From Journal of the Chemical Society [Section] B: Physical Organic (1967), (7), 712-

16. Language: English, Database: CAPLUS

Long-range couplings in the 1,3-dioxane series are reported. A clear
demonstration of these couplings is given by prepg. sym. and unsym.
spiroanalogs of the dioxanes, to render magnetically identical protons
non-identical. Coupling consts. found are unusually large for satd.,
unstrained systems, and a possible effect of the electronegativity of
substituents is discussed. 17 references

Carbon-13 magne

1. Carbon-13 magnetic resonance. Upfield shifts caused by

nitrogen, oxygen, and fluorine atoms located at the γ position and
antiperiplanar to the nucleus observed
By Eliel, Ernest L.; Bailey, William F.; Kopp, Laurence D.; Willer, Rodney L.; Grant, David M.;
Bertrand, Richard; Christensen, Kenner A.; Dalling, Don K.; Duch, Michael W.; et al.
From Journal of the American Chemical Society (1975), 97(2), 322-
30. Language: English, Database: CAPLUS
Addnl. data considered in abstracting and indexing are available from a
source cited in the original document. Upfield shifts in the NMR of the C-
13 nucleus are found in the antiperiplanar arrangement (I) when X = N,
O, or F (compared with X = C or H) except when X is located at the
bridgehead of a bicyclic compd. No appreciable shifts are found for X =
Cl or S.
Substances Reactions Citing Full Text Link 0 Comments 0 Tags
Carbon-13 magne

2. Carbon-13 magnetic resonance. Conformation in some

tert-butyl-1,3-dioxanes
By Jones, Alan J.; Eliel, Ernest L.; Grant, David M.; Knoeber, M. C.; Bailey, William F.
From Journal of the American Chemical Society (1971), 93(19), 4772-
7. Language: English, Database: CAPLUS
The natural abundance carbon-13 NMR spectra of 12 tert-butyl-1,3-
dioxanes and pertinent supporting data are described. The chem. shifts
of the ring and substituent C atoms are affected by the positions and by
the conformations of the substituents. Substituent shift correlations can
in most instances be transferred from cyclohexane derivs. to their
heterocyclic analogs provided one takes into consideration the
deshielding effects of the ring oxygens on axial 5-substituents.
Substances Reactions Citing Full Text Link 0 Comments 0 Tags
Conformational an

3. Conformational analysis. XVI. 1,3-Dioxanes

By Eliel, Ernest L.; Sister M. Carmeline Knoeber
From Journal of the American Chemical Society (1968), 90(13), 3444-
58. Language: English, Database: CAPLUS
A series of conformationally biased 2-, 4-, and 5-alkyl-1,3-dioxanes were
studied through acid-catalyzed equilibration of diastereoisomers and by
N.M.R. spectroscopy. The preferences of the alkyl substituents for the
equatorial (over the axial) position are substantially different from
corresponding preferences in cyclohexane and depend on the location in
the dioxane ring. Quant. these preferences (in kcal./mole) are 2-Me,
≥3.55; 4-Me, 2.9; 5-Me, 0.8; 5-Et, 0.7; 5-iso-Pr, 1.0; 5-Ph, 1.0; 5-tert-Bu,
1.4. The data are rationalized in terms of the shape of the 1,3-dioxane
ring and the size of the free electron pair on O. The preference of the
1,3-dioxane ring for the chair over the skew-boat conformation is estd. to
be at least 4 kcal./mole.
Substances Reactions Citing Full Text Link 0 Comments 0 Tags
Conformational an

4. Conformational analysis. XIII. Validity of the

nuclear magnetic resonance method of establishing conformational
equilibriums
By Eliel, Ernest L.; Martin, Robert J. L.
From Journal of the American Chemical Society (1968), 90(3), 682-
9. Language: English, Database: CAPLUS
The basis for the N.M.R. method of detg. conformational equil. in
substituted cyclohexanes is examd. Comparison of conformationally
analogous 3- and 4-tert-butyl-substituted cyclohexyl derivs. indicates that
the signals for the C1-1 proton therein are not the same; conformational
equil. derived from the signal position in the 4-tert-butyl compds. and the
corresponding monosubstituted compd. are consistent with similar equil.
obtained by other methods, but those derived from 3-tert-butyl compds.
are out of line. However, in proton resonance of 2-tert-butyl- and 5-tert-
butyl-substituted 1,3-dioxanes, the tert-butyl group does affect the
signals of certain ring and methyl substituent H in positions
corresponding to the 4 position in cyclohexane. In the case of 19F
resonance, in both 3-tert-butyl- and 4-tert-butyl-1,1-difluorocyclohexanes
the position of the fluorine signals is affected by the alkyl substituent.
Comparison of cis- and trans-4-tert-butyl-cyclohexyl chlorides with
cyclohexyl chloride at -81 to -91° as a means of ascertaining the
equatorial and axial CHCl signals suggests that the 4-tert-butyl compds.
are better suited for this purpose, inasmuch as the signal position
changes with temp. and an extrapolation is required to utilize the
measured low-temp. shifts. However, 4-tert-butyl compds. are apparently
not good models for 19F shifts or for proton shifts in heterocyclic systems.
46 references.
Substances Reactions Citing Full Text Link 0 Comments 0 Tags
Enhanced long-ra

