The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities
This article provides insight into the various factors by which electroneg. substituents affect the kinetic acidity of arenes and, more specifically, naphthalenes. Both 1- and 2-(trifluoromethyl)naphthalenes were consecutively treated with an organometallic or lithium dialkylamide-type base and carbon dioxide. Due to single electron-transfer triggered side reactions, the yields of (trifluoromethyl)naphthoic acids were moderate to poor. 1-(Trifluoromethyl)naphthalene was exclusively attacked at the 2-position as expected. The 2-isomer reacted with tert-butyllithium in the presence of potassium tert-butoxide solely at the 1-position, but with sec-butyllithium in the presence of N,N,N',N'-tetramethylethylenediamine concomitantly at the 3- and 4-positions. Authentic samples of the key acids were prepd. based on independent, unambiguous methods. [on SciFinder (R)]
WOS:000228308200019
2005
5
798
803
CAN 143:7251
22-4
Physical Organic Chemistry
Institut des Sciences Chimiques (ISIC-BCh),Ecole Polytechnique Federale,Lausanne,Switz.
Journal
written in English.
852103-57-2P (Methyl 1-(trifluoromethyl)-2-naphthoate) Role: ANT (Analyte), SPN (Synthetic preparation), ANST (Analytical study), PREP (Preparation) (The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 110-18-9 (TMEDA); 594-19-4 (tert-Butyllithium); 598-30-1 (sec-Butyllithium); 865-47-4; 38227-87-1 (Lithium 2,2,6,6-tetramethylpiperidine) Role: RGT (Reagent), RACT (Reactant or reagent) (The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 1534-69-6P (2-(Trifluoromethyl)-1-naphthoic acid); 50318-07-5P (3-(Trifluoromethyl)-2-naphthoic acid); 255051-43-5P (3-(Trifluoromethyl)-1-naphthoic acid); 852103-58-3P (1-(Trifluoromethyl)-2-naphthoic acid); 852103-60-7P (8-(Trifluoromethyl)-1-naphthoic acid) Role: SPN (Synthetic preparation), PREP (Preparation) (The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 106750-88-3 (6,7-Dibromo-1,4-dihydronaphthalene-1,4-epoxide) Role: RCT (Reactant), RACT (Reactant or reagent) (deoxygenation; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 17135-74-9 (1,8-Dibromonaphthalene); 852103-62-9 (2,4-Dibromo-1-chloronaphthalene) Role: RCT (Reactant), RACT (Reactant or reagent) (iodination; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 13214-70-5P (2,3-Dibromonaphthalene) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (iodination; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 26458-04-8 (1-(Trifluoromethyl)naphthalene) Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (metalation/quenching; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 117539-58-9P (1-Bromo-2-(trifluoromethyl)naphthalene); 852103-59-4P (1-Bromo-8-(trifluoromethyl)naphthalene); 852103-61-8P (2-Bromo-3-(trifluoromethyl)naphthalene); 852103-64-1P (4-Bromo-1-chloro-2-(trifluoromethyl)naphthalene) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (metalation/quenching; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 581-90-8 (2-(Trifluoromethyl)naphthalene) Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (metalation; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 852103-65-2P (4-Chloro-3-(trifluoromethyl)-1-naphthoic acid) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (redn.; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 90948-03-1 (1-Bromo-2-iodonaphthalene) Role: RCT (Reactant), RACT (Reactant or reagent) (trifluoromethylation; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities); 4044-58-0P (1-Bromo-8-iodonaphthalene); 102153-44-6P (2-Bromo-3-iodonaphthalene); 852103-63-0P (4-Bromo-1-chloro-2-iodonaphthalene) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (trifluoromethylation; The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities)
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