US4259510A — Preparation of trifluoromethylphenyl nitrophenyle…

Claim 1

Independent Claim 263 words

A process for preparing a compound of the formula ##STR30## wherein X is hydrogen, halo, trifluoromethyl or lower alkyl; X' is hydrogen, halo, cyano, lower alkyl, lower alkoxy, carboxy, carbalkoxy, carbalkoxyalkoxy, alkoxycarbalkoxy, carbalkenyloxy, carbamoyl, mono- and dialkylcarbamoyl or trifluoromethyl, and X" is halo or trifluoromethyl with the proviso that when X" is halo X is trifluoromethyl, which comprises treating a compound of the formula: ##STR31## wherein X and X" are as defined above and X 2 is fluoro or chloro with an alkali or alkaline earth metal hydroxide at a temperature in the range of from about 50° to about 100° C. for a period of time in the range from 5 hour to about 5.5 days in a solvent system comprising a dipolar, aprotic solvent having a dielectric constant in the range of from about 30 to about 70, said solvent being inert or substantially inert to said hydroxide, and a non-nucleophilic, hydroxylated cosolvent that increases the solubility of hydroxide to afford a trifluoromethylphenate of the formula ##STR32## wherein X and X" are is as defined above and M is an alkali metal or alkaline earth metal cation, which may be isolated upon acidification as the free phenol or reacted with a halonitrobenzene of the formula: ##STR33## wherein X' is as defined above and halo is fluoro or chloro in a dipolar, apiotic solvent at temperatures ranging from 20°-130° C. for halo being fluoro and from 50°-130° C. for halo being chloro for a period of from one hour to six days depending upon the nature of M, halo, X and X'.

Claim 2

Dependent Claim 263 words

A process for preparing a compound of the formula ##STR30## wherein X is hydrogen, halo, trifluoromethyl or lower alkyl; X' is hydrogen, halo, cyano, lower alkyl, lower alkoxy, carboxy, carbalkoxy, carbalkoxyalkoxy, alkoxycarbalkoxy, carbalkenyloxy, carbamoyl, mono- and dialkylcarbamoyl or trifluoromethyl, and X" is halo or trifluoromethyl with the proviso that when X" is halo X is trifluoromethyl, which comprises treating a compound of the formula: ##STR31## wherein X and X" are as defined above and X 2 is fluoro or chloro with an alkali or alkaline earth metal hydroxide at a temperature in the range of from about 50° to about 100° C. for a period of time in the range from 5 hour to about 5.5 days in a solvent system comprising a dipolar, aprotic solvent having a dielectric constant in the range of from about 30 to about 70, said solvent being inert or substantially inert to said hydroxide, and a non-nucleophilic, hydroxylated cosolvent that increases the solubility of hydroxide to afford a trifluoromethylphenate of the formula ##STR32## wherein X and X" are is as defined above and M is an alkali metal or alkaline earth metal cation, which may be isolated upon acidification as the free phenol or reacted with a halonitrobenzene of the formula: ##STR33## wherein X' is as defined above and halo is fluoro or chloro in a dipolar, apiotic solvent at temperatures ranging from 20°-130° C. for halo being fluoro and from 50°-130° C. for halo being chloro for a period of from one hour to six days depending upon the nature of M, halo, X and X'.

Claim 3

Dependent Claim 142 words

The process of claim 1 for preparing a compound of the formula ##STR34## wherein X and X' are as defined in claim 1 which comprises treating a compound of the formula: ##STR35## wherein X and X 2 are as defined in claim 1 with an alkali metal or alkaline metal hydroxide in a solvent system comprising a non-nucleophilic hydroxy containing solvent and a dipolar, aprotic solvent selected from dimethylsulfoxide tetrahydrothiophene-1,1-dioxide or hexamethylphosphoric triamide to afford a compound of the formula ##STR36## wherein X and M are as defined in claim 1 and then treating said compound with a halobenzene of the formula ##STR37## wherein X' is as defined above at a temperature in the range of from about 20° to 130° C. in a dipolar, aprotic solvent selected from dimethyl sulfoxide, dimethylformamide, N-methylacetamide, tetrahydrothiophene 1,1-dioxide, hexamethylphosphoric triamide, 1,4-dioxane, ethylene carbonate or 1,2-dimethoxyethane.

Claim 4

Dependent Claim 216 words

The process of claim 2 wherein the non-nucleophilic hydroxy containing compound is selected from among ##STR38## wherein R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different groups selected from hydrogen; straight or branched lower alkyl, substituted or unsubstituted phenyl substituents wherein phenyl substituents may be alkyl, halo, lower alkoxy, a benzyl, and the like; R 8 is lower alkyl; n and n 2 are 0 or 1; n 1 is 0 to 2, n 3 is an integer of from 1 to 10; n 4 is 2 to 4 provided that n 1 is 2 only when n and n 2 are both 0, otherwise the sum of n 1 and n 2 may not simultaneously be greater than 1; when n 3 is greater than 2, the sum of n and n 2 may not simultaneously be greater than 1 and n 1 must be 0; when R 7 is hydrogen, n' must be zero and the sum of n and n 2 must be 1 such that at least 3 of the groups R, R' plus either the pair R 2 and R 3 or the pair of R 5 and R 6 must not be hydrogen.

Claim 5

Dependent Claim 25 words

The process of claim 3 wherein the hydroxy compound is selected from tert-butanol, pinacol, pentaeythritol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-2,3,4-pentane triol, 2,4-dimethyl-3-pentanol, 2,2,2-trimethyl-3-pentanol, 2,2-dimethyl-1-propanol, 2,5-dimethyl-3-hexane-2,5-diol, 1-methyl-1-cyclohexanol or 2-isopropyl-1-cyclopentanol.

Claim 6

Dependent Claim 36 words

The process of claim 2 wherein the solvents are employed in the ratio of from about 1 part to about 30 parts of the non-nulceophilic hydroxy solvent to about 100 parts of the dipolar, aprotic solvent.

Claim 7

Dependent Claim 35 words

The process of claim 5 wherein the solvents are employed in the ratio of from about 5 to about 20 parts of the non-nucleophilic hydroxy solvent to about 100 parts of the dipolar, aprotic solvent.

Claim 8

Dependent Claim 24 words

The process of claim 2 wherein X is chloro, X' is hydrogen, methoxy, ethoxy, carboxy, methoxyethoxycarbonyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, sodium carboxylate or potassium carboxylate.

Claim 9

Dependent Claim 10 words

The process of claim 7 wherein X' is sodium carboxylate.

Claim 10

Dependent Claim 10 words

The process of claim 7, wherein X' is potassium carboxylate.

Claim 11

Dependent Claim 9 words

The process of claim 7, wherein X' is methoxycarbonyl.

Claim 12

Dependent Claim 9 words

The process of claim 7 wherein X' is ethoxycarbonyl.

Claim 13

Dependent Claim 9 words

The process of claim 7 wherein X' is methoxyethoxycarbonyl.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1984-03-30	1984-09-29	1985-03-31	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1988-03-30	1988-09-29	1989-03-31	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1992-03-30	1992-09-29	1993-03-31	$7700.00	Window Closed / Lapsed

Preparation of trifluoromethylphenyl nitrophenylethers

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag