GB2168697A - Intermediates useful in the preparation of pesticides containing a haloallylbenzyl group - Google Patents

Intermediates useful in the preparation of pesticides containing a haloallylbenzyl group Download PDF

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GB2168697A
GB2168697A GB08516680A GB8516680A GB2168697A GB 2168697 A GB2168697 A GB 2168697A GB 08516680 A GB08516680 A GB 08516680A GB 8516680 A GB8516680 A GB 8516680A GB 2168697 A GB2168697 A GB 2168697A
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Michael Elliott
Norman Frank Janes
Richard Leonard Elliott
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National Research Development Corp UK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
    • C07C33/48—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts with unsaturation outside the aromatic rings
    • C07C33/483—Monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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Abstract

Novel compounds of formula II E <IMAGE> wherein M represents a group of formula -CHO or a group of formula <IMAGE> wherein D represents hydrogen or a cyano group and Y represents a hydroxyl group or a halogen, A represents an alkyl group, n is 0 to 4 and X represents a halogen are useful in the preparation of pesticides of formula I <IMAGE> wherein RCOO represents a residue of an acid RCO2H, which acid, or an ester-forming derivative of which acid, on reaction with alpha -cyano-3-phenoxybenzyl alcohol or an ester-forming derivative thereof, gives rise to an alpha -cyano-3-phenoxybenzyl ester having pesticidal properties.

