IE49794B1 - Herbicidal substituted diphenyl ethers - Google Patents

Description

The present invention relates to compounds graphically represented by Formula 11, as defined below, those compounds exhibiting useful herbicidal properties and also being useful as intermediates In the formation of the compounds of Formulae I and III defined and claimed ir. Fatent Specification No. ATiTS· In Fatent Specification Nc. 49^3 tr.ere are described ar.d claimed compounds IQ of Formula 1 which have herbicidal properties ana which, in both their anti and syn forms, are graphically represented hy Foraula It ft) I wherein X is nitro (-NOj), a halogen, preferably chloro (C1-), or cyano (-CN); ? and Z are each independently hydrogen or chlorine; fi is hydrogen or an alkyl of up to three carbon atoms, preferably ®ethyl {-CHj); 1» hydrogen or «ethyl (-CB3}; and i» hydrogen, an alkyl of up to ten carbon atoas, preferably an alkyl of up to four carbon atoas (aethyl is especially preferred), or an agronomically acceptable soluble sale ion, e.g. a metal ion such as sodium, potassium, lithium, or ammonium (MB4+), or a mono-, di-, or trialkyl substituted ammonium ion, e.g. trimethyl ammonium or monoeihanol ammonium ions (preferred are sodium, potassiurt and ammonium) .

In Patent Specification No. 4^43 there are also described and claimed compounds cf formula Ill Which have herbicidal 10 properties, are useful as intermediates in the formation of the compounds of Formula I, and are graphically represented by the Formula ill: wherein X, 7, Z and R are as defined for Formula I.

IS According to the present inventioa compounds of Formula II axe provided which have useful herbicidal properties, have utility in the formation of the compound· Of Formulae I and III defined and claimed in Patent Specification No. 4rm and which 2{j are graphically represented by Formula II:49794 wherein: X is nitro (-NO2), a halogen, preferably chloro (-C1), or cyano (-CN); Y and Z are each independently hydrogen or chlorine; and R is hydrogen or an alkyl of up to three carbon atoms, preferably methyl I-CH3).

Some examples of compounds of general Formula II are: ~(2-chloro-4-trifluoromethylphenoxy)-2-n-nitrobenz10 aldehyde, -(4-trifluoromethyIphenoxy)-2-nitrobenzaldehyde, - (2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobenzaldehyde, - (2-chloro-4-trifluoromethyIphenoxy)-2-nitroaceto15 phenone, -(2-chloro-4-trifluoromethyIphenoxy)-2-nitropropiophenone, -(4-trifluoromethyIphenoxy)-2-nitroacetophenone, -(4-trifluoromethylphenoxy)-2-cyanobutyrophenone, -(2-chloro-4-tr'ifluoromethylphenoxy)-2-bromopropiophenone, -(2,6-dichlor0-4-trifluoromethyIphenoxy)-2-fluoroacetophenone, -(4-trifluoroaethylphenoxy)-2-nitro-isobutyr©phenone, 5-(2-chloro-4-trifluoromethylphencxy)-2-chlorobenzaldehyde, -(2-chloro-4-trifluoroaethylphenoxy)-2-cyanobenz5 aldehyde, -(4-trifluoronethyIphenoxy)-2-chlor©propiophenone. Although all of the compounds of Formula II as disclosed herein, are useful for the purposes disclosed herein, -some compounds are preferred over others. In the compounds described herein, Z is preferably hydrogen; X is preferably a cyano, more preferably chloro (Cl), but especially nitro (NOj); Y is preferably chloro (-C1); and R is preferably hydrogen or methyl (CH3). λ very useful group of compounds graphically represented by Formula II are those of Foraula IV: IV H02 in which Y, Z and R are as defined above.

Examples of very useful ketones and aldehydes represented by Foraula IV are those in which: I. R is hydrogen, e.g.: -(2-chloro-4-trifluoromethylphencxy)-2-nitrobenzaldehyde, - (4-trifluoromethylphenoxy)-2-nitrobenzaldehyde, - (2,6-dichloro-4-trifluoromethylphenoxy) -.2-ni trobenzaldehyde. 11. R is an alkyl of up to three carbon atoms, e.g·: 5 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitroacetophenone, - (2-chloro-4-trifluororaethylphenoxy) -2-nitropropiophenone, -(4-trifluoromethylphenoxy)-2-nitroacetophenone.

