88790-35-6

Upstream product

• 98-82-8 Isopropylbenzene 
• 78-83-1 2-methyl-propan-1-ol 
• 3805-10-5 2,2-(dimethyl)-2-phenylacetaldehyde 
• 1888-75-1 isopropyllithium 
• 617-94-7 1-methyl-1-phenylethyl alcohol 
• 1195-98-8 2-methyl-2-phenylpropionitrile 
• 78-84-2 isobutyraldehyde 
• 4148-93-0 2-phenyl-2-propyl phenyl sulfide 

Downstream Products

• 91496-41-2 2-(1,1-dimethyl-2-oxopropyl)benzoic acid 
• 31952-55-3 α,α-dimethyl-2-carboxyphenylacetic anhydride 

Relevant academic research and scientific papers

On rearrangements by cyclialkylations of arylpentanols to 2,3-dihydro-1H-indene derivatives. Part 2. An unexpected rearrangement by the acid-catalyzed cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol under formation of trans-2,3-dihydro-1,1,2,3-tetramethyl-1H-indene

The acid catalyzed-cyclialkylation of 4-(2-chloro-phenyl)-2,4-dimethylpentan-2-ol (1) gave two products: 4-chloro-2,3-dihydro-1,1,3,3-tetramethyl-1H-indene (2) and also trans-4-chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-indene (3). A mechanism was proposed in Part 1 (cf. Scheme 1) for this unexpected rearrangement. This mechanism would mainly be supported by the result of the cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol (4), which, with respect to the similarity of ion II in Scheme I and ion V in Scheme 2, should give only product 5. This was indeed the experimental result of this cyclialkylation. But the result of the cyclialkylation of 1,1,1,2′,2′,2′-hexadeuterated isomer [2H6]-4 of 4 (cf. Scheme 3) requires a different mechanism as for the cyclialkylation of 1. Such a mechanism is proposed in Schemes 5 and 6. It gives a satisfactory explanation of the experimental results and is supported by the result of the cyclialkylation of 2,4-dimethyl-3-phenylpentan-3-ol (9; Scheme 7). The alternative migration of a Ph or of an i-Pr group (cf. Scheme 6) is under further investigation.

Cumyl phenyl sulfide forms bicumyl instead of cumyllithium upon reductive lithiation. Thiophenoxide as a leaving group in nucleophilic substitution by SET

Upon reduction with aromatic radical-anions, cumyl phenyl sulfide (Is) yields mainly bicumyl (2) rather than the expected cumyllithium (3), despite a literature report, herein revealed to be in error, chat anion 3 is produced. Related examples from the literature are compiled. A suggested mechanism involves a single electron transfer from the generated cumyllithium (3) to the cumyl phenyl sulfide (Is) leading to thiophenoxide anion and two cumyl radicals, which mainly couple in a solvent cage. Such a thiophenoxide displacement by anion 3 has been demonstrated experimentally. Para tert-butyl groups, either on the phenyl or cumyl ring, increase the ratio of the cumylithium to the bicumyl, presumably by sterically inhibiting the pi complexation thought to be necessary for electron transfer.

PHOTOSUBSTITUTION OF BENZYL HYDROGENS WITH ALCOHOLIC MOIETIES. SELECTIVE FORMATION OF ALKYLBENZENE CARBINOLS

Irradiations of alkylbenzene compounds with various alcohols in an air atmosphere, resulted in substitution of the benzyl hydrogens with alcoholic moieties in a very selective mode.