JPS60136562A - 1-(6-phenoxy-2-pyridyl)ethanol and manufacture - 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 The present invention provides novel 1-(6-phenoxy-2-pyridyl)
The present invention relates to enantiomers of ethanol, methods for its preparation and its use for the synthesis of microbicide compounds.

In particular, the present invention relates to the following formula I: (wherein 7 is (+) or (-), and X and Y are independently of each other a hydrogen atom, a rogen atom, a nitro group, a carbon atom number 1 alkyl group having 1 to 4 carbon atoms;
represents a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms. ) is concerned with the enantiomer represented by

In the above definition, the rogen atom is a fluorine atom, a chlorine atom,
Represents a bromine or iodine atom.

Suitable alkyl, haloalkyl, alkokino, alkenyl or alkynyl groups for X and Y may be straight chain or branched. Examples of each group include, for example, methyl group, methoxy group, trifluoromethyl group, ethyl group, ethoxy group, propyl group, inpropyl group, n-butyl group, vinyl &, clobenyl, ethynyl, and It is a propynyl group.

Preferred enantiomers of formula I are those in which rice is (+
) or (-), and X is a hydrogen atom, a halogen atom, a nitro group, or -c =
cii and Y represents a hydrogen atom.

Particularly preferred enantiomers of formula I are: Rice is (+) and still (-), X represents a hydrogen atom or a halogen atom, and Y represents a hydrogen atom.

The enantiomers of formula I can be obtained by separating racemic 1-(6-phenoxy-2-pyridyl)ethanol on an optically active carrier material. Accurate selection of carrier material is essential for successful separation. Surprisingly, the present inventors have demonstrated that racemic 1-(6-phenoxy-2-pyridyl)ethanol or their acetates are highly effective for microcrystalline cellulose, particularly microcrystalline triacetyl sek 0 . 2 average (
It was discovered that enantiomers represented by the formula (2) can be separated by chromatography on hendiyl cellulose.

Is racemic 1-(6-phenoxy-2-pyridyl)ethanol known? (US Pat. No. 4525)
No. 574 Meisosho) or a known method. Surprisingly, however, the known racemic 1-(6-7 enoxy-2-pyridyl) ethanol, an ester with potent pesticidal and acaricidal activity, can be reacted with the acids customary for birethroids. can be prepared from an optically active alcohol represented by formula 1. For example, the following acids can be used for the reaction of the enantiomer of formula (1) with 1-(6-7 enoxy-2-pyridyl)ethanol.

a) 1ζ [In the formula, the bird represents a hydrogen atom, ■The field represents, (In each group, 〇 represents a methyl group or a halogen atom, and X2 represents a methyl group, a trifluoromethyl group, a halogen atom, or a P-
Chlorophenyl foundation, Yl represents a halogen atom, and ¥2 represents a hydrogen atom or a halogen atom. 〕,〕) 也tamei (during the ceremony.

X3 is a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 4
an alkyl group, an alkoxy group having 1 to 4 carbon atoms,
C1-C4 haloalkyl group, C1-C4 haloalkyl group
to 4 haloalkoxy&, -COCIi3 or methylenedioxy group, and l'L3 represents an inglovir group or a cyclovir group. ).

Example 1 Production of enantiomers by chromatographic separation of racemic alcohol represented by the following formula Glass column (1,2
51X5a5ffi) to triacetylcellulose 3
6g [Prepared by known method: Ri0 Madographia (C
chromatograpbia), 277 (197
5)) and fill with a 95:5 mixture of ethanol/water.

6.5 pf of a racemic compound of the formula: is applied thereto and chromatographed on this carrier.

The racemate is chromatographed with ethanol/water (95:5) at a flow rate of 24 m1i/b under a pressure of 15 bar. The effluent was measured using a polarimeter [Parky 7-L-q-(
Perkin-Elmer) 241MC) and UV
Follow the flow curve of a spectrophotometer (Shimadzu UV-120-02). A two-channel recorder records the concentration and optical rotation of the substance.

The optical rotations of the two enantiomers are calculated from the elution curves.

[α]565-+89°±2° (C=0.033: Ethano-/L/H2095: 5)
('')365 ''''-91°±2° (c=0.042; Ethanol 7H, 95:5.)V
l-V.

Example 2 Preparation of enantiomers by chromatographic separation of racemic alcohols of the formula
Chromatograph through L4aX25ffi) using a 9:1 mixture of hexane/isopropanol at a flow rate of 11.2 m 17 min.

Separation factor: 1.15 S = separation factor = 1.0 Example 3 Preparation of enantiomers of racemic alcohol of the following formula: a) Chromatographic separation of the two semi-compounds of acetate.

20 μm of racemic acetate was passed through a column of triacetylcellulose (1,25-×50 scratches; 14I of triacetylcellulose) and developed with a 95:5 mixture of ethanol/water at a flow rate of 35 me/b for refrigerating. . Measure the optical rotation of both enantiomers of acetate.

[α] ・=+77°±5°56 (c=α58; ethanol) [α]436−−76°±5° (c=α58; ethanol) Separation coefficient = 7.9 b) Saponification of acetate Pure (+) and (-) acetate (Example 5)
a) 5mg and 2CO11s W for 1 hour in ethanol/
Reflux in a 10 nia mixture α3- of water.

The mixture is diluted with 5 tttl of chloroform and dried over sodium sulfate. After filtration and evaporation of the solution, the residue is purified by chromatography on silica gel (developing solvent: chloroform) to give the enantiomer 'i (4) of the following formula: % formula % ) ).