5. Enhanced long-range coupling constants in

cyclic systems
By Anderson, John Edgar
From Journal of the Chemical Society [Section] B: Physical Organic (1967), (7), 712-
16. Language: English, Database: CAPLUS
Long-range couplings in the 1,3-dioxane series are reported. A clear
demonstration of these couplings is given by prepg. sym. and unsym.
spiroanalogs of the dioxanes, to render magnetically identical protons
non-identical. Coupling consts. found are unusually large for satd.,
unstrained systems, and a possible effect of the electronegativity of
substituents is discussed. 17 references.
Substances Reactions Citing Full Text Link 0 Comments 0 Tags
Steric factors and

6. Steric factors and benzene solvent shifts

in N.M.R. (nuclear magnetic resonance) spectroscopy
By Anderson, J. Edgar
From Tetrahedron Letters (1965), (51), 4713-17. Language: English, Database: CAPLUS
The 1,3-dioxanes with preferred chair conformation are well adapted for
solvent-effect studies since all the protons are generally identified and a
wide range of solvent shifts from -0.25 to 0.6 ppm. is obtained in each
mol. Changes brought about by substituents are readily observed and
steric factors affecting the size and nature of the interaction can be
demonstrated. Spectra were measured on 0.4M solute in CCl4 and C6H6
as the inactive and active solvents. A plot of solvent shift vs. the mole
fraction of C6H6 in CCl4 is a straight line, indicating a 1:1 complex. The
equil. const. for complex formation was obtained from a plot of (mole
fraction C6H6/fraction of total solvent shift) vs. the mole fraction C6H6
(Tyrrell, CA 62, 11459h), but such plots for the series I (R = H2) (II) and I
(R = Me2) (III) are very nearly horizontal, indicating that the complex is
less stable than the dissocd. state of the 2 mols. Thus C6H6 and 1,3-
dioxanes give very weak complexes. The solvent shifts ΔδCCl4C6H6
(difference in shift of a signal in inactive CCl4 and interacting C6H6) for
the series II (R' = Me3C, Me2CH, Et, Me) and III (R' = Me3C, Me2CH, Et,
Me) were measured and tabulated. In both series more than 95% of the
conformation is at equil. with the 2-alkyl group equatorial. In the II series,
the 4-, 5-, and 6-positions are shielded, the 2-axial position is little
affected, and the protons at the 2-equatorial position are deshielded.
This is compatible with location of the C6H6 mol. as in the diagrams (IV,
V). If the interaction with C6H6 is of the type dipole-induced dipole, the
nucleophilic C6H6 mol. would be expected to prefer position V. All the
protons in the 4-, 5-, and 6-positions in compds. of series III are shielded
less by 0.15 to 0.30 ppm. than those in the corresponding compds. of
series II. The changes could be explained on the basis of IV with the axial
Me group in position 5 topping the end of the C6H6 mol. away from the
dioxane ring. Axial groups on the other side of the mol. as in compds. VI
and VII have similar but less marked effect. Compared with the compds.
in series II, the 6-axial proton is much less shielded (0.13) as is the 2-axial
proton and, in VII, the 6-equatorial proton. That equatorial substituents
have little effect is shown by compds. VIII and IX. In VIII, the protons in
the 4,6-positions leave almost identical shifts and, in IX, all the shifts.
Thus, although the C6H6-dioxane complex is specific, it is not possible to
state on which side of the dioxane ring the C6H6 mol. is located, since
axial groups on either side of the dioxane mol. change the solvent effect.
Steric factors can invalidate a direct comparison of solvent shifts of
similarly located protons in different mols.