Organic Magnetic Resonance. 1976, Vol. 8 , pp. 439 to 443.

Investigation of Substituent Effects of Chalcones by

13C n.m.r. Spectroscopy
E. Sol'aniova"
Chemical Institute U K , Mlynskci dolina, 816 00 Bratislava, Czechoslotiakiu
Y

S. Toma "
Department of Organic Chemistry, Komensky University, Smeralooa 2, 801 00 Bratislava, Czechoslocakia

S. Gronowitz
Division of Organic Chemistry I , Chemical Center, Uniiiersity of Lund, P.O.B. 740, 220 07 Lund, Sweden

(Received 10 December 1975; accepted 19 April 1976)

Abstract-rJC chemical shifts for 23 papa- and mera-substituted
chalcones of the types 1 and 2 have been determined. The aromatic
shieldings are compared with previous results for other aromatic
derivatives. Correlations of the 13Cchemical shifts of vinyl carbons
and carbonyl carbons as well as ring carbons with Hammett o
parameters, T electron densities and the reactivity parameters
of Swain and Lupton provide a consistent picture of electronic
effects transmitted through the carbon framework of the com-
pounds studied.
INTRODUCTION
DHAMIand Stothers1r2 have presented the results of
an extensive study of 13Cn.m.r. spectra of a large number
of different substituted acetophenones and styrenes.
The results of this study again proved the validity
of the additivity of substituent effects on aromatic
shieldings, first noted by L a ~ t e r b u r . ~Dhami and
Stothersl found a linear correlation of the chemical
shifts of C-p carbons with Hammett c constants in
a study of n.m.r. spectra of styrenes. Attempts
to correlate the chemical shifts of C-cc carbons failed.
Reynolds and c o - w o r k e r ~ ~have
, ~ studied and
lH n.m.r. spectra of a large number of 4-substituted
styrenes and phenylacetylenes. Correlations of vinyl
lH and 13C chemical shifts of styrenes as well as ethynyl
IH and chemical shifts and their charge densities
with field ( F ) and resonance ( R ) parameters provide
a self-consistent picture of electronic effects in these
compounds. The above results support their conclusions
that IH and 13C chemical shifts can be used to monitor
changes in ground-state electron distributions in aromatic
derivatives, and two parameter correlations (with F
and R or cI and cr,J can be used to deduce mechanisms
of transmission of electronic effects.
Savin and co-workers6 have studied lH n.m.r. spectra
of a,@-unsaturated carbonyl compounds, RC,H,CH.-
CH-CHO and RCGH4CH=CH-COC(CH3)3. They
found correlations of the chemical shifts o f the ethylenic
protons H-ot with substituent constants 0 1 and H-p
with d' constants. Substituent effects are transmitted
primarily by the resonance mechanism to H-ot, and by
the inductive mechanism to H-/I.
The purpose of this investigation was to determine
13C chemical shifts for some para- and rneta-substituted
* Author to whom correspondence should be addressed.
'? Heyden & Son Limited.
Prmted in Northern Iteland.
chalcones of types 1 and 2, and to determine as com-
pletely as possible the electronic distributions in these
compounds. Our aim was also to determine to what
extent chemical shifts reflect this electronic distri-
bution and to interpret the mechanisms of transmission
of substituent effects i n these two series of chalcones.
EXPERIMENTAL
Synthesis of compounds
Chalcones of series 1 and 2 are known compounds and were
synthesized by the base catalysed Claisen-Schmidt reaction of
the appropriate benzaldehyde and acetophenone, and their physical
constants are given in our previous work.' Purities of compounds
were checked by their melting points and n.m.r. spectra.
Recording of spectra
n.m.r. spectra were obtained a t 15.0 MHz using a JEOL
JNM-FX 60 spectrometer with a built-in JEOL 980 A computer
with 12 K memory. The proton noise decoupling technique
was used for all spectra. The r.f. pulse width was 6 ,us, corres-
ponding to a pulse angle of 45", and the pulse repetition rate
was 1 s. The shifts were determined with an accuracy of 3: 0.1
ppm. Spectra were measured for deuteriochloroform solutions,
a t a concentration of 20%, to enable use of the deuterium reson-
ance as internal lock signal. TMS was used as an internal standard.
The SCF C1 method in the T electron version was used to
study the effect of substituents on the T electron structure of
22 monosubstituted derivatives of tran.s-chalcone.8
RESULTS
13Cchemical shifts are given in Tables 1 and 2, and the
substituent-caused shifts (the shifts relative to un-
substituted chalcone) are given in Tables 3 and 4.
I
2
Fiti 1.
439
440 E. SOLCANIOVA, S. TOMAand S. GRONOLVITZ

