1,3-Dehydroadamantane Explained

1,3-Dehydroadamantane or tetracyclo[3.3.1.1<sup>3,7</sup>.0<sup>1,3</sup>]decane is an organic compound with formula C10H14, which can be obtained from adamantane by removal of two hydrogen atoms to create an internal bond. It is a polycyclic hydrocarbon, and can be viewed also as being derived from [3.3.1]propellane by addition of a methylene bridge between the two larger rings.

Like other small-ring propellanes, this compound is substantially strained and unstable.

Synthesis

1,3-Dehydroadamantane was obtained in 1969 by Richard Pincock and Edward Torupka,[1] by reduction of 1,3-dibromoadamantane according to the scheme below:

Reactions

Oxidation

On standing in solution, it reacts with oxygen from air (with a half-life of 6 hours), yielding a peroxide. The latter converts to a dihydroxide by reaction with lithium aluminium hydride.

Polymerization

Like [1.1.1]propellane, 1,3-dehydroadamantane can be polymerized by breaking the axial bond and joining the resulting radicals into a linear chain:

In this scheme, 1,3-dehydroadamantane is reacted with acrylonitrile in a radical polymerization initiated with lithium metal in tetrahydrofuran. The resulting alternating copolymer has a glass transition temperature of 217 °C[2]

See also

Notes and References

  1. Richard E.. Pincock. Edward J.. Torupka . 1969 . Tetracyclo[3.3.1.1<sup>3,7</sup>.0<sup>1,3</sup>]decane. Highly reactive 1,3-dehydro derivative of adamantane . . 91. 16 . 4593 . 10.1021/ja01044a072.
  2. Shin'ichi . Matsuoka . Naoto . Ogiwara . Takashi . Ishizone. 2006 . Formation of Alternating Copolymers via Spontaneous Copolymerization of 1,3-Dehydroadamantane with Electron-Deficient Vinyl Monomers . J. Am. Chem. Soc. . 128 . 27 . 8708–8709 . 10.1021/ja062157i . 16819846.