The present invention will now be further illustrated by way of the following Examples which illustrate a method for the synthesis of compounds of Formula II and which also illustrate a method for the synthesis of compounds of Formulae I and III utilizing the compounds of Formula II :a. Formation of the Carboxy Compounds of Fotaola 1 1. Formation of the ketone and aldehyde compounds other than the 2-cyano substituted compounds. 20 The appropriately substituted p-chlorobenzotrifluoride is reacted with an appropriately substituted salt of a metal-3-substituted carbonyl phenoxide or its ketal or acetal or a cation of sodium (Na+) or potassium (K+), preferably K+, to form a compound of Formula II, where X is hydrogen, which is then halogenated or nitrated by standard methods to form a 48794 compound of Formula II, which is separated from the reaction mixture. 2. Formation of the 2-cyano substituted ketone and aldehyde compounds.

Tbe compounds of general Formula II (where X · cyano) may be prepared by reduction of the carbonyl compound (or its acetal or ketai) of general Formula II (where X * nitro) to the amino compound (X NH2) followed by diazotization and treatment with CuCN, affording the cyanocarbonyl compound (general Formula II where X « cyano). Subsequent conversion to the oxime (Formula III where X cyano) and carboxy oximes (Formula I where X cyano) can be accomplished by methods described herein. b· Formation of Oximes of Formula III. 1. Procedure when R is Hydrogen.

When R is hydrogen, the appropriate aldehyde represented by Foraula II wherein R is hydrogen; for example (0.001 mole) is dissolved in 20 millilitres of tetrahydrofuran (THF) and 12 millilitres of absolute ethanol. To this stirred solution is added hydroxylamine hydrochloride (.012 mole) in 1 millilitre of water, and then .6 grams (.015 mole) sodium hydroxide in 5 millilitres of water. Tbe solution is stirred overnight at ambient temperature and the tetrahydrofuran and ethanol are stripped off in vacuo, leaving a two-phase system. The oil phase is dissolved in chloroform '.BCCL^; and then separated from the aqueous phase. The chloroform layer is then extracted with water, and with a saturated sodiUM chloride solution, and then dries ever anhydrous magnesium sulfate [M5SO4/. Filtration and evaporation affords the crude product of the oximes of Formula III wherein R is hydrogen. The crude product can be recrystal tired in carbon tetrachloride [CCI4,. 2. Procedure when R is ar. Alkyl of up to Three Carbon Atoms.

An alternative procedure is used when R in Formula II is an alkyl described herein. This procedure employs anhydrous conditions. For example (0.0056 sole) of the appropriate carbonyl compound of Formula II, wherein R is an alkyl as defined herein, is dissolved in 20 millilitres of a 1:1 mixture of absolute ethanol and dry benzene. To this solution is added .77 grams of hydroxylamine hydrochloride in 15 millilitres of absolute ethanol and 1.12 grams of any organic tertiary amine, such as triethylamine, which is preferred. Th® solution is heated to reflux and the water formed in the reaction is azeotroped off. After refluxing for 18 hours, the solvent is removed in vacuo, the residue is dissolved in chloroform, extracted with water and saturated sodium chloride 0794 solution, and dried over anhydrous magnesium sulfate. Filtration and evaporation affords the crude product oximes of general Formula III where R is alkyl. c. Procedure for Forming Carboxylate.

The appropriate oxime of general Formula III, prepared as above, (0.004 mole) is dissolved in four millilitres of an alkanol of up to four carbon atoms and is added to an alkoxide solution (0.0045 mole of sodium). To this solution is added 0.0045 mole of the appropriate -halo-substituted carboxylate compound where the halo is chlorine, bromine, or iodine, preferably bromine, and the reaction is followed by thin layer chromatography. The solution can be heated at reflux, if the reaction is sluggish. The product of general Formula I is obtained either by filtration of the product, or by evaporation of the solvent, and dissolving the residue in Chloroform, extracting with water, drying and then evaporating the chloroform solvent.

Sodium hydride can be used in place of the sodium alkoxide, and the solvent can be an ether e.g. tetrahydrofuran, or diethyl ether.

The compounds where R2 is hydrogen, such as 5-{2-chloro-4-trifluromethylpbenoxy)-2-nitroacetophenone oxime-0-acetic acid, are prepared by simple hydrolysis of tne esters, followed by acidification and extraction or filtration of the product. ' The compounds where R^ is an agronomically acceptable soluble salt ion are made by reacting the appropriate acid with the appropriate base.

The following Examples illustrate the synthesis of compounds of general Formula I by the general procedure described above, i.e. utilizing the compounds according to the present invention of Formula II.

