24797-40-8

Upstream product

• 106-38-7 para-bromotoluene 
• 3282-30-2 pivaloyl chloride 
• 927-83-3 di-t-butyldiazene 
• 106-42-3 para-xylene 
• 108-88-3 toluene 
• 132907-18-7 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene 
• 594-19-4 tert.-butyl lithium 
• 104-82-5 4-Methylbenzyl chloride 
• 507-20-0 tertiary butyl chloride 

Downstream Products

• 136708-03-7 p-(2,2-dimethylpropyl)benzyl acetate 
• 136708-00-4 α-tert-butyl-p-methylbenzyl acetate 
• 32018-31-8 4-pivaloyl-benzoic acid 
• 65687-52-7 4-(2,2-dimethylpropyl)benzoic acid 

Relevant academic research and scientific papers

REACTIVITY OF 3,6-DIMETHOXY-3,6-DIMETHYLCYCLOHEXA-1,4-DIENE: NUCLEAR VERSUS BENZYLIC NUCLEOPHILIC SUBSTITUTION

The treatment of cis/trans-3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (ca. 1/1 mixture; easily prepared electrochemically in multigram scale from p-xylene) under acidic conditions (acetic, trifluoroacetic, sulfuric, or a Lewis acid) yields almost exclusively 2-methoxy-1,4-dimethylbenzene 4, through a trasposition reaction.The use of aqueous hydrochloric or hydrofluoric acid gives 2,5-dimethylphenol 12, and with hydrogen chloride a mixture of 2- and α-chloro-p-xylene (13, 14) is isolated.Different oxygen-, nitrogen-, and sulfur-containing nucleophiles (alcohols,thiols, or hydrazoic acid) react with 3 under acid catalysis giving the corresponding products resulting from a nuclear or/ and benzylic substitution on p-xylene (15 - 20).The reaction of compound 3 with organolithium reagents affords exclusively benzylic products 21 in a regiospecific manner.In all cases the mixtures of isomers are separated by column chromatography.The lithiation of compound 3 with lithium powder or lithium naphthalenide fails, giving p-xylene.A probable mechanism is proposed for the studied reactions.

Chemistry of the tert-Butyl Radical: Polar Character, ρ Value for Reaction with Toluenes, and the Effect of Radical Polarity on the Ration of Benzylic Hydrogen Abstraction to Addition to Aromatic Rings

We have reexamined the reactions of tert-butyl radicals with toluenes and have obtained a ρ value of 0.49 +/- 0.04 at 80 deg C.The new, independent system involves the quantification of all of the principal products from the reaction of tert-butyl radicals with mixtures of toluene and substituted toluene.Five major products contain benzyl fragments and are formed in significant yields: two symmetrical bibenzyls, the cross bibenzyl, and the two neopentylbenzenes that result from combination of tert-butyl and the two benzyl radicals.Attack on the side chain is a major reaction of free tert-butyl radicals and is the only significant reaction that they undergo other than cage and termination reactions. tert-Butyl radicals do not add to the ring of toluenes.Data on the relative rates of addition to benzenes and hydrogen abstraction from toluenes are collected for a series of radicals including hydrogen atoms; methyl, isopropyl, and tert-butyl radicals; and p-nitrophenyl, p-bromophenyl, and phenyl radicals.The data demonstrate that more electrophilic radicals have a larger tendency to add to rings whereas more nucleophilic radicals have a larger tendency to abstract benzylic hydrogens.