Infrared Spectra of Nicotine and Some of Its Derivatives

C. R O L A N D E D D Y and A B N E R EISNER
Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department o f Agriculture, Philadelphia 18, Pa.

Ultraviolet spectrophotometry has been used for the

identification and characterization of tobacco alkaloids Table I. Infrared Bands Common to All Six Alkaloids,
and related substances, but the ultraviolet spectra with Pyridine Bands for Comparison
cannot be used to distinguish among alkaloids having Wave No., K.
Dihydro-
equivalent degrees of conjugated unsaturation. Infra- meta- Meta- My- Nico- Nico- Nor- Pyri-
red spectra are presented in this paper for nicotine and nicotine nicotine oarnine tine tyrine nicotine dine ( 2 )
five related alkaloids. These spectra are quite different 713 707 715 714 703
1025 1025 1025 1026 1030
for compounds having identical ultraviolet curves. 1127 1118 1117 1125 ..
Rapid and unambiguous identification of any one of 1186 1193 1191 1190 ..
1420 1414 1418 1427
these alkaloids is possible by comparison of the spec- 1476 1473 1478 1479 1482
1572 1567 1577 1577 1572
trum of an unknown with these infrared curves. The sh 1591 1592 1592 1583
1916 1915 1912 1914 1923
absence of an N-H stretching vibration in the spectrum 2960 2967 2970 2970 2960
of myosmine suggests that the accepted structure of
this alkaloid is incorrect.
tine and nornicotine, whose ultraviolet spectra are essentially

N ICOTINE, nornicotine, and some of the myosminss and

nicotyrines derived from them as dehydrogenation prod-
ucts have been prepared a t this laboratory in a state of high
identical, show pronounced differences in the infrared, the
most prominent being the stretching band a t 3294 kaysers (1).
In general, those alkaloids having nitrogen-hydrogen groups
purity. Their ultraviolet spectra were presented and discussed show this pronounced band near 3300 K., while the band is absent
in earlier papers (S, 9). The infrared spectra of six of these in the tertiary-nitrogen alkaloids. One seeming exception is
alkaloids are presented in this paper. Although the ultraviolet myosmine, which shows no band in the 3300 K. region, even in the
spectra were not capable of distinguishing among the various solid state as a mineral-oil mull. This raises the question once
alkaloids possessing equivalent degrees of conjugated unsatura- more of the structure of myosmine. Although the accepted
tion, the infrared spectra are distinctive and allow unambiguous formula is I, it has been suggested (7, 8) that there may be
identification of any one of these alkaloids. In particular, nico- tautomeric equilibrium with structure 11. Some of the chem-

WAVES PER CENTIMETER

WAVELENGTH, MICRONS

WAVES PER C E N T I M E T E R
4 1100
~ l 0 0 " ~ " " " "
1000
' 1 1 1 ' 1 1 ' '
spo 1 1 ' 1 1 1 1 '
8 00
I 1 1 1
700
1 I 1
COMPOUND
DIHYDROMETAN ICOTINE

80 SOURCE AN0 PURITY

EASTERN REQIONAL RES. LAB.
95-100 %
60 /- 18

f B I A STATE LIOUID

40
7
I TEMPERATURE

1 -P U R E LIQUID
25.C

0.03mrn.
8 - 2 4 . 1 W L . I N CCI, 0.41mm

20 LABORATORY
USOA- BAIC

I EASTERN REGIONAL R E S L A B
P W I L A D E L P H I b 18. PA
0; I025 ,
9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 150
WAVELENOTW, MICRONS

Figure 1. Infrared Spectrum of Dihydrometanicotine

1428
 WAVES PER CENTIMETER
5000 4000 3000 2500 2000 1500 1400 1300 1200 I I00

2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 95

I100 1000 900 800 700

100-'"~1."'! 1 1 1 1 ' 1 1 1 ' I 1 I I I I I I I I I I I 1

80 7 f- A
B M E T A N ICOT IN E

SOURCE AND PURITY

E I S T E R N REGIONAL R E S L A B

60 1 ' I B
h '
STLTE LIOUID
I023 795 TEMPERITURE 30'C
CELL LENGTH OlOmn
40 A - PURE LIQUID
A
0-593G'L I N CCI,
i
I I
967 /%TAL 906 707 US DA-BAlC
E A S T E R N REGIONAL RES L A B
Z J I
9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13 5 14.0 14.5 15.0
WAVELENGTH, MICRONS
Figure 2. Infrared Spectrum of Metanicotine

WAVES PER CENTIMETER

5000 4000 3000 2500 2000 1500 1400 1300 1200 I100

2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

I100 1000 900 800

I I I I I
700
j
. I I t

Ai
COMPOUND

PA MYOSMINE
I\.
j I/ I
SOURCE AND

99-100 X
PURITY
E A S T E R N REGIONAL R E S L A 0

! I
ST4TE SOLUTION
TEMPERATURE 30' C

40 1-52 I GIL IN CCL.

