Reactions of caryophyllene, isocaryophyllene, and their epoxy derivatives with acetonitrile under ritter reaction conditions

Article abstract of DOI:10.1007/s11178-005-0065-6

Acid-catalyzed reactions between acetonitrile and caryophyllene, isocaryophyllene, caryophyllene 4β,5α-epoxide, and isocaryophyllene 4β,5β-epoxide affording optically active amides with a tricyclic skeleton were investigated. 2004 MAIK "Nauka/Interperiodica".

Full text of DOI:10.1007/s11178-005-0065-6

Russian Journal of Organic Chemistry, Vol. 40, No. 11, 2004, pp. 1593 -1598. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11,
004, pp. 1641-1646.
2
Original Russian Text Copyright Ó 2004 by Yarovaya, Korchagina, Rybalova, Gatilov, Polovinka, Barkhash.
Reactions of Caryophyllene, Isocaryophyllene, and Their Epoxy
Derivatives with Acetonitrile under Ritter Reaction Conditions
O.I. Yarovaya, D.V. Korchagina, T.V. Rybalova, Yu.V. Gatilov, M.P. Polovinka, and V.A. Barkhash
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences
Novosibirsk, 630090 Russia
e-mail: ooo@nioch.nsc.ru
Received March 23, 2004
Abstract-- Acid-catalyzed reactions between acetonitrile and caryophyllene, isocaryophyllene, caryophyllene
4b,5a-epoxide, and isocaryophyllene 4b,5b-epoxide affording optically active amides with a tricyclic skeleton were
investigated.
The study of acid-catalyzed reactions of epoxy
derivatives from terpene series and their comparison with
the reactions of original terpenoids opens the way to
understanding the effect of cation center formation on
the final result of transformations. We formerly
demonstrated that dissolution of a mixture of citral 6,7-
epoxides in a system acetonitrile-sulfuric acid (Ritter
reaction conditions) resulted in formation of substituted
oxazolines [1]. The formation of 2-oxazolines from
epoxides and nitriles is known [2], but we did not find
any publications on the use of terpene epoxides as
reagents for synthesis of compounds with an oxazoline
ring; the preparation of diamides by Ritter reaction with
a-pinene epoxide was reported in [3].
We explored in this study the behavior of
caryophyllene, isocaryophyllene, and their monoepoxy
derivatives under conditions of Ritter reaction. The
dissolution of caryophyllene (I) in a system acetonitrile-
sulfuric acid followed by treating with anaqueous sodium
hydrogen carbonate afforded optically active tricyclic
amides II and III with caryolane and clovane skeletons
*
at a ratio 3:1 respectively (Scheme 1).
Scheme 1.
+
+
&+ &1ꢀꢁ+ 2
1+
2
,
,,
+
&+ &1ꢀꢁ+ 2
2
,
,,
*
The atoms in compounds on Schemes are numbered analogously to their notation in the NMR spectra.
1070-4280/04/4011-1593Ó2004 MAIK “Nauka/Interperiodica”

1594
YAROVAYA et al.
4
,8
Scheme 2.
bicyclo[5.4.0.0 ]undecane was observed in ginseng
derivatives [4, 5], in the rearrangement products of
nerolidol [6] and neoclovene [7]. In the crystal of
compound V the molecules are connected by hydrogen
+
+
2
+
ꢀꢁ&+ &1ꢀꢁ+ 2
1
...
bonds NH O into screw-like chains twisted (1D-motive)
around screw axis of the fourth order. The parameters
of the hydrogen bonds N H O are as follows: N–H
1
...
1
.
..
...
°
0
.86, H O 2.05, N O 2.889(6) A, angle NHO 165°.
,9
9
The skeleton of compound V is identical to that of
compound VII [7] obtained by quenching with water a
solution of ion A salt generated by dissolving neoclovene
(
VI) in a system HSO F–SO FCl at–120°C (Scheme 3).
3 2
Nonclassic s-delocalized structure of ion A was proved
using NMR spectral data.
The neoclovene is known to be one of the principal
products of acid-catalyzed cyclization of the isocaryo-
phyllene. The above cited findings suggest that the
formation mechanism of tricyclic compound V involves
isocaryophyllene (IV) isomerization into the neoclovene
followed by rearrangement into cation A, trapping of the
latter by acetonitrile and subsequent reaction with water
resulting in compound V. Actually, the dissolution of
neoclovene (VI) in the system acetonitrile-sulfuric acid
afforded compound V as the only reaction product thus
confirming our assumptions on the reaction mechanism.
Structure of compounds V molecule according to x-ray
diffraction data.
Scheme 3.
In order to extend the number of natural epoxy
compounds brought into Ritter reaction we investigated
reaction of acetonitrile catalyzed by sulfuric acid with
4b,5a-epoxide of caryophyllene (VIII) and 4b,5b-
epoxide of isocaryophyllene (IX). It was shown that
amides X and XI formed in a good yield (Scheme 4).
Cations arising on the epoxy ring opening suffered the
known rearrangements [8] resulting in ions with the
clovane-type skeleton. These ions were trapped by
acetonitrile molecules, and the subsequent hydrolysis
provided the corresponding N-alkylamides. The optically
active compounds X and XI differ from each other only
by the configuration of the hydroxy group.
+
ꢀꢁ&+ &1ꢀꢁ+ 2
9
9,
2+
+
62 ) 62 )&O
ꢂꢃꢄ &
It should be noted that transformations of caryo-
phyllene, its isomers, and oxygen-containing derivatives
are well documented [9]. Inasmuch as caryophyllene is
a polyfunctional and conformationally labile compound,
its acid-catalyzed rearrangements afford with rare
exception [10] complex mixtures of substances.
Therefore we demonstrated that the nucleophilic addition
of nitriles to carbocations known as “Ritter reaction”
provided a convenient method for investigation of
multistage rearrangements, since the presence in the
reaction mixture of a weak nucleophile (nitrile) gave a
$
9,,
The dissolution of isocaryophyllene (IV) under the
same conditions furnished mainly optically active
compound V whose structure was established by X-ray
diffraction analysis. The structure of molecule V is
presented on the figure. The six-membered rings in the
molecule are in the chair conformation, and the five-
membered one has an envelope form with deviation of
8
atom C by 0.738(9) E from the plane where are located
the other atoms. The same ring conformation in a
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

REACTIONS OF CARYOPHYLLENE, ISOCARYOPHYLLENE, AND THEIR EPOXY DERIVATIVES
1595
Scheme 4.
+
+
+
&+ &1ꢀꢁ+ 2
+
2
ꢀ
2
+
&
+2
2
+
9,,,
2
;
+
2
+
&+ &1ꢀꢁ+ 2
2+
$
ꢁ
2+
1+
2
+
+
2
,;
;,
possibility, on the one hand, to stabilize carbocations
arising in the course of the reaction; on the other hand,
the most labile and short-lived cations had not enough
time to react with the weak nucleophile. Thus the reaction
either furnished relatively simple product mixtures or
individual substances obtained from highly reactive and
polyfunctional compounds like terpenoids. All amides
prepared in this study were unknown before.
group is a-oriented in compound X and b-oriented in
compound XI. It should also be mentioned that the analysis
1
3
of the C NMR spectra of clovane-type compounds with
a- and 9b-hydroxy groups shows the characteristic
9
1
2
feature of the chemical shifts of C atoms, and therefore
the latter can be applied to assignment of the 9-hydroxy
group configuration. In the compounds with the a-OH
1
2
group the C carbon signals appear in the region ~35–
7 ppm and in the compounds with the b-OH group the
Let us consider some details of establishing the
3
structure of compounds synthesized. The b-configuration
similar signal is located at ~42–44 ppm [8, 13]. Note that
1
2
to the methylene group C H in compound II we
13
2
the chemical shifts in the C NMR spectra of compounds
1
13
assigned on comparison of the H and C NMR spectra
of the compound with the corresponding spectra of
kindred compounds with 12a- and 12b-methylene bridges
X and XI and related substances XIIa, b have close
2
values except of the peaks of the C atoms.
[
11]. Note also that the chemical shifts of carbon atoms
1
3
in the C NMR spectra of compound V have values
close to those in the spectra of hydroxy derivative VII
taking into account the different effect of OH and
+2
NHCOCH groups on the chemical shifts of the adjacent
2+
3
atoms [7].
