Thermochemistry of Organic and Heteroorganic Species. Part V. Photoionization Studies of Isomerization and Fragmentation of Polysubstituted Cyclopropenes: 3-Methyl-3-Acetyl- and Related Compounds

Abstract

Appearance energies for molecular and some fragment ions from 3-methyl-3-acetyl-, 1,2-dimethyl-3-acetyl-, 1,2-dimethyl-3-hydroxycarbonyl- and 1,3-dimethyl-2-(1-methyl)vinylcyclopropenes and model compounds 2,3-dimethylfuran and 1-methylindene were measured by photoionization mass spectrometry. It was shown that, in all cases, the structure of the [M – Me]⁺ ion does not correspond to the expected structures of substituted cyclopropenium ions. Possible schemes for formation of [M – Me]⁺ ions are given. Isodesmic reactions were systematically applied for calculation of the heats of formation for 35 possible C₅H₅O⁺ isomers from 3-methyl-3-acetyl-cyclopropene. In addition, the heats of formation for more than 30 other unsaturated ions and free radicals were estimated with the help of series of isodesmic reactions. A new value of 160 kJ mol⁻¹, as compared with the currently used value of 215.5 kJ mol⁻¹, for the cyclopropylmethyl free radical is suggested. The publication represents the further development of the methodology for the heat of formation estimation procedure for even-electron ions and free radicals.

Keywords

photoionization thermochemistry aromatic ions

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References

Domnin

I.N.

Takhistov

V.V.

Ponomarev

D.A.

, Eur. Mass Spectrom. 4, 151 (1998).

Takhistov

V.V.

Ponomarev

D.A.

, Org. Mass Spectrom. 29, 395 (1994).

Takhistov

V.V.

, Organic Mass Spectrometry (Russ.), Nauka, Leningrad and references therein (1990).

Lias

S.G.

Bartmess

J.E.

Liebman

J.F.

Holmes

J.L.

Levin

R.D.

Mallard

W.G.

, J. Phys. Chem. Ref. Data 17, Suppl. 1, (1988).

Levsen

, Fundamental Aspects of Organic Mass Spectrometry. Verlag Chemie, Weinheim (1978).

Willett

G.D.

Baer

, J. Am. Chem. Soc. 102, 6769 (1980).

Burgers

P.C.

Holmes

J.L.

Lossing

F.P.

Mommers

A.A.

Povel

F.R.

Terlouw

J.K.

, Can. J. Chem. 60, 2246 (1982).

Lias

S.G.

Liebman

J.F.

Levin

R.D.

, J. Phys. Chem. Ref. Data 13, 695 (1984).

Meot-Ner (Mautner)

Sieck

L.W.

, J. Am. Chem. Soc. 113, 4448 (1991).

10.

Domnin

I.N.

Lakshin

A.M.

Misharev

A.D.

Orlov

V.M.

Takhistov

V.V.

, J. Org. Chem. USSR. Engl. Transl. 21, 1149 (1985).

11.

Holmes

J.L.

Terlouw

J.K.

Burgers

P.C.

, Org. Mass Spectrom. 15, 140 (1980).

12.

Lossing

F.P.

Holmes

J.L.

, J. Am. Chem. Soc. 106, 6917 (1984).

13.

Pottie

R.F.

Lossing

F.P.

, J. Am. Chem. Soc. 85, 269 (1963).

14.

Lossing

F.P.

Traeger

J.C.

, J. Am. Chem. Soc. 97, 1579 (1975).

15.

Takhistov

V.V.

Ponomarev

D.A.

Misharev

A.D.

Orlov

V.M.

Pihlaja

, J. Gen. Chem. (Russ.) 64, 110, (1994).

16.

Lias

S.G.

Ausloos

, J. Chem. Phys. 82, 3613 (1985).

17.

(a) Komendantov

M.I.

Domnin

I.N.

Bulucheva

E.V.

, Tetrahedron 31, 2495 (1975); (b) Schafer

Allan

Boyarskaya

I.A.

Domnin

I.N.

, Chem. Phys. 167, 241 (1992).

18.

Boyarskaya

I.A.

