Use of Degrees of Unsaturation

in Solving Urganic Structural Problems

LeRoy H. Klemm
University of Oregon, Eugene, OR 97403
Determination of the complete structural formula of a
newly isolated or synthesized organic compound may in-
volve extensive, sophisticated procedures, including
chemical transformations and spectral studies. In general,
for each new compound produced in chemical research one
obtains elemental analysis and, thereby, a molecular for-
mula for the substance. A common structural problem en-
countered in organic chemistry textbooks, homework, and
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This result is consistent with the usual structural for-
mula O which indicates three double bonds plus one ring.
In fact, when one has a hydrocarbon with DU > 4 one
should be on the alert for the possible presence of an aro-
matic ring.
A simple structural problem was posed in the first chap-
ter of an older textbook (7), which, unfortunately, does not
introduce DU to the reader. Application of DU should as-

examinations provides the molecular formula of the com-
pound considered. In this communication I show that valu-
able structural information is easily calculated from the
molecular formula and that this can help greatly in an in-
itial mental assessment of structural features present in
the compound.
The calculation provides a numerical quantity variously
called the degree(s) of unsaturation (DU) (1), in this arti-
sist in solving the problem, as follows.
A compound shown by analysis to have the formula C9H10
gives benzoic acid on vigorous oxidation. What are the four pos-
sible structures for this compound?
Solution: C9H20
-

CgHu)
cle, elements of unsaturation (2), units of unsaturation (3),
index of hydrogen deficiency (4), sum of double bonds and H10 or DU = 5

rings (SODAR) (5), or simply a ring or unsaturation (6).

The presentation of DU differs considerably in these refer-
ences. In SODAR one must consider a triple bond as the
equivalent of two double bonds. In ref 6 the term unsatu- There must be
ration refers to a double or triple bond and must be distin-
guished from degrees of unsaturation. In refs 4 and 6 the 5-4=1
authors consider hydrocarbons only and, thereby, limit the
usefulness of the DU concept. References 3 and 5 extend degree of unsaturation in a side chain.
the calculation to molecules containing halogen or oxygen, c9h10-c8h5 c3h5 =

whereas refs 1 and 2 include nitrogen atoms as well. for the side chain, which can contain one ring or one double
None of these references considers organic molecules bond. In other words, it can be
with other elements, particularly sulfur, silicon, and
phosphorus, which are also presented here. Extension to CH2
other elements is also possible. Surprisingly, none of the —ch |
, —c=ch2 , —CH2CH=CH2 , Of —ch=chch3
numerous other recent or historically well-known or- xch2 ch3
ganic chemistry textbooks examined even mentions the
DU concept. Without use of DU, the student may tend to overlook the
possibility of cyclopropylbenzene as an answer. The fourth
Calculations for a Hydrocarbon of these side chains can exist as cis and trans isomers, so
five structures are, indeed, possible. However, such
First, consider what degrees of unsaturation mean in a isomerization is not introduced in the book until later.
hydrocarbon. The standard of reference (i.e., DU 0) is a
=

saturated molecule or alkane, C„H2n+2. The DU for another

hydrocarbon (Z) containing n carbon atoms per molecule
equals the number of molecules of H2 that must, at least in
theory, be added to Z to obtain the alkane, or alternatively
must be removed from the alkane to produce Z. If Z has the
molecular formula C„H2n, then Z is short two hydrogen at-
oms or one H2 molecule for an alkane, and DU = 1. Z could
have either one ring structure or one double bond. If Z,
instead, has the formula C„H2n_2 then its DU = 2, and Z
could have one of these possible structural features: two
rings, two double bonds, one ring plus one double bond, or
one triple bond.
Benzene, C6H6, for example, is compared with hexane,
C6Hw, as shown below.
C6H14
-c6h6
Hs or 4H2. Therefore, DU= 4
Calculations for Molecules with Heteroatoms
To handle molecules containing elements other than
carbon and hydrogen, first calculate the molecular formula
of the hydrocarbon, called the equivalent hydrocarbon
(EH), which would have the same DU as the compound
being considered. This is accomplished by a series of sim-
ple rules applied consecutively in any order to the molecu-
lar formula, as follows.
1. Replace all halogen atoms (i.e., monocovalent atoms) by
an equal number of hydrogen atoms in the formula.
2. Delete oxygen and sulfur (i.e., dieovalent atoms) from the
formula.
3. Delete all nitrogen atoms (i.e., tricovalent atoms) from the
formula as NH units. Do likewise for phosphorus as PH units.
4. Replace silicon atoms (i.e., tetracovalent atoms) by carbon
atoms, or alternatively delete all silicon atoms as SiH2 units.

