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GB1591960A - Phenyl alkanoic acid esters and insecticidal and acaricidal uses thereof - Google Patents

Phenyl alkanoic acid esters and insecticidal and acaricidal uses thereof Download PDF

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GB1591960A
GB1591960A GB1807978A GB1807978A GB1591960A GB 1591960 A GB1591960 A GB 1591960A GB 1807978 A GB1807978 A GB 1807978A GB 1807978 A GB1807978 A GB 1807978A GB 1591960 A GB1591960 A GB 1591960A
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isopropyl
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Wyeth Holdings LLC
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American Cyanamid Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • A—HUMAN NECESSITIES
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    • 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
    • A01N37/38—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 having at least one oxygen or sulfur atom attached to an aromatic ring system
    • 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
    • A01N37/44—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/48—Nitro-carboxylic acids; 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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    • C07C41/01—Preparation of ethers
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    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Description

(54) PHENYL ALKANOIC ACID ESTERS AND INSECTICIDAL AND ACARICIDAL USES THEREOF (71) We, AMERICAN CYANAMID COMPANY, a corporation organised and existing under the laws of the State of Maine, United States of America, of Berden Avenue, Township of Wayne, New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to novel derivatives of phenylalkanoic acids, and to the use of the novel compounds as insecticides or acaricides. The invention is a modification of that forming the subject of our co-pending Application No. 40043/77 (Serial No.
1582775).
The compounds of this invention are m-phenoxybenzoyl esters of 2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl-)phenyl-alkanoic acids represented by the formula:
wherein RCF2X-, Y and Z, are all meta or para to the carbon to which the alkanoic acid ester group is attached, and X is O, S, SO or SO,; Y and Z are each H, Cl, F, Br, NO2, CH3 or OCH,; R is H, F, Cl, CHF2 or CF2; R2 is ethyl, n-propyl, isopropyl, isopropenyl or t-butyl; R, is H CN or -C-CH, and Rz is H, F, Cl, CH2 or OCH,, provided that at least one of Z, Y and R4 must be other than hydrogen.
The invention includes the optical isomers embraced by formula I.
As will be described in greater detail hereafter, the compounds of the present invention are useful insecticidal and acaricidal agents. Thus, the present invention, in another of its aspects provides a method for controlling insects and acarina, comprising contacting the insects and acarina, their habitat, breeding grounds of feed, with an insecticidally or acaricidally effective amount of a compound of formula (I). The invention further provides a method for the systemic control of insects and acarina that feed on the body fluids of livestock and domestic animals, comprising orally or parenterally administering to the animal host a systemically effective amount of a compound of Formula I.
A preferred class of compounds of this invention are those in which X is O or S, and within this class are particularly preferred compounds of the formula:
wherein R is H or F; R2 is ethyl, n-propyl or isopropyl, more especially isopropyl; R3 is as defined above but more especially CN; and R4 is F, Cl, CH3 or OCH3, preferably F. Compounds of formula II wherein X is O are especially preferred.
Preparation of the mono and disubstituted haloalkyl (oxy-, thio-, sulfinyl-, and sulfonyl-)phenylalkanoic acid-m-phenoxybenzyl esters, ru-ethyl-m-phenoxybenzyl esters or the cu-cyano-m-phenox-ybenzoyl esters of the invention is illustrated in the following flow diagram and examples. Various optical isomers of the compounds of the invention result from the preparations described.
FLOW DIAGRAM
where Z and Y are H, Br or Cl
where Z and Y are H, Br or Cl
FLOW DIAGRAM continued
FLOW DIAGRAMS continued
FLOW DIAGRAM continued
FLOW DIAGRAM continued
RCF2X;3CHCOOH+SOCl2 ene RC FXA COCI + hO-CH $ Pyridine Y 2 R3 Benzene RCF2XCH-CO--O-CH- 9R! ZYPI2 I P3 The invention is illustrated by the Examples which follow.
EXAMPLE 1.
Preparation of α-Isopropyl-4-trifluoromethoxyphenylacetyl chloride.
A solution of α-isopropyl-4-trifluoromethoxyphenylacetic acid (1.2 g) and thionyl chloride (0.6 ml) in benzene (5 ml) is refluxed for 4 hours. Evaporation of the solvent and excess thionyl chloride gives the acid chloride which is used as such for esterification in Examples 2 and 3.
EXAMPLE 2.
Preparation of α-Cyano-m-phenoxybenzyl α-isopropyl-4-trifluoromethoxyphenylacetate.
A solution of α-isopropyl-4-trifluoromethoxyphenylacetyl chloride (4.58 mmol) in ether (5 ml) is added to an ether (20 ml) solution of a-cyano-m-phenoxybenzyl alcohol (4.58 mmol) and pyridine (0.5 ml). The mixture is stirred overnight and filtered. The filtrate and the washings are evaporated and the residual oil is purified on 5 X 2 mm silica gel plates using 1:1 methylenechloride-hexane as eluent. The band with Rf = 0.55 is extracted with ether and evaporated to give the desired ester (0.85 g).
IR (neat) 1755 cm-3; nmr (CDC1S) 8 6.8-7.6 (m, 13H, ArH), 6.31 and 6.28
3.27 [d, J = 7Hz, 1H, CH-CH(CH:)-i, 2.0-2.6 [m, 1H, CH(CH52], 0.6-1.2 (four doublets, J = 7Hz, 6H, isopropyl CH3); 19F chemical shift 58.8 8 relative to CECI1,.
EXAMPLE 3.
Preparation of m-Phenoxybenzyl α-isopropyl-4-trifluoromethoxyphenylacetate.
To a solution of m-phenoxybenzyl alcohol (1.89 g) and pyridine (1 ml) in methylene chloride (6 ml) is added a methylene chloride (7 ml) solution of α-isopropyl- 4-trifluoromethoxyphenylacetyl chloride, prepared from the corresponding acid (2.46 g) as illustrated in Example 1. After stirring the reaction mixture overnight, it is washed with water, dilute hydrochloric acid solution, dilute potassium hydroxide solution, water and evaporated to an orange oil. Purification by silica gel chromatography gives the desired ester (2.76 g).
IR (neat) 1738 cm-1; nmr (CDCl,) 8 6.73-7.45 (m, 13H), 5.03 (S, 2H), 3.20 (d, J = 10.5Hz, 1H), 2.26 (m, 1H), 0.66 and 0.94 (two d, J = 6.6Hz, 6H).
EXAMPLE 4.
Preparation of a-Isopropyl-4-hydroxyphenylacetic acid.