Description

SPECIFICATION Intermediates useful in the preparation of pesticides containing a haloallylbenzyl group THIS INVENTION relates to intermediates for use in the preparation of pesticides. These pesticides are described and claimed in British Application No. 8314514, (Serial No. 2121039), from which this Application is divided.
Intermediates of the present invention may be used in the preparation of a compound of formula I:
wherein: D represents hydrogen or a cyano group; X represents halogen; A represents an alkyl group (typically a C1-C6 alkyl group); n is 0 to 4; RCOO. represents a residue of an acid RCO2H, which acid, or an ester-forming derivative of which acid, on reaction with alpha-cyano-3-phenoxybenzyl alcohol or an ester-forming derivative thereof, gives rise to an alpha-cyano-3-phenoxybenxyl ester having pesticidal properties.
The present invention provides a compound of formula IIE:
wherein M represents a group of formula -CHO or a group of formula
wherein Y represents a hydroxyl group or halogen, D represents hydrogen or, when Y represents OH, D can also represent a cyano group, A represents an alkyl group, n is 0 to 4 and X represents a halogen.
It is generally preferred that D represents hydrogen and for the substituent group -CH=CHX to be disposed at the 3 br 4 position in the benzene ring with respect to the group M.
Compounds in which the hydrogens in the double bond of the substituent group are disposed in the Z configuration (whether or not in the isomerically pure form) are of particular interest; the compound 4(Z-3-chloroallyl)benzyl alcohol being of particular interest. The group A when present typically represents methyl, and compounds in which two alkyl, e.g. methyl, groups are disposed at the 2,6 position in the ring with respect to the group M are of especial interest.
X preferably represents fluorine, chlorine or bromine, chlorine being particularly preferred.
Intermediates lIE in which M represents a group
and Y represents -OH may be produced from compounds of formula IIE wherein M represents OHC-.
In accordance with a further aspect of the present invention, a compound IIE wherein M represents
Y represents OH and D represents hydrogen is produced from a compound IIE wherein M represents OHC- by reduction thereof. Such reduction may be hydride reduction using a reagent such as lithium aluminium hydride.
In accordance with a further aspect of the present invention, a compound IIE wherein M represents the group
Y represents OH and D represents a cyano group is produced from a compound IIE wherein M represents OHC- by treatment with an alkali metal cyanide. The reaction is typically conducted under acidic conditions in a homogenous reaction mixture comprising an aqueous organic solvent.
Intermediates IIE in which M represents the group
Y represents halogen and D represents hydrogen may be produced from intermediates ilE in which M represents the group
Y represents -OH and D represents hydrogen, in accordance with a further aspect of the present invention by treatment of the latter intermediates with a halogentating reagent of the class employed for conversion of carboxylic acids to acyl halides e.g. SO(hal)2, typically wih pyridine or P(hal)3, hal representing chlorine or bromine.
Compounds IIE in which M represents OHC- may be produced in accordance with a further aspect of the present invention by reaction of a Grignard reagent of formula IIB:
wherein P represents bromine or iodine and K represents a ketal group, typically ethylene ketal -OCH2 . CH2O- with a complex formed between a compound Q-CH2-CH=CH-X wherein Q represents bromine or chlorine, typically chlorine, and, respectively, cuprous bromide or a mixture of lithium and cuprous chlorides, followed by treatment of the reaction mixture with mild aqueous acid e.g. NH4CI.
Compounds IIE in which M represents OHC- may alternatively be produced in accordance with a further aspect of the present invention by reaction of a compound of formula IIC:
with selective hydride reducing agent such as sodium dihydrobis(2-methoxyethoxy) aluminate followed by hydrolysis of the ketal group using for example dilute acid. The latter method is especially suitable when X represents fluorine. Both E and Z isomers of the 3-haloallylbenzaldehyde are generally produced and can be separated by known techniques such as distillation or chromatography e.g. gas chromatography.
Compounds IIC may be produced by a Wittig reaction of a compound of formula IID:
with a halocarbon CX2W2 in which W represents a halogen the atomic weight of which is no less than the.atomic weight of X, preferably, when X represents fluorine, in the presence of zinc powder.