EXAMPLE I.

Synthesis of 5-(2-chloro-4-trifluoromethylphenoxy) 2-nitroacetophenone oxime-0-(acetic acid, methyl ester a. Preparation of 3-(2-chloro-4-trifluoromethylphenoxy)acetophenone.

To a 250 millilitre flask containing a solution of 13.92 grams of the potassium salt of 3-hydroxyacetophenone in 30 millilitres of dry dimethylsulfoxide (DMSO), was added 17.12 grams (0.08 aole) of 3,4-dichlorobenzotrifluoride. The reaction solution was heated to 175°C for six hours, and then cooled and stirred at ambient temperature for 18 hours. The bulk of the DMSO was removed in vacuo, and the remaining dark residue was stirred with diethyl ether for 15 minutes and filtered. The filtrate was extracted once with water, once with IN sodium hydroxide, once with a saturated sodium chloride solution, dried over anhydrous MgSO4, filtered, η decolourized with charcoal, and evaporated to dryness leaving 16.04 grams of dark red oil comprised of 3-(2-chloro-4-trifluoromethylphenoxy) acetophenone.

The material was further purified by passing through a neutral, grade III alumina column. b. Nitration of 3-(2-chloro-4-trifluoromethylphenoxy) acetophenone.

To a 100 millilitre flask containing a solution of 26 millilitres of concentrated sulfuric acid (B2SO4), and 16 millilitres of ethylenedichloride (EDC), which was cooled to 0‘C., 6.28 grams, (0.02 mole) of the dark red oil of 3-(2-chloro-4-trifluoromethylphenoxy) acetophenone (prepared above) was added dropwise to form a brownish-black solution. When the addition of 3-(2-chloro-4-trifluoromethylphenoxy)acetophenone was completed, dry potassium nitrate (KNO3), (2.0 grams, 0.020 mole) was added in small portions over a 20 minute period so as to maintain the reaction mixture below 4*C. Tbe reaction mixture was stirred for 0.5 hours at O’C. It was then poured into 250 millilitres of ice and water, and the resulting mixture was mixed with 200 millilitres of chloroform, (CHCI3). The organic layer was separated, and then extracted twice with water, once with a saturated sodiua chloride solution, and then dried over anhydrous magnesium sulfate, and then filtered. The organic solvent was evaporated off to yield 6.51 grams of an orange oil which analysis showed was a mixture of two positional isomers, one of which was -(2-chloro-4-trifluoromethylphenoxy)-2-nitroaceto5 pbenone. The mixture was separated into two fractions by high pressure liquid chromotography (HPLC) using diethyl ether as the eluant.

The diethylether was stripped from fraction /1, leaving 2.37 grams of an orange oil comprised of -(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone whicn had the following; Nuclear magnetic resonance [(NMR) (CDCI3)): 2.475 (singlet, 3H) ; 6.78-8.215 (multiplet, 6H). Infra Red (IR): 1710, 1575, 1520, 1400, 1315 cm*l Mass Spectra (MS) molecular ion at m/e 359. c. Synthesis of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime.

A 100 millilitre flask vas charged with a solution of 2.0 grams (0.0056 mole) of the orange oil, - (2-chloro-4-trifluoromethyIphenoxy) -2-nitroacetophenone, in 10 millilitres of absolute ethanol and 10 millilitres of dry benzene. A solution of hydroxylamine hydrochloride (0.77 grams, 0.011 mole) in 15 millilitres of absolute ethanol was added followed by addition of 1.12 grams (0.011 mole) of an acid acceptor (triethylamine). The reaction mixture was than refluxed; when 20 millilitres of solvent was distilled off, an additional 15 millilitres of benzene was added. Refluxing was continued until. 15 millilitres of solvent distilled off, and then the remaining solution was refluxed for 16 hours, with the formation of a mixture of the syn and anti isomers of 5-(2-chloro-4-trifluoromethylpftenoxy)-2-nitroacetophenone oxime. The solvent was stripped from the mixture, and the residue was dissolved in chloroform.

X0 The chloroform solution was extracted twice with water, then with a saturated solution of sodium chloride, and then dried over anhydrous magnesium sulfate.

Tbe chloroform solution was filtered and the solvent (chloroform) was evaporated to yield 2.03 grams of an orange oil comprised of 5-(2-chloro-4trifluoromethylphenoxy)-2-nitroacetophenone oxime (anti and syn), which had tbe following: Mass spectra (MS): molecular ion at m/e 374 (Syn and Anti MMR (CDCI3)s 2.13S (singlet, 3S), 6.91-8.17E (multiplet, 6H); 9.33S (singlet, IB).