1.
TADLE I3cCHEMICAL SHIFTS IN ppm FOR SOMEpllra- A N D WEfU-SUBSTITUTED CHALCONES, SERIES 1, USING TMS AS INTERNAL STANDARD

0-I h-2 2-3 0-4 0-5 0-6

0-a I)$ 0-co fbI' 0-2' 8-3' h-4' b-5' 0-6' Others
- _-~_
121.91 134.91 128.73 128.73 128.41 128.73 128.73
144.48 190 09
138.15 130.35 130.35 132.63 130.35 130.35
122.48 130.27 1 11.68 151.86 I 1 1.68 130.27
I 16.64 145.61 I90 09 39.94
139.04 128.24 128.24 131.97 128.24 128.24
125.32 I 30.5 I 114.93 149.02 I 14.93 130.5I
118.01 145.45 I90 58 138.95 128.40 128.40 132.10 128.40 128.40
127.59 130.19 114.36 161.60 114.36 130.19
119.64 144.55 190 09 55.19
138.47 128.40 128.40 132.46 128.40 128.40
132.14 128.48 129.62 140.90 129.62 128.48
121.01 144.71 190 25 21.51
138.31 128.48 128.48 132.54 128.48 128.48
d 129.54 129.54 119.80 140.09 1 19.80 129.54
121.10 144.15 24.68
138.36 128.57 128.57 132.62 128.57 128.57
131.08 130.23 I 15.99 163.95 115.99 130.23
121.59 143.25 189 84 138.06 128.48 128.48 132.62 128.48 128.48
133.35 129.54 129.13 136.27 129.13 129.54
122.3 I 143.09 189 76 137.98 128.48 128.48 132.79 128.48 128.48
133.76 129.70 132.14 124.75 132.14 129.70
122.48 143.17 I89 84 137.98 128.57 128.57 132.79 128.57 128.57
141.07 128-89 124.18 148.12 124.18 128.89
125-81 141.55 189 18
137.66 128.89 128.89 133.27 128.89 128.89
136.19 I 1 6.29 159.97 113.38 129.86 121.01
122.31 144.64 190 25
138.14 128.48 128.48 55.19
132.70 128.48 128.48
136.76 127.83 134.90 127.83 130.10 126.70
123.08 142.77 I89 60 137.90 128.57 128.57 I32 86 12857 128.57
137.01 133.1 I 127.1 1 130.75 130.35 127.11
123.12 142.69 189 60 137.90 128.57 128.57 132.86 128.57 128.57
137.66 124.67 -a 122.23 130.03 134.25
- rL
124.67 141.55 13766 128.57 128.57 133.1 I 128.57 128.57

a Chemical shifts not assignzd due to low solubility of compounds.