;,,DꢀꢁE
2
The b-orientation of substituents at C in compounds
III, X, and XI was assigned basing on the published data
for clovane-2,9-diols prepared from 4b,5a-epoxide of
caryophyllene and 4b,5b-epoxide of isocaryophyllene [12].
Similar values of the chemical shifts and identical coupling
EXPERIMENTAL
1H and 13C NMR spectra were registered on
spectrometer Bruker AM-400 (400.13 and 100.61 MHz
respectively) from samples dissolved in CDCl .As internal
2
constants of proton H signals prove their identical a-
3
orientation.As suggest the values of the vicinal coupling
reference served the chloroform signals (d 7.24, d
H
C
9
constants of H protons and the protons of the contiguous
76.90 ppm). The structure of compounds was elucidated
from NMR spectral data basing on analysis of coupling
1
0
9
methylene groups C H , in compound X proton H is in
2
1
1
the equatorial position, and in compound XI the respective
proton is in the axial position. Inasmuch as the C rings
exist in the chair conformation, consequently the hydroxy
constants in the double resonance H- H spectra and
1
3
from C NMR spectra registered with selective and off-
resonance proton decoupling, from two-dimensional
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

1596
YAROVAYA et al.
1
3
1
1
correlation C- H spectra on direct (COSY, using J
(1S,2S,5R,8S)-N-(4,4,8-Trimethyltricyclo-
C,H
2,3
2,5
20
1
35 Hz) and long-range (COLOC, J 10 Hz) coupling,
[6.3.1.0 ]dodec-1-yl)acetamide (II). [a]
97.0° (C
C,H
5
80
1
3
1
-1
and from one-dimensional correlation C- H spectra on
long-range coupling (LRJMD, 2 JC,H 10 Hz). The
structure of compound V was established by X-ray
diffraction analysis. The X-ray study was carried out on
diffractometer Bruker P4 (MoK -radiation, graphite
monochromator, room temperature, q/2q-scanning).
Crystals of compound V tetragonal: a = b = 10.1572(18),
c 15.656A, V 1615.2(7) A , space group P4 . C H NO.
M 263.41, Z 4, d 1.083 g/cm , m 0.066 mm , crystal
habit 1.20 ´ 0.09 ´ 0.05 mm, 2q<50°. The structure was
solved by the direct method and refined by the least-
squares method in the anisotropic approximation till wR2
.1908, S 1.054 for 1578 independent reflections (R
.0588 for 951 F>4s) with the use of software package
SHELX-97. Hydrogen atoms were placed from geometric
considerations. The corrections for extinctions were not
taken into account. The atomic coordinates can be
available from the authors.
7.0, CHCl ). IR spectrum (CCl ), n,cm : 1669.0 (C=O),
3
4
,3
1
3439.0 (NH). H NMR spectrum, d, ppm: 0.83 C
15
14
13
(
(
C H ), 0.93 s (C H ), 0.94 s (C H ), 1.00–1.13 m
3 3 3
9
7
12a
3
H , H ), 1.17 d (H , J12a,12e 13 Hz), 1.22 d.d (H , J
3,3'
3'
a
10, J3,2 10 Hz), 1.24–1.60 m (6H), 1.68 d.d (H , J 10,
5
10'
12e
J3',2 8 Hz), 1.71 m (H , H ), 1.75 d.m (H , J 13 Hz),
18
2
1
.88 c (C H ), 2.22 d.d.d (H , J 12, J2,3 10, J2,3' 8 Hz),
2.28 m (H ), 5.25 br.s (H ). C NMR spectrum, d,
ppm: 55.29 s (C ), 41.05 d (C ), 37.97 t (C ), 34.00 s
C ), 46.01 d (C ), 22.85 t (C ), 37.93 t (C ), 34.06 s
3
11'
2,5
13
°
3
16
3
17 29
–1
3
1
2
3
c
4
5
6
7
(
(
(
8
9
10
11
C ), 37.21 t (C ), 19.81 t (C ), 35.63 t (C ), 46.03 t
12
13
14
15
C ), 20.56 q (C ), 30.35 q (C ), 33.89 q (C ), 168.93
0
0
1
7
18
+
s (C ), 24.12 q (C ). Found, m/z: 263.22466 [M] .