(Syn and Anti) IR: 3100 (broad), 1605, 1575, 1520, 1400 cm-1. d. Formation of the Syn and Anti Isomers of 5-(2chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-0-(acetic acid, methyl ester).

A solution of 0.10 grams (0.0045 millilitres of sodium metal in 5 millilitres of methanol under nitrogen was charged into a 25 millilitre flask. When all of the sodium had reacted, 1.50 grams (0.004 mole) of the 5-(2-cnloro-4-tnfluoromethvlphenoxy)-2-nitroacetophenone oxime (anti and syn) (prepared above) dissolved in 5 millilitres of methanol was added, and the solution stirred. Methylbromoacetate (0.68 grams, 0.0045 mole) was added to the solution; the resulting mixture was stirred at ambient temperature under nitrogen for eighteen (18) hours, and was then refluxed for two hours. The solvent was stripped from the solution and the residue was dissolved in chloroform (CHCI3) . The CHCI3 solution was extracted twice with water, once with a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. The CHCI3 solution was filtered, and the solvent removed by evaporation to yield 1.68 grams of an orange oil containing the isomers of 5-(2-chloro-4trifluoromethylphenoxy)-2-nitroacetophenone oxime-0(acetic acid, aethyl ester). The orange oil was purified by chromatography by dissolving it into 3 millilitres of ethyl ether and placing it on top of a 49784 •even inch by 21 millimetre column of grade Ill alumina. The column was eluted with diethyl ether and the desired fractions were collected. The solvent was removed to yield 0.72 grams of a yellow oil comprised of anti and*syn isomers of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester), which had the following: MS: Molecular ion at m/e 446 Syn and Anti IR: 1760, 1605, 1575, 1520, 1320 cm*^· Syn and Anti NMR (CDCI3): 2.23b (singlet, 3H), 3.67$ and 3.725 (singlet, 3H), 4.47$ and 4.67* (singlet, 2H), 6.78-8.255 (multiplet, 6H).

Upon dissolving the yellow oil in ethanol (or methanol), pale yellow crystals were obtained with a melting point of 89-92’C.

EXAMPLE II Synthesis of the Anti and Syn Isomers of 5-(2chloro-4-tr ifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, ethyl ester).

A solution of 0.14 grams (0.0060 mole) of sodium metal in 8 millilitres of methanol under nitrogen gas was charged into a 50 millilitre flask. Nhen all of the sodium had reacted, 2.0 grams (0.0053 mole) of the orange oil, anti and syn isomers of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime (prepared as in Example Ic) were added, and the solution was stirred. Ethyl-2-bromopropionate (1.06 grams, 0.0059 mole) were added to the solution and resulting mixture was stirred at ambient temperature under nitrogen gas for fifty-one (51) hours. The solvent was stripped from the solution, and the oil residue was stirred in diethyl ether, filtered, and washed well with diethyl ether. The filtrate was washed twice with water, once with a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. The diethyl ether solution was then filtered, and the solvent removed by evaporation to yield 2.23 grams of an orange oil containing the anti and syn isomers of 5-(2-chloro-4-trifluroaethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, ethyl ester). The orange oil was purified by chromatography by dissolving it in diethyl ether and adding it to the top of an eight inch by 21 millimetre column of neutral grade III alumina. The column was eluted witn diethylether and the first component to come off the column was the desired product. The solvent was removed to yield 1.13 grams of a yellow oil comprised of anti and syn isomers of 5-(2-chloro4-trifluorometbylphenoxy)-2-nitroacetophenone oxime-0(acetic acid, ethyl ester). • 49794 EXAMPLE III Synthesis of 5-(2-chloro-4-trifluoroaethylphenoxy)-2-chlorobenzaldoxime-0-(ace.tic acid, ethyl ester). a. Preparation of 3-(2-chloro-4-trifluoroaethylphenoxy)-benzaldehyde dimethyl acetal.

To a solution of 80.7 grams (0.39 mole) of the potassium (K+) salt of 3-hydrexybenzaldehyde dimethyl acetal in 170 millilitres of dry DMSO was added 77.04 grams (0.36 mole) of 3,4-dichlorobenzotrifluoride.