The compounds of the invention exhibit optical isomerism in that the carbon atom bearing the substituent D can exist in the R or S configuration and the present invention includes compounds in which the configuration is substantially completely R or in which configuration is substantially completely S or mixtures thereof.
The compounds of the present invention can be in the form of single isomers but, having regard to the fact that the compounds have at least one centre of asymmetry, the compounds of the invention will normally be in the form of isomer mixtures.
The invention is illustrated by the following Examples.
Temperatures are in "C.
EXAMPLE I 4(Z-3-chloroallyl)benzaldehyde Dry Mg (1.15 g) under dry N2 in a flask is covered with THF (10 ml) and a crystal of 12 added.
5 ml of a solution of 4-bromobenzaldehyde ethylene acetal (10.0 g) in THF (40 ml) is added and kept until it becomes warm, when it is cooled to 15 , and the remainder of the acetal added over 15 minutes, then stirred for an additional 1 hour. A mixture of ground lithium chloride (0.35 g) and copper (I) chloride (0.70 g) dissolved in THF is prepared, treated with Z-1,3-dichloropropene (8.0 g) produced by spinning band distillation of commercially available 1,3-dichloropropene comprising a mixture of the E and Z isomers and cooled to 200. The above Grignard solution (under moisture excluding conditions) is then added to this solution during 5 minutes, and allowed to warm to 20 with stirring for 16 hours.Saturated aqueous ammonium chloride is added and the organic layer evaporated under reduced pressure to a small residue, which is dissolved in THF (100 ml), cooled to -10", treated with 3N HCI (50 ml), then stirred at 20 for 1 hour. The product is partitioned between ether and water, and the ether layer washed with saturated aqueous NaHCO2, H20, saturated aqueous NaCI, dried (MgSO4) and the residue chromatographed on Florisil (Registered Trade Mark). The fraction eluted by 15% diethyl ether in petroleum ether bp 600 - 800C is collected and purified by preparative HPLC. Yield 1.12 g (14%) n2,01.5655.
EXAMPLE 2 4(Z-3-chloroallyl)benzyl alcohol The aldehyde (0.22 g) of Example 1 in ether (5 ml) is added to lithium aluminium hydride (0.08 g) in ether (5 ml), and the mixture stirred at 20 for 1 hour. After successive dropwise additions of water (80 i'l), 15% NaOH) (80 i'l) and water (240 ul), the resulting clear ether layer (+washings) is evaporated to a residue of 4(Z-3-chloroallyl)benzyl alcohol yield 0.19 g (86%)N2D 1.5529.
EXAMPLES 3 TO 6E Aldehydes of formula 11E are generally prepared by following the method described in Example 1, yield and refractive index given in Table 3- and 4-(3-Bromoallyl)benzaldehyde are prepared as described in Example 1 respectively from 3- and 4-bromobenzaldehyde but using a mixture of E and Z isomers of 1,3-bromopropene and cuprous bromide in place of the mixture of lithium chloride and cuprous chloride. The resultant aldehyde is separated into E and Z isomers by HPLC on silica eluted with 4% diethyl ether in petroleum ether, bp 60"-80"C.
2,6-Dimethyl-4-bromobenzaldehyde ethylene acetal for conversion to 2,6-dimethyl-4-(Z-chloroallyl)-benzaldehyde is prepared by an adaptation of the method described in Organic Synthesis, Volume V p.139, for the prepartion of 2-bromo-4-methylbenzaldehyde as follows: A. Formaldoxime A mixture of paraformaldehyde (11.5 g, 0.383 mole) and hydroxylamine HCI (26.2 g, 0.377 mole) are heated in water (160 ml) until a clear solution is obtained (ca 10 minutes at 80"C).
Hydrated sodium acetate (50.8 g) is added, and the mixture is refluxed for 15 minutes giving a 10% aqueous solution of formaldoxime.
B. Diazonium salt Concentrated HCI (56.4 ml) is added slowly with cooling (15"C), to a mixture of bromoxylidine (50.0 g, 0.25 mole) and water (80 ml). The purple suspension turns into a grey suspension and more water (80 ml) is added. The mixture is then cooled in ice/salt to below 5"C. Sodium nitrite (17.5 g, 0.254 mole) in water (40 ml) is added dropwise, keeping the temperature below 5"C.
Stirring is continued for 15 minutes, to given an orange solution and some purple suspension.
The solution is made neutral by addition of NaOAc (21.9 g) in water (40 ml). The mixture is filtered through a coarse sinter and kept cold.
C. Aldehyde Hydrated copper sulphate (6.5 g) is dissolved in water and mixed with the aqueous formaldox- ime, Na2SO3 (1.0 g) and aqueous solution of sodium acetate (160 g in 170 ml). This mixture is maintained at ca. 10 with an ice/water bath and stirred vigorously. The aqueous diazonium solution is added in portions via a funnel, effervescence occurring. Stirring is continued overnight. Concentrated HCI (250 ml) is added in the morning and the mixture is refluxed for 90 minutes, then steam distilled, 2000 ml of distillate being collected. This is extracted with ether (2X200 ml), washed with saturated aqueous NaHCO3, H20, saturated aqueous NaCI, dried over MgSO4 to give 34.2 g of an orange liquid which solidifies on cooling.
