68359-57-9

Usage

InChI:InChI=1/C13H9FO2/c14-12-7-6-10(9-15)8-13(12)16-11-4-2-1-3-5-11/h1-9H

Synthetic route

cyfluthrin (68359-37-5) → 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (55701-05-8)

Conditions	Yield
With sodium hydroxide In methanol for 2h; Heating;

4-fluoro-3-phenoxybenzyl bromide (68359-55-7) + 1-Nitropropane (108-03-2) → 4-fluoro-3-phenoxybenzaldehyde (68359-57-9)

Conditions	Yield
In ethanol

4-fluoro-3-phenoxy-benzaldehyde ethyleneacetal (77771-05-2) → 4-fluoro-3-phenoxybenzaldehyde (68359-57-9)

Conditions	Yield
With hydrogenchloride In ethanol; water; toluene

cis-α-cyano-3-phenoxy-4-fluoro-benzyl 2,2-dimethyl-3-(2-chloro-vinyl)cyclopropanecarboxylate → 3-Methylbutenoic acid (541-47-9) + 3-(2-chloro-vinyl)-2,2-dimethylcyclopropanecarboxylic acid (60310-82-9) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + C8H11ClO + 2-(4-fluoro-3-phenoxyphenyl)-2-hydroxyethanenitrile (76783-44-3) + 4-fluoro-3-phenoxy benzoic acid (77279-89-1)

Conditions	Yield
In hexane for 17h; UV-irradiation;

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → 4-fluoro-3-phenoxy benzoic acid (77279-89-1)

Conditions	Yield
With dihydrogen peroxide; acetic acid In ethanol for 4h; Heating;	100%
With potassium permanganate In water for 2h; Heating;	65%
With dihydrogen peroxide; acetic acid at 60 - 80℃; for 2h;

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → 4-fluoro-3-phenoxyphenylmethanol (68359-53-5)

Conditions	Yield
With formic acid; C20H29ClIrN4(1+)*Cl(1-) In ethanol; water at 80℃; for 0.25h; chemoselective reaction;	98%
With sodium hydroxide In diethyl ether; water
With sodium hydroxide In diethyl ether; water
With sodium hydroxide In diethyl ether; water

potassium cyanide + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + C9H9Br2Cl2F3O → C23H18Br2ClF4NO2

Conditions	Yield
With tetrabutylammomium bromide In water; benzene at 15 - 20℃; for 10h;	95%

sodium cyanide (773837-37-9) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + cis-2,2-dimethyl-3-(2-chloropropenyl)cyclopropanecarboxylic acid chloride → cis-α-cyano-4-fluoro-3-phenoxybenzyl-2,2-dimethyl-3-(2-chloropropenyl)cyclopropanecarboxylate

Conditions	Yield
With triethylamine In water; toluene at 20℃; for 4h;	95%

potassium cyanide + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + (1R)-trans-2,2-dimethyl-3-(2-chloropropenyl)cyclopropanecarboxylic acid chloride → (1R)-trans-α-cyano-4-fluoro-3-phenoxybenzyl-2,2-dimethyl-3-(2-chloropropenyl)cyclopropanecarboxylate

Conditions	Yield
With pyridine In cyclohexane; water at 20℃; for 4h;	93%

Dibenzyl phosphite (17176-77-1) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → dibenzyl α-hydroxy(4-fluoro-3-phenoxy)benzylphosphonate

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 14h;	92%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + permethric acid chloride (52314-67-7) + sodium sulfate (7757-82-6) → 3'-phenoxy-4'-fluoro-benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-carboxylate (68359-33-1)

Conditions	Yield
In water; ethyl acetate	91.5%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 2-amino-N'-hydroxychroman-3-carboxamidine (1384471-91-3) → N-(4-fluoro-3-phenoxybenzylidene)-3-(5-(4-fluoro-3-phenoxyphenyl)-1,2,4-oxadiazol-3-yl)-3,4-dihydro-2H-chromen-2-amine (1384471-90-2)

