TY  - JOUR
AB  - Bis(pentamethylcyclopentadienyl) ketone (1) reacts at low temperatures with LiAlH4 to form in good yields (pentamethylcyclopentadienyl)methanol (2) and its corresponding intramolecular Diels-Alder product 3 in a ca. 2:1 ratio. The alcohol 2 is separated from the tetracyclic compound 3 by crystallisation at -70°C from hexane/pyridine as pyridine adduct. The pyridine-free alcohol 2 is available by repeated dissolving of the adduct in hexane and removal of the volatile components in vacuo. The alcohol tends to intramolecular [4 + 2] cycloaddition even at room temperature with formation of 3. A derivatization of 2 is possible by deprotonation with alkyllithium compounds, which leads to the alcoholate 4, and subsequent treatment with phosgen and tosyl chloride, thus affording the chloroformate 6 and the tosylate 7, respectively, in good yields. The thermolabile tosylate 7 decomposes to pentamethylbenzene or, under basic conditions, to the pentacyclic compound 7.
DA  - 1994
DO  - 10.1002/cber.19941270118
KW  - bis(pentamethylcyclopentadienyl)methanol
KW  - Tosylate
KW  - Chloroformate
KW  - Bis(pentamethylcyclopentadienyl)methanol
KW  - intramolecular
KW  - Diels-Alder reaction
LA  - ger
IS  - 1
M2  - 107
PY  - 1994
SN  - 0009-2940
SP  - 107-112
T2  - Chemische Berichte
TI  - Bis(pentamethylcyclopentadienyl)methanol: Synthese, Struktur und Derivatisierung
UR  - https://nbn-resolving.org/urn:nbn:de:0070-pub-17743657
Y2  - 2024-11-22T04:22:06
ER  -