The assignment of chemical shifts for the ethylenic
carbons was based on the following considerations.
In monosubstituted styrenes, the resonance of C-cr
(nearer to the phenyl ring) falls in a quite well-defined
region, 133-138 ppm.2s4 In the chalcones we have
studied, the chemical shifts for the same carbon atom
(in this paper referred to as C-p, see Fig. 1) fall in
the region 141.5-147 ppm. The low field shift can be
caused by the electron withdrawing benzoyl group
attached to the neighbouring carbon. The other carbon
of the ethylenic bond, C-cc, also lies at lower field
(1 16-126 ppm) than the corresponding carbon in
styrenes.
TABLE
2. I 3 c CXEMlC.4L SHIFTS IN pp.71 FOR
It is interesting that in series 1 the range of the shifts
-
caused by the substituent is much more noticeable at
C-0: (Ad 9 ppm), while for C-/3 it is only -4 ppm.
-
In series 2 the effect of the substituent is the opposite,
i.e. C-0 (Qs 3 ppm) is more sensitive to the substituent
effect, while at C-0: the whole effect is only -1 ppm.
The assignment of the carbonyl group was unambig-
uous in all cases (except for thep-NHCOCH, derivative)
since it appears as a single band at the lowest field.
carbonyl shielding is very small (Ad -
I n both series, the influence of the substituent on the
1.4 ppm is the
observed difference between p-NH, and p-NO,). The
calculated m= electron densities also confirm that the
SOME p.7rU- A N D InPfU-SUBSTITUTED CHALCONES, SERIES 2, USING TMS AS INTERNAL STANDARD

ii-1 6-2 h-3 h-4 0-5

X b-x h-B 0-co 0-2' 0-3' h-4' 0-5' d-6
6-6' Others
__ ~ _ _- ~-.__ _ _ ~ ~ _ _ _ - - ~
134.91 128.73 128.73 128.41 128.73 128.73
H 121'91 144'48 190'09 138.15 130.35 130.35 132.63 130.35 130.35
134.98 128.73 130.11 128.24 130.11 128.73
p-OCH, 121'75 143'66 188'14 130.67 130.67 113.71 163.30 113.71 130.67 55'28
134.90 128.57 128.57 128.24 128.57 128.57 21.59
p-CH, '21'91 144'15 189.44 135.55 129.22 130.19 143.34 130.19 129.22
134.73 128.89 130.51 128.40 130.51 128.89
P-F 121'42 144'88 188'38 134-73 131.33 115.62 165.49 115.62 131.33
134.57 128.81 128.81 128.40 128.81 128.81
p-CI 121'34 145'04 136.44 130.51 129.78 139.04 129.78 130.51
134.57 128.87 129.87 128.41 129.87 128.87
p-Br 121'26 145'11 188.79 136.85 130.52 131.81 127.76 131.81 130.52
134.41 128.81 128.97 128.64 128.97 128.81
p-CN 121'10 146-34 188'70 141.39 131.08 132.46 117.93 132.46 131.08 115'90
134.41 129.05 129.38 128.73 129.38 129.05
p-NOz 121'42 146'75 188'95 143-01 131.16 123.86 154.26 123.86 131.16
134.57 128.40 128.81 128.40 128.81 128.40
m-CI 121'18 145'37 188'55 139.69 129.78 134.82 132.46 130.60 126.38
134.65 128.97 130.10 128.48 130.10 128.97
m-Br 121'34 145.53 188'70 140.01 131.49 122.96 135.46 130.75 126.94
134.41 129.05 129.86 128.73 129.86 129.05
m-NO, 120'77 146.75 187.82 139.60 123.21 148.53 126.94 131.16 134.09
 Investigation of substituent effects of chalcones by I3C n.m.r. spectroscopy 44 1

TABLE
3. RELATIVE
13CCHEMICAL SHIFTS (ppm) FOR CHALCONES I N SERIES 1 COMPARED WITH UNSUBSTITUTED CHALCONE

C-Cr c-P co c-1 c-2 c-3 c-4 c-5 C-6

c-1' c-2' c-3' c-4' c-5' C-6'
__ -
- 12.43 1.54 - 17.05 23-45 - 17-05 1.54
- 5.27 1.13 0.00 0.89 -2.11 -2.11 - 0.66 -2.11 ....2. 1 1
- 8.59 1.78 -13'80 20.61 - 13.80 I .78
-3.90 0.84 0.49 0.80 - 1.95 - 1.95 -0.53 ~~ 1.95 -. I .95