The solution was heated in an oil bath of 150-155° for four hours and then stirred overnight at ambient temperature. _ The solvent was then stripped in vacuo and the residue stirred with CHCI3 and filtered. The filtrate was washed with fl2O, 0.5 N NaOH and saturated NaCl solution and dried over anhydrous MgSO4. Filtration and decolourization with charcoal and evaporation of solvent afforded 114.8 grams of a light orange oil comprised of 3-(2-chloro-4-trifluorometbyIphenoxy)benzaldehyde dimethyl acetal. b. Preparation of 5-(2-chloro-4-trifluromethyl phenoxy)-2-chlorobenzaldehyde. λ 200 millilitre (ml) three-necked flask was charged with ten (10.0) grams (0.029 mole) of the above-mentioned 3-(2-chlorc-4-trifluoroaethylphenoxy) benzaldehyde dimethyl acetal and 90 millilitres of dry ethylene dichloride. The solution was cooled in an ice bath, and then a catalytic amount (approximately 0.2 grams) of ferric chloride was added to the solution. Chlorine gas addition was started at a moderate rate and continued for one (1) hour at O’C., and then the solution was stirred for an additional two (2) hours at O’C. The reaction solution was then purged with nitrogen overnight at ambient temperature.

It was then extracted with water (HjO) and the HjO layer extracted with chloroform (CHCI3). The organic layers of ethylene dichloride and chloroform were x combined and again washed with HjO (the HjO being brought to pH 6 with IN NaOH). Tbe organic layer was then washed with saturated NaCl solution and dried over anhydrous MgSO4· Filtration and evaporation afforded 11.74 grams of a pale yellow oil comprised of S-(2-chloro-4-trifluoromethyIphenoxy)-2-chlorobenzaldehyde, which had tbe following NMR, IR, and MS: NMR: (CDCI3) 6.87-7.605 (multiplet, 6H), 10.37$ (singlet, IH).

IR: 1695, 1605, 1590, 1500, 1415, 1320 cml.

BS: Molecular ion at m/e 334. c. Preparation of 5-(2-chloro-4-tnfluoromethyl·phenoxy)-2-chlorobenzaldoxiae.

A 100 millilitre flask was charged with 3.34 grans (.01 mole) of the prepared 5-(2-chiorc-4-trifluoromethylphenoxy)-2-chlorobenzaldehyde, 20 millilitres of tetrahydrofuran (THF) and 12 millilitres of absolute ethanol. To this solution was added 0.S3 grans (.012 mole) of hydroxylamine hydrochloride in ten (10) millilitres of water, and then 0.60 grans (.015 mole) of NaOH in five (5) millilitres of H20. After stirring the solution at ambient temperature for approximately eighteen (18) hours, the solution was •tripped (in vacuo) of the organic solvent and the aqueous residue taken up in a mixture of H2O/CHCI3.

Tbe organic layer was phase separated, washed with saturated NaCl solution and dried over anhydrous MgSO4.

Filtration and evaporation afforded 3.01 grams of a beige solid. This material was recrystallized in 40 milliliters of hexane, affording 1.24 grams of beige crystals comprised of -(2-chloro-4-trifluoromethyl-phenoxy-2-chlorobenzaldoxime (anti and syn) which had an m.p. of 109-112®C. and tbe following NMR and IR: MR: (CDCI3) 6.83-7.70S (multiplet, 6H), 8.45S (singlet, IH), 8.975 (singlet, IH).

IRs 3340-3110, 1605, 1590, 1570, 1485, 1400, 1320 cm-1. d. Preparation of 5-(2-cnloro-4-trifluoromethylphenoxy)-2-chlorobenzaldoxime-O-(acetic acid, methyl ester).

A 25 millilitre flask was flushed with dry nitrogen (Nj) and then charged with .09 grams (.0037 mole) of sodium and 5 millilitres of dry methanol.

When all of the sodium nad reacted, 1.24 grams (.00355 mole) of tne 5-(2-cnloro-4-trifluoromethylphenoxy)-2chlorobenzaldcxime in 4 millilitres of methanol was added. After stirring for 15 minutes, 0.57 grams (.0037 mole) of methyl bromoacetate was added and the solution was stirred overnight (under dry nitrogen) at ambient temperature.