Conditions	Yield
for 0.0833333h; Irradiation;	91%

sodium cyanide (773837-37-9) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + cis/trans-2,2-dimethyl-3-(2-chloropropenyl)cyclopropanecarboxylic acid chloride → cis/trans-α-cyano-4-fluoro-3-phenoxybenzyl-2,2-dimethyl-3-(2-chloropropenyl)cyclopropanecarboxylate

Conditions	Yield
With pyridine In cyclohexane; water at 20℃; for 4h;	91%

pyridine-2,6-dicarbohydrazide (5112-36-7) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → N'2,N’6-bis [(4-fluoro-3-phenoxyphenyl)methylidene]pyridine-2,6-dicarbohydrazide

Conditions	Yield
With acetic acid In ethanol Reflux;	89%

4-bromo-β-nitrostyrene (3156-37-4) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + β-naphthol (135-19-3) → C31H19BrFNO2

Conditions	Yield
With ammonium acetate; sodium hydroxide In water at 80℃; for 8h; Green chemistry;	87%

ethyl 4-[4-(methylthio)phenyl]-6-methyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (292871-44-4) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + chloroacetic acid (79-11-8) → CH3SC6H4C6HN2SOCH3CO2CH2CH3CHC6H3FOC6H5

Conditions	Yield
With sodium acetate; acetic anhydride; acetic acid for 3h; Heating;	84%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + toluene-4-sulfonic acid hydrazide (1576-35-8) → N'-[(4-fluoro-3-phenoxyphenyl)methylidene]-4-methylbenzenesulfonohydrazide

Conditions	Yield
In ethanol Reflux;	84%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + m-tyramine (588-05-6) → C21H18FNO2

Conditions	Yield
With acetic acid at 50℃; for 5h; Pictet-Spengler Synthesis; Molecular sieve; Inert atmosphere;	83%

tert-butyl diethylphosphonoacetate (27784-76-5) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → tert-butyl (E)-3-(3'-phenoxy-4'-fluorophenyl)prop-2-enoate (1393363-56-8)

Conditions	Yield
Stage #1: tert-butyl diethylphosphonoacetate With methylmagnesium bromide In tetrahydrofuran; diethyl ether at 20℃; for 0.25h; Inert atmosphere; Stage #2: 4-fluoro-3-phenoxybenzaldehyde In tetrahydrofuran; diethyl ether for 15h; Horner-Wadsworth-Emmons olefination; Inert atmosphere; Reflux; optical yield given as %de; diastereoselective reaction;	82%

indole (120-72-9) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → C29H21FN2O

Conditions	Yield
With sulfated anatase titania In neat (no solvent) at 20℃; for 0.5h; Green chemistry;	82%
With BiCl3-loaded montmorillonite K10 In neat (no solvent) at 20℃; for 0.666667h; Green chemistry;	82%

(2-nitroethenyl)benzene (102-96-5) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + formamide (77287-34-4, 77287-35-5, 60100-09-6) + malonic acid dimethyl ester (108-59-8) → 6-(4-fluoro-3-phenoxyphenyl)-5-nitro-4-phenylpiperidin-2-one

Conditions	Yield
Stage #1: (2-nitroethenyl)benzene; malonic acid dimethyl ester With sodium hydroxide In methanol at 0℃; for 0.75h; Stage #2: 4-fluoro-3-phenoxybenzaldehyde; formamide In methanol Reflux;	78%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-1,3-thiazole-5-carbohydrazide → (E)-2-(3-cyano-4-isobutoxyphenyl)-N’-(4-fluoro-3-phenoxybenzylidene)-4-methylthiazole-5-carbohydrazide

Conditions	Yield
With acetic acid In ethanol for 8h; Reflux;	72%

1,5-dioxaspiro[5.5]undecane-2,4-dione (1658-27-1) + (2-nitroethenyl)benzene (102-96-5) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → 2-aza-1,3-di(4-fluoro-3-phenoxyphenyl)-4-nitro5-phenyl-8,15-dioxa-7,16-dioxodispiro[5,2,59,26]hexadecane

