19301-54-3

Usage

Classification

Adamantane derivative

Structure

Bicyclic compound with a ketone group and a chlorine atom attached to the carbon backbone

Stereochemistry

(1S,4R) designation, indicating the arrangement of substituent groups on the carbon atoms

Usage

Used in organic synthesis and pharmaceutical research as a building block for the preparation of various chemical compounds and drug molecules

Value

Its unique structure and reactivity make it a valuable tool in the development of new materials and pharmaceuticals

Upstream product

• 21898-84-0 4-oxohomoadamantan-5-one 
• 19213-96-8 4e-Chlor-adamantanon-(2) 
• 19213-96-8 4^e-chloro-2-adamantanone 
• 700-58-3 2-Adamantanone 
• 594-19-4 tert.-butyl lithium 
• 26278-43-3 4^a-Hydroxytricyclo<3.3.1.1^3,7>decan-2-on 
• 21932-98-9 endo-Bicyclo<3.3.1>non-6-ene-3-carboxylic acid 
• 19439-22-6 (1S)-4(a)-Brom-adamantanon-⁽²⁾ 
• 5202-69-7 (+)-(1R)-2-carboxyadamantane-4,8-dione 

Downstream Products

• 19213-96-8 4e-Chlor-adamantanon-(2) 
• 113335-68-5 2,2,4^e-trichloroadamantane 
• 19213-96-8 4^e-chloro-2-adamantanone 
• 113335-68-5 2,2,4^a-trichloroadamantane 
• 95935-36-7 7-endo-pivaloylbicyclo(3.3.1)non-2-ene 
• 132259-84-8 7-endo-(di-tert-butylhydroxymethyl)bicyclo-(3.3.1)non-2-ene 
• 132156-54-8 2,11,11-trimethyl-15-oxa-2,4-ethanoadamantane 
• 132259-88-2 4-endo-tert-butyl-3,4-exo-epoxyprotoadamantane 
• 132156-40-2 2^e-tert-butyl-4^a-chloroadamantan-2^a-ol 

Relevant academic research and scientific papers

The nature of the electronic factor governing diastereofacial selectivity in remotely substituted (X) 2-adamantyl cations: 5-X versus 4-X substitution

A limited series of 4eq-substituted (X) 2-methyleneadamantanes (6, Y=CH2, X=F, Cl, Br, I, and SnMe3) has been synthesized and diastereoselectivities for their hydrochlorination (HCl/CH2Cl 2) have been determined. Diastereoselectivities for the fluorination (DAST/CH2Cl2) of secondary alcohol mixtures, obtained from the hydride reduction of the precursor ketones (6,Y=O) to the alkenes, have also been measured. A comparison of this selectivity data for nucleophilic trapping of 4eq-substituted (X) 2-adamantyl cations (4, R=H and Me) with the corresponding information for 5-substituted (X) 2-adamantyl cations (1, R=H and Me) has revealed important distinctions between the two series. In particular, whereas extended hyperconjugative effects appear to be the predominant electronic effect governing facial selectivity in the 5,2-series, electrostatic influences prevail in the 4,2-disposition. Copyright

Solvent and Temperature Effects in π-Route Cyclization

endo-Bicyclo[3.3.1]non-6-ene-3-carboxylic acid (1) was prepared and the solvent and temperature effects on the π-route cyclization were studied. The stereochemistry of the products strongly depends on the reaction temperature and the solvent used. The interpretation of the mechanism and product distribution based on experimental data is supported by theoretical investigation.

Syntheses and NMR Spectra of Substituted 2-tert-Butyladamantan-2-ols

The synthesis of a number of substituted 2-tert-butyladamantan-2-ols from the corresponding ketones is described.In addition to these addition reactions, some unexpected rearrangements were observed.Reaction mechanisms are proposed to rationalize the experimental results. 13C NMR spectra of some adamantanes are discussed in terms of substituent interaction effects.

REACTION OF ADAMANTANONE, DIAMANTANONE, AND THEIR DERIVATIVES WITH THIONYL CHLORIDE

In reaction of adamantanone, diamantanone, and their chloro or oxo derivatives with thionyl chloride the oxo group is replaced with two chlorine atoms under formation of geminal dichloro derivatives.The presence of a chlorine atom or an oxo group in both ketones reduces the reaction rate.The reaction rate decreases with decreasing distance between the substituent and the carbonyl group.Ketones with chlorine atom in α- or β-axial position do not react with thionyl chloride.The reaction is accelerated by hydrogen chloride whereas in the presence of pyridine no reaction was observed.

REACTION OF 5-OXO-4-OXAHOMOADAMANTANE WITH THIONYL CHLORIDE

On reaction with thionyl chloride 5-oxo-4-oxa-homoadamantane gives rise to a mixture of 4a-chloro- and 4e-chloro-2-adamantanone.The carbonyl group of chloroadamantane further reacts with thionyl chloride under formation of 2,2,4e-trichloroadamantane.In the same way adamantanone reacts with thionyl chloride, giving rise to 2,2-dichloroadamantane.

A Cyclic Voltammetry Study of the Cation Radical Catalyzed Oxygenation of Tetraalkyl Olefins to Dioxetanes

Cyclic voltammetry studies allow estimation of the rate constant for addition of O2 to biadamantylidene cation radical (1.+) to be 5600 M-1 s-1 at room temperature and for the cleavage of biadamantylidene dioxetane cation radical to oxygen and 1.+ > 800 s-1.Chlorination of the adamantane skeleton slows the overall rate of oxygen addition, and the face selectivity for oxygenation of 5(Cl) is 25:1 in favor attack from the olefin face syn to the chlorine.The implications of these findings for the mechanism of the reaction are discussed.

BECKMANN REARRANGEMENT OF ADAMANTANONE OXIME AS A ROUTE TO DITOPIC AND TRITOPIC SECONDARILY SUBSTITUTED ADAMANTANE DERIVATIVES

The reaction in mixtures of adamantanone with hydroxylamine hydrochloride was studied in hydrochloric, hydrobromic, and hydroiodic acid solutions.In hydrochloric and hydroiodic acids, mixtures of isomers of 4-chloroadamantan-2-one and 4-iodoadamantan-2-one, respectively, are formed, whereas in hydrobromic acid in the presence of excess hydroxylamine hydrochloride, three stereoisomers of 4,8-dibromoadamantan-2-one appear.All the stereoisomeric haloketones were isolated by elution adsorption chromatography on silica gel or by crystallization.For the pure substances, their infrared, mass, and NMR spectra were measured.