered Kokichi, an aromatic alkane derivative represented by ), which is an excellent insecticide that exhibits a wide insecticidal spectrum and high insecticidal activity even against resistant pests. An object of the present invention is to provide synthetic intermediates for these compounds and manufacturing methods that can easily produce them.

[Means and Effects for Solving the Problems] The present inventors expressed the general formula (1) (wherein, X and Y represent a hydrogen atom or a fluorine atom).

) is the aromatic alkene derivative represented by the general formula (l
The inventors discovered that the compound represented by Vl is an important synthetic intermediate for the synthesis of a new insecticide, and completed the present invention. That is, compound (IV) can be obtained by reducing the compound (1) of the present invention. The compound of the present invention represented by the general formula (1) has not been described in any literature, and is a novel compound discovered for the first time by the present inventors.

The present inventors also investigated the method for producing the compound of the present invention represented by the general formula (I), and found that it could be easily synthesized by the following method, thereby completing the present invention.

The method for producing an aromatic alkene derivative represented by the general formula (■) according to the present invention shows an aldehyde represented by the general formula (II) and the general formula (III), and R is -8(OR+
)2 or one zero (ph)3= group. Here, R1 represents a lower alkyl group, and Z represents a halogen atom. ) in the presence of a base.

That is, as shown in the reaction of the following formula, the production method according to the present invention (II) (In) general formula (II
2,2,3,3-tetramethylcyclopropylacetaltehyde represented by the formula (III) and the phosphorus compound represented by the general formula (III) are subjected to the so-called Wittig reaction (Witti reaction).
The compound of the present invention is obtained by the following reaction. In the general formula (III), the substituent R1 represents a lower alkyl group, including medyl, ethyl, propyl,
Examples include straight chain or branched alkyl groups having 1 to 6 carbon atoms such as isopropyl, butyl, pentyl, etc., and the substituent Z is preferably a chlorine atom, a bromine atom or an iodo atom.

The base used in this reaction is sodium hydroxide,
Examples include alkali metal hydroxides such as potassium hydroxide, sodium methoxide, sodium ethoxide, potassium metal alkoxides, methyllithium, methyllithium, lithium hydride, and potassium hydride.

Although not essential, it is desirable to use a solvent to improve yield. Water, diethyl ether, or tetrahydrofuran (hereinafter referred to as T H F
(!: omitted), ethers such as 1,4-dioxane, inpropyl ether, ethylene glycol dimethyl needle, diethylene glycol dimethyl ether, aliphatic hydrocarbons such as hexano, heptane, aromatic compounds such as benzene, toluene, etc. There are several types, and they can be used singly or in combination.

When a reaction is carried out in a two-layer system by mixing water and an organic solvent, it is preferable to use a phase transfer catalyst such as triedylbenzylammonium chloride or l-ethylbenzylammonium bromide.

The reaction temperature and reaction time can vary widely depending on the starting materials, but are generally -20 to 150°C;
Preferably, the temperature is 0 to 100°C, and the reaction time is 20 to 20 hours, preferably 0.5 to 10 hours.

Regarding the molar ratio of these reaction reagents, the phosphorus compound is 05 to 20 times mole to the aldehyde, preferably 10 to
The base may be in large excess relative to the phosphorus compound, but is usually 10 to 30 times, preferably 1.
It is in the range of 0 to 10 times the mole.

In the above reaction formula, 2,2 represented by general formula (II)
.

6,6-Tetramethylcyclopropylace1-aldehyde can be produced, for example, by the following method: O (V) (■ H3CH3 (II), i.e., 2,2,3,5-tetramethylcyclopropylmethanol (■ ) is chlorinated with thionyl chloride to obtain the 4-chloro-1-pentene derivative (Vl), which is reacted with magnesium to obtain the Grignard
Reagent and then reaction with methyl orthoformate to obtain (■) dimethylacecour. Treat this with acid and get 2,2
, 3.3-tetramethylcyclopropylacetaldehyde (If) is synthesized.

The other raw material compound, the phosphorus compound represented by the general formula (III), can be produced, for example, by the following method.

(■ (■, RJ(oR,), ) (In the formula, R1 represents a lower alkyl group, and Z represents a halogen atom.) That is, benzyl halide (■1) So-called arbuzof with trialkyl phosphorous acid Reaction (Arubuzo
The corresponding phosponate esters [(III), R=PO(OR,)2) can be synthesized by reaction). On the other hand, when (■) is reacted with triphenylphosphine, the corresponding phosphonium salt [
(III), R=P+(ph), z-) can be synthesized.

The compounds represented by the general formulas (II) and (VD) are new compounds that have not been described in any literature.

〔Example〕

Next, the present invention will be explained in more detail by giving synthesis examples and reference examples.