-7.32 1.46 -14'37 33.19 - 14.37 1.46

-- 2.27 0.07 0.00 0.32 - 1.95 -- 1.95 -0.17 -1.95 -1.95
~ 2.77 -0.25 0.89 12.49 0.89 -0.25
- 0.90 0.23 0.16 0.16 -1.87 - 1.87 -0.09 - 1.87 - 1.87
-- 5.37 0.8 1 - 8.93 11.68 -8.93 0.8 I
-0.81 -0.33 -a
0.21 -1.78 - 1.78 --0.01 - 1.78 --- 1.78
-3.83 1 -50 - 12-74 35.22 --12,74 I .50
- 0.32 -1.23 ---0.25 -0.09 -1.87 - 1.87 -0.0 1 - 1.87 1.87
-1.56 0.8 1 0.40 7.54 0.40 0.81
0.40 -1.39 -0.33 - 0.17 -1.87 - 1.87 0.1 6 - 1.87 - 1.87
-1.15 0.97 3.41 -3.66 3.41 0.97
0.57 -1.31 ---0.25 -0.17 - 1.78 -1.78 0.16 -- I .78 1.78
6.16 0.16 -4.55 19.39 4.55 0.16
3.90 -2-93 -0.91 -- 1.46
- 0.49 - 1.46 - 1 '46 0.64 ~~ 1.46
1-28 -~ 12.44 31.24 - 15.03 1.13 7.72
0.40 0.16 0.16 -0.01 ~-1.87 - 1.87 0.07 - I ,87 -. 1.87

1-85 -0.90 6.17 - 0.58 I .37 ---2.03

1.17 -1.71 -0.49 -0.25 - 1.78 - 1.78 0.23 - 1.78 -- 1 '78
2.10 4.38 - 1.62 2.34 1.62 -. 1.62
I .21 - 1.79 -0.49 --0'25 -1.78 - 1.78 0.23 1.78 - 1.78
2.75 -4.06 -R. 6.50 1.30 5.52
-a
-
2.76 -2.93
-0.49 -1.78 - I .78 0.48 -1.78 - 1.78

Chemical shifts not assigned due to low solubility of compounds.

charge density at the carbonyl carbon is only slightly
affected by the substituent (see Table 5).s This obser-
vation of no pronounced substituent effect on the
carbonyl chemical shifts was noted and discussed in
detail by Dhami and Stothers for substituted acetophe-
nones. s9
All phenyl carbons were identified by assuming the
rule of additivity. The chemical shifts of all carbons
of the substituted ring were compared in series 1 with
corresponding ~ t y r e n e s ~
and
, ~ in series 2, carbons of
the substituted ring were compared with the corres-
ponding acet0phenones.l The only difficulty was to
assign the unsubstituted chalcone, since differences in
the chemical shifts for C-2, C-3 and C-4 are very small.
We presumed that the effect of the -CH=CH-CO-Ph
group is very similar to that of the C1 group on the
phenyl ring. The value of the relative chemical shift
4. RELATIVE
TABLE 13CCHEMICAL SHFTS (ppm)
for C-1 of the unsubstituted chalcone from benzene
is 6.2 ppm; the comparable value for chlorobenzene
is 6.4 ppm, and for C-4 it is -0.29 and -2.0 ppm,
respectively.1° According to these values and also to
reactivity studies, the observed shielding for the para
carbon indicates a slightly increased r electron density
at this position which is due to electron release by the
-CH=CH-CO-Ph group to the phenyl ring, or at
least no deactivation of the phenyl ring. It follows
from this that the upfield signal belongs to C-4, and
that C-2 and C-3 have the same chemical shifts. There
are differences in the assignment of chemical shifts for
carbons C-2, C-3 and C-4 of ~ t y r e n e s . * ~ ~StotherslO
.l~,~l
and Reynolds4 attribute the signal at highest field to
C-2 and the signal at lowest field to C-3. Dhami and
Stothers' and Levy and Nelsonll attribute the signal
at the lowest field to C-4. The assignments of C-1,
FOR CHALCONES IN SERIES 2 COMPARED WITH UNSUBSTITUTED CHALCONE

X C-Cr c-B co c-1 c-2 c-3 c-4 c-5 C-6

c-1' c-2' c-3' c-4' c-5' C-6'