8 - 5 3 5 GlL IN ACETONE

, I
20
1 USDA-BAIC
707 EASTERN REGlON4L RES L 4 B

0
go 95 100 105 110 115 120 125 130 135 140 145 150

WAVELENGTH, MICRONS
Figure 3. Infrared Spectrum of Myosmine 1429
 WAVE LENGTH. MICRONS

Figure 4. Infrared Spectrum of Nicotine

SOURCE 4 N D P U R I T Y
E A S T E R N REGIONAL

98-100% 1
STATE LIQUID
TEMPERATURE 25.C

4 - P U R E LIQUID, OlOmm
8-363W L I N C C I . . 041mm

E A S T E R N REGIONAL RES L A B
I P H I L A D E L P H I A 18, PA. I
WAVELENGTH, MICRONS

1430 Figure 5. Infrared Spectrum of Nicotj-rine

V O L U M E 26, NO. 9, S E P T E M B E R 1 9 5 4 1431
NAVES PER CENTIMETER
5000 4000 3000 2500 2000 I500 1400 1300 I200 I100

1618

20.

at
- 0
w
0
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95
a
z WAVELENGTH, MICRONS
+
c

z
a
K I I I I I I I I I I I I
c B
8 C
NORNlCOTl N E
1 c
80. 1040 8
902 SOURCE 4ND PURITY
EASTERN REGIONAL RES L A 0
1
I

\I
60. 809
1026 TEMPERATURE 30.C
CELL L E N G T H O10mrn
40
A-PURE LIQUID
0 - 5 2 2 G / L I N CCI.

20
\f
/\
\ USDA-0AIC

ObA 1 EASTERN REGIONAL R E S L A 0

P H I L A D E L P H I A 18, PA

ical reactions of myosmine ( 4 ) can also be interpreted in terms of
11. Absence of a nitrogen-hydrogen band in the infrared suggests
that the predominant tautomer in the equilibrium is I1 rather
than the accepted structure. Witkop (11) has also called atten-
tion to the 1621 K. band as a possible C=N vibration in the 5-
membered ring. Its much greater strength in myosniine than
similar bands in metanicotine and nicotyrine suggests a C==X
rather than a C=C linkage.
I I1
Table I lists the major bands common to all six of these alka-
loids, together with some of the bands of pyridine ( 2 ) . Since the
pyridine ring is common to all of these alkaloids, it is to be es-
pected that many of their vibrational frequencies should corre-
spond with pyridine frequencies. N o simple assignment of bands
to the five-membered ring in these alkaloids can be made from this
small number of compounds. Although Pleat, Harley, and
Wiberley ( 5 )have proposed using the 13.966-micron(716 K.) band
of nicotine for analytical purposes, Table I shows that a band
near this location is characteristic of all these alkaloids containing
the pyridine ring. This band corresponds to the strongest funda-
mental vibration of the pyridine spectrum ( 2 ) .
EXPERIMENTAL
Methods of preparation and purification of these compounds
have been described (9). Figures 1 and 5 were obtained with a
Beckman IR-2 spectrophotometer, using the slit-drive mechanism
suggested by Shreve and Heether (6). The transmittances were
obtained by the method of Willis and Philpotts (IO). Figures
2, 3, 4, and 6 were obtained with a Beckman IR-3 spectropho-
tometer, which records transmittance directly and has considerably
higher resolution. Sodium chloride prisms were used in both
instruments.
The term “kayser” (K.) is used in this paper as a unit of wave
number, as recommended by the Joint Commission for Spec-
troscopy (1 ).
ACKNOWLEDGMENT
The authors gratefully achnowledge the assistance of Jane R.
Willis, Mary-Anne Morris, and Henry 8. Walens in ob-
taining and processing the infrared spectra.
LITERATURE CITED
(1) Bakker, C. J.. J . Opt. SOC. Amer., 43, 410 (1953).
( 2 ) Corrsin, L., Fax, B. J., and Lord, R. C., J . Chem. Phys., 21,
1170 (1953).
(3) Haines, P. G., and Eisner, A, J. Am. Chem. SOC.,72, 1719
(1950).
(4) Haines, P. G., Eisner, A., and Woodward, C. F., Ibid., 67,
1258 11945).
~ ~, .
Pleat, G. B., Harley, J. H., and Wiberley, S. E., J . Am. Pharm.
Assoc., 40, 107 (1951).
Shreve, 0. D., and Heether, M . R., A x . 4 ~ CREM.,
. 22,836 (1950).
SpLth, E., and Mamoli, L., Ber., 69B, 757 (1936).
Spath, E., Wenusch, A., and Zajic, E., Ibid., 69B,393 (1936).
Swain, hI. L., Eisner, .4.,Woodward, C . F., and Brice, B. A,,
J . Am. Chem. Soc., 71, 1341 (1949).
Willis, H. A., and Philpotts, 4 . R., Trans. Faraday Soc., 41,
187 (1945).
Witkop, Bernhard, private communication.
C I V E D for review March 11, 1954. Accepted June 7, 1954.