Synthesis of 5- and 6-acyl-1-cyano and -1-ethoxycarbonyl cycloalkenes

Article abstract of DOI:10.1081/SCC-120023510

Conjugated addition of primary