Chain-length effects upon the interaction of remote functional groups. The low energy electron impact mass spectra of. cap alpha. ,. omega. -dialkoxyalkanes examined by ion cyclotron resonance spectroscopy

Journal Article · Wed Jan 01 00:00:00 EST 1975 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00842a008· OSTI ID:7260410

Morton, T H; Beauchamp, J L

The techniques of ion cyclotron resonance spectroscopy have been used to investigate the analogy between bimolecular ion-molecule reactions and intramolecular mass spectral rearrangements of a series of bifunctional ethers, CH/sub 3/O(CH/sub 2/)/sub n/OR, n = 1 -- 6 and R = H, CH/sub 3/, or C/sub 2/H/sub 5/. The first step in exploring this analogy has been the examination of the ion-molecule reactions of simple ethers. The second step has been the investigation of the rearrangement ions produced from bifunctional ethers by low energy electron impact. The third step has been a probe of selectivity using deuterium labels. It is found that intramolecular hydrogen transfer is highly regioselective, while the bimolecular analog is not. More pronounced deviations from the analogy arise with variation of the length of the methylene chain separating the functional groups. This indicates a selectivity in the rearrangement process which has no analog in ion-molecule reactions, and this chain-length selectivity has been probed by deuterium labeling and by examination of the ion-molecule reactions of the rearrangement ions. The term vinculoselection is proposed to designate a reaction of a polyfunctional molecule in which a specific chain length or spatial separation between functional groups is requisite for the reaction to occur. Thermodynamic and structural factors affecting vinculoselective reactions of cations from bifunctional ethers are discussed.

• Research Organization: California Inst. of Tech., Pasadena
• DOE Contract Number: AT(04-3)767-8
• OSTI ID: 7260410
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 97
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ISOTOPE EFFECTS
DME
CHEMICAL REACTIONS
ETHERS
METHYLAL
ELECTRON-MOLECULE COLLISIONS
ION CYCLOTRON RESONANCE SPECTROSCOPY
MASS SPECTROSCOPY
COLLISIONS
ELECTRON COLLISIONS
HYDROGEN ISOTOPES
ION SPECTROSCOPY
ISOTOPES
LIGHT NUCLEI
MOLECULE COLLISIONS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
SPECTROSCOPY
STABLE ISOTOPES
400104* - Spectral Procedures- (-1987)
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400302 - Organic Chemistry- Isotope Effects- (-1987)