Determination of the signs of long-range proton spin coupling constants by nuclear magnetic triple resonance

Abstract

In a nuclear magnetic resonance spectrum of the type AMX, the relative signs of the spin coupling constants J _AM and J _MX cannot be determined by double resonance experiments if J _AX is unobservably small or zero, but the problem can be solved by the simultaneous application of three radio-frequency fields. This technique is described and demonstrated, and it is suggested that it should prove particularly useful for relating the signs of long-range spin coupling constants to couplings of known sign. Applied to the molecule of 3-bromothiophene-2-aldehyde, this experiment establishes that the long-range coupling to the aldehyde proton has the same sign as the vicinal coupling.