AU702043B2 - Dihalopropene compounds, insecticidal/acaricidal agents containing same, and intermediates for their production - Google Patents

Description

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AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

(ORIGINAL)

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0 00, Name of Applicant: Actual Inventors: Address for Service: Invention Title: Sumitomo Chemical Company, Limited Noriyasu SAKAMOTO, Sanshiro MATSUO, Masaya SUZUKI, Taro HIROSE, Kazunori TSUSHIMA, Kimitoshi UMEDA DAVIES COLLISON CAVE, Patent Attorneys, 1 Little Collins Street, Melbourne, 3000 Dihalopropene compounds, insecticidal/acaricidal agents containing same, and intermediates for their production The following statement is a full description of this invention, including the best metLjd of performing 't known to me: -~--SCPql~ ~sl~e~ P:\OPER\PDB\36728-95.SPE- 20/4/98 1A-

DESCRIPTION

DIIALOPROPENE COMPOUNDS, INSECTICIDAL/ACARICIDAL AGENTS CONTAINING SAME, AND INTERMEDIATES FOR THEIR PRODUCTION The present invention relates to dihalopropene compounds, insecticidal/ acaricidal agents containing these compounds as active ingredients, and intermediates for their production.

As disclosed in JP-A 48-86835/1973 and JP-A 49-1526-1974, for example, it is well known that some kinds of propene compounds can be used as an active ingredient of insecticides.

In view of their insecticidal/acaricidal activity, it cannot always be said that 1. these compounds are satisfactorily effective for the control of noxious insects, mites and ticks.

15 The present inventors have intensively studied to find a compound having excellent insecticidal/acaricidal activity. As a result, AU 36728/95, hde entire contents of which are incorporated herein by reference, describes particular dihalopropene compounds which have satisfactory insecticidal/acaricidal activity for the control of noxious insects, mites and ticks.

20 Thus, AU 36728/95 provides a dihalopropene compound of the general formula:

C

R

2 Ry Z- -y CH 2

CH=CX

2

I

-17- wherein Z is oxygen, sulfur or NR 4 (wherein R 4 is hydrogen or C 1

-C

3 alkyl); Y is oxygen, sulfur or NH; X's are independently chlorine or bromine; R 2 R and R 10 are independently halogen, C 1

-C

3 haloalkyl or C 1

-C

3 alkyl; t is an integer of 0 to 2; and R 1 is Q1, Q 2 Q3 Q4 Q45 Q6 or Q7 of the general formula: R7 Aft R 6 R

P

.Q R" R' R' I 1 I

CH

R R I s pI i R" R 7 I I

CH

R

6

Q

2

R

5

R

7 1 1 C CH

R

6

P

*000 s S 4..

Q3 Q 4 R R' R 7 1 14 A-B C I C 1 R 12 6 S R 6 s -p R" 0 R 5 R 7 R" R 5

R

A -4O± -tCH O R R 14) I I I

A-C(R'

3

C(R

4

-C-O--C--CH

QI

RO

-P

wherein A is an optionally substituted heterocyclik, ng group, provided that when A is an optionally substituted heterocyclic ring gr-oup containing two oxygen atoms and a condensed benzene ring, A is optionally substituted 1,3-benzodioxolan-2-yl or optionally substituted 1,4-benzodioxan-2-yl; B is oxygen, S(O)q, NR 9

C(=G

1

)G

2 or G 1

C(=G

2 q is an integer of 0 to 2; R 9 is hydrogen, acetyl or C 1

-C

3 alkyl; G 1 and G 2 are indepen- (qL ~LC r P:\OPER\PDB36728-9.SPH 23/12/98 -3dently oxygen or sulfur; R 5

R

6

R

7 R"11 and R' 2 are independently hydrogen, C C 3 alkyl or trifluoromethyl; k3 and 1 4 are independently hydrogen,,C 3 C alkyl, trifluoromethyl or halogen; p is an integer of 0 to 6; and s is an integer of 1 to 6.

2-(3-Methanesulfonyloxypropyloxy)-5-trifluoromethyl pyridine is useful in the preparation of compounds of general formula I wherein R1 is trifluoromethyl-pyridin-2-yloxy)propyl, see for example pages 21 to 43 and Table page 125, radical 18, of AU 36728/95.

i 10 Accordingly, the present invention provides 2-(3- S methanesulfonyloxypropyloxy)-5-trifluoromethyl pyridine.

As described in AU 36728/95, the dihalopropene compounds may be S prepared by production processes A H.

In one example, 3,5-dichloro- l-(3,3-dichloro-2-propenyloxy)-4-[3-(5trifluoromethyl-pyridin-2-yloxy)propyloxy]benzene (compound 36 of AU 36728/95) I may be prepared by Production Process F using 2-(3-methanesulfonyloxypropyloxy)-5trifluoromethyl pyridine.

Production Process F affords compounds of AU 36728/95 wherein Y and Z are both oxygen, R1 is Q 2 or Q 3 and B is B' (wherein B is oxygen, sulfur or N-9 [wherein R is as defined above]). In this process, a compound of the general formula: p 4 -4-

R

5

R

7

R

2

HB

1 CH-O CHzCH CXz [X)

R

6

R

3 wherein B, R, R 2

R

3

R

5

R

7

R

10 p, t and X are each as defined above, is reacted with a compound of the general formula:

R"

A-L or L [xI] R 1 2

JS

wherein A, R 1

R

1 2 and s are each as defined above and L is halogen, chlorine, bromine, 5 iodine), mesyloxy or tosyloxy.