Semenov

S.G.

Domnin

I.N.

, J. Org. Chem. USSR, Engl. Transl. 28, 191 (1992).

19.

Levin

R.D.

Lias

S.G.

, Ionization Potential and Appearance Potential Measurements, 1971–1981. Washington (1982).

20.

Orlov

V.M.

Krivoruchko

A.A.

Misharev

A.D.

Takhistov

V.V.

, J. Gen. Chem. (Russ.) 61, 2073 (1991).

21.

Orlov

V.M.

Krivoruchko

A.A.

Takhistov

V.V.

, Izv. Acad. Nauk USSR, ser. khim. 905 (1988).

22.

(a) Stevenson

D.P.

, Discuss. Faraday Soc. 10, 35 (1951); (b) Audier

H.E.

, Org. Mass Spectrom. 2, 289 (1969).

23.

Exner

, in A Critical Compilation of Substituent Constants in Correlation Analysis in Chemistry: Recent Advances, Ed by Chapman

N.B.

Shorter

, Plenum Press, New York and London, p. 439 (1978).

24.

Pedley

J.B.

Naylor

R.D.

Kirby

S.P.

, Thermochemical Data of Organic Compounds, 2nd Edn. Chapman and Hall, London (1986).

25.

CRC Handbook of Chemistry and Physics, 1996–1997, Ed by Lide

D.R.

, CRC Press, Boca Raton (1997).

26.

Shaw

, “Thermochemistry of Acetylenes”, in The Chemistry of the Carbon—Carbon Triple Bond, Ed by Patai

, John Wiley & Sons, Chichester, p. 1 (1969).

27.

Orlov

V.M.

Krivoruchko

A.A.

Takhistov

V.V.

, Izv. Acad. Nauk USSR, ser. khim. 2619 (1985).

28.

Benson

S.W.

, Thermochemical Kinetics. Wiley, New York (1976).

29.

Wiberg

K.B.

, Angew. Chem. 98, 312 (1986).

30.

Ausloos

, J. Am. Chem. Soc. 103, 3931 (1981).

31.

Greenberg

Tomkins

R.P.T.

Dobrovolny

Liebman

J.F.

, J. Am. Chem. Soc. 105, 6855 (1983).

32.

Kormornicki

A.K.

Dykstra

C.F.

Vincent

M.A.

Radom

, Chem. Phys. 167, 241 (1992).

33.

Grabowski

J.J.

Simon

J.D.

Peters

K.S.

, J. Am. Chem. Soc. 106, 4615 (1984).

34.

Steele

W.L.

Gammon

B.E.

Smith

N.K.

Chickos

J.S.

Greenberg

Liebman

J.F.

, J. Chem. Thermodyn. 17, 505 (1985).

35.

Ponomarev

D.A.

Takhistov

V.V.

, J. Mol. Struct. 435, 259 (1997).

36.

McMillen

D.F.

Golden

D.M.

, Ann. Rev. Phys. Chem. 33, 493 (1982).

37.

Baidin

V.N.

Domnin

I.N.

Prokhorenko

O.A.

de Meijere

, J. Org. Chem. USSR, Engl. Transl. 20, 1515 (1984).

38.

Loginov

Yu.

Takhistov

V.V.

Vatlina

L.P.

, Org. Mass Spectrom. 16, 239 (1981).

39.

Takhistov

V.V.

, D. Sci. Thesis, Leningrad (1989).

40.

Colussi

A.J.

Amorebieta

V.T.

Grela

M.A.

, J. Chem. Soc. Faraday Transactions 88, 2125 (1992).

41.

Berkowitz

Ellison

G.B.

Gutman

, J. Phys. Chem. 98, 2744 (1994).

42.

Holmes

J.L.

Lossing

F.P.

Mayer

P.M.

, J. Am. Chem. Soc. 113, 9723 (1991).

43.

Curtis

L.A.

, private communication (see Reference 41).

44.

McKean

D.C.

, Int. J. Chem. Kinet. 21, 445 (1989).

45.

Murad

Inghram

M.G.

, J. Chem. Phys. 40, 3263 (1964).