2,2,5,5-Tetramethyltetrahydrofuran Explained

2,2,5,5-tetramethyltetrahydrofuran (TMTHF) or 2,2,5,5-tetramethyloxolane (TMO) is a heterocyclic compound with the formula, or (CH3)2(C(CH2)2OC)(CH3)2. It can be seen as derivative of tetrahydrofuran (oxolane) with four methyl groups replacing four hydrogen atoms on each of the carbon atoms in the ring that are adjacent to the oxygen. The absence of hydrogen atoms adjacent to the oxygen means that TMTHF (TMO) does not form peroxides, unlike other common ethers such as tetrahydrofuran, diethyl ether and CPME.

The compound has been demonstrated as a non-polar solvent in research chemistry, having similar properties to toluene[1] [2] and as a reagent in chemical synthesis.

Natural occurrence

The compound is produced in small quantities by the mycelium of Tuber borchii, a mushroom similar to the truffle.[3]

Synthesis and chemistry

The compound is easily prepared by the ring closure of 2,5-dimethylhexane-2,5-diol using acid catalysts. Zeolites have been shown to be particularly high yielding[1] but sulfuric acid can also be used.

TMTHF reacts with benzene in the presence of triflic acid to form 1,1,4,4-dimethyltetralin and symmetric tetramethyloctahydroanthracene. This and other similar reactions can be used for the selective preparation of derivatives of naphthalene, anthracene, and tetracene, and other fused-ring aromatic hydrocarbons.[4]

TMTHF undergoes photolysis by UV; in aqueous solution, the products are mainly methane, ethane, and 2-hydroxy-2,5,5-trimethyltetrahydrofuran. [5] The dehydration of TMTHF yields alkenes like 2,5-dimethyl-2,4-hexadiene and 2,5-dimethyl-1,5-hexadiene.[6]

Reaction with fluorine substitutes it for all hydrogen atoms to yield perfluoro(2,2,5,5-tetramethyltetrahydrofuran) (bp 99 C, mp -31 C).[7]

See also

Notes and References

  1. Fergal Byrne, Bart Forier, Greet Bossaert, Charly Hoebers, Thomas J Farmer, James H Clark, Andrew J Hunt (2017) 2, 2, 5, 5-Tetramethyltetrahydrofuran (TMTHF): a non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon solvents. Green Chemistry, volume 19, issue 15, pages 3671-3678.
  2. Alessandro Pellis, Fergal P Byrne, James Sherwood, Marco Vastano, James W Comerford, Thomas J Farmer (2019) Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters. Green Chemistry, volume 21, issue 7, pages 1686-1694.
  3. Bruno Tirillini, Giorgio Verdelli, Francesco Paolocci, Paolo Ciccioli, Massimiliano Frattoni (2000)The volatile organic compounds from the mycelium of Tuber borchii Vitt.. Phytochemistry, volume 55, issue 8, pages 983–985,
  4. István Ledneczki, Peter Forgo, Árpad Molnár (2007), Fused polycyclic hydrocarbons through superacid-induced cyclialkylation of aromatics. Catalysis Letters, volume 119, pages 296–303.
  5. Knut Hildebrand, Heinz-Peter Schuchmann, Clemens Von Sonntag (1989), The vacuum UV photolysis of aqueous solutions of two saturated ditertiary ethers: A product and CIDNP study, Journal of Photochemistry and Photobiology, Series A: Chemistry, volume 48, pages 219–232.
  6. Árpad Molnár and Miháli Bartók (1987), Studies on the chemistry of diols and cyclic ethers - 52: Mechanism and stereochemistry of dehydration of oxolanes to dienes. Tetrahedron, volume 43, issue 1, pages 131–141.
  7. Hsu-Nan Huang, Daniel F. Persico, Richard J. Lagow, Leland C. Clark Jr. (1988), Synthesis of unusual perfluorocarbon ethers and amines containing bulky fluorocarbon groups: New biomedical materials. Journal of Organic Chemistry, volume 53, pages 78-85.

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