Example 11-(4-fluoro-6-phenoxyphenyl)-3-(2,2,3,3-tetramethylcyclopropyl)flopenz synthesis (1) 4-chloro-3,3,4-1-umethyl- Synthesis of 1-Pentene 60ml of thionyl chloride was stirred at a bath temperature of 80°C.To this was added a solution of 70g of 2.2,3.3-tetramethylcyclopropylmethanol dissolved in 2°Oml of pyridine.
The mixture was added dropwise over 0 minutes and stirred for 1 hour. Pour the reaction mixture into ice water.
The extract was washed with a saturated aqueous solution of sodium bicarbonate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained dark red oil was distilled under reduced pressure to give 4-chloro-6,3,4-1-umethyl-
1-5.2 g of pentene, p, as ~90°IC/
Obtained as a colorless liquid at 92 Torr. This product crystallized when left at room temperature.

δCD(J, (ppm), 1°18(6H,s
), 1.54 (6H.

MS s), 4.92-5.08 (2H, m), 5.89-6
17 (11(, m) (2) 2,2,3,5-Tetramethylcyclopropylacetaldehyde synthesis 1.1 g of magnesium anhydrous 'J) J (F 20 ml
The mixture was heated to reflux while stirring under a nitrogen stream. A catalytic amount of iodine was added to this, and then the 4-chloro-3 obtained in (1)
A solution of 5.2 g of 3,4-1-umethyl-1-pentene in anhydrous THF (using 10 ml of anhydrous Tnrr) was added dropwise over 50 minutes. After adding 10 ml of methyl orthoformate and then 100 ml of anhydrous benzene to the reaction mixture, the internal temperature was reduced to 8.
THF was distilled off under normal pressure until the temperature reached 6°C. The reaction mixture was stirred at the same temperature for 2 hours, cooled with ice, and 100 ml of a saturated aqueous solution of ammonium chloride was added little by little. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, 2, 2, 3.
14 g of 3-tetramethylcyclopropylacetaldehyde dimethyl acetal was obtained. Add this to 2 oml of acetone
After adding 4 ml of water, 2 drops of methanesulfonic acid were added and the mixture was stirred at 50°C for 2 hours. 5 oz of water to the reaction mixture
ml and extracted with ether, and the extract was diluted with hydrogen carbonate l-
After washing with a saturated aqueous solution of IJum, it was dried over anhydrous sulfuric acid (IJum). The solvent was distilled off under reduced pressure and 2.2
, 0.90 g of 3,3-tetramethylcyclopropylacetaldehyde was obtained as a colorless, fade-like substance.

nD 1.4510 eat ν (crn-1): 29B0,2930,28
65゜aX 1720.1450.1ri75 δCD” (1)pm): 0.48(IH,t
J=7.0Hz).

M.S. 0.96 (6H, s), 1.15 (6H, s).

2.30 (2H, dd, J=7.0Hz, J=2
．． IHz) 9.77 (IH, t, J = 2.1Hz) (3
) 3-phenoxy-4-fluorobenzyldimethylphosphoner l-1,45,! 7 with anhydrous T■IF10m
The mixture was stirred at room temperature under a nitrogen stream. After adding 3.0 ml of n-butyllithium (5-thihexane solution) and stirring for 1 hour, add the 2,2,5.3-tetramethylcyclopropylacetaldehyde THF solution obtained in (2) (using 2 ml of anhydrous THF). The mixture was added and stirred for 2 hours. 50 ml of water was added to the reaction mixture and extracted with benzene. The extract was washed with water, dried, and the solvent was distilled off under reduced pressure. The obtained oily residue was purified by column chromatography to obtain 1-(4-fluoro-3-phenoxyphenyl)-
0.20# of 3-(2,2,3.3-tetramethylcyclopropyl)propene was obtained as a colorless oil.

20, 0 n Dl. 5 4 5 2 n8a'''(Crn-'): 2920,1585
, 1510.

ν 1490, 1290, 1270.1210δ0D” (T
)pm): 0.26 (IH, t, J=7.8Hz
).

MS 0, 98 (6H, s), 1.15 (6H, s), 2.0
~2.2 (2H, m), 5.9-6.4 (2H, m).

6.9'-7,4 (8H, m) Elemental analysis value: C22H,,,FO CHF Calculated value (%) 81,45 7,77 5.8
6 Measured value (@81,33 7.69 5.78 Example 2 1 (3-phenoxyphenyl)-3-(2,
Synthesis of 2,3,3-tetramethylcyclopropyl)propene 6-funinoxybenzyldimethylphosphonate 10
0g to anhydrous THF10m/! The mixture was stirred at room temperature under a nitrogen stream. To this, potassium tert-butoxide i,
After adding o o g and stirring for 1 hour, 2.2, 3.5-
Tetramethylcyclopropylacetaldehyde 0.20
g of 'T'HF solution (using 2 ml of anhydrous THF) was added and stirred for 3 hours. The reaction mixture was worked up in the same manner as in Example 1 (3) to give 1-(6-phenoxyphenyl)-3-
0.030# of (2,2,3,3-tetramethylcyclopropyl)propene was obtained as a colorless oil.

