The reactions of various amines (RNH2: R = H, CH3, C2H5 and i-C3H7) with the methoxy methyl cation (CH2OCH3) have been investigated using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and the experimental results are complemented with ab initio calculations. The amines show clear trends in their reactivities with variable degree of: (1) nucleophilic substitution, (2) addition-elimination and (3) hydride abstraction. In all cases, addition–elimination dominates over nucleophilic substitution, and for R ≠ H the observed reactions occur at the collisional limit. The potential energy profiles for all three reaction types correlate with the basicities of the amines: i.e. the more basic the amine—the more favorable is the reaction. In other words, nucleophilicity follows basicity in the gas phase.
LowryT.H. and RichardsonK.S., Mechanism and Theory in Organic Chemistry.Harper & Row (1981).
2.
SmithM.B. and MarchJ., March's Advanced Organic Chemistry: Reactions, Mechanisms and Structure.John Wiley & Sons, New York, USA (2001).
3.
Bache-AndreassenL. and UggerudE., Int. J. Mass Spectrom.195/196, 171 (2000).
4.
Bache-AndreassenL. and UggerudE., Int. J. Mass Spectrom.210/211, 459 (2001).
5.
Bache-AndreassenL. and UggerudE., Organic & Biomolecular Chemistry1, 705 (2003).
6.
MeerweinH.BodenbennerK.BornerP.KunertF. and WunderlichK., Ann.632, 38 (1960).
7.
OlahG.A. and BollingerJ.M., J. Am. Chem. Soc.89, 2993 (1967).
8.
HarrisonA.G.IvkoA. and Van RaalteD., Can. J. Chem.44, 1625 (1966).
9.
ShannonT.W. and McLaffertyF.W., J. Am. Chem. Soc.88, 5021 (1966).
10.
DunbarR.C.ShenJ.MelbyE. and OlahG.A., J. Am. Chem. Soc.95, 7200 (1973).
11.
StaleyR.H.CordermanR.R.FosterM.S. and BeauchampJ.L., J. Am. Chem. Soc.96, 1260 (1974).
12.
MatsumotoA.OkadaS.TaniguchiS. and HayakawaT., Bull. Chem. Soc. Jpn48, 3387 (1975).
13.
SmithR.D.HeroldD.A.ElwoodT.A. and FutrellJ.H., J. Am. Chem. Soc.99, 6042 (1977).
14.
Van DoornR. and NibberingN.M.M., Org. Mass Spectrom.13, 527 (1978).
15.
PauJ.K.KimJ.K. and CaserioM.C., J. Am. Chem. Soc.100, 3831 (1978).
16.
NibberingN.M.M., Phil. Trans. R. Soc. London, Ser. A293, 103 (1979).
17.
KimJ.K.BonicampJ. and CaserioM.C., J. Org. Chem.46, 4236 (1981).
18.
UggerudE., Topics in Current Chemistry225, 3 (2003).
19.
de KoningL.J.NibberingN.M.M.van OrdenS.L. and LaukienF.H., Int. J. Mass Spectrom. Ion Proc.165/166, 209 (1997).
20.
IkezoeY.MatsuokaS.TakebeM., and ViggianoA., Gas Phase Ion-Molecule Reaction Rate Constants Through 1986, Maruzen, (1987).
21.
FrischM.J.TrucksG.W.SchlegelH.B.ScuseriaG.E.RobbM.A.CheesemanJ.R.ZakrzewskiV.G.MongomeryJ.A.StratmannR.E.BurantJ.C.DapprichS.MillamJ.M.DanielsA.D.KudinK.N.StrainM.C.FarkasO.TomasiJ.BaroneV.CossiM.CammiR.MennucchiB.PomelliC.AdamoC.CliffordS.OchterskiJ.PetersonG.A.AyalaP.Y.CuiQ.MorokumaK.MalickD.K.RabuckA.D.RaghavachariK.ForsmanJ.B.CioslowskiJ.OrtizJ.V.B.BaboulA.G.StefanovB.B.LiuG.LiashenkoA.PiskorzP.KomaromiI.GompertsR.MartinR.L.FoxD.J.KeithT.Al-LahamM.PengC.Y.NanayakkaraA.GonzalesC.ChallacombeM.GillP.M.W.JohnsonB.G.ChenW.WongM.W.AndresJ.L.GonzalesA.Head-GordonM.ReplogeE.S. and PopleJ.A., GAUSSIAN 98, Gaussian Inc. (1998).
22.
RoothanC.C.J., Rev. Mod. Phys.23, 69 (1951).
23.
MöllerC. and PlessetM.S., Phys. Rev.46, 618 (1934).
24.
ScottA.P. and RadomL., J. Phys. Chem.100, 16502 (1996).
25.
SuT. and ChesnavichW.J., J. Chem. Phys.5183 (1982).
26.
WilsonP.F.McEwanM.J. and Meot-NerM., Int. J. Mass Spectrom. Ion Proc.132, 149 (1994).
27.
OkadaS.AbeY.TaniguchiS. and YamabeS., J. Am. Chem. Soc.109, 295 (1987).
28.
HammerumS. and SollingT.I., J. Am. Chem. Soc.121, 6002 (1999).
29.
OlmsteadW.N. and BraumanJ.I., J. Am. Chem. Soc.99, 4219 (1977).