Solvent was then removed in vacuo, the residue dissolved in CHCI3, and extracted with water and saturated NaCl solution and dried over anhydrous MgSO4· Filtration and evaporation of the solvent afforded 1.53 grams of a pale yellow oil. This was dissolved in 2 millilitres of CHCI3 and added to the top of a silica gel-60 column (35 gram, 70-230 mesh, activity 2-3) and eluted with CHCI3. The eluant was collected in 10 millilitre fractions and analyzed hy thin layer chromatography (TLC). Evaporation of the appropriate fractions (of the first component off the column) afforded 1.02 grams of a clear, colourless oil comprised of 5-(2-chloro-4-trifluoromethylphenoxy)-248784 chlorobenzaldoxime-O-(acetic acid, methyl ester), which had the following: NMR: (CDCI3) 3.758 (singlet, 3H); ,4.715 (singlet, 2H); multiplet centered at 7.315 (6H)t 8.568 (singlet, IH).

IR: 1760, 1740, 1595, 1565, 1500, 1465, 1320 cm'1 MSs Molecular ion at m/e 421.

EXAMPLE IV Synthesis of 5-(2-chlorc-4-trifluoromethylphenoxy) -2-chlorobenzaidoxime-O-(2-propionic acid, aethyl ester). λ 25 millilitre flask was flushed with dry nitrogen (N2) and charged with 6 millilitres of dry MeOH and .15 grams (.0065 mole) of sodium. When all of the sodium had reacted, 2.09 grams (.006 aole) of the 5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzaldoxime (prepared as in Example Ia) in 6 millilitres of MeOH was added in one portion and stirred for approximately fifteen (15) minutes at ambient temperature.

To this solution was added 1.12 grams (.0062 aole) of ethyl-2-broaopropionate in one portion. The resulting solution was stirred at ambient temperature under dry nitrogen overnight.

Solvent was then stripped and the residue dissolved in CHCl3/H2O, phase separated and -the CHCI3 layer extracted with saturated NaCl solution and dried over anhydrous MgSO4. Filtration and evaporation of solvent left 3.0 grams of a crude oil. This was dissolved in 2 millilitres of CHCI3 and applied to the top of a silica gel-60 column (wet-packed with CHCI3) (40 gram, 70-230 mesh, activity 2-3) and eluted with CHCI3. The eluant was collected in 1C millilitre fractions and analyzed cy thin layer chromatography (TLC). Evaporation of the appropriate fractions (fractions 6-13; afforded 1.94 grams of a clear, colourless oil comprised of 5-(2-chloro-4-trifluoroaethylphenoxy,-2-cnlorobenzaldoxime-O-(2-propionic acid, methyl ester) , which bad the following: NME (COCI3) : 1.46$ (doublet, 3H);-3.S7$ (Singlet, 3H) ; 4.73$ (quartet, IH); 7.18$ (multiplet, 6H); 8.44$ (singlet, IH); IR: 1760, 1610, 1600, 1565, 1500, 1465, 1320 carl and MS: Molecular ion at m/e 435.

While the invention has been described with reference to specific details of certain illustrative embodiments, it is not intended that it shall be limited thereby except insofar as such details appear in the accompanying claims.

Claims (5)

1. A compound of Formula II: wherein: X is nitro i-NO 2 ), a halogen, or cyano (-CN); 5 y and z are each independently hydrogen or chlorine: and R is hydrogen or an alkyl of up to three carbon atoms.

2. A compound as claimed in claim 1, wherein X is nitro.

3. A compound as claimed in claim 1 or claim 2, wherein X is chloro.

4. A compound as claimed in any of claims 1 < to 3, wherein R is methyl.

5. A compound as claimed in claim 1 selected from 5-(2-chlor0-4-trifluoromethylphenoxy)-2-nitrobenzaldehyde, 5-(4-trifluoromethylphenoxy)-2-nitrobenzaldehyde, 5-(2,S-dichloro-4-trifluoromethylphenoxy)2-nitrobenzaldehyde, 5-(2-chloro-4-trifluoromethyl20 phenoxy)-2-nitroacetophenone, 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiophenone, 5-(4-trifluoromethylphenoxy)-2-nitroacetophenone, 5-(4-trifluoromethylphenoxy)-2-cyanobutyrophenone, 5-(2-chloro-4-trifluoromethylphenoxy)-2-bromopropiophenone, 5-(2,6-dichloro-4-trifluoromethylphenoxy)-25 fluoroacetophenone, 5-(4-trifluoromethylphenoxy)-2nitro-iaobutyrophenone, 5-(2-chloro-4-trifluorometnylphenoxy)-2-chloroben2aldehyde, 5- (2-chloro-4-trifluoromethyIphenoxy) -2-cyanoben2alder.y5e, and 5- (4-trif luoromethy Iphenoxy) -2-chlor opr opiophenor.e.