C H NO. Calculated M 263.22490.
1
7
29
(
3S,3aS,7R,9aS)-N-(1,1,7-Trimethyldecahydro-
3
(
a,7-methanocyclopentacyclo­oct-3-yl)acetamide
2
0
III). [a] –38.0° (C 4.2, CHCl ). IR spectrum (CCl ),
580
3 4
–
1
1
n,Cm : 1665.2 (C=O), 3444.8 (NH). H NMR spectrum,
d, ppm: 0.82 s (C H ), 0.84 s (C H ), 0.91 d.d.d (H ,
J9 13, J9a,10a 13, J9a,10e 5 Hz), 0.97 s (C H ), 0.98 d
The purity of initial compounds was checked and the
reaction products were analyzed by GLC on a
chromatograph Biokhrom-1 equipped with various
columns: (a) a glass capillary column 53000´0.26 mm,
stationary phase XE-60; b) a quartz capillary column
1
5
13
9a
3
3
1
4
a,9e
H12a, J1
3
12e
(
1
1
(
1
13 Hz), 1.26 d.d.d (H , J 13, 2.5, 2.5 Hz),
2a,12e
3
10
.32 d.d (H , J 13, J3,3' 12 Hz), 1.40–1.58 m (2H ),
3
,2
3
'
18
.54 d.d (H , J 12, J 6 Hz), 1.93 s (C H ), 4.06 d.d.d
H , J 13, 6, J2 9 Hz), 5.54 br.d. (H , J 9 Hz), 0.99–
.36 m (8H, other protons). C NMR spectrum, d, ppm:
3.80 s (C ), 57.79 d (C ), 45.83 t (C ), 37.54 c (C ),
51.07 d (C5), 20.41 t (C6), 32.98 t (C7), 29.99 c (C8),
3
',2
3
1
3000´0.22 mm, stationary phase SE-54, flame-ionization
detector, carrier gas helium.
2
16
,16
1
3
The reagents used in the study were as follows:
caryophyllene (I) separated from clove oil, [a] –13.8°
C 4.3, CHCl ), isocaryophyllene (IV), [a] –20.0° (C
.4, CHCl ) obtained by caryophyllene(I) isomerization
3
1
2
3
4
4
2
0
5
80
2
0
(
3
580
9
10
11
12
4
2
2
0.34 t (C ), 18.68 t (C ), 33.28 t (C ), 43.17 t (C ),
5
13
14
15
17
4.52 q (C ), 30.74 q (C ), 32.62 q (C ), 169.45 s (C ),
by procedure [14], 4b,5a-epoxide of caryophyllene
1
8
+
3.40 q (C ). Found, m/z: 263.22492 [M] . C H NO.
17 29
2
0
(
VIII), [a]5 – 46.4° (c 5.6, CHCl ), and 4b,5b-epoxide
80
3
Calculated M 263.22490
Transformation of isocaryophyllene (IV) in a
system acetonitrile–sulfuric acid . To a solution of
2
0
of isocaryophyllene (IX), [a]5 –11.3° (c 12.4, CHCl3)
prepared by treating the original sesquiterpenes with
monoperphthalic acid by method [15].
80
0
.5 g of isocaryophyllene in 10 ml of acetonitrile was
added at stirring 0.2 ml of sulfuric acid, after stirring for
min the reaction mixture was neutralized with a
saturated solution of Na CO . On storage from the
Transformation of caryophyllene (I) in a system
acetonitrile–sulfuric acid . To a solution of 0.5 g of
caryophyllene in 10 ml of acetonitrile was added at stirring
.2 ml of sulfuric acid, after stirring for 5 min the reaction
mixture was neutralized with a saturated solution of
Na CO , the reaction products were extracted into
dichloromethane, the organic extract was washed with
water and dried with MgSO . The mixture of reaction
products (0.48 g, 74%) [compounds (II)/(III) ratio 3:1
GLC)] was separated by column chromatography on
5
2
3
0
organic layer precipitated colorless needle-like crystals
of amide V, mp 213–214°C. The reaction product was
filtered off, washed with hexane; the separated crystals
of compound V weighed 0.19 g (30%), and the mother
liquor containing according to GLC data ~75 % of amide
V weighed 0.28 g.