20.4 nl, 1・5542 neat ν (α-1>: 2990, 2940, 288
0°1600.1580,1500,1385°125
0.1220 Elemental analysis value "22H2110 CH Calculated value (% + 86.23 8.55 Measured value ((6) 86.22 8.49 Example 3
1(3-(4-fluorophenoxy)phenyl:] −
5 (2,2,+,!+-tetramethylcyclopropyl)
Synthesis of propene 6-(4-fluorophenoxy)benzyldimethylhumesphoner l-1, OOg in 10 ml of anhydrous THF.
The mixture was stirred at room temperature under a nitrogen stream. After adding 2.5 ml of n-butyllithium (15% hexane solution) and stirring for 1 hour, a THF solution (using 2 ml of anhydrous THF) of 2,2,5,3-tetramethylcyclopropylacetaldehyde 0.209 was added. The mixture was stirred for 3 hours. The reaction mixture was worked up in the same manner as in Example 1 (3) to give 1-1:3-
(4-fluorophenoxy)phenyl) -5-(2,
2,3,3-tetramethylcyclopropyl)propene 0
．． 2F was obtained as a colorless oil.

nD 1.5330 neat.

ν (cm-'): 2980, 2920, 286
5゜1600.1575, 1500.14B0゜144
0.1220.1200 Elemental analysis value: c, , , H,F.

CHF Calculated value (%), 81.45 7.77 5.
86 measurement value book) 81,27 7.80
5.70 Example 4l-(4-fluoro-3-(4-fluorophenoxy)phenyl)-3-(2,2,5,5
Synthesis of -tetramethylcyclopropyl]propene 3-(
4-fluorophenoxy)-4-fluorobenzyldimethylphosphonate 1.00J7 and 2.2,5.3-
Tetramethylcyclopropylacetaldehyde 018g
and 100 g of potassium kushari-butoxide were reacted in the same manner as in Example 2.
-fluorophenoxy)phenyl)-3-(2,2,3
, 3-tetramethylshifrobukomapir]propene was obtained as a colorless oil.

20.0 nD 1・5422 Elemental analysis value: C2□H24F20 C) (F Calculated value (%) 77.17 7.06 11
．． 10 measurements (@ 77.21 6.98
11.02 Reference Example 1 Synthesis of 1-(4-fluoro-6-phenoxyphenyl)-3-(2,2,3,3-tetramethylcyclopropyl)propane 1-(4-fluoro-3-phenoxyphenyl) −3(
2,2,5,3-tetramethylcyclopropyl)propene 0.25.9 and 5% Pd-C (50% quartz) 0.0
5g, ethyl acetate 25g for 200m/! Charge the autoclave, replace the inside of the autoclave with nitrogen, and then with hydrogen.
The mixture was pressurized with hydrogen to 25 kg/ff1o and stirred at room temperature for 3 hours. After the reaction is complete, the reaction mixture is filtered, and the filtrate is concentrated under reduced pressure to give 1-(4-fluoro-6-phthoxyphenyl) -! 1-(2,2,3,3-te]-ramethylcyclopropyl)propane 0239 was obtained as a colorless oil.

neat ('): 2940, 2880, 16
00゜ν ax 1520.1500, 1290.1220δ0D”(p
pm)20.88((SH,S),1.05(6H,S
).

MS 0.8-1.8 (5H, m), 2.53 (2H, t,
J=7.5H7), 6.7-7.3 (8H, m) Elemental analysis value: C22H2□FO CHF Calculated value (@80,94 8,34 5
．． 82 measured value (%1 Bo, 78 8,22
It can be easily manufactured by the 5.70 method.

Reference Example 2 20 parts of 1-(4-fluoro-6-fetsugisiphenyl]-ro-(2,2,3,3-butramethylcyclopropyl)propane obtained in Reference Example 1 were added to Tsuru H!- 10 parts of Ru 355 (manufactured by Toho Chemical ■, surfactant) and 70 parts of Xylene 17
The mixture was uniformly stirred and mixed to obtain an emulsion. This emulsion was diluted with water so that the concentration of the active ingredient was 100 ppm, and -
The chemical solution was applied to rice seedlings (3-leaf stage) planted in Wagner pots with a radius of 1:10,000 using turntable 2 until it dripped lightly. After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 female adult resistant leafhoppers (native to the Middle Periphery) were released into the seedlings, left to stand at room temperature, and the mortality rate was examined 24 hours later. All tests were conducted in duplicate. As a result, the insect mortality rate was 100
It was Chi.

〔Effect of the invention〕

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X and Y represent a hydrogen atom or a fluorine atom. ) Aromatic alkene derivatives represented by (2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) The aldehyde represented by and general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, X and Y represents a hydrogen atom or a fluorine atom,
R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -P^■
(Ph) indicates a _3Z^■ group. Here, R_1 represents a lower alkyl group, and Z represents a halogen atom. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) (In the formula, .) A method for producing an aromatic alkene derivative represented by