Volume 72 Numbers May 1995 425

Then compare the resultant EH with the corresponding al-
From rule 1
kane, as previously, and calculate DU for the original com-
«
pound, C20H37ClIN2O3PS2Si C20H39N2O3PS2Si
From rule 2
Examples
C2i)H39N203PS2Si » C20H39N2PSi
Compound A
From rule 3
Compound A has the formula C7H5Br02S. Replacing
bromine with hydrogen gives C20H39N2PS1 <=> CooHggSi
C7HsBr02S C7H602S
From rule 4 (replacing silicon by C)
where the symbol <=> means is equivalent to. Deleting oxy-
gen and sulfur gives C20H36Si « C21H36 = EH
C7He02S « C7H6 = EH
Then
C7H16-C7H6 =
H10 or 5H2 =
C2iH44 -

C21H36 H8
DU =5 DU =4 for C
One can now propose numerous possible structures for Rationalization for DU Values
A. Three examples are given below.
Now consider the reasons why calculating
DU actually works correctly. First we look at
0 cases, illustrated by chlorine, oxygen, nitro-
H S 0-0 CH2
1 il l l † gen, and silicon, where only one heteroatom
H C=C-C=C-C-C-CH2 .)CH-C=C-C=C -s- Br (i.e., an atom other than carbon or hydrogen)
l
Br H
CH2" 1 is present in the functional group, as given in
O
examples 1-9.

Count the DU in each structure as a check on the an-

CH3CHCH2CH3 ch3ch2och3 ch3ch2ch2oh
swer. Sulfoxide, sulfone, and sulfonyl groups are written
with semipolar (also called dative or coordinate cova- ci
lent) bonds, rather than as S-O double bonds, as given
in some textbooks. This allows consistency with the DU
concept, follows the structural preference of some chem-
ists (including this author), and avoids the problem of CH3CCH3 ch3ch2 n ch3 CH3CCH3
worrying about the oxidation state of the sulfur. In fact, o H NH
the middle structure shows a peroxide, in which the oxy-
6
gen has the unusual oxidation state of 1. Oxidation
—

states can be ignored in the use of DU. Also, semipolar

H
bonds do not count as degrees of unsaturation. Cases in-
volving nitrogen in various oxidation states are shown ch3ch2c=n ch3ch=c=nh CH3—Si—ch2ch3
in the next example. H

Compound B
Draw five possible structures for compound B, molecular
In 1 the monocovalent halogen atom has merely replaced
formula C5H9NO2-
a monocovalent hydrogen atom from a hydrocarbon. Thus,
Solution one obtains the equivalent hydrocarbon by reversal of this

CsH9N02 e C6H9N <=> CjHg = EH process, and without any change in DU. Three situations
or arise for dicovalent oxygen. It may occupy a position be-
CsH12-C5Hg =
H4 2H2
tween two carbon atoms (as in 2) or between a carbon and
Hence, a hydrogen (as in 3). Alternatively, it may be doubly
DU = 2 bonded to a carbon atom (as in 4).
Possible structures with nitrogen in different functional In 2 and 3 one visualizes simply extruding the oxygen
groups and various oxidation states are the following. atom to leave a hydrocarbon (propane here) behind. The
presence of the oxygen atom has not changed DU at all. In
CH3 4 (DU= 1) it is apparent that the oxygen atom has replaced
CH.30- C "C=N two hydrogen atoms from a parent hydrocarbon. For 5 ex-
CHgOH trusion of an NH unit is analogous to removal of oxygen in
2, whereas removal of NH from 6 is analogous to removal
HO of oxygen from 4. For the nitrile 7 we visualize tautomeri-
"N OH zation of the molecule (no loss of hydrogen atoms) to 8.
II I
H-C-CH—C-H Then we can remove NH to leave DU 2. In 9 replacement =

CH2-CH2 of silicon by carbon or extrusion of SiH2 does not change

the value of DU.
CompoundC Some cases where more than one heteroatom is present

Calculate the DU for compound C of molecular formula in a functional group may be visualized as illustrated be-
C20H37ClIN2O3PS2Si. low.

426 Journal of Chemical Education

 >C=^>
Two pure substances form a crystalline molecular com-
CH3CH2OCI <=> CH3CH2OH CH3CH3 DU= 0
pound or complex.