2
3
4
(
SiO (100–160 mm) (gradient elution with hexane
containing from 0.5 to 10% of ethyl ether). We isolated
.23 g (36%) of compound II as colorless fluffy crystals
mp 160–163°C) and 0.11 g (17%) of compound III.
(1S,3aR,4R,7aS)-N-(2,2,4,7a-Tetramethylocta-
2
2
0
hydro-1,4-ethanoinden-3a-yl)acetamide (V). [a]5
80
–
1
0
(
–16.4° (C 5.0, CHCl ). IR spectrum (CCl ), n, cm :
3
4
1
1670.1 (C=O), 3440.8 (NH). H NMR spectrum, d, ppm:
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

REACTIONS OF CARYOPHYLLENE, ISOCARYOPHYLLENE, AND THEIR EPOXY DERIVATIVES
1597
1
2
13
14
0
(
(
.80 s (C H ), 1.03 s and 1.19 s (C H , C H ), 1.10 s
reaction was carried under conditions identical to those
used in preparation of compound X. From 0.3 g of
isocaryophyllene 4b,5b-epoxide (IX) was isolated 0.21 g
(54%) of compound XI.
3
3
3
1
5
11
2
9
C H ), 1.12 s (H ), 1.24–1.35 s (2H, H , H ), 1.37 d.d
3
H , J 3.5, J4,3 2.5 Hz), 1.41–1.64 s (4H, H , H , H ,
H ), 1.75–1.93 s (3H, H , H , H ), 1.94 s (C H ), 2.28
d and 2.36 d (2H , J 15 Hz), AB system, 5.45 br.s
H ). C NMR spectrum, d, ppm: 40.15 c (C ), 33.62 t
C ), 25.86 t (C ), 56.08 d (C ), 36.41 s (C ), 45.05 t
C ), 68.07 s (C ), 45.83 s (C ), 33.68 t (C ), 21.43 t
C ), 34.88 t (C ), 26.85 q (C ), 28.16 q and 34.07 q
4
10
3
11'
4
,3'
2
'
10'
9'
3'
18
3
6
6
,6'
(3S,3aS,6S,7R,9aS)-N-(6-Hydroxy-1,1,7-tri-
1
6
13
1
(
(
(
(
(
methyldecahydro-3a,7-methanocyclopentacyclo-
2
3
4
5
20
octan-3-yl)acetamide (XI). [a]580 –46.4° (c 5.6,
6
7
8
9
–1
CHCl ). IR spectrum (CCl ), n, cm : 1665.4 (C=O),
3
4
1
0
11
12
1
13
3
0
443.0 (NH). H NMR spectrum, d, ppm: 0.82 s (C H ),
3
.91 s (C H ), 0.96 s (C H ), 1.02 d (H ', J
13 Hz), 1.06–1.16 m (4H, 2H , 2H ), 1.16–1.25 m (2H,
13, J 2.5 Hz), 1.31 d.d (H ,
J3 13, J3,3' 12 Hz), 1.34 m (H ), 1.42 m (H ), 1.50 d.d
(H , J 12, J3',2a 6 Hz), 1.64 d.d.m (H , J
J10e,9a 5 Hz), 1.91 s (C H ), 3.07 d.d (H , J
1
3
14
15
17
18
C , C ), 30.52 q (C ), 169.48 s (C ), 24.26 q (C ).
Found, m/z: 263.22516 [M] . C H NO. Calculated M
63.22490.
15
14
12
3
3
12',12
+
7
11
1
7
29
2
5b
6
12
3
H , H ), 1.29 d.d (H , J
1
2,12'
6
'
10a
Reaction of caryophyllene 4b,5a-epoxide with
,2a
3
'
10e
acetonitrile under conditions of Ritter reaction. To
a solution of 0.45 g of caryophyllene 4b,5a-epoxide (VIII)
in 4.5 ml of acetonitrile was added at stirring 0.2 ml of
concn. sulfuric acid, after stirring for 5 min the reaction
mixture was neutralized with a saturated solution of
Na CO , the reaction products were extracted into
dichloromethane, the organic extract was washed with
water and dried with MgSO . The crude reaction product
0.46 g) containing according to GLC predominantly
compound X was washed from compurities with hexane
and ethyl ether (acetamide X was sparingly soluble in
these solvents). We isolated 0.31 g (56%) of compound
X.