This residue is added with cooling to a 40% 5 aqueous solution of sodium metabisulphite (50 9+75 ml H20). This is stirred overnight, the cream precipitate becoming thicker. The precipitate is filtered, washed with water, then ether. The precipitate is suspended in water and concentrated H2SO4 added with cooling. The mixture is refluxed gently for 90 minutes, cooled, extracted with ether and the ethereal extracts are treated with saturated aqueous NaHCO3, H20, saturated aqueous NaCI and dried over MgSO4 and the solvent is removed to give 13.34 g aldehyde (25%) as white needles.
D. Acetal A mixture of aldehyde (30.7 g), ethylene/glycol (8.94 g), ptoluenesulphonic acid (0.4 g) and benzene (150 ml) is refluxed in a Dean & Stark apparatus overnight, and 2.6 ml H20 is collected.
The mixture is cooled and stirred with K2CO3 for 30 minutes, filtered and the K2CO3 washed with ether and solvent removed. The solid residue is distilled (mp ca 100 ) in vacuo to yield the product, bpt 108-118 (0.05 mm.Hg), 34.33 g (93%).
3- and 4-(3-Fluoroallyl)benzaldehyde are prepared by the following method for 3-(3-fluoroallyl)benzaldehyde: A. 3-(Formylmethyl)benzaldehyde ethylene ketal 3-Allylbenzaldehyde ethylene ketal (2.0 g, prepared using Cu(l)Br only and allyl bromide by the method of Example 1 from 3-bromobenzaldehyde ethylene ketal but omitting hydrolysis with 3N HCI) in dichloromethane (70 ml) at --780 is subjected to a stream of ozone until a slight excess has been introduced (15 minutes). Whilst still cold acetic acid (15 ml), water (1.5 ml) and zinc (10 g) are added to the mixture which is allowed to warm to -5"C. After filtering through Celite (Registered Trade Mark), the mixture is diluted with water, extracted with dichloromethane, and the extract washed (saturated sodium bicarbonate) and dried.Distillation gives the product (1.6 g), bp 58-65 /0.1 mm.Hg, n20 15304.
B. 3(3-Difluoroallyl)benzaldehyde ethylene ketal A solution of triphenylphosphine (6.0 g) in dimethyl acetamide (10 ml) is added under nitrogen to a stirred mixture of dibromodifluoromethane (4.8 g), and the aldehyde from A (1.5 g) in dimethylacetamide (15 ml) at 0 during 15 minutes. After 30 minutes at 20 , zinc dust (0.5 g) is added in small portions, and the mixture is then warmed to 100" for 1 hour. After cooling the mixture is filtered, shaken with water and extracted three times with ether. The extract material is chromatographed on Florisil (Registered Trade Mark) to yield the product (0.9 g), n20, 1.5172, after a fraction consisting predominantly of triphenylphosphine.
C. 3(3-Fluoroallyl)benzaldehyde The difluroroketal (0.5 g) from B and sodium dihydro-bis(2-methoxyethyoxy)aluminate (1 g of a 70% solution in toluene) in toluene (10 ml) are heated to 110 for 7 hours, then cooled. The reaction mixture is stirred with 3N HCI (30 ml) at 20 for 2 hours, then the organic layer (combined wth an ether extract of the aqueous layer) is washed, dried and evaporated to yield the product (0.32 g), n20 1.5440, shown by 'H NMR to be a mixture of E and Z isomers. TABLE I Aldehydes of formula IIE
Configura Ex. Position tion in yield refractive of (A)n of of side side chain X (%) index (D20) (nD chain 3 H 4 E Cl 8 1.5671 5 H 3 E C1 7 1.5660 6 2,6-dimethyl 4 Z Cl 11 1.5663 6A H 3 E Br 4 1.5866 6B H 3 Z Br 2 1.5820 6C H 4 E(80%) Br 3 1.5861 + 6D H 4 Z(90%) Br 7 1.5830 + 6E H 3 E + Z F 36 1.5440 EXAMPLES 7 TO 10 Alcohols of formula lIE are prepared by following the method described in Example 2, the yield and refractive index given in Table II.
TABLE II Alcohols of formula IIE (D = H)
Configura Ex. Position tion in yield refractive 20 No. (A)n of side side chain X (%) index (nD20 chain 7 H 4 E C1 93 1.5567 8 - H 3 Z C1 98 1.5561 9 H 3 E C1 96 1.5578 10 2,6-dimethy 4 Z C1 75 1.5584 lOA H 3 E Br 95 1.5767 10B H 3 Z Br 82 1.5738 lOC H 4 E(80%) Br 100 1.5709 + 10D H 4 Z(90%) Br 100 1.5729 + 10E H 3 E+Z(ca.5.1) F 70 1 1.5316 EXAMPLE ii 4-(Z-3-chloroallyl)benzaldehyde cyanohydrin The aldehyde of Example 1 (0.3 g) and potassium cyanide (0.5 9) in water (1.4 ml) and THF (5 ml) are treated with 40% sulphuric acid (1.5 ml) with cooling to 3 to 8 . After 1 hour at 20 , water is added and the reaction mixture is extracted with ether. The extracts are washed with water and saturated NaCI, dried over MgSO4 and then evaporated to a residue of alpha-cyano-4 (Z-3-chloroallyl)benzyl alcohol (0.33 g, 96%) n200 1.5549.
EXAMPLES 12 TO 14 Cyanohydrins of formula IIE are prepared by following the method described in Example 11, the yield and refractive index being given in Table Ill.
TABLE III
Configura Ex. Position tion in yield refractive No. (A) D of side side chain X (%) index (n20) n - D chain 12 H CN 4 E C1 98 1.5505 13 H CN 3 Z Cl 98 1.5454 14 H CN 3 E C1 78 1.5408