CH3CH20N=0 <=> CH3CH2N-O DU= 1 Two examples are

CH3CH2ON^
o •
anthracene»l,3,5-trinitrobenzene, Ci4H10»C8H-]N3Og, mp
164°, a stoichiometric complex (ID
•
Ci4H22»4.4CH4N2S, p-di-f-butylbenzene»tbiourea inclusion
complex, a nonstoichiometric, crystalline complex (12, 13)
For calculation of DU one should treat each component
separately. Experimentally, the worker is prepared for
these cases inasmuch as the two components of the com-
CH3CH2S-C=N CH3CH2C=N du= 2 plex are deliberately mixed to obtain a crystalline product.
CH3CH2N=C=0 DU =2 Two pure substances react chemically to form a salt.
Examples are ammonium trifluoroacetate (8)
Limitations on DU Calculation C2H4F3N02 or CF3C02" NH4+
The author has encountered five situations in which a andIV-methylpyridinium iodide (commonly called pyridine
calculation of DU may give a useless, doubtful, or errone- methiodide), C6H8IN or [C5H5NCH3]+I“, mp 117° (14). Us-
ous result, as indicated here, unless one recognizes and cir-
ing the molecular formulas directly, one calculates DU val-
cumvents the problem. ues of 0 and 3. However, from the known structural

The compound does not have an EH. formulas,

Examples HN03, H2S04, CS, NH4C1, C2N2, and CO.
are
Calculations of DU should not be made from the molecular
formulas in such trivial cases. An example of the difficulty F-C-C-O' NH4+ ( ^N-CHa
I

that arises is illustrated by comparison of CO and C02.

One might be inclined to write an EH as CH0 in both cases.
This would give DU = 2 for both compounds—wrong for we see that the correct DU values are 1 and 4.
CO, but correct for C02. The erroneous DU values arise because nitrogen is tetra-
covalent in these salts, rather than tricovalent as assumed
The molecular formula as derived from elemental analy- in Rule 3. One can circumvent this problem by considering
sis may include solvent of crystallization or adherence. these salts as molecular compounds CF8C02H«NH3 and
CBHBN*CH3I and treating them as in the preceding sec-
Three examples include
• oxalic acid dihydrate, Structural Studies on an Unknown Amine
C2H204»2H20, mp 106° (8)
» a heterocyclic disulfone dtsul-
The following tests and observations were made on liquid amine A. Complete the third column with
fonamide with one-half mole of the structural inference that you make from each numbered test observation. (The blank third column
2-butanone of crystallization, has been filled in with the
expected answers.)
C26H28N2S408.1/2C4H80, mp
328°(d)(9)
Test or Reaction Result or Observation Structural Inference
•
propargyl phenylpropiolate, a
liquid which distills in vacuo 1. Elemental analysis on A 1. Mol. formula of A is C9H13N. 1. For A, DU= 4.
with retention of water as
2. Hinsberg test on A 2. White ppt forms. 2. A is a secondary amine.
C12Hg02.l/2H20, bp 68.5° (0.5
It is insoluble in HgO or in
mm) or C12H802«1/4H20, bp
120° (0.8 mm) (10) aqueous HCI.
3. Polarimetry on A 3. A is dextrorotatory. 3. A contains a chiral carbon
In all of these cases one obtains atom.
a meaningful DU calculation
4. Vigorous oxidation of A 4. After reaction, the addition of 4. For B, DU = 5.
only by ignoring the solvent pre- (boiling Na0H-KMn04-H20) HCI gives white solid B. C7H6O2. B is probabiy C6H5CO2H.
sent. Thus, for oxalic acid the
molecule C2H204 corresponds to 5. Treatment of A with CH3I 5. Compound C, C10H16IN 5. A forms a monomethiodide.
forms.
EH C2H2 and DU 2, correct
= =

values. If the molecular formula 6. Treatment of A with 6. A reacts to give a crystalline 6. A is a primary or secondary
Ph-N=C=S solid. amine.
is taken as C2H0O6 instead, one
concludes erroneously that DU = 7. Write structural formulas for
0. In an experimental situation A, B. and C.
be alert to the possible retention
of solvent in the sample being
analyzed. When the presence of
solvent is suspected, check the 8. Write a balanced equation for H H H
sample by spectral or other reaction 5. l

means to ascertain the appropri- C-NHCH3 + CH3I C-N(CH3)2

ate molecular formula for calcu- CHS ch3+
lation of DU.