A mixture of Icu-isopropyl-4-methoxyphenvlacetonitril (40.0 g) and hydrobromic acid (48%, 200 ml) is refluxed at 12d1280C. using an oil bath for 14 hours. The reaction mixture is diluted with ice and water, extracted several times with ether, washed with water and evaporated to a solid residue. The solid is boiled with chloroform (200 ml) cooled, filtered and dried; yield, 23.8 g; melting point 172-1740C; ir (Nuiol) 3250-2900 (broad, OH), 1690 cm-' (C=O).
Comparable results are obtained substituting α-ethyl-4-methoxyphenylacetonitrile or α-n-propyl-4-methoxyphenylacetonitrile to synthezise α-ethyl-4-hydroxyphenyl)- acetic acid and α-n-propyl-4-hydroxyphenylacetic acid, respectively.
EXAMPLE 5.
Preparation of α-Isopropyl-4-difluoromethoxyphenyl acetic acid.
Into an 800C. magnetically stirred mixture of 10.00 g (0.515 mol) of a-isopropyl- 4-hvdroxyphenvlacetic acid, 65 ml of dioxane. 19.08 g (18.56 g real, 0.464 mol) of sodium hydroxide, and 30 ml of water is bubbled 46 g (0.532 mol) of cblorodifluoromethane over a period of 4 hours. The reaction mixture is poured into 250 ml of ice water and the resulting mixture is washed with ether, acidified with concentrated hydrochloric acid to pH 3, and then extracted with 200 ml of ether. The ether solution is washed once with 100 ml of water, dried with sodium sulfate, filtered, and then evaporated to give a white paste. A mixture of hexane and methylene chloride is added and the resulting mixture is filtered to remove the solid which is the starting material. The filtrate is evaporated to give 5.41 g of a clear brown oil. It is estimated that the product was at least 85% pure by nmr. NMR (CDCl3-d5 pyridine), # 7.43 (d, J = 8.2Hz, 2H) # 7.08 (d, J = 8.2Hz, 2H), # 6.57 (t, J = 74.3Hz, 1H), s 3.63 (s, imp.), # 3.25 (d, J = 10 Hz, 1H)* # 2.37 (m, 1H), # 1.19 (d, J = 6.5Hz, 3H), ,8 0.78 (d, J = 6.5Hz 3H), # 13.82 (s, 1H).
Comparable results are obtained substituting a-ethyl-4-hydroxyphenylacetic acid or -n-propyl-4-hydroxyphenylacetic acid to synthesize a-ethyl-4-difluoromethoxy- phenylacetic acid and a-n-propyl-4-difluoromethoxyphenylacetic acid, respectively.
EXAMPLE 6.
Preparation of α-Isopropyl-3-bromo-4-hydroxyphenylacetic acid.
A mixture of α-isopropyl-4-hydroxyphenylacetic acid (20 g, 0.103 mol) in chloroform (250 ml) is cooled to 0 C and bromine (16. 5g, 0.103 mol) in chloroform (15 ml) is added over 30 minutes. The reaction solution is stirred at 0 C for 30 minutes and then allowed to warm to room temperature. The solvent is evaporated and the residue is crystallized from hexanes-benzene to give the monobromo derivative (22.1 g); melting point 1130C to 1160C.
EXAMPLE 7.
Preparation of α-Isopropyl-3-bromo-4-difluomethoxyphenylacetic acid.
Using the procedure described in Example 5, α-isopropyl-3-bromo-4-hydroxy- phenylacetic acid (18.0 g) is converted to the corresponding difluoromethoxy acid.
The desired acid is obtained by separation of the unreacted starting material by chromatography on silica gel using 2.5% methanol in chloroform as eluent as a waxy solid (4.7 g). This crude acid is used as such in Example 8 and 9.
EXAMPLE 8.
Preparation of m-Phenoxybenzyl a-isopropyl-3-bromo-4-difluoromethoxyphenylacetate.
By using a-isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid and procedures of Examples 1 and 3, the product is obtained as a pale yellow gum. NMR (CDCls), # 6.8-7.7 (m, 12H, ArH), 6.45 (t, J=74Hz, 1H, OCHF2), 5.10 (bs, 1H, CH2) 3.18 (d, J=9Hz, 1H, CH-CH(CH,)2), 1.0 and 0.71 (2d, J=6Hz, 6H, isopropyl EXAMPLE 9.
Preparation of -Cyano-m-phenoxybenzyl α-isopropyl-3-bromo-4- difluoromethoxyphenylacetate.
By using α-isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid and procedures of Examples 1 and 2, the product is obtained as a yellow gum. NMR (CDCl3) # 6.97.7 (m, 12H, ARH), 6.50 (t, J=74Hz, 1H, 0OCHF2, 6.33 and 6.36 (2S, 1H, CH-CN), 3.25 (d, 1H, CH-CH(CH3), 0.6-1.1 (4d, 6H, isopropyl CH3).
EXAMPLE 10.
Preparation of α-Isopropyl-3-chloro-4-hydroxyphenylacetic acid.
A mixture of a-isopropyl-4-hydroxyphenylacetic acid (30 g, 0.154 mol) in chloroform (600 ml) is cooled to 0 to 50 C. and chlorine gas (12.0 g, 0.169 mol) is bubbled slowly. The solvent is removed and the product is obtained by crystallization from benzene-hexanes m.p. 125-1280C.
EXAMPLE 11.
Preparation of a-cyano-m-phenoxybenzyl a-isopropyl-3-chloro-4- difluoromethoxyphenylacetate.
By using α-isopropyl-3-chloro-4-hydroxyphenylacetic acid und procedures of Examples 5, 1, and 2, the product is obtained as a gum. NMR (CDCl,) # 6.8 to 7.5 (m, 12H, ArH), 6.50 (t, J=74Hz, 1H, OCHF2), 6.33 and 6.30 (2S, 1H, -CH-CN), 3.25 (d, J=1OHz, 1H, CH-CH(CH,)2).
Analysis calculated for C26H22ClF2NO4: C 64.26; H 4.56; N 2.88; Cl 7.30; F 7.82; Found: C 64.27; H 4.70; N 2.94; Cl 7.20; F 7.78.
EXAMPLE 12.
Preparation of m-Phenoxybenzyl α-isopropyl-3-chloro-4-difluoromethoxy- phenylacetate.
By using a-isopropyl-3-chloro-4-hydroxyphenylacetic acid and procedures of Examples 5, 1 and 3, the product is obtained as a yellow oil. NMR (CDC12) # 6.8 to 7.6 (m, 12H, ArH), 6.47 (t, J=74Hz, OCHF2), 5.07 (bs. 2H, CH2).
Analysis calculated for C25H23ClF204: C 65.15; H 5.03; Cl 7.69; F 8.24 Found: C 65.46; H, 5.05; Cl 7.73; F 8.08.
Eample 13.
Preparation of α-Isopropyl-3,5-dichloro-4-hydroxyphenylacetic acid.