Claims (12)

1. A compound of formula IIE
wherein M represents a group of formula -CHO or a group of formula
wherein Y represents a hydroxyl group or halogen, D represents hydrogen or, when Y represents OH, D can also represent a cyano group, A represents an alkyl group, n is O to 4 and X represents a halogen.
2. A compound according to claim 1 wherein M represents a group of formula -CHO or a group of formula
wherein D represents hydrogen, X represents bromine, chlorine or fluorine and the configuration of hydrogen about the double bond in the substituent -CH2CH=CHX is Z, the substituent being disposed at the four position with respect to the group M.
3. A compound according to claim 1 or claim 2 wherein A represents a C,-C6 alkyl group.
4. A compound according to any one of claims 1 to 3 wherein M represents a group -CHO.
5. A compound according to any one of claims 1 to 3 wherein M represents a group of formula
6. A compound according to claim 1 hereinbefore specifically mentioned.
7. A process for the preparation of a compound according to claim 1 wherein M represents a group of formula
wherein Y represents a hydroxyl group and D represents hydrogen which comprises reducing a compound according to claim 1 wherein M represents a group of formula -CHO.
8. A process for the preparation of a compound according to claim 1 wherein M represents a group of formula
wherein Y represents a hydroxyl group and D represents a cyano group which comprises treating a compound according to claim 1 wherein Y represents a group of formula -CHO with an alkali metal cyanide.
9. A process for the preparation of a compound according to claim 1 wherein M represents a group of formula
wherein Y represents a halogen and D represents hydrogen which comprises treating a corresponding compound according to claim 1 wherein Y represents a hydroxyl group with a halogenating reagent of the class employed for conversion of carboxylic acids to acid halides.
10. A process for the preparation of a compound according to claim 1 wherein M represents a group of formula -CHO which comprises reacting a gripnard reagent of formula II B
wherein A and n are as defined in claim 1, P represents bromine or iodine and K represents a ketal group, with a complex formed between a compound Q-CH2-CH=CH-X wherein Q represents bromine or chlorine and, respectively, cuprous bromide or a mixture of lithium and cuprous chlorides, followed by treating the reaction mixture with mild aqueous acid.
11. A process for the preparation of a compound according to claim 1 wherein M represents a group of formula -CHO which comprises reacting a compound of formula II C
wherein A, X and n are as defined in claim 1 and K is as defined in claim 10 with a selective hybride reducing agent followed by hydrolysis of the ketal group.
12. A process according to any one of claims 7 to 11 substantially as herein described with reference to any one of the Examples.
GB08516680A 1982-05-25 1985-07-02 Intermediates useful in the preparation of pesticides containing a haloallylbenzyl group Expired GB2168697B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0255236A2 (en) * 1986-06-30 1988-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
US5082587A (en) * 1988-09-23 1992-01-21 Janulis Eugene P Achiral fluorine-containing liquid crystals

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0255236A2 (en) * 1986-06-30 1988-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
EP0255236A3 (en) * 1986-06-30 1990-05-09 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
US5082587A (en) * 1988-09-23 1992-01-21 Janulis Eugene P Achiral fluorine-containing liquid crystals

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GB8516680D0 (en) 1985-08-07
GB2168697B (en) 1986-11-26

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