A Very Brief, Rapid, Simple, and Unified Method for

Estimating Carbon-13 NMR Chemical Shifts

The BS Method1
Ben Shoulders
The University of Texas, Austin, TX 78712
Steven C. Welch2
University of Houston, Houston, TX 77004

Carbon-13 NMR has become an important and essential Table 1. The BS Method for sp3 Carbon Atoms
tool in the structural elucidation of organic molecules (1,2).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Several recent textbooks now routinely discuss 13C NMR (3- A, A', B, B', C are atoms other than H.

6). Carbon-13 NMR chemical shifts as well as the multiplic- base =

0 ppm base structure: 13C[-A-B-C]4
ities of these chemical shifts are very useful data in deter-
Downloaded via UNIV DE ALICANTE on November 17, 2022 at 17:32:43 (UTC).

7.5 ppm
mining the structural units in organic compounds (1, 4, 7,8). A = =
B

Many noise-decoupled 13C—'H NMR chemical shift assign- sp3 Corrections (Code]
ments can be made on the basis of comparison with reference
compounds or by structure-shift correlation tables (1-3, 9). 1. C-Me group not attached to a-CH2-:—2.4 ppm. [C-MeNA]
Off-resonance n-'C—1H decoupling permits the determination 2. C-Me group attached to a-CH2-:—0.4 ppm [C-MeAT]
of multiplicities. Other techniques that are useful in assign- 3. C(13) is a CH3 group with a C carbon atom:—0.4 ppm [Me]
ing 13C NMR chemical shifts are two-dimensional 13C-!H 4. C(13) is a-CH2-and the third atom
NMR experiments (10), lanthanide shift NMR experiments other than H in the chain: 2.5 ppm. [3rdM]
5. C(13) is tertiary: —1.5 ppm X # of B atoms [T]
(2, 2), labelling techniques (2, 2), and empirically derived
6. C(13) is quaternary: —4.4 ppm X # of B atoms [Q]
additivity rules for calculating 13C NMR chemical shifts (2, 7. C(13) is allylic or frans-allylic: 5 ppm [AL]
2). 8. C(13) is cis-allylic: —1.25 ppm [c-AL]
Substituent effects on 13C NMR chemical shifts are addi- 9. C(13) is propargylic: —10 ppm [P]
tive. The estimation of I3C NMR chemical shifts based upon 10. C( 13) is in a cyclopropane ring:—32.6 ppm [R3]
these empirical additive substituent effects has proven to be 11. C(13) is in a cyclobutane ring: —6.7 ppm [R4]
very useful in interpreting 13C NMR spectra. Methods for 12. C(13) is in a cyclopentane ring:—3.5 ppm [R5]
calculating 13C NMR chemical shifts have been published 13. C(13) is in a cyclohexane ring:—2.2 ppm [R6]
for alkanes (22,22), alkenes (13), alkynes (14), and substitut- 14. C( 13) is in a cycloheptane ring:—0.6 ppm [R7]
ed benzenes (25). Two elaborate and sophisticated methods 15. C(13) is on all axis of symmetry:—2.7 ppm [S]
have been published which provide reasonably accurate cal-
16. A-sp3 oxygen atoms: 37.5 ppm X # of oxygen atoms [AO]
17. A-sps nitrogen atoms: 22.5 ppm X # of nitrogen atoms [AN]
culation of 13C NMR chemical shifts (16,17); however, these 18. A-sp3 bromine atoms: 22.5 ppm X # of bromine atoms [ABr]
two methods are cumbersome and complicated with exten- 19. A-sp3 chlorine atoms: 30 ppm X # of chlorine atoms [ACS]
sive tables of correction data. The purpose of this paper is 20. B-sp2 oxygen atoms of an aldehyde or ketone: 6.1 ppm [BO]
the introduction of a very brief, rapid, simple, and unified 21. C-sp3 oxygen atoms: —3.2 ppm X # of oxygen atoms [CO]
method for estimating ,3C NMR chemical shifts called the 22. C-sp2 oxygen atoms: -5.0 ppm X § ol oxygen atoms [Csp20]
BS Method. The method is so brief and simple that students
can memorize and utilize it to interpret 13C NMR spectra
with ease.
The largest factor in determining the chemical shift of a of +7.5 ppm. Thus using these factors alone the estimated
carbon atom in an NMR experiment is the hybridization of chemical shifts for each of the carbon atoms of propane is
the carbon atom. This factor is so large that there are three +15 ppm. The experimental values are 15.6 ppm for the
different base scales for each of the three types of hybridiza- methyl carbon and 16.1 ppm for the methylene carbon. Ad-
tion (sp3, sp2-alkenes, sp-alkynes) presented herein. (See ditional small corrections can be made for a more accurate
Tables 1-3.) The base for sp3-hybridized carbon atoms is the estimation of 13C chemical shifts. See Table 1 for corrections
same as that for the 5 scale for 13C NMR. (See Table 1.) That and Table 2 for examples of their applications.
is, the chemical shift of TMS (tetramethylsilane) is defined The first of these small corrections is the y effect. The y
as the zero point for the 5 scale. effect results from steric interactions between the 1,4-non-
The base structure for a sp3-hybridized carbon atom is bonded 13C atom and the C atom (or y atom) 2, 2. In the case
13C[-A B C]4, where A, B, and C are atoms other than hy- of 13C atoms the y effect is seen primarily with a methyl
drogen atoms. (See Table 1.) The important factors to be group (7) or oxygen atom (8) in the C position (7 position).
considered for a sp3-hybridized carbon atom is the number The 13C atom will experience a shift of —2.5 ppm if there is a
of A and B atoms other than hydrogen atoms. Each A and B C methyl group that is not attached to a methylene group
atom other than hydrogen causes a shift in the 13C resonance (-CH2-). Carbons 1 and 5 of compound 1 exemplify this
correction. The I3C resonance will be shifted —0.4 ppm if the
C atom is a methyl group attached to a methylene group. See
carbons 4 and 8 in compound 1, In either case the C methyl
This brief, rapid, simple, and unified method of estimating ,3C
1