A mixture of α-isopropyl-4-hydroxyphenylacetic acid (30 g, 0.155 mol) in chloroform (500 ml) is chilled in ice-salt bath and chlorine gas (ca 30-35 g) is bubbled at 0 to 5 C. for 90 minutes. The solution is stirred at 0 to 5 C. for an additional hour and allowed to warm to room temperature. The solvent is evaporated and the product is obtained by crystallization from hexanes as a white solid (29.8 g); m.p. 152-154 C.
EXAMPLE 14.
Preparation of α-Isopropyl-3,5-dichloro-4-difluoromethoxyphenylacetic acid.
By using α-isopropyl-3,5-dichloro-4-hydroxyphenylacetic acid and procedure of Example 5, the above acid is obtained as an oil. The nmr of the product indicates that it contains 15 mole percent (approx.) of the starting material, and is used as such in Example 15.
EXAMPLE 15.
Preparation of n-Cyano-m-phenoxybenzyl a-isopropyl-3,5-dichloro-4 difluoromethoxyphenylacetate.
By using α-isopropyl-3,5-dichloro-4-difluoromethoxyphenylacetic acid and proce dures of Examples 1 and 2, the product is obtained as a yellow gum, NMR (CDCl3) # 6.9-7.7 (m, 11GH, ArH), 6.67 (t, J=74Hz, 1H, OCHF2), 6.33 and 6.40 (2S, 1H, CH-CN), 3.23 (d, J=10Hz, 1H, CH-CH(CH3)2, 0.6 to 1.1 (d, 6H, isopropyl CH3).
Analysis calculated for C22H22Cl2F2NO4: C 60.01; H 4.07; N 2.69; Found: C 59.78; H 4.30; N 2.31.
EXAMPLE 16.
Preparation of m-Phenoxybenzyl α-isopropyl-3,5-dichloro-4-difluoromethoxy- phenylacetate.
By using α-isopropyl-3,5-dichloro-4-difluoromethoxyphenylacetic acid and procedures of Examples 1 and 3, the product is obtained as a gum.
Analysis calculated for C9 H22CloF204: C 60.61; H 4.48; Cl 14.32; F 7.67; Found: C 60.50; H 4.60; Cl 14.13; F 7.52.
EXAMPLE 17.
Preparation of α-Isopropyl-3-methyl-4-difluoromethoxyphenylacetic acid.
3-Methyl-4-methoxyphenylacetonitrile is converted to the above compound using procedures of Examples 4 and 5. The product is contaminated with some α-isopropyl- 3-methyl-4-hydroxyphenylacetic acid as indicated by nmr. However, the material is used as such for esterification in Example 18 where the final ester is purified by chromatography.
EXAMPLE 18 Preparation of α-cyano-m-phenoxybenzyl α-isopropyl-3-methyl-4- difluoromethoxyphenylacetate.
Using the acid obtained in Example 17 and the procedures of Examples 1 and 2, the ester is obtained as a viscous oil. NMR (CDCl3) # 6.8-7.6 (m. 12H, ArH), 6.45 (t, J=7411z, 1H, OCHF2), 6.48 and 6.53 (2S, 1H, C11-CN), 2.25 (S, 3H, CR3).
Analysis calculated for C7,H?,sF2NO: C 69.66; H 5.41; N 3.01.
Found: C 70.05; H 5.86; N 2.83.
EXAMPLE 19.
Preparation of 3-Fluoro-4-methoxyphenylacetonitrile.
A mixture of 4-(bromomethyl)-2-fluoroanisole (45.8 g, 0.21 mol), trihexylamine (1.4 g) and sodium cyanide '20.5 g, 0.42 mol) in water (50 ml) is heated at 60650C for 18 hours. The mixture is cooled and extracted in its ether, washed with water, saturated sodium chloride solution and dried (Na,SO4). Evaporation of the solvent gives a solid, (33.2g): m.p. 4246"C.
EXAMPLE 20.
Preparation of fr-Isopropyl-3-fluoro-4-methoxyphenylacetonitrile.
A mixture of 3-fluoro-4-methoxyphenylacetonitrile (30 g, 0.18 mol), 2-bromopropane (27.7 g, 0.225 mol), benzyltriethylammonium chloride (2.3 g, 0.01 mol) and sodium hydroxyde solution (50%, 66 ml) is heated at 55 for 1 hour and cooled.
The mixture is diluted with water, extracted with ether, washed with water, 1NHCl, water and dried (Na2SO4). Evaporation gives the product as a brown oil (30.7 g).
NMR spectmm shows the benxylic proton as a doublet at 3.6 .
EXAMPLE 21.
Preparation of α-Isopropyl-3-fluoro-4-difluoromethoxyphenylacetic acid.
Starting with α-isopropyl-3-fluoro-4-methoxyphenylacetonitrile and following the procedures of Examples 4 and 5, the product is obtained as a brown oil. NMR snectrum shows that the product is contaminated with the starting material. Hence this crude reaction mixture is subjected to the chlorodifluoromethane reaction two more times as described in Example 5 to give the nroduct as a brown oil. NMR spectrum indicates that the product is approximately 96% by weight.
EXAMPLE 22.
Preparation of a-cyano-m-phenoxybenzvl a-isopropyl-3-fluoro-4-difluoro- methoxyphenylacetate.
Starting with α-isopropyl-3-fluoro-4-difluoromethoxyphenylacetic acid and follow ing the nrocediires of Examples 1 and 2. the final ester is nrepared as vellow oil.
NMR (CDCl) # 6.8 to 7.5 (m, 12H, ArH), 6.63 (t, J= 74Hz, 1H, OCHF2), 6.33 and 6.37 (2S, 1H, CH-CN).
Analysis calculated for C2GH22F3NO.: C 66.52; H4.72; N 2.98; Found: C 66.27; H 4.87; N 2.99.
EXAMPLE 23.
Preparation of α-Isopropyl-3-nitro-4-hydroxyphenylacetic acid.
A mixture of α-isopropyl-4-hydroxyphenylacetic acid (18.2 g, 0.094 mol) in acetic acid (130 ml) is heated to 40 C and nitric acid (70%, 9.56 g, 0.095 mol) is added at such a rate that the reaction temperature is maintained at 3840 and never exceeded 45 C. The reaction mixture is stirred at 40 -42 C overnight and poured into ice-water. The yellow solid is collected by filtration, washed and dried (19.1 g); m.p. 103105O.
EXAMPLE 24.
Preparation of α-Isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid.
Using α-isopropyl-3-nitro-4-hydroxyphenylacetic acid and procedure of Example 5, the above is prepared as a crude material containing unreacted starting material. However, repeating of the Freon 22 reaction as described in Example 5 three times using the crude product obtained after each cycle, the product is finally obtained as a fine beige solid (hexanes): m.p. 88-90 .
EXAMPLE 25.
