5567. Longifolene

Nomenclature

CAS number: 475-20-7
[1S-(1α,3aβ,4α,8aβ)]-Decahydro-4,8,8-trimethyl-9-methylene-1,4-methanoazulene; junipene; kuromatsuene.
C15H24; mol wt 204.35.
C 88.16%, H 11.84%.

Description and references

Tricyclic sesquiterpene present to the extent of 5-10% in Indian turpentine oil which is produced commercially from the Himalayan pine, Pinus longifolia Roxb., Pinaceae: J. L. Simonsen, J. Chem. Soc. 117, 570 (1920). Structure: R. H. Moffett, D. Rogers, Chem. Ind. (London) 1953, 916; P. Naffa, G. Ourisson, ibid. 917. Abs config: G. Ourisson, Bull. Soc. Chim. Fr. 1955, 895. Identity of longifolene with junipene and kuromatsuene: S. Akiyoshi et al., Tetrahedron 9, 237 (1960). Total synthesis of naturally occurring (+)-form: E. J. Corey et al., J. Am. Chem. Soc. 86, 478 (1964); of the (±)-form: eidem, ibid. 83, 1251 (1961); J. E. McMurray, S. J. Isser, ibid. 94, 7132 (1972); R. A. Volkmann et al., ibid. 97, 4777 (1975). Review of chemistry of longifolene and its derivs: S. Dev, Acc. Chem. Res. 14, 82-88 (1981); idem, Fortschr. Chem. Org. Naturst. 40, 50-104 (1981).

Chemical structure

Properties

Viscous oil, bp706 254-256°, bp15 126-127°. [α]D18 +42.73°. d418 0.9319; nD20 1.5040. Insol in water; sol in benzene.

Derivative

Borane deriv.

Nomenclature

Dilongifolylborane.
C30H51B; mol wt 422.54.
C 85.28%, H 12.17%, B 2.56%.

Properties

Heavy, snow-white, shiny plates, mp 160-161° (sealed, evacuated capillary). Strongly dimeric. Sparingly sol in common organic solvents. Prepn and use in hydroboration: P. K. Jadhav, H. C. Brown, J. Org. Chem. 46, 2988 (1981).

Use

Borane deriv as a chiral hydroborating agent.