Enantiomers of acetates and alcohols of F are also obtained by L, one of them, and the other: Example 4 1-Methyl-(6-phenoxy-2-picolyl)-1
-几-7-5-(2,2-dichlorovinyl)-2,2
--) Production of methyl cycloglohan carboxylate 1-R-cis-5-(2,2-dichlorovinyl)-2,
2-dimethylcyclopanecarboxylic acid chloride 12
A solution of 1.4 I of pyridine dissolved in 5 ml of toluene was added to a water-cooled solution dissolved in 20 af of 1f toluene, and then a compound 3I of the following formula was added to 1 ml of toluene.
Add the solution dissolved at 0 mA'. Then 200 q of 4-dimethylaminopyridine are added to the slightly yellowish suspension and the reaction mixture is stirred for 16 hours at room temperature.

After adding 100ml of toluene,
m 1m k water-cooled 1 N1-1CI! ,10%
Then, with a saturated solution of COa, saturated NaHCO3 and NaCj', Mg50. Dry with. The solvent was then removed under reduced pressure, and the crude product was purified on silica gel with toluene as the developing solvent, and R-
α-Methyl-(6-phenoxy-2-picolyl)1-R
-7-3-(2,2-dichlorovinyl)-,2,2-
Dimethyl cyclopropane carboxylate (compound 1)
obtain: 20° nD = 1.5605 [α) D = +116° ± 1° (c = 1.07 in benzene) The following esters are also prepared in a similar manner: 2) S-α- Methyl-(6-phenoxy-2-picolyl)1-cis-3-(2,2-dico o hini A
/ ) -2,2-dimethylcyclopropanecarboxylate n20° = 1.555M [α), = -696 ± 1° (c = 0.957 (in benzene)] 3) -a-methyl-6- (6-phenoxy-2-picolyl)1-R-1 lance-3-(2゜2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate n20° = 1.5581 [a) D = +77°± 1' (c=0.74 (in benzene)) 4) S-α-methyl-(6-7 enoki 7-2
-picolyl) 1-B, -) lance-5-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate 21゜nD = 1.5581 [α], = = -s + s°± 1° (C=[L83 (in benzene)] Example 5 Cotton plants were injected with a test solution containing 1.25#, 0.6F or 0.5g of the compound of Example 4 per H,01001. After the spray coating has dried, the plants are coated with Heliothis virenocene x.
virescens; L1 stage) species. Two plants are used for each test compound and test species and the mortality rate is calculated after 24 and 48 hours.

The test is conducted at 24° C. and 60° relative humidity.

Heliothis guiresse yx (
The activity against the larvae of Heliothis virescens) species is shown in the table below.

Claims (1)

[Claims] (Formula I: (in the formula, rice is (+) or (-), -bi, and X and Y each independently represent a hydrogen atom, a halogen atom, a nitro group, C 1 -C 4 alkyl group, C 1 -C 4 alkyl group
represents a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms. ) enantiomer. (2) In the formula l, X is a hydrogen atom, a halogen atom, a nitro group, or 10=O
Enantiomers according to claim 1, in which H represents a hydrogen atom. (3) The enantiomer according to claim 2, wherein in the formula I, X represents a hydrogen atom or a halogen atom, and Y represents a hydrogen atom. (4) The enantiomer according to claim 5, which is represented by the following formula: Claim 3: l The enantiomer described in claim 3. (6) The engineering device according to claim 5, 6, which is represented by the following formula: (7) The enancouomer according to claim 6, which is represented by the following formula: (8) The enantiomer according to claim 3, which is represented by the following formula: (9) The enantiomer according to claim 3, which is represented by the following formula: 01 The enantiomer described in Section 1 of the scope of Patent No. 8, which is represented by the following formula: αυ The enantiomer according to claim 3, which is represented by the following formula: The enantiomer according to claim 2, which is represented by the following formula: 0.1 The enantiomer according to claim 2, which is represented by the following formula: a4 The enantiomer according to claim 2, which is represented by the following formula: 09 The enantiomer according to claim 2, represented by the following formula: %WF. 2. Enantiomers according to claim 1 for use in the production of microbicide compounds. The enantiomer according to claim 16, which is used for the production of αη biretroid compounds. Ql IL-α-methyl-(6-phenoxy-2-picolyl)1-1-cis-5(212-dichlorovinyl)
-2,2-dimethylfuclopropane carboxylate,
S-α-methyl-(6-phenoxy-2-picolyl)1
-几一7su-5-(2,2-dichlorovinyl)-2t2
-dimethylfuclopropane carboxylate, 几-σ-
Methyl-(6-phenoxy-2-picolyl)1-■Mo-trans-5-(2゜2-dichlorovinyl)-2,2-
Dimethylfuclopropane carboxylate or S-a
-Methyl-(6-phenoxy2-picolyl)1-it
-Tojinos-5-(2,2-dichloroviny)+/)-2
, 2-dimethylcycloglonocarboxylate. (In the formula, X and Y are hydrogen atoms independently of each other.)・Rogen atom,
Nitro group, C1-C4 alkyl group, C1-C4/-roalkyl group, C1-C4 alkokene group, C2-C5 alkenyl group or C2-C4 alkyl group 5 represents an alkynyl group. ) on microcrystalline cellulose, in particular microcrystalline triacetylcellulose violet or tribenzoylcellulose, or b) the racemic alcohol of formula I: (wherein X and Y The racemic acetate-1 represented by the formula b1 is separated by chromatography on microcrystalline cellulose, and the resulting pure acetate-1 enantiomer is subsequently saponified to produce the alcohol. or (-), and X and Y have the meanings given above. ) A method for producing the enantiomer represented by