Preparation of a-Cyano-m-phenoxybenzyl a-isopropyl-3-nitro-4-difluoro- methoxyphenylacetate.
Using α-isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid and procedures of Examples 1 and 2, the product is obtained as a yellow oil.
Analysis calculated for C2^H22F2N20: C 62.90; H 4.47; N 5.64; Found: C 62.51; H 4.77; N 5.58.
EXAMPLE 26.
Preparation of fr-Cyano-m-phenoxybenzyl a-isopropyl-3-methoxy-4-difluoro methoxyphenylacetate.
Using a-isopropyl-3-methoxy-4-difluoromethoxyphenylacetic acid and procedures of Examples 1 and 2, the product can be prepared as a gum.
EXAMPLE 27.
Preparation of m-(m-Flouorophenoxy)benzaldehyde.
The sodium salt of 3-fluorophenol is prepared by mixing 3-fluorophenol (15.13 g, 0.135 mol) and sodium methoxide (7.29 g, 0.135 mol) in pyridine (115 ml). The reaction is heated to 1100C during which 34 ml of pyridine-methanol is distilled off.
The reaction is cooled to 800C and m-bromobenzaldehyde (25.0 g, 0.135 mol) and copper (I) chloride (4.05 g, 0.049 mol) are added. The reaction mixture is refluxed overnight. The following day, most of the pyridine is removed by distillation and the reaction is cooled and diluted into toluene (80 ml). The solids are filtered and the filtrate is washed with 20% HCI, water, 5% NaOH, and water, respectively and evaporated to a dark brown oil. Vacuum Distillation gives the product as a clear liquid (6.6 g): b.p 82-88 C (0.5 mm).
Analysis calculated for C13H9FO2; C 72.22; H 4.20; F 8.79; Pound: C 72.03; H 4.30; F 8.60.
EXAMPLE 28.
Preparation of substituted α-Cyano-m-phenoxybenzyl esters of fluoroalkoxyphenylacetic acids.
Starting with either α-isopropyl-4-difluoromethoxyphenylacetic acid or α-isopropyl- 4-trifluoromethoxyphenylacetic acid and the cyanohydrin of an appropriately substituted aldetyde, and using procedures of Examples 1 and 2, the following esters are prepared:
Analysis Analysis R R4 NMR Assignments Calculated found 6.8 to 7.5 (m, 12H, ArH), C 66.51 C 66.48 H p-F 6.47 (t, J=74Hz, 1H, OCHF2), H 4.73 H 4.95 6.30, 6.36 (2S, 1H, -CH-CN), N 2.98 N 2.64 6.8 to 7.5 (m, 12H, ArH) C 64.06 C 63.85 F p-F 6.32, 6.37 (2S, 1H, -CH-CN), H 4.35 H 4.31 3.30 (d, J-1OHz, 1H, CH-CH(CH3)2) N 2.87 N 2.63 6.8 to 7.4 (m, 12H, ArH), C 66.52 C 66.68 6.43 (t, J=74Hz, 1H, OCHF2), H 4.72 H 4.80 H O-F 6.30 and 6.34 (2S, 1H, -CH-CN), N 2.98 N 3.04 3.27 (d, J-lOHz, 1H, CH-CH(CH,)2) F 12.14 F 12.05 6.5 to 7.5 (m, 12H, ArH), C 66.52 C 66.80 6.33 and 6.39 (2S, 1H, -CH-CN), H 4.72 H 4.77 H m-F 6.47 (t, J-74Hz, 1H, OCHFi), N 2.98 N 2.89 3.28 (d, J-1OHz, IH, CH-CH(CH3)2) F 12.14 F 11.93 # # 6.8 to 7.5 (m, 12H, ArH), C 64.27 C 64.54 6.45 (t, J-74Hz, 1H, OCHF2), H 4.56 H 4.92 H p-Cl 6.30, 6.33 (2S, 1H, CH-CN), N 2.88 N 2.82 3.25 (d, J-1OHz, 1H, CH-CH(CH,)2), 0.6 to 1.2 (d, 6H, isopropyl CH3) 6.8 to 7.4 (m, 12H, ArH) C 67.35 C 67.30 6.47 (t, J-74Hz, 1H, OCHF2), H 5.23 H 5.46 H p-OCH3 6.28, 6.33 (2S, CN-CN), N 2.91 N 2.92 3.80 (S, 3H, OCH3) 6.8 to 7.5 (m, 12H, ArH), C 69.67 C 69.37 6.50 (t, J=74Hz, 1H, OCHF2), H 5.41 H 5.72 H p-CH3 6.33, 6.37 (2S, 1H, CH-CN), N 3.01 N 2.82 2.40 (S, 3H, CH3) 6.8 to 7.5 (m, 12H, ArH), C 61.97 C 62.05 F p-Cl 6.37 and 6.41 (2S, 1H, -CHZ-CN), H 4.20 H 4.25 3.33 (d, J=10Hz, CH-CH(CH3)2), N 2.78 N 2.52 0.6 to 1.2 (4d, bH, isopropyl CH,)
Analysis Analysis R R4 NMR Assignments Calculated found 6.8 to 7.4 (m, 12H, ArH), C 67.07 C 65.28 F p-CH3 6.37 and 6.41 (2S, IH, -CH-CN) H 5.00 H 5.18 2.40 (S, 3H, CH3) N 2.90 N 2.26 6.9 to 7.5 (m, 12H, ArH), C 64.92 C 64.04 F p-OCH3 6.25 and 6.30 (2S, 1H, CH-CN), H 4.84 H 4.87 3.63 (S, 3H, OCH,) N 2.80 N 2.65 EXAMPLE 29.
Preparation of a-Ethynyl-m-phenoxybenzyl alcohol.
Acetvlene is dried through three traps, dry-ice acetone, conc. sulfuric acid and calcium chloride. and bubbled at about 5 psi pressure into drv THF (100 ml) for 10 minutes. Ethyl magnesium bromide (commercial, 0.14 mol) is added drop after drop over 2 hours at such a rate that the evolution of ethane is slow and steady.
After the addition. acetvlene is bubbled through for 15 minutes. m-Phenoxybenzaldebvde (27.7 g, 0.14 mol) in the THF (25 ml) is added to the reaction of 15 to 200C. The reaction is allowed to raise to room temperature and stirred overnight.
The complex is decomposed with saturated ammonium chloride solution. The product is extracted with ether, washed with water and dried (Na > SO.). Evaporation of the solvents, followed by vacuum distillation, gives the alcohol (21.5 g).
EXAMPLE 30.
Preparation of a-Ethynyl-m-phenoxybenzyl α-isopropyl-4-trifluormethoxy- phenylacetate.