Conditions	Yield
Stage #1: 1,5-dioxaspiro[5.5]undecane-2,4-dione; (2-nitroethenyl)benzene With triethylamine In ethanol at 20℃; for 3h; Michael Addition; Stage #2: 4-fluoro-3-phenoxybenzaldehyde With ammonium acetate In ethanol at 45℃; for 20h; Mannich Aminomethylation;	71%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + ethyl acetoacetate (141-97-9) + malononitrile (109-77-3) → 6-amino-4-(4-fluoro-3-phenoxyphenyl)-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile

Conditions	Yield
With hydrazine hydrate; morpholine triflate In ethanol; water for 8h; Reflux; Green chemistry;	67%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 5-amino-1-(2-hydroxy-2-phenylethyl)-1H-pyrazole-4-carbohydrazide → (E)-5-amino-1-(2-hydroxy-2-phenylethyl)-N’-(4-fluoro-3-phenoxybenzylidene)-1H-pyrazole-4-carbohydrazide

Conditions	Yield
In methanol; ethanol at 100℃; for 18h;	65%

1-methoxy-4-(2-nitro-vinyl)-benzene (3179-10-0) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + formamide (77287-34-4, 77287-35-5, 60100-09-6) + malonic acid dimethyl ester (108-59-8) → 6-(4-fluoro-3-phenoxyphenyl)-4-(4-methoxyphenyl)-5-nitropiperidin-2-one

Conditions	Yield
Stage #1: 1-methoxy-4-(2-nitro-vinyl)-benzene; malonic acid dimethyl ester With sodium hydroxide In methanol at 0℃; for 0.75h; Stage #2: 4-fluoro-3-phenoxybenzaldehyde; formamide In methanol Reflux;	63%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 2-amino-4,6-di-tertbutylphenol (1643-39-6) → 2,4-di-tert-butyl-6-{[(4-fluoro-3-phenoxyphenyl)methylene]amino}phenol

Conditions	Yield
for 2h; Heating;	62%

1-methoxy-4-(2-nitro-vinyl)-benzene (3179-10-0) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 1,3-cylohexanedione (504-02-9) → 2-(4-fluoro-3-phenoxybenzylideneamino)-3-(4-methoxyphenyl)benzofuran-4-ol

Conditions	Yield
With piperidine; ammonium acetate In N,N-dimethyl-formamide at 20℃; for 7h; Michael Addition; Reflux;	61%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + 3-(4-Ethoxyphenyl)-3-methyl-2-butanone (89765-17-3) → 1-(4-Fluoro-3-phenoxyphenyl)-4-(4-ethoxyphenyl)-4-methylpent-1-ene-3-one (89765-18-4)

Conditions	Yield
With potassium hydroxide In ethanol at 20℃; for 6h; Condensation;	60%

4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + ethyltriphenylphosphonium bromide (1530-32-1) → (E)-1-fluoro-2-phenoxy-4-(prop-1-en-1-yl)benzene

Conditions	Yield
With potassium carbonate In 1,4-dioxane at 110℃;	56.8%

cycl-isopropylidene malonate (2033-24-1) + 1-methoxy-4-(2-nitro-vinyl)-benzene (3179-10-0) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → 8-aza-7,9-di(4-fluoro-3-phenoxyphenyl)-11-(p-methoxyphenyl)-3,3-dimethyl-10-nitro-2,4-dioxa-1,5-dioxospiro[5,5]undecane

Conditions	Yield
Stage #1: cycl-isopropylidene malonate; 1-methoxy-4-(2-nitro-vinyl)-benzene With triethylamine In ethanol at 20℃; for 3h; Michael Addition; Stage #2: 4-fluoro-3-phenoxybenzaldehyde With ammonium acetate In ethanol at 45℃; for 20h; Mannich Aminomethylation;	55%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) → 3-(4-fluoro-3-phenoxyphenyl)-3,4-dihydroisocoumarin

Conditions	Yield
With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 20℃; for 16h; Glovebox; Inert atmosphere;	55%

(E)-1-methoxy-4-(2-nitrovinyl)benzene (3179-10-0, 5576-97-6) + 4-fluoro-3-phenoxybenzaldehyde (68359-57-9) + malonic acid dimethyl ester (108-59-8) → C26H23FN2O7