-0.16 - 0.82 0.07 0.00 1.38 -0.17 1.38 0.00

p-OCH, -1.95 -7.48 0.32 - 16.64 30.67 - 16.64 0.32
0.00 --0.33 -0.01 -0.16 -0.16 -0.17 -0.16 -- 0.16
p-CHz -0.65
- 2.60 -1.13 -0.16 10.71 -0.16 -1.13
-0.18 0.16 1.78 -0.01 1.78 0.16
P-F -0.49 0.40 -1.71
-3.42 0.98 - 14'73 32.86 - 14.73 0.98
-0.34 0.08 0.08 - 0.01 0.08 0.08
p-CI -0.57 0.56 - 1.47
-1.71 0.16 -0.57 6.41 -0.57 0.16
-0.34 0.14 1.14 0.00 1.14 0.14
p-Br -0.65 0.63 -1.30
-1.30 0.17 1.46 -4.87 1.46 0.17
-0.50 0.08 0.24 0.23 0.24 0.08
p-CN -0.81 1.86 -1.39 3.24 0.73 2.1 1 - 14.70 2.1 1 0.73
-0.50 0.32 0.65 0.32 0.65 0.32
P-NO, -0.49 2.27 -1.14 4.86 0.81 - 6.49 22.00 -6.49 0.81
-0.34 -0.33 0.08 -0.01 0.08 -0.33
m-C1 -0.73 0.89 -1.54 1.54 -0.57 0.25
4.47 -0.17 -3.97
-0.26 0.24 1.37 0.07 1.37 0.24
m-Br -0.57 1.05 - 1.39
1.86 1.14 -7.39 2.83 0.40 -3.41
-0.50 0.32 1.13 0.32 1.13 0.32
m-NO -1.14 2.27 -2.27
1.45 -7.14 18.18 -5.69 0.81 3.74
442 5. TOMAand S. GRONOW~TZ
E. SOGANIOV.L,

C-1' and also carbons carrying substituents were un- TABLE6. RESULTSOF CORRELATIONS OF 13C CHEMICAL SHIFTS OF
ambiguous in view of their low intensities. The assign- CHALCONES WITH HAMMETT 0 PARAMETERS AND 7~ CHARGE DENSITIES