Volume 72 Numbers May 1995 427

tion. Again the formation of such salts is usually deliberate
and, hence, the problem can be anticipated.
The substance is a free radical.
For simplicity we will consider only the case where the
free radical results from removal of a monocovalent atom,
particularly a hydrogen atom, from a parent stable mole-
cule to leave a stable free radical. The formation of the free
radical galvinoxyl, C29H41O2 (8), by abstraction of a hydro-
gen atom from its precursor, will illustrate the
point. The precursor has DU = 9. For galvinoxyl itself the
EH is C2C1H41 and a calculated DU = 9.5. Finding a nonin-
tegral value for DU should immediately alert a student to
the possibility that some covalency rule does not apply to
the molecule under consideration, or that an error has
arisen somewhere.
Complete Solution
of a Structural Determination Problem
To illustrate the use of DU plus other information in the
complete solution of a structural determination problem I
present here a typical sort of question taken from an hour
examination during the third term of a three-term (i.e.,
one academic year) organic chemistry lecture course at the
University of Oregon. The students will have just com-
pleted the textbook chapter on amines and will have con-
ducted an experiment (during the previous term) on the
identification of an unknown liquid amine by a combina-
tion of measurement of boiling point, chemical tests, and
determination of melting point on one or more crystalline
derivatives. For the laboratory experiment the student
was provided with a sheet of names of 30 possible amines
with their boiling points, as well as melting points on some
of their crystalline derivatives. The stockroom personnel
then handed out coded samples, one to each student at
random. The examination question follows. (See the table.)
The total question was worth 30 points: 9 points for part
7 and 3 points for each of the other parts. Because the ex-
amination was given to a class of 150-250 students in a
room where students sit in adjacent seats, two other modi-
fications of this question were made for A as CgHuN (a
primary amine) and A as C10Hi5N (a tertiary amine). Then
examination papers were distributed in 1-2-3-1-2 or-
...
428 Journal of Chemical Education
der. An average grade on this question was 20-24 points
with 10-15% of the class obtaining full credit. There were
always some who failed to recognize the presence of a ben-
zene ring and others who tried to write a structure for A
directly, based only on its molecular formula.
In honors sections of organic chemistry the author
would introduce spectral data ('H and l3C NMR, mass, IR,
and sometimes even UVj as part of the experimental por-
tion. The students were then provided with some sheets of
IR and NMR tables. In a short course in organic chemistry
for students who do not take laboratory, I still use DU and
structural problems, but only based on information from
the textbook and lectures.
Conclusion
The concept of degrees of unsaturation in organic chem-
istry is readily understood and applied by students in un-
dergraduate organic chemistry. It facilitates solving of
problems in structural determination, where one applies
experimental and theoretical concepts to the development
of one (or more) rational structural formulas from an in-
itial molecular formula. Use of the DU concept should be
made a standard part of every beginning organic chemis-
try course.
Literature Cited
1. McMurry, J. Organic Chemistry; Brooks/Cole: Monterey, CA, 1984; pp 124-125.
2. Wade, L. G. Organic Chemistry; Prentice-Hall: Englewood Cliffs, NJ, 1987; pp 243-
245.
3. Ege, S. N. Organic Chemistry; Heath; Lexington, MA, 1984: pp 351-354.
4. Solomons, T. W. G. Organic Chemistry; 4th ed.; Wiley: New York, 1988; pp 247-248.
5. Carey, F. A. Organic Chemistry; McGraw-Hill: New York, 1987; pp 168-169. See also
Atkins, R. C.; Carey, F. A. Organic Chemistry—A Brief Course; McGraw-Hill: New
York, 1990; pp 265-266.
6. Fessenden, R. J.; Fessenden, J. S. Organic Chemistry; Brooks/Cole: Monterey, CA,
1986; p 89.
7. Roberts, J. D.; Caserio, M. C. Basic Principles of Organic Chemistry; Benjamin, New
York, 1964; p 21.
8. Aldrich Catalog of Fine Chemicals; Aldrich Chemical: Milwaukee, WI, 1988-1989.
9. Klemm, L. H.; Lane, W.; Hall, E. J. Heterocycl. Chem. 1991, 28, 187.
10. Klemm, L. H.; Klemm, R. A.; Santhanam, R S,; White, D. V J. Org. Chem. 1971,36,
2169.
11. Ref 7; p 875.
12. Fieser, L. F.; Williamson, K. L.
Organic Experiments; 6th ed.; Heath: Lexington, MA,
1987; pp 146-149.
13. Fieser, L. F.; Fieser, M, Reagents for Organic Synthesis; Wiley: New York, 1968; p
1164.
14. Shriner, R. L.; Fuson, R, C.; Curtin, D. Y, The Systematic Identification of Organic
Compounds; 4th ed.; Wiley: New York, 1956; pp 228-229, 296,