Conditions	Yield
Stage #1: (E)-1-methoxy-4-(2-nitrovinyl)benzene; malonic acid dimethyl ester With sodium hydroxide In methanol at 0℃; for 0.75h; Stage #2: 4-fluoro-3-phenoxybenzaldehyde With ammonium acetate In methanol at 20 - 85℃; for 40h;	53%

Upstream product

• 68359-37-5 cyfluthrin 
• 68359-55-7 4-fluoro-3-phenoxybenzyl bromide 
• 108-03-2 1-Nitropropane 
• 77771-05-2 4-fluoro-3-phenoxy-benzaldehyde ethyleneacetal 

Downstream Products

• 143680-39-1 (R)-1-cyano-1-(4-fluoro-3-phenoxyphenyl)methyl acetate 
• 143680-40-4 (S)-(+)-1-cyano-1-(4-fluoro-3-phenoxyphenyl)methyl acetate 
• 89765-18-4 1-(4-Fluoro-3-phenoxyphenyl)-4-(4-ethoxyphenyl)-4-methylpent-1-ene-3-one 
• 77279-89-1 4-fluoro-3-phenoxy benzoic acid 
• 68359-53-5 4-fluoro-3-phenoxyphenylmethanol 
• 147379-66-6 4-fluoro-α-methyl-3-phenoxybenzyl alcohol 
• 81658-87-9 3-(4-chlorophenoxy)-4-fluorobenzaldehyde 
• 124865-31-2 Ethyl 2-(4-fluoro-3-phenoxy-benzylidene)-4-methyl-3-oxopentanoate 
• 133333-82-1 1-cyclopropyl-1-(4-trifluoromethoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1,3-butadiene 
• 117842-01-0 1-(4-fluoro-3-phenoxyphenyl)-2-propen-1-ol 
• 68359-33-1 3'-phenoxy-4'-fluoro-benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-carboxylate 
• 1820573-27-0 (1R)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid (R,S)-α-cyano-3-phenoxy-4-fluoro-benzyl ester 
• 116272-45-8 1-(4-fluoro-3-phenoxy-phenyl)-2,2,2-trifluoro-ethanol 
• 113079-73-5 ethyl 3-(4-fluoro-3-phenoxyphenyl)acrylate 

Relevant academic research and scientific papers

Design, synthesis, and insecticidal activities of novel monohalovinylated pyrethroids

A series of novel monohalovinylated pyrethroids are designed and synthesized to replace one halo atom with a hydrogen atom on the double bond of dihalopyrethroids. Bioassays indicate that some of the synthesized compounds, such as 3j and 1j, exhibit high insecticidal activities against mosquitoes (Culex pipiens pallens), oriental armyworms (Mythimna separata), alfalfa aphids (Aphis medicagini), and carmine spider mites (Tetranychus cinnabarinus). Photolytic results of E-cis-1j suggest that monohalovinylated pyrethroids are photodegraded more easily than compound 12.

Process for the preparation of chiral isofluoroenes

There is provided a process for the preparation of a chiral insecticidal and acaricidal compound of formula I. Also provided are intermediate compounds useful in the process of the present invention.

Preparation of 4-fluoro-3-phenoxy-benzal-dehyde acetals and intermediates therefor

The new compound STR1 is prepared and converted to the new acetal STR2 which is reacted with an alkali phenolate or alkaline earth metal phenolate in the presence of copper or a copper compound as a catalyst and in the presence of a diluent at a temperature between about 100° and 200° C. to produce the new acetal STR3 which can be hydrolyzed to the corresponding aldehyde which is a known intermediate for pyrethroid-like insecticides.

Preparation of aldehydes by heating an α-hydroxyphosphonic acid ester

A process for the preparation of an aldehyde of the formula in which R is an optionally substituted alkyl, alkenyl, alkinyl, cycloakyl, cycloalkenyl, aralkyl, aralkenyl, aryl or heteroaryl radical, comprising heating an α-hydroxyphosphonic acid ester of the formula STR1 the aldehyde of the formula (I) can be used as an intermediate in the production of pest-combating agents.