ment of carbons in the unsubstituted rings in both

Series Parameter p 6, r S.d. N
series was based on the fact that the effect of the sub-
stituent is very small on all carbons of the unsubstituted C-Gc 5.259 -0.620 0.992 0.326 13
ring compared with the unsubstituted chalcone. C-p -2'651 -0.667 0.947 0.444 13
C-1 10'497 -2'989 0.949 1.716 13
DISCUSSION C-1' -0.903 0.101 0.984 0.082 13
The results of correlations of 13C chemical shifts with 1 C-4' 0.753 -0.017 0.994 0.040 13
C-a, 139.620 1.429 0963 0.738 12
Hammett LT parameters (Table 6 ) show that in series 1 C-P, 217.445 -1.623 0.907 0.605 12
C-a is more sensitive to the effect of polar substituents C-1, 152.211 1-315 0931 2.049 12
and so there is an excellent correlation (r = 0.992). C-cc -0.944 -0.336 0.935 0.128 9"
Quite a good correlation was also obtained for C-/3 C-p 2.863 0.021 0.991 0.149 10
(r = 0-947), but with a slope of opposite sign. This C-1 -0.538 -0.129 0.960 0.060 10
2 C-1' 9.446 -3.185 0925 1.467 10
fact reflects first of all the polarizability of the ethylenic C-4 0.480 -0.087 0.960 0,053 10
bond to which the carbonyl group is attached, which C-p, 183.746 1.172 0.934 0,393 10
causes a decrease of the electron density on C-/3 and a
consequent decrease in the effective shielding on C-P. p = slope; r == correlation coefficient; S.d. = standard de-
Quite good correlations were also found for ring carbons viation; N = number of substituents in regression analysis.
C-1, C-1' and C-4'. 'p-NO, omitted.
In series 2 the situation is opposite to that in series To obtain information about the resonance and the
1. C-@is more sensitive (three times) to the effect of inductive (field) contributions to the chemical shifts we
substituents, with a negative slope, while the C-a attempted a correlation with the Swain-Lupton equation.12
correlation has a positive slope. Again good correlations Table 7 shows the results which we have obtained for
were also achieved for C-1, C-1' and C-4. para substituted chalcones. We have also performed
We have also carried out correlations of 7r electron correlations with the p-dimethylamino derivative using
densities with the carbon chemical shifts of the values4 of -0.097 for F and -0.568 for R. The results
chalcones studied (Table 6). We believe that, similarly were essentially unchanged. Good correlations were
to the case of styrenes,* substituent-induced changes obtained with F and R parameters not only with the
in the -CH=CH-CO- group charge density are I3C chemical shifts but also with the T charge densities
dominated by changes in T electron density. The results for C-a, C-@,CO, C-1, C-2, C-1', C-2' and C-4' of series
of the correlations confirmed this assumption. The 1. In series 2, good results were obtained for C-cc, C-p,
fact that good correlations were found for C-a, C-j3 and CO, C-1, C-2, C-3, C-4 and (2-1'. We assume that in
C-1 of series 1 and no correlation was found for C-a of chalcones, as in styrenes and phenyla~etylenes,~,~ three
series 2 confirms the supposition that in series 2 resonance types of through-bond substituent effects can be con-
effects are mainly localized in the substituted phenyl sidered: inductive effects, resonance effects and T
ring. inductive effects. As seen from the results in Table 7
5.
TABLE CALCULATED (SCF) EXCESS 7~ ELECTRON CHARGE DENSI- for series 1, inductive effects contribute more to the
TIES FOR CARBONS IN THE -CO-cH=CH- GROUP OF SUBSTITUTED chemical shifts of C-p. In contrast, resonance effects
CHALCONES I N SERIES 1 AND 2 RELATIVE TO UNSUBSTITUTED CHAL- should primarily affect the 7r electron density at C-a.
CONE ( x 104)
Corresponding correlations of F and R parameters for
Series X co c-cc c-p c-1 some derivatives of styrenes4and phenyla~etylenes~ show
-482 110 -867 TABLE7. CORRELATION OF RELATIVE l3C CHEMICAL SHIFTS OF
-85
para-SUBSTITUTED CHALCONES SERIES 1 AND 2 VS FIELD F AND
-66 -395 96 -722
RESONANCE R SUBSTITUENT PARAMETERS
-18 -150 49 -311
-24 -220 76 -480 ~ ~ ~~~~~ ~

- - - - Series Chemical f* r* 6, S.d. r N

-6 -67 24 -153 shifts
-7 -67 25 - 142
- 12 -123 44 -239 C-a 2.306 6,364 0.083 0.294 0.994 8
8 126 -68 184 c-B -2.216 -1.781 -0.091 0.224 0'984 8
-5 -51 51 43 co -0.716 -0.672 0.039 0.023 0.985 7
-3 -24 24 17 c-1 2.764 14.495 -0.641 10.409 0.949 8
-3 -48 46 23 1 c-2 1.306 -3'496 -0.688 0.048 0.990 8
13 112 -81 66 c-1' -0.470 -0'952 0.060 0'067 0.955 8
C-2'; C-3' 0.177 0.563 -1.765 0,008 0.953 6'
-18 42 -65 -313 c-4' 0.380 0.874 0.055 0.006 0.995 8
-17 59 -91 -484
-4 17 -27 -155 C-CC -0.784 -0.455 -0.097 0,007 0.989 6b
-4 20 -29 -143 c-P 1.509 2.885 0.097 0.076 0.992 7
-12 38 -56 -242 co -0.914 2.152 -0.407 0.045 0.963 60
-10 -22 30 61 c-1 -0.342 -0.515 -0.112 0.020 0.950 7
-16 -49 66 5 2 c-2 0.407 -0.078 -0.181 0.012 0.928 7
9 17 -16 17 c-3 1.545 2.931 -0.526 0.010 0.968 6d
17 32 -32 17 c-4 0.297 0.420 -0.103 0.005 0.981 7
- 23 -51 60 62 c-1' 2.531 14.523 -0.785 1.689 0.989 7