Using the above alcohol in Example 29 and -isopropyl-4-trifluoromethoxyphenyl- acetic acid and following the procedures of Examples 1 and 3, the product is obtained as yellow gum. The NMR snectrum showed the characteristic alkynyl proton as a multiplat at 2.52 8 and benzylic protons at 6.35 #.
Analysis calculated for C,,H,,F,O,: C 69.22; H 4.95; Found: C 68.17; H 4.11.
By a similar procedure, using the alcohol in Example 29 and a-isopropyl-4difluoromethoxypbenylacetic acid, the a-ethynyl-m-phenexybenzyl a-isopropyl-4difluoromethoxyphenylacetate is prepared Analysis calculated for C27H2,F20,: C 71.99; H 5.37; Found: C 71.59; H 5.53.
EXAMPLE 31.
Resolution of α-Isopropyl-4-difluoromethoxyphenylacetic acid.
A warm solution (600C) of (- )-2-phenylamine (4.96 g) in aqueous ethanol (60% ethanol, 20 ml) is added to a warm solution (60 C) of the racemic acid (20 g) in aqueous ethanol (60% ethanol, 50 ml with magnetic stirring. As the solution is allowed to cool slowly to room temperature, the salt precipitates out as white crystalline solid. The mixture is allowed to stand overnight and the solids are collected filtration, washed with aqueous ethanol (10 ml) and dried (9.5 g): m.p. 184-188
EXAMPLE 32.
Preparation of ( + ) -Cyano-rn-phenoxybenzyl ( # ) a-isoprupyl-4- difluoromethoxyphenylacetate.
The resolved (i)-acid obtained in the above example is converted to the ester using the procedures of Examples 1 and 2. ND23=1.5432; NMR (CDCla) ss 6.8 to 7.5 (m, 13H, ArH), 6.43 (t, J=7Hz, 1H, OCHF2), 6.30 and 6.23 (2S, 1H, CH-CN), 3.27 (d, J=1OJz, 1H, CH-CH(CH3)2).
EXAMPLE 33.
Resolution of α-Isopropyl-4-trifluoromethoxyphenylacetix acid.
A mixture of the racemic acid (26.2 g) and (-)-α-phenethylamine (12.1 g) in aqueous ethanol (60% ethanol, 2 1) is heated to dissolution on a steam bath and allowed to cool slowly to room temperature. The salt is collected by filtration and dried (16.9 g): m.p. 189--193". The salt is crystallized twice from aqueous ethanol (60 /C ethanol, 1 1 and 600 ml respectively): m.p. 194-196 (8.0 g). The (+)acid is obtained by neutralization of the salt with dilute hydrochloric acid and extraction with ether and evaporation of the solvent: [α]DR.T.=+35.5 (CHCl3., C=6.0 g/100 ml).
EXAMPLE 34.
Preparation of (-1-) -Cyano-m-phenoxybenzyl (+ ) -a-isopropyl-4- trifluoromethoxyphenylacetate.
By using the (+ )-α-isopropyl-4-trifluoromethoxyphenylacetic acid and procedures of Examples 1 and 2, the product is obtained as pale yellew oil: [er]DR T=6.1 (CIICIl,, C=5 g/100 ml).
Compounds of the invention are highly effective as contact and stomach poisons for osidide ticks and for a wide variety of insects, particularly Dipterous, Lepidop terous, Coleopterous and Homopterous insects. They are unusual among pyrethroids, in that they exhibit a very extended residual insecticidal activity on plant tissue, they are effective in the soil, and are surprisingly effective for the control of ixodidae and the protection of animals against attack by insects and ixodidae when administered to the animals orally or parenterally or applied thereto as a topical or acarididal formulation. They do not require admixture with a stabilizing agent to achieve insecticidal and acaricidal comnositians having stabilized effects; however, they may be used in combination with other biological chemicals; for example, pyrethroid synergists such as piperonyl butoxide, sesamex or n-octyl sulfoxide of isosafrole. They may also be used in combination with conventional insecticides such as the phosphates, carbamates, formamidines, chlorinated hydrocarbons or halohenzoylureas. To achieve control of insects and/or harvested crops, including stored grain, the insecticidal compounds of this invention may be applied to the foliage of plants the insect's habitat and/or the insect's food supply. Generally, the active compound is applied in the form of a dilute liquid spray; however, it may also be applied as an aerosol, a dust, a granular, or a wettable powder formulation.
Liquid sprays which are particularly useful are oil sprays and emulsifiable concentrates which can be further diluted for application. While they are, respectively, prepared as liquid concentrates; for convenience in handling and shipping, these formulations are usually disnersed in water at the site of their use and then applied as a dilute spray to the plant foliage, soil or surface of the area being treated.
A typical emulsifiable concentrate useful for Drotecting a variety of crops, such as cereals, cole crons, cucurbits. corn. cotton, tobacco, soybeans, ornamentals and shrubs, may comprise about 20% by weight of the active agent: 4% bv weieht of an emulsifying agent, conventionally employed in the preparation of pyrethroid formulations; 4% by weight of a surfactant; 25% by weight of an organic solvent such as cyclohexanone; and about 47% by weight of a petroleum solvent having a minimum aromatic content of about 83 volume %.
For use as animal systemic insecticidal anl acaricidal agents, the compounds of this invention can be acaricidal agents, the compounds of this invention can be adminis tered to the animal host either orally or parenterally. When given orally, it may be in any convenient form designed for oral administration such as a bolus, capsule, tablet or as an oral drench. The active agent may also be incorporated in an edible animal feedstuff such as a nutritionally balanced diet containing from 0.0001% to 0.1%, and preferably 0.001% to 0.05% by weight of feed of the active compound.
If desired, the systemic insecticidal and acaricidal agent may be introduced into the body of the animal by subcutaneous, intramuscular or intraperitoneal injection, such that it may be distributed through the animal's body by the action of the animal's circulatory system. In practice, the systemic agent may be dissolved or dispersed in a pharmaceutically acceptable carrier, such as water, propylene glycol, vegetable oil or glycerol formal, for administration.
Advantageously, the systemic agents have a good margin of safety and are effective for protecting a variety of animals, particularly livestock and domestic animals, such as cattle, sheep, horses, dogs and cats from attack by e.g. fleas, mosquitoes, flies and ticks.
EXAMPLE 35.
Insecticidal Activity.
The insecticidal activity of compounds of this invention is demonstrated in the following tests, wherein Tobacco budworm, Heliothis virescens (Fabricius) Western Potato Leafhopper, Empoasca abrupta (DeLong) and Bean Aphid, Aphis fable (Scopoli), are employed as test insect species. Procedures employed are as follows: Tobacco Budworm, Heliothis virescens (Fabricus).
First Instar.
