Chemical Properties
clear colourless liquid
Uses
1,3-Dimethyladamantane is a dimethylated adamantane derivative. Memantine impurity A. Memantine Related Compound A (1,3-Dimethyladamantane).
Application
1,3-Dimethyladamantane was used in the synthesis of 1,3-dibromo-5,7-dimethyladamantane.
Definition
ChEBI: 1,3-dimethyladamantane is a polycyclic alkane and a member of adamantanes. It derives from a hydride of an adamantane.
General Description
1,3-Dimethyladamantane undergoes C-H insertion reaction with phenylchlorocarbene. It reacts with with molecular oxygen in the presence of
N-hydroxyphthalimide combined with cobalt salts to yield 3,5-dimethyladamantan-1-ol and 5,7-dimethyladamantane-1,3-diol.
Synthesis
GENERAL METHODS: A thiocarbonate solution was prepared by dissolving 5 g (107 mg, 0.200 mmol) of 1-bromo-3,5-dimethyladamantane in CPME (0.5 mL). Subsequently, a solution of n-Bu3SnH (75.7 mg, 0.260 mmol) and AIBN (6.6 mg, 0.040 mmol) in CPME (1.5 mL) was slowly added dropwise by syringe pump to the above thiocarbonate solution, and the reaction lasted for 30 min at 90 °C. After completion of the reaction, the mixture was continued to be stirred at the same temperature for 30 min, followed by concentration. The residue was purified by 10% w/w K2CO3-silica gel fast column chromatography using gradient elution (hexane → hexane/EtOAc = 100/1 → 50/1 → 20/1) to afford 6 g of cis-consistently cyclized product (53.6 mg, 0.140 mmol, 70% yield) and a mixture of cis- and trans-consistently diastereoisomers (22.0 mg. 0.0572 mmol, 29% yield, cis-trans ratio of 2.8:1). For spectral analysis, these isomers were separated by repeated column chromatography.
References
[1] Tetrahedron, 2013, vol. 69, # 10, p. 2251 - 2259
[2] Organic Letters, 2008, vol. 10, # 4, p. 533 - 536
[3] Journal of Organic Chemistry, 1983, vol. 48, # 16, p. 2762 - 2765