a Uncalculated. + +
* Coefficients forequation A8 = 6, fF r R ; S.d. = standard
Calculated T electron density for unsubstituted chalcone: deviation in ppm; r = correlation coefficient; N = number of
CO =0.7268; C-CC == 1.0279; C-B = 0.9136; C-1 = substituents in regression analysis. NH,, Cl omitted; NO2
1,0093; C-1' = 1'0177. omitted; CN omitted; * C1 omitted.
 Investigation of substituent effects of chalcones by 13Cn.m.r. spectroscopy 443

TABLE8. CORRELATION
OF RELATIVE 13C CHEMICAL SHIFTS FOR Acknowledgements-The stay in Lund of E.S. was made possible
SOME DERIVATIVES OF STYRENES,* PHENYLACETYLENES' AND CHAL- by a grant from the Swedish Institute.
CONES 1 WITH F AND R PARAMETERS

f* r* r REFERENCES
Styrenesa 2.83 7.45 0.998 1. K. S. Dhami and J. B. Stothers, Can. J. Chem. 43,479 (1965).
C-G( Acetylenes' 2.86 5.23 0.988 2. K.S. Dhami and J. B. Stothers, Can. J. Chem. 43, 510 (1965).
Chalcones 1 2.31 6.36 0.994 3. P. C. Lauterbur, J. Am. Chem. Sac. 83, 1846 (1961).
Styrenes 2.75 16.59 0.993 4. G.K. Hamer, I. R. Peat and W. F. Reynolds, Can. J. Chem.
c-1 Acetylenes 2.93 18.60 0.990 51, 897 (1973).
Chalcones 1 2.76 14.50 0,949 5. D. A. Dawson and W. F. Reynolds, Can. J. Chem. 53, 373
(1 975).
+ +
f * , r* = weighting factors of equation A8 = 6, f F rR. 6. V. I. Savin, R. G. Gainullina, V. V. Zverev and J. P. Kitaev,
r = correlation coefficient. In styrenes and phenylacetylenes zh. Org. Khim. 11, 1169 (1975).
C-a corresponds to C-/?in chalcones. 7. S. Toma, Collect. Czech. Chem. Commun. 34, 2771
very similar values forf* and r* weighting factors for (1969).
8. J. Legka and P. Zahradnik, Collect. Czech. Chem. Commun.
C-a and C-1 as we have found for chalcones of type 1. 38, 3365 (1973).
The situation is the opposite in series 2. Inductive 9. K. S. Dhami and J. B. Stothers, Tetrahedron Lett. 12, 631
effects are greater for C-cr and resonance effects are (1964).
greater for C-P. Thus, the increased field dependence and 10. J. B. Stothers, Carbon-I3 N M R Spectroscopy, Academic
the decreased resonance dependence for C-a again Press, New York, 1972, p. 197.
11. G. C. Levy and G . L. Nelson, Carbon-I3 Nuclear Magnetic
confirm the increased localization of resonance interac- Resonance for Organic Chemists, Wiley-Interscience, New
tions in the phenyl group. A similar localization of York, 1972, p. 65.
resonance effects in the phenyl group was noted for 12. C. G. Swain and E. C. Lupton Jr, J. Am. Chern. SOC.90,
a-t-buty1~tyrenes.l~While in a-t-butylstyrenes the steric 4328 (1968).
~I

hindrance minimizes conjugation between the phenyl and 13. G. K. Hamer, I. R. Peat and W. F. Reynolds, Can. J. Chem.
51, 915 (1973).
vinyl groups, in the case of chalcones the carbonyl group 14. V. M. Nikitchenko, S. V. Cukerman and V. F. Lavrushin,
functions as a partial insulator of the conjugation.14 Zh. Obsch. Khim. 33, 2563 (1963).