A cotton plant with two true leaves expanded is dipped for 3 seconds with agitation in a test solution (35% water/65% acetone) containing 300, 100 or 10 ppm of test compound. Each leaf is placed in a cup with a wick and a piece of cheesecloth infested with 50-100 newly hatched larvae is added before covering the cup with a lid. After 3 days at 800F, 50% r.h., the cups are examined and the kill of newly hatched larvae noted. Data obtained are reported as percent killed in Table I.
Bean Aphid, Aphis fabae (Scopoli).
Five cm fiber pots, each containing a nasturtium plant 2 inches high and infested with 100 to 150 aphids 2 days earlier are placed on a 4 rpm turntable and sprayed with a 35% water/65% acetone solution containing 100, 10, 1.0 and 0.1 ppm of test compound for two revolutions using a "DeVilbiss" (registered Trade Mark) Atomizer and 20 psi air pressure. The spray tip is held about 15 cm from the plants and the spray directed so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their sides on white enamel trays. Mortality estimates are made after one day at 700F., 50% r.h.
Data are reported as percent mortality determined at the rate indicated (Table I).
Western Potato Ieafhopper, Empoasca abr7dpta (DeLong).
A Sieva lima bean plant with the primarv leaf expanded to 3 to 4 inches is dipped into a 35% water/65% acetone solution containing 100, 10 or 1 ppm of test compound. The dipped plant is placed in the hood to dry and then a 2.5 cm piece of the tip cf one leaf is cut off and placed in a 40 inch petri dish with a moist filter paper in the bottom. From 3 to 10 second-instar nymphs are placed in the dish and the dish is then covered. Mortality counts are made after holding the thus-prepared dishes for 2 days at 80"F and 50% r.h. Data obtained are reported in Table 1. In these tests, permethrin is used as a standard or check.
TABLE I Insecticidal Evaluation
a O ~ ~~ O Tobacco Budworm ~ ~ Larvae o E 8 8 o o o o II o o o o o OP O 0 0 0 a > CO-CHO 100 100 0 100 90 0 100 100 75 o ()CH3 oE o o o o oa o o c o a *-I WE 100 100 W o E 100 100 70 m 0 O E - ---------------- cH3 o o o o Y > o-E 100 100 100 100 100 100 90 u g i5 ..
X X X X O a n 3 h 3 ;; a h tD b ÇD t 5 O ~ ~ 6 TABLE I- continued Insecticidal Evaluation
o I o o oa Budworm E 1st o Leafhopper Aphis ss 100 10 100 -------------- --------- a a 100 100 " 50 E - .~ U n o oo i c o E s o s o rcQ 100 100 s = 5b i3~b .- ~b ( g iS TABLE I - continued Insecticidal Evaluation
o o o o oa E o o o o < o E o o ~ o E o o 100 100 100 100 100 o CH(CH3)2 OCH3 a 7 CHClH{OiCl3lCHOF 100 100 100 100 60 G 100 0o O 0m a oE o 8 8 oa o o c3 c my 100 100 100 0 100 0 O o- & o Z o E o o o o HS Cl()CH2ffipD 100 CL 0E 100 50 H H0 100 100 0 Br X 9 Q X X X X A W~t B~t I N Bx i,3 B TABLE - continued Insecticidal Evaluation
% Mortality E m o o o Larvae ist Instar , 300 --------- ------------ 0.1 Compound ppm ppm ppm ppm pprn ppm ppm ppm ppm ppm cN ---- ~---- ---------- -------------- ------------- X I I s I o" o o o 100 o O 90 r ~ - ~ ~ ~ ~~~ se e " o cN E s o o E O ~ FtJ g E 8 s S * 9 W 100 80 P 100 W - 100 100 50 3 ( > 3 n & TABLE I - continued Insecticidal Evaluation
- -n Tobacco 0 =: 3a 100 10 HEG 100 10 1 0.1 a ci cl ~ rH E 100 100 100 100 ~ 100 100 100 cM oE o---- ------------ 3 O E ~ E o E o o ,) o E o ~ F o C o X C 5E a rN EXAMPLE 36.
Insecticidal Activity.
The insecticidal activity of compounds of the present invention is further demonstrated by the following tests.
The procedures employed for evaluation against mosquito larvae, Mexican Bean Beetles and Southern Armyworms are as follows: Malaria Mosquito, Anopheles quadrimaculatus (Say).
One milliliter of a 35% water/65% acetone solution containing 300 ppm of test compound is pipetted in a 400 ml beaker containing 250 ml of deionized water and stirred with the pipette, giving a concentration of 1.2 ppm. Aliquots of this solution are taken and further diluted to 0.4 to 0.04 and 0.004 ppm. A wax paper ring 0.6 cm wide to fit inside the beaker is floated on the surface of the test solution to keep the eggs from floating up the meniscus curve and drying out on the side of the glass.
A spoon made of screen is used to scoop up and transfer about 100 eggs (0-24 hours old) into the test beaker. After 2 days at 80 F., 50% r.h., observations of hatching are made. Percent mortality records are presented in Table II.
Mexican Bean Beetle, Epilachna varivestis (Mulsant).
Sieva lima bean plants (2 per pot) with primary leaves 7.5 to 10 cm long, are dipped in the 300, 100, 10 or 1 ppm test solution and set in the hood to dry. One leaf is removed from a plant and placed in a 10 cm petri dish containing a moist filter paper on the bottom and 10 last-instar larvae (13 days from hatching). The day after treatment, another leaf is removed from the plant and fed to the larvae after removing the remains of the original leaf. Two days after treatment, the third leaf is fed to the larvae, this usually being the last needed. The fourth leaf is used on the third day after treatment if the larvae have not finished feeding. The test is now set aside and held until adults have emerged, usually in about 9 days after treatment began. After emergence is complete, each disc is examined for dead larvae, pupae or adults; deformed pupae or adults; larvalpupal intermediates or pupal-adult intermediates; or any other interference with normal molting, transformation and emergence of pupae or adults.
Data obtained are reported in Table II.
Southern Armyworm, Spodoptera eridania (Cramer).
Methods: Sieva lima bean plants, with two expanded 7.5 to 10 cm primary leaves, are dipped three seconds with agitation in the treatment solutions and then set in a hood to dry.
After the leaves are dry they are excised and each excised leaf is placed in a 10 cm petri dish containing a piece of moist filter paper and 10 third-instar southern armyworm larvae approximately 1 cm long. The petri dishes are covered and placed in a holding room for 2 days at a temperature of 809F. and 50% relative humidity.
Mortality counts are made after 2 days. Results obtained are presented in Table II.