13,
11,
3
',3
10e,10a
1
8
9a
3
9a,10a
2
a
J9a,10e 5 Hz), 4.08 d.d.d (H , J
6 Hz), 5.65 br.d (H , J
13, J2a,16 9, J2a,3'
9 Hz). C NMR spectrum,
2a,3
1
6
13
1
6,2a
1
2
3
d, ppm: 43.24 s (C ), 56.88 d (C ), 45.69 t (C ), 37.47 s
(C ), 51.38 d (C ), 19.94 t (C ), 26.86 t (C ), 35.10 s
4
5
6
7
2
3
8
9
10
11
(C ), 77.34 d (C ), 27.21 t (C ), 32.24 t (C ), 41.99 t
1
2
13
14
15
(C ), 24.42 q (C ), 30.65 q (C ), 28.40 q (C ),
4
17
18
+
(
169.61 s (C ), 23.26 q (C ). Found, m/z: 279.21971 [M] .
C H NO . Calculated M 279.21982.
1
7
29
2
The authors are grateful to the Russian Foundation
for Basic Research (grant no. 02-07-90322) for financial
aid in acquiring a license of the Cambridge Structural
Database and for access to the STN Database (grant
no. 00-03-32721) via STN-Center of the Novosibirsk
Institute of Organic Chemistry.
(
3S,3aS,6R,7R,9aS)-N-(6-Hydroxy-1,1,7-tri-
methyldecahydro-3a,7-methanocyclopentacyclooct-
-yl)acetamide (X). [a] –50.2° (c 4.1, CHCl ). IR
580
3
spectrum (CCl ), n, cm : 1664.8 (C=O), 3444.7 (NH).
2
0
3
–
1
4
1
13
H NMR spectrum, d, ppm: 0.82 s (C H ), 0.86 s
3
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1
5
11e
14
12
(
J1
C H ), 0.87 m (H ), 0.94 s (C H ), 0.97 d.d (H ,
3
3
1
. Yarovaya, O.I., Korchagina, D.V., Salomatina, O.V.,
7
13, J 2.5 Hz), 0.99 m (H ), 1.23–1.37 m (5H,
H , H , 2H , H ), 1.42 d.d.d (H , J
5 Hz), 1.49 d (H , J
J3',3 12, J3',2a 6 Hz), 1.55 m (H , J
J10e,9e 2.5, J10e,11e 2.5 Hz), 1.87 d.d.d.d (H , J
J10a,11a 14, J10a,11e 5, J
2,12'
5b
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7
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1a, 10e
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0e
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1
14, J10e,11a 5,
10e,10a
1
0a
14,
10a,10e
1
8
3 Hz), 1.90 s (C H ), 2.16
3, J9e,10e 2.5 Hz), 4.04
13, J2a,16 9, J2a,3' 6 Hz), 5.67 br.d (H ,
10a,9e
3
9
e
br.s (OH), 3.19 d.d (H , J
9
e,10a
2
a
16
d.d.d (H , J
2
a,3
1
3
1
J16,2a 9 Hz). C NMR spectrum, d, ppm: 43.32 s (C ),
7.49 d (C ), 45.53 t (C ), 37.33 s (C ), 50.29 d (C ),
0.31 t (C ), 32.85 t (C ), 34.58 s (C ), 74.59 d (C ),
5.31 t (C ), 27.37 t (C ), 35.40 t (C ), 24.33 q (C ),
0.62 q (C ), 28.05 q (C ), 169.64 s (C ), 23.36 q (C ).
Found, m/z: 279.22026 [M] . C H NO . Calculated:
79.21982.
Reaction of isocaryophyllene 4b,5b-epoxide with
acetonitrile under conditions of Ritter reaction. The
2
3
4
5
5
2
2
3
5
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6
7
8
9
1
0
11
12
13
6
1
4
15
17
18
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7
29
2
2
7. Khomenko, T.M., Korchagina, D.V., Gatilov, Yu.V.,
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