The reaction is preferably effected in an inert solvent in the presence of a suitable base.

Examples of the solvent which can be used are ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as 1,2-dimethoxyethane, tetrahydro- 10 furan, dioxane and dialkyl CI-C 4 ethers diethyl ether, diisopropyl ether); N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulforane, acetonitrile, nitromethane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene and xylene; and water. If necessary, a mixture of these solvents can be used.

Examples of the base which can be used are hydroxides of alkali mlals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates of alkali metals or alkaline earth metals, such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alkoxides CI-C 4 such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; organic bases 9~S~399~81L I such as triethylanine and pyridine. If necessary, catalysts such as ammonium salts triethylbenzylammonium chloride) may be added to the reaction system at a ratio of 0.01 to I mole per mole of the compound of the general formula The reaction temperature is usually set within the range of -20'C to 150*C or the boiling point of a solvent used in the reaction, preferably -5*C to 100'C or the boiling point of a solvent used in the reaction.

The molar ratio of the starting materials and dehydrating agents to be used in the reaction can be freely determined, but it is favorable to effect the reaction at an equimolar ratio or a ratio closer thereto.

After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as organic solvent extraction and concentration, and the desired compound of the present invention can be isolated. Further, purification can be carried ;o o sut bhv an ordinary technique such as chromatography, distillation or recrystallization.

P e 0 Tato |o vi r 00 l^ 0 copoud o th prsen invntin cn b islatd. urter, uriicaioncanbe arredP l~s I- I_ JII P:\OPER\PDB\36728-95.SPE-20/4/98 -6- Production Example 1: Production of compound (36) by production process F First, 2-(3-methanesulfonyloxypropyloxy)-5-trifuoromethylpyridine was prepared as follows.

A mixture of 12.6 g of 1,3-propanediol and 100 ml of N,N-dimethylformamide was stirred under a nitrogen stream, to which 3.30 g of an oily mixture containing sodium hydride was added in small portions at room temperature over 30 minutes.

After further stirring continued at room temperature for 1 hour, 20 ml of a DMF solution of 10.0 g of 2-chloro-5-trifluoromethylpyridine was added dropwise over 40 minutes.

After further stirring continued under a nitrogen stream at room temperature overnight, 100 ml of about 2 N diluted hydrochloric acid was a'^'ed over 15 minutes to stop the reaction. The reaction mixture was extracted twice with toluene at a total volume of 500 ml. The combined toluene layer was successively washed with diluted hydrochloric acid and aqueous sodium bicarbonate solution, dried with magnesium sulfate, and concentrated to obtain an oily product. The oily product was dissolved in 300 ml of hexane by heating, followed by recrystallization, which afforded 5.3 g of 2-(3-hydroxyas almost pure crystals (44% yield), m.p. ,6.6 °C.

A mixture of 4.0 g of 2-(3-hydroxypropyloxy)-5-trifluoromethylpyridine, 3.4 ml of triethylamine and 25 ml of toluene was vigorously stirred under a nitrogen S 20 stream, while cooling in chilled water bath to 5 C. Then, 1.63 g of methanesulfonyl chloride was added dropwise to this mixture at such a rate that the reaction temperature did not exceed 10°C, and the chilled water bath was removed. After further stirring continued at room temperature for 1.5 hours, 250 ml of water was added thereto, and the mixture was vigorously stirred for further 30 minutes, followed by phase separation.

The toluene layer was washed once with water, dried with magnesium sulfate, and concentrated, which afforded 5 g of 2-(3-methanesulfonyloxypropyloxy)-5- 1 ttrifluoromethylpyridine as an oily prodnct (92% yield). i SjA C P:\OPER\PDB\36728-95.SPE 20/4/98 -7- 1 H-NMR 8 (ppm) [CDC1 3 TMS] 8.39 (1H, br, 7.75 (1H, dd), 6.80 (1H, 4.0-5.0 3.00 (3H, 2.30 (2H, quint.) A mixture of 5 g of 2-(3-methanesulfonyloxypropyloxy)-5-trifluoromethylpyridine, 5 g of 4-(3,3-dichloro-2-propenyloxy)-2,6-dichlorophenol, 2.64 g of potassium carbonate and 300 ml of N, N-dimethylformamide was vigorously stirred at room temperature for 4 days. Then, 300 ml of 2 N hydrochloric acid was added to this mixture, and extracted twice with toluene at a total volume of 300 ml. The combined toluene layer was successively washed with 2 N hydrochloric acid and aqueous sodium bicarbonate solution, dried with magnesium sulfate, and concentrated to obtain about 8 g of an oily product. The oily product was subjected to silica gel chromatography, which afforded 6.0 g of 3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)propyloxy]benzene (70% yield).

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Claims (2)

1. 2-(3 DATED this 20th day of April 1998 Sumitomo Chemical Company Limited By its Patent Attorneys DAVIES COLLISON CAVE 0009 0 09 0 9 7 L Y~, ;L 1~jj~ P:kOPER\PDfl36728.9S.SPE 20/4/98 ABSTRACT

2-(3 -methanesulfonyoxypropy 00eq 000 00 0000 00 0 00 000 '~1