TABLE II Insecticidal Evaluation
/c I I Mosquito Larvae Southern Armyworm Mexican Bean Beetle 1.2 0.4 0.04 0.004 1000 100 10 300 100 10 1 O, a o 100 100 100 E 100 90 c 100 40 ~ o ; o E o o o o a ~ E O E O O c: 80 100 100 80 100 100 f a 3 50 8 8 > E E o e E O O NO 100 100 100 100 100 100 100 50 C f f f f 5 E D i,5 TABLE II - continued Insecticidal Evaluation
3 0 0 0 0 m" Larvae Southern Armyworm Mexican Bean o o s 0.4 0.04 0.004 1000 100 10 300 100 10 1 Compound ppm ppm ppm Oo o cl 2 ~ ~ o E o 50 100 100 c: 100 100 100 0 E oE o o o o + E3 G as 100 100 100 100 100 8 100 om ~I, a E 0lI1;;YtPOyȯ om 100 100 100 100 100 o 100 100 100 0 06 o I 9a II tG cH{;);O- > my[LO t 100 100 E o ~ vl E 8 b 4 X 4 o Ç X b t 5 bE bE 15- 14 .
TABLE II - continued Insecticidal Evaluation
-u E o o o ~ Mosquito Larvae Southern Armyworm Mexican Bean v 1.2 0.4 0.04 0.004 1000 100 10 300 100 10 1 X o ppm i oOo 8 oE o o F3 CBcH-cB-B-lHB a 100 100 . 100 100 , 100 100 50 ~ c o, g s o, a bk 100 ------ ----------- V: O v O o o' > 100 E 100 100 100 100 100 100 1 .H 8 8 1 2 ce,E ~ 100 o - 100 100 0 100 - - (BH3)2 X C X 9 b X X b r 6 Z b 5b 8 , TABLE II - continued Insecticidal Evaluation
I I I I Mosquito Larvae Southern Armyworm Mexican Bean Beetle 1.2 0.4 0.04 0.004 1000 100 10 300 100 10 1 I ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm o CU-a)-O-CUO 100 E o cH(cK)2 ~ < : 100 100 80 50 100 E 0 - - 8 o o o o s I o, I 8 80 100 100 E 100 100 70 100 o - Cl t E OoO o C " E ~~~.~~~~ s 100 - - - 100 90 0 < P 9 9 9 X b X b 5 r f 5 TABLE II - continued Insecticidal Evaluation
- iortality Mosquito Larvae Southern Armyworm Mexican Bean Beetle 12 I 004 0004 1000 100 10 300 100 10 a, ppm ppm ppm ppm ppm ppm ppm ----2~~4C cl Ill E 100 - - - 100 100 0 100 - - AX S oD 9 ta Eb v w EXAMPLE 37.
Insecticidal Activity.
Two-Spottd Spider Mite, Tetranychus urticae (Koch).
Sieve lima bean plants, with primary leaves three 7.5 to 10 cm long, are infested with about 100 adult phosphate-resistant mites per leaf 4 hours before use in this test, in order to allow egg laying before treatment. The infested plants are dipped for 3 seconds with agitation into the 1000, 300, 100 or 10 ppm solution, and the plants are set in the hood to dry. After 2 days at 80 F., the adult mite mortality is estimated on one leaf under a 10X stereoscopic microscope. The other leaf is left on the plant an additional 5 days and then examined at 10X power to estimate the kill of eggs and of newly hatched nymphs, giving a measure of ovicidal and residual action, respectively.
Tests results are provided in Table III.
Tobacco Budworm, Heliothis virescens (Fabricus).
Third Instar.
Three cotton plants with just expanded cotyledons are dipped in 1000 or 100 ppm solution and placed in the hood to dry. When dry, each cotyledon is cut in half, and 10 leaf sections are each placed in a 29 g plastic medicine cup containing a 1.25 cm dental wick saturated with water and one third-instar budworm larva is added.
The cup is capped and held for 3 days at 80 F. 50% r.h., after which mortality counts are made. Test results are provided in Table III.
Cabbage Looper, Trichplusia n (Hübner).
Third Instar.
A true leaf on a cotton plant is dipped into the test solution containing 1000, 100 or 10 ppm of test compound, agitated for 3 seconds ,and removed to dry in an exhaust hood. When dry, the leaf is placed in a 9.0 cm petri dish with moist filter naner on the bottom. Ten third-instar larvae are added and the lid placed on the dish.
Mortality counts are made after 3 davs at 80"F and 50 t 10% r.h.
Data obtained are reported in Table III below.
TABLE III Insecticidal Evaluation
O o E | o o o ' oE o o o o c ç o A o o o Mites Tobacco Budworm Cabbage Looper L ao a ED 300 o o 1000 100 1000 100 o o ppm ppm ppm ppm ppm ppm ppm ppm ppm vJm E 0 l 100 No 100 100 o" oE o 1 8 o(z Z 0C0 100 0 - - 50 - 100 100 0 owe OCH3 CII ------ ----------- o < . p: ma F2CHB --------- 100 100 0 - 100 100 100 100 100 H c; Ho o o o X X X X t X X h X O , ]~. . Go5 5~s 6. o E 8 6 8 > ( 8 K 8 t TABLE II - continued Insecticidal Evaluation
o E s = qs 3rd Ins tar o Resistant Mites Tobacco Budworm Cabbage o o 1000 300 100 10 1000 100 1000 100 10 O ppm ppm ppm ppm ppm ppm ppm ppm ppm C'HB 100 100 G - OOH 80 100 100 90 o (cH3)2 o o o o oa oo o oo rc, 9" 100 80 100 100 100 100 who I I I I oE o O o I CH' a e! 100 0 - - EJ 8 o o 8 E 8 o c \2 t riS 3 t 5 ~ ç v ;E5 CE o N TABLE III - continued Insecticidal Evaluation
o 8 o a a oE o 8 Ooo 8 Compound ppm ppm ppm ppm ppm ppm ppm ppm ppm 9 8 8 8 W o 100 E o o 100 100 100 G O o s s o, o, LI S e( ao" 100 100 0 . o I I I q~; I I I CHO ' 100 50 - - 90 10 100 80 0 o s o E ~~ 8 Om E2BHB ---------- oa t Y c o i5 5 = B b 5 . Qu .-EAd OVO O i5 O EXAMPLE 38.
Ixodicidal Activity.
Effective control of acarina larvae is demonstrated in the following tests with larvae of Boophilus microplus, a one-host tick which can remain on a single host through its three life stages: i.e. larvae, nymph and adult. In these tests, a 10% acetone/90% water mixture contains 700, 100, 1, 0.1, 0.01, 0.001, 0.004 or 0.00001 ppm of test compound. Twenty (20) larvae are enclosed in a pipette sealed at one end with a gauze material and solution containing the test compound is then drawn through the pipette with a vacuum hose, thereby simulating a spray system. The ticks are then held for 48 hours at room temperature and mortality is determined. The results achieved are set forth below in Table IV.
