922

Rotational barriers about the exoc clic C— N bond in 2-aryl substituted

4ÅN,N-dirnethylatninotncthylene 2-oxazolin-5-oncs : An NMR study
Kurn•' K Singh.Marv" K S'ngh A M

Received 4 revisedand March 1996

The barriers to rotatton about the exocyclicC —N bond in 2 •ryl substituted

omethyIeneb2-oxaroltn•S-oneshave tg•en determined by complete line analyst' of the NMR
of the N.N«hmethylprotons The energy barners are attributed to the long range electronÉ
effect 01 rsubsutuents 01 2•aryl ring The barrter hc•ghts have teen correlated With Jlamrnett's substi-
tuem constant o. It has teen found that the electron withdrawingsubstituents(NC),.O) •n pore
rs»qtvonor 2•ryI ring enhance the barrier heights.The opr»site has teen observed Withelectron dep
nanngsubstituents.

The rotational barrier about the carbon-nitrogen ly one electron withdrawing group at another end
bond in amides or thioamides have been extens- of the vinyl group. In such cases, molecular dy-
tvely studied by NMR spectroscopy'. In all this na.•nicsare either too fast or too slow to srrrnit
barrier is associated with the partial double bond study using dynamic NMR techniques. The barri-
character of the bond. The precise value of er to rotation in this type of compound is also af-
the barrier in amid5 is attributed to steric and fected by the group attached at each end of the
electronic nature of the substituents. Piccini-Leo- C —C bond which has stabilizing effect on the
pardi et al 2 and et aLYhave reported dipolar transition state. The barrier to rotation
that the electron donating substituents attached to lowered when a methyl group is introduced onto
amide carbonyl groups result in lowering of the the carbon atom that bears the dimethylamino
barrier to rotation.Direct resonanceinteractions group.
also play a role'. Steric factors are evident too l* Since we have synthesized a series of 2-aryl
with larger substituents producing lower barriers substituted
because of ground-state repulsive forces. Further, oxazolin-5-ones6•7 (2) from the derivative of a-
the conformational rate process in enamino ke- amino acid during the study of Vilsmeier-Haack
tones I, in which the aminovinyl group is att- reagent, show two sharp singlets of equal popula-
ached to a carbonyl group, has also tren investi- tion for the protons of two methyl groups of N,N-
gated'. The barrier to rotation about the C—N dimethylamino function in their 'H NMR spectra,
bond in this system is therefore expected to be suggesting the existence of some slow rate proces
high because of the contribution of the dipolar ca- in these molecules. Therefore, we report herein
nonicaJ structure I 'S. This argument also suuests the application of IH-DNMR to these systerm to
that the bond in the enamino ketones ex- investigate the rotational barrier about the exo-
hibits reduced double bond character, whereas cyclic C—N bond. The 'H NMR spectrum
the C —C bond connecting the carbonyl and the N-dirnethylaminomethylenen-}henyl-
vinyl group shows some double bond character. 2-oxazoIin-5-one(2a) in CDCI, at 25'C displays
a two proton multiplet ranging from 6 8.00-7.78
The dynamic process about the C —N bond is of-
ten observed when enamino compounds bear on-

HJC —H ¯
HJC o-

1 2 2'
 SINO" NMRsurr»v OV VS C -N "ONO 921

for orthc»phenvlprotons and a multiplet jangtng

from b 48-7.26 for another three protons of
rhenv' ring. singlet at 7 ('4 for vtnvlic
and two stnglets at S? and IS for the
of two methyl groups of the exocycltcN.N.
d•methvlanunofunctton On critical
the structure of the molecule appears to conqst of
vM»logue of amide where dimethy
moiety ts attached to a lactonic cmbony! group
I Icnce.the batnet to rotationabout the exocycljc
C -N bond tn this system is also expected to be
high' It also suuests that the former C —Cbond
in the oxatolone 2 wouldexhibit reduceddouble
bond character. whereas the fonner C —C bond
connecting the lactomc and exocyclic vi-
nyl group would show some double tx»ndcllarac-
ter. However. the C —C single bond is a part of a
rigid oxatolone ring. Further. only one of the is-
omers (preferably Zisomer, which is thermody-
nanucally more stable)' Of the cotnpound is ex-
clusively obtained. Therefore these compounds
( 2a•e' would not give any information on barrier
to rotationabout the C —Cdoublebond and the I—VT 'Il NMR spectrumof 2•
C —Csingle bond. We therefore confined our stud-
ies to restncted rotation about the amino nitrogen of the order of 18.91 kcal/mol at 373• K
to vinyl carbon bond. Furthettnore, the steric and (DMSO-CC).
electroniceffectsare excludedbecauseof the abs- It is evident from the data given in TableI that
ence of substituents in a-position relative to the the barrier heights are not the same for all the
dimethylarmno group. a-Substituent to carbonyl compounds. This suggests that the p-subsutuents
group is a part of oxazolone ring, which has plan- of 2-phenyl ring also affect the barrier heights. al-
ar structure.wouldnot show steric effect.There- though the effect of substituents in this regard is
fore. the two signals of N.N-dimethylammomoie- not very large. However. the directionof the in-
ty are due to the contributionof canonicalstruc- crease or decrease in barrier heights is based on
ture 2 • in the ground state. The two signals of N. the electroniceffect of substituents.Substitution
N-dimethylamino group at different chemical of a p-methyl or rmethoxy group for hydrogen in
shifts are temperature dependent and hence var- phenyl ring reduces the barrier height about the
iable temperature NMR spectral studies have C —Nbond.Such a result is reasonableconsider-
been carried out to determinethe barrier heights ing the increase in electron density on the a-
in the compounds 2a-e (Table I). Energy bat tier carbon, relative to dimethylamino group. On the
(AG) about the exocyclic C —N bond have been contrary. the presence of an alectron withdrawing
calculatd at coalescence using Erying•s rate equa- group such as NO: or CI increases the barrier
tion tmn. The variable temperature 'H NMR spec- height.In order to establishthe sensitivityof bar-
trum of 2a is shown in Figure 1. The rotational ricr height towards electronic effect alone12, we
barner about the C—N bond in this moleculeis correlated the barrier heights (AG) with Ham-

Table I—The barriers to the rotation in 2•-e

Compd Values(ppm)01 kc
methylsignals (sec (K) ikcal mole ' )
3.290, 3.620 33 73.49 393 19.98
2d 3.242.3.594 32 71.26 378 19.22
2. 3.218.3.603 34 75.72 373 18 91
2b 3.223.3.610 77.9.' 368 IR 63
OCII, 3.206.3.591 34.42 75.72 363 18.39
 h All

K thank'

J'i€on'I O

J 101' hem
mot gub•t'tucnt constant (o .j. The results of re- 6 K K & Singh R M J
analysts of 'he least squares Hammett plot
V'cure show that the correlation coefficient is K MK SinghR M J
0 and thc standard deu:uion for AGS is O..S5
o it is 0.34, T he fairly good linear 8 Kolle U. Koji' Mann•.chreciA.
1980.
correlation observed with A and o indicates 9 Canvjela C G.nc•a J I Melemjer E.
clear's the significant conjugqtion between the
groups such as rmcthoxyphenyl and the exocyc- Thomas W A in Annual NMR
double bond wa the ring C —N bond. It is also Vnl.l.editedb' E Mooney'Academic
interesting to note that the mean position or the donn 1968p 44
qgnol'. or dtmcthylamino group is almost the Il S & Iloim C H.
Gutowsky
122K
'Table Il) in all compounds. i.e. independent 12 E L. I & V M S.
of the substitucnts whcrcas the difference in 1988.163.