NMR chemical shifts has been named the BS Method in honor of the
developer Ben Shoulders.
2
Author to whom correspondence should be addressed. A simple
computer program on the BS Method is also available.
group will also be shifted —0.4 ppm. See carbons 1,7, and 8 in
compound 1. The 13C NMR chemical shifts calculated by the
method of Lindeman and Adams (1,12) are listed for com-
parison purposes.

Volume 64 Number 11 November 1987 915

 Table 2. Selected Examples for sp3-Hybridized Carbon Atoms
(base 0 ppm)
'

L&A Method (13)

calc'd calc’d (exp) calc'd (exp)
Carbon BS Method ppm ppm ppm Carbon BS Method ppm ppm

1 1A + 1B + (C-MeNA) + Me 12.1 10.9 (11.3) 1 1A + 2B + Me 21.1 (23.3)

2 2A + 2B + 3rdM 32.5 29.6 (29.7) 2 3A + 1B + T+ AO 66.0 (67.2)
3 3A + 2B + T 34.5 34.6 (34.7) 3 2A + 3B + (C-MeAT) + 3rdM 39.6 (39.2)
4 2A + 3B + (C-MeAT) + 3rdM 39.6 36.2 (36.5) 4 2A + 2B + (C-MeNA) + 3rdM 26.8 (28.3)
5 2A + 2B + (C-MeNA) + 3rdM 30.0 29.7 (29.5) + CO
6 2A + 1B 22.5 22.9 (23.3) 5 2A + 1B 22.5 (22.9)
7 1A + 1B + Me 14.6 13.9 (14.1) 6 1A + 1B + Me 14.6 (13-9)
8 1A + 2B + (C-MeAt) + Me 21.7 19.1 (19.3)

calc’d (exp) calc'd (exp)

Carbon BS Method ppm ppm Carbon BS Method ppm ppm

1 1A + 3B + Me 29.6 (29.9) 1 1A + 1B + Me + CO 11.4 (9.9)

2 4A + 1B + (C-MeNA) + Q 30.6 (30.4) 2 2A + 2B 30 (30.3)
3 2A + 5B + 3rdM 55.0 (53.5) 3 3A + 2B + (C-MeAt) + T + AO 71.6 (72.3)
4 3A + 1B + (C-MeNA) + T 26.0 (25.3) 4 2A + 3B + (C-MeAT) + 3rdM 39.6 (39.4)
5 1A + 2B + Me 22.1 (24.7) 5 2A + 1B + CO 19.3 (19.4)
6 1A + 1B + Me 14.6 (14.0)

no. __ __ (exp)
H (exp) (2, 16, 19)
3 X = H, X = OH,
6
calc'd (exp) V = OH Y =
H
Carbon BS Method ppm ppm Carbon BS Method calc'd ppm PPm

1 2A + 1B + AO 60.0 (61.9) 1 3A + 2B + T + R6 + AO + S 67.1 (70.1) (61.7)

2 2A + 2B + 3rdM 32.5 (32.8) 2 2A + 3B + R6 35.3 (35.4) (33.0)
3 2A + 2B + (C-MeAT) + CO 26.4 (25.8) 3 2A + 3B + (C-MeNA) + R6 29.6 (25.4) (20.7)
4 2A + 2B + 3rdM 32.5 (32.0) + CO
5 2A + 1B 22.5 (22.8) 4 3A + 5B + T + R6 + S 49.8 (47.0) (47.9)
6 1A + 1B + Me 14.6 (14.2) 5 4A + 2B + Q+ S 33.5 (31.8) (32.1)
6 1A + 3B + Me + S 26.9 (27.2) (27.1)

The 13C atom will experience a shift up to —7.5 ppm when
the C atom is a sp3 oxygen atom. The magnitude of this shift
is inversely dependent upon the steric proximity of the C
oxygen atom to the 1SC atom. A good approximation for
nonrigid molecules is -3,2 ppm times the number of C-sps
oxygen atoms. Carbon 3 in compound 3, carbon 4 in com-
pound 4, and carbons 1 and 5 in compound 5 exemplify this
correction. However, when 13C is in a more rigid structure;
such as, carbon 3 of 4-tert-butylcyclohexanol (6) (2, 18, 19)
the correction of —3.2 ppm for a C-sps oxygen atom is inade-
quate. In this case the calculated shift for carbon 3 is 29.6
ppm. This is 4.2 ppm too high for the equatorial alcohol (X =
H, Y OH) and 8.9 ppm too high for the axial alcohol (X
= =
OH, Y H). Therefore, in the case of an equatorial C-sp3-
=
oxygen atom a correction of —7.5 ppm is more appropriate.
For an axial C-sp3 oxygen atom a correction of —12.1 ppm is
a better choice. Another small y effect is seen with C-sp2
oxygen atoms. The 13C resonance will be shifted -5.0 ppm
for each C-sp2 oxygen atom. See correction 22 in Table 1.
Another small effect for sp3 carbon atoms is seen when the
i3C is both a methylene group and the third atom other than
hydrogen from the end of the chain. This third methylene
effect produces a shift of +2.5 ppm for the 13C resonance. See
carbons 2, 4, and 5 in compound 1. The substitution pattern
on l3C also has an effect on the chemical shift. When 13C is
trisubstituted there is a shift of —1.5 ppm times the number
of B atoms. See carbon 3 in compound 1 or carbon 4 in
compound 2. Likewise, when 13C is tetrasubstituted the cor-
rection is —4.4 ppm times the number of B atoms. See carbon
2 in compound 2 or carbon 5 in compound 6.
Functional groups in molecules cause changes in the
chemical shift of carbon atoms in close proximity. The func-
tional group may have a different electronegativity than
carbon and thus donate or withdraw electron density from
the l3C atom. See examples in compounds 3 to 6. The func-
tional group may be conjugated or it may have magnetic
anisotropy, that is, the functional group may have a magnet-
ic field that is felt at. carbon atoms nearby. The functional
group may also have some steric interaction. The influence
of each of these factors varies with the functional group. An
example, of this phenomenon can be found in alkenes. If the
l3C atom is allylic or trans-allylic the resonance will be shift-
ed +5.0 ppm; however, if the ]3C atom is cis-allylic the
absorption will be shifted -1.25 ppm. The latter shift results
again from a y steric effect. Examples of these allylic correc-
tions can be seen in carbons 1 and 4 in compounds 7 and 8,
respectively. In the case of alkynes where the !3C atom is
propargylic the resonance is shifted —10 ppm. See carbon
atom 3 in compound 11 and carbons 1 and 4 in compound 12
for examples of this propargylic correction.
Ring size has an effect on the chemical shift of sp3-hybrid-
ized carbon atoms. If the sp3-hybridized 13C atom is in two or

916 Journal of Chemical Education

more rings, only one correction is used. Generally, the small-
er or smallest ring determines the correction. The correc-
tions for ring sizes are cyclopropane, —32.6 ppm; cyclobu-
tane, —6.7 ppm; cyclopentane, —3.5 ppm; cyclohexane, —2.2
ppm; and cycloheptane, —0.6 ppm. See an example of this
ring correction in compound 9. In those rare occasions where
molecular symmetry exists in cyclic compounds there is an
infrequently used correction of —2.7 ppm for 13C atoms that
Table 3. The BS Method for sp2 Carbon Atoms
(Alkenes)
A, A1, B, B' are atoms other than H.
base 121.5 ppm base base structure:
=
are on the axis of symmetry. See compound 9 for an example
of this symmetry correction.
The effects of other electronegative atoms are listed in
Table 1. If I3C is bonded to an A-sp3 oxygen atom the correc-
tion is +37.5 ppm times the number of oxygen atoms. See
examples in compounds 3-6. Similarly if 13C is attached to
either an A-sp3 nitrogen or bromine atoms the resonance is
shifted +22.5 ppm times the number of nitrogen or bromine
atoms. If the 13C is bonded to a chlorine atom the correction
is +33 ppm times the number of chlorine atoms. Finally,
when the B atom is a sp2 oxygen atom of an aldehyde or
ketone the position of the 13C resonance is shifted + 6.1 ppm.
The base structure for a sp2-hybridized carbon atom of an
alkene or aromatic hydrocarbon (19) is [B'—A'—]2C=13C-
[B'-A' -]2C='3C[-A-B]2 [—A—B]g, where A, A', B, and B' are atoms other than

A = B =
7.5 ppm, A' = —7.5 ppm hydrogen atoms. (See Table 3.) The base value for alkenes
and aromatic hydrocarbons is +121.5 ppm. In these cases
sp3 Corrections [Code] both the A and B atoms cause a shift of +7.5 ppm for the 13C
resonance, whereas an A' atom results in a correction of —7.5
1. A-sp3oxygen atom: 16.7 ppm [Asp3Oj
2. A'-sp3 oxygen atom: —30 ppm
ppm. See the examples in compounds 7 to 10 (Table 4).
[A'sp30]
3. B-sp2 or sp3 oxygen atom: —7.5 ppm [BO]
Again functional groups play an important role in the shift of
4. B'-sp2 oxygen atom: 17.5 ppm
the 13C resonance. When 13C atom is attached to an A-sp3
[B'sp20]
oxygen atom the shift is +16.7 ppm; however, when the A'
atom is an sp3 oxygen atom when the correction is —30 ppm.
Table 4. Selected Examples of sp2-Hybridized Carbon Atoms See compound 10 for examples of these corrections. When
(Alkenes: base = 121.5 ppm) there is a B-sp2 or -sp3 oxygen atom present the resonance
i a
for the 13C is shifted —7.5 ppm; however, when a B'-sp2
^2^ 6
oxygen atom is present the correction is +17.5 ppm.
7 The base structure for a sp-hybridized carbon atom of an
calc'd (exp) alkyne is B'—A'—C=13C—A—B, where, A, A', B, and B' are
Carbon BS Method ppm ppm
atoms other than hydrogen atoms. The base value for an
alkyne is +72.5 ppm (see Table 5). Each A atom results in a
1 1A + 1B + Me + AL 19.6 (17.7)
2 1A + 1A' 121.5 (125.1)
3 1A+ 1B + 1A' 129 (131.7)
Table 5. The BS Method for sp Carbon Atom (Alkynes)
4 2A + 2B + (C-MeNA) + 3rdM 35 (35.3)
+ AL
A, A', B are atoms other than H.
5 2A + 1B 22.5 (23.2)
6 1A + 1B + Me 14.6 (13.7) base: 72.5 ppm base structure: B'-A'-C=,3C-A-B
A = 7.5 ppm, B =
5 ppm, A' =
—5 ppm

Table 6. Selected Examples of sp-Hybridized Carbon Atoms

calc'd (exp)
Carbon BS Method (Alkynes: base = 72.5 ppm)
ppm ppm
1 3

+ 1B + Me + (c-AL) 13.4
1 1A (12.6) 2
\_
2 1A+ 1 A' 121.5 (124.0) ~\
3 1A + 1B+ A' 1 129 (137.2)
11
4 2A + 2B + (C-MeNA) + 3rdM 28.8 (29.4)
+ (c-AL) calc’d (exp)
5 2A+ 1B 22.5 (22.6) Carbon BS Method ppm ppm
6 1A + 1B + Me 14.6 (13.7)
1 1A' 67.5 (67.4)
2 1A 4 IB 85 (82.8)
3 2 A + 2B + (C-MeAT) + 3rdM 22.1 (17.4)
+ P
9
4 2A + 2B + 3rdM 32.5 (29.9)
calc'd (exp) 5 2A + 1B 22.5 (212)
Carbon BS Method ppm ppm 6 1A + 1B + Me 14.6 (12.9)

1 2A' 106.5 (107.1)

2 2A + 2B 151.5 (149.7)
3 2A + 3B + AL + R6 40.3 (36.2) 12
4 2A + 2B + R6 27.8 (28.9)
5 2A + 2B + R6 4- S 25.1 (26.9) calc'd (exp)
Carbon BS Method ppm ppm

1 1A + 1B + P 4.6 (1.7)
10 1A + 1A'
2 75 (73.7)
calc'd (exp) 3 1A + 1B + 1 A' 80 (76.9)
Carbon BS Method ppm ppm 4 2A + 2B + (C-MeNA) + 20 (19.6)
(C-MeAT) + 3rdM + P
1 1A + 1B + A-spaO 153.2 153.2 5 2A + 1B 22.5 (21.6)
2 1A' + A'-sp30 84 84.2 6 A + B + Me 14.6 (12.1)

Volume 64 Number 11 November 1987 917

shift of +7.5 ppm and each B atom causes a shift +5.0 ppm;
however, each A' atom results in a correction of —5.0 ppm.
See compounds 11 and 12 (Table 6) for examples.
In conclusion, the BS Method is a very brief, rapid, simple
and unified method for estimating 13C NMR chemical shifts
for a variety of organic molecules. The BS Method is easily
remembered and utilized by students who are learning to
interpret 13C NMR spectra. The method does, however, pro-
duce unreliable results for large molecules with a large de-
gree of branching, steric strain, or hydrogen bonding effects.
Acknowledgment
We thank the Robert A. Welch Foundation for the sup-
port of the Science of Chemistry in the State of Texas (SCW,
grant number E-518).
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1976.
918 Journal of Chemical Education
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