TABLE IV
% Mortality R Y Z R2 R3 at - ppm H H H CN p-Cl 100 &commat; 100 ppm H H H CN p-OCH3 75&commat;100 H H H CN p-CH3 100 &commat; 100 H H H CN p-F 100 &commat; ol; 30 &commat; .01 H H H CN m-F 100 &commat; 100 H H H CN o-F 100 &commat; 100 F H H CN p-Cl 80 &commat; 100 F H H CN p-CH3 100 &commat; 0.1; 10 &commat; 0.01 F H H CN p-OCH3 90 &commat; 100 F H H CN p-F 75 &commat; .01; 20 &commat; .001 F H H -C#CH H 100 &commat; 100 H CH3 H H H O &commat; 100 H Br H H H 0&commat;100 H Br H CN H 100 &commat; 700 H Cl H H H 100 &commat; 100 H Cl H CN H 75 &commat; 100 H Cl Cl H H 40 &commat; 100 H Cl Cl H CN 90 <R EXAMPLE 39 The effectiveness of compounds of the invention for controlling adult Boophilus micropl21s ticks is determined in the following tests, wherein test compound is made up in solutions as described in Example 38, excepting that sufficient compound is used to give solutions containing 500, 125, 62, 37.9, 32, 31, 15, 16, 8, 2 or 0.25 ppm of test compound.
Adult engorged female ticks are then dipped in the test solutions for 3 seconds and placed in individual containers and held for 48 hours in a room maintained at 800 F. and 50% r.h. At the end of the holding period, the ticks are examined and egg deposits counted. Eggs are then left to hatch and final results are read in percent reduction of viable eggs. Engorged females that do not deposit eggs are considered dead. Data obtained are reported below in Table V.
TABLE V
Percent reduction of Percent reduction of R Y Z R2 R3 viable eggs at ppm.

Claims (18)

H H H CN p-Cl 94 &commat; 125; 80 &commat; 31 ppm H H H CN p-CH3 85 &commat; 125; 52 &commat; 31 H H H CN p-F 94.9 &commat; 125; 37.9 &commat; 32 H H H CN m-F 94 &commat; 125; 52 &commat; 31 H H H CN o-F 99 &commat; 500; 65 &commat; 125 F H H CN p-CH, 89 &commat; 16; 73 &commat; 8 F H H CN p-F 96 &commat; 8; 49.6 &commat; 2 F H H H H 67 &commat;.25 F H H H H O &commat; 500 a-ethyl F H H H H O &commat; 500 a-ethyl F H H CN H O &commat; 500 F H H CN H 98 &commat; 62; 47 &commat; 8 WHAT WE CLAIM IS:
1. A compound having the formula:
wherein RCF.2X-, Y and Z are all meta or para to the carbon to which the alkanoic acid ester group is attached, and X is O, S, SO or SO2; Y and Z are each H, Cl, F, Br, NO3, CH3 or OCH3; R is H, F, Cl, CHF2 or CF3; R2 is ethyl, n-propyl, isopropyl, isopropenyl or t-butyl; R3 is H, CN or -C#CH, and R4 is H, F, Cl, CH3 or SOCH, provided that at least one of Z, Y and R, must be other than hydrogen.
2. A compound according to Claim 1 of the formula
wherein R is H or F; X is O or S; R2 is ethyl, n-propyl or isopropyl; R, is as defined in Claim 1; and R4 is F, Cl, CH3 or OCH3.
3. A compound according to Claim 2, wherein R2 is isopropyl; R, is CN, X is 0; and R4 is F.
4. A compound according to Claim 2; a-cyano-m-(p-fluorophenoxy)benzyl a isopropyl-4-difluoromethoxyphenylacetate.
5. A compound according to Claim 2; a-cyano-m-(p-fluorophenoxy)benzyl aisopropyl-4-trifluoromethoxyphenylacetate.
6. A method for preparing a compound of the formula:
wherein RCF,X-, Y, Z, R2, R, and R4 are as defined in Claim 1, which comprises reacting
in the presence of pyridine.
7. A method for controlling insects and acarina comprising contacting the insects and acarina, their habitat, breeding grounds or feed, with an insecticidally or acaricidally effective amount of a compound according to any one of Claims 1 to 5.
8. A method for the systemic control of insects and acarina that feed on the body fluids of livestock and domestic animals, comprising orally or parenterally administering to the animal host a systemically effective amount of a compound according to any one of Claims 1 to 5.
9. A method according to Claim 8, wherein the compound is orally administered to the host animal.
10. A method according to Claim 8, wherein the compound is parenterally administered to the host animal.
11. An insecticidal composition, comprising a compound according to any one of Claims 1 to 5, and a solid or liquid carrier therefor.
12. A composition according to Claim 11 for use in a method according to to livestock or domestic animals wherein the carrier is a pharmaceutically acceptable carrier.
13. A comoosition according to Claim 11 for use in a method according to Claim 7, wherein the carrier is a liquid and the composition also comprises an emulsifying agent and a surfactant.
14. A compound according to Claim 1 and substantially as described in any one of Examples 8, 9, 11, 12. 15, 16, 78 22, 25. 26, 28, 30 or 32.
15. A method for the preparation of a compound according to Claim 1 substantially as described in any one of Examples 8, 9, 11, 12, 15, 16, 18, 22, 25, 26, 28, 30 or 32.
16. A compound according to Claim 1, whenever prepared by a method according to Claim 6 or Claim 15.
17. A method for controlling insects or acarina, according to Claim 7 and substantially as described in any one of Examples 34-39.
18. An insecticidal composition according to Claim 11 and substantially as described in any one of Examples 34-39
GB1807978A 1976-10-01 1978-05-05 Phenyl alkanoic acid esters and insecticidal and acaricidal uses thereof Expired GB1591960A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US72881876A 1976-10-01 1976-10-01
US72881776A 1976-10-01 1976-10-01
US81460077A 1977-07-11 1977-07-11
US05/890,721 US4178460A (en) 1976-10-01 1978-03-20 2-Haloalkyl(oxy-, thio-, sulfinyl-, or sulfonyl)-phenylalkanoic acids
US05/890,568 US4199595A (en) 1976-10-01 1978-03-20 M-phenoxybenzyl and α-cyano-M-phenoxybenzyl esters of 2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl)phenylalkanoic acids

Publications (1)

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GB1591960A true GB1591960A (en) 1981-07-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056119A1 (en) * 1981-01-09 1982-07-21 BASF Aktiengesellschaft Substituted diphenyl ethers, herbicides containing them and their use as herbicides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0056119A1 (en) * 1981-01-09 1982-07-21 BASF Aktiengesellschaft Substituted diphenyl ethers, herbicides containing them and their use as herbicides
US4744812A (en) * 1981-01-09 1988-05-17 Basf Aktiengesellschaft Substituted diphenyl ethers, herbicides containing these compounds and their use as herbicides

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