Adamantane

Adamantane (tricyclo[3.3.1.1^3,7]decane) is a colourless, crystalline compound with a camphor-like odour.^[1][2] With a formula C₁₀H₁₆, it is a cycloalkane and also the simplest diamondoid. Adamantane was discovered in petroleum in 1933.^[3] Its name derived from the Greek adamantinos (relating to steel or diamond), due to its diamond-like structure.^[4] Adamantane is the most stable isomer of C₁₀H₁₆.

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Synthesis

Adamantane was first synthesised by Prelog in 1941.^[5] A more convenient method was found by Schleyer in 1957, from dicyclopentadiene by hydrogenation followed by acid-catalysed skeletal rearrangement.^[6][7]

Uses

Adamantane itself enjoys few applications since it is merely an unfunctionalised hydrocarbon. It is used in some dry etching masks.^[8] It is also used in some polymer formulations.

In solid-state NMR spectroscopy, adamantane is a common standard for chemical shift referencing.^[9]

In dye lasers, adamantane may be used to extend the life of the gain medium; it cannot be photoionised under atmosphere because its absorption bands lie in the vacuum-ultraviolet region of the spectrum. Photoionization energies have been determined recently for adamantane as well as for several bigger diamondoids.^[10]

Adamantane derivatives

Adamantane derivatives are useful in medicine, e.g. amantadine, memantine and rimantadine. Condensed adamantanes or diamondoids have been isolated from petroleum fractions, where they occur in small amounts. These species are of interest as molecular approximations of the cubic diamond framework, terminated with C-H bonds. 1,3-Dehydroadamantane is a member of the propellane family.

Due to its stability, specific steric properties and conformational rigidity, the 1-adamantyl group is a (bulky) substituent in organic and organometallic chemistry. Some of the first persistent carbenes featured adamantyl substituents.

Adamantane analogues

Many molecules adopt cage structures with adamantanoid structures. Particularly useful compounds with this motif include P₄O₆, As₄O₆, P₄O₁₀ (= (PO)₄O₆), P₄S₁₀ (= (PS)₄S₆), and N₄(CH₂)₆.^[11]

References

1. ^ SID 152429 -- PubChem Substance Summary. Retrieved on 14 October, 2005.
2. ^ ADAMANTANE(TRICYCLO(3.3.1.1)DECANE). Retrieved on 14 October, 2005.
3. ^ Landa, S.; Machácek, V. (1933). "". Collection Czech. Chem. Commun. 5: 1.
4. ^ Alexander Senning. Elsevier's Dictionary of Chemoetymology. Elsevier, 2006. ISBN 0444522395.
5. ^ Prelog, V., Seiwerth,R. (1941). "". Berichte 74: 1644 and 1769.
6. ^ Schleyer, P. von R. (1957). "A Simple Preparation of Adamantane". J. Am. Chem. Soc. 79: 3292-3292. doi:10.1021/ja01569a086.
7. ^ Schleyer, P. von R.; Donaldson, M. M.; Nicholas, R. D.; Cupas, C. "Adamantane", Organic Syntheses, Coll. Vol. 5, p.16 (1973); Vol. 42, p.8 (1962).
8. ^ ^  WATANABE, KEIJI; et al. (2001). RESIST COMPOSITION AND PATTERN FORMING PROCESS. United States Patent Application 20010006752. Bandwidth Market, Ltd. Retrieved on 14 October, 2005.
9. ^ Corey R. Morcombe and Kurt W. Zilm (2003). "Chemical Shift referencing in MAS solid state NMR". J. Magn. Reson. 162: 479-486. doi:10.1016/S1090-7807(03)00082-X.
10. ^ K. Lenzke, L. Landt, M. Hoener et al. (2007). "Experimental determination of the ionization potentials of the first five members of the nanodiamond series". J. Chem. Phys. 127: 084320. doi:10.1063/1.2773725.
11. ^ Vitall, J. J., "The Chemistry of Inorganic and Organometallic Compounds with Adamantane-Like Structures", Polyhedron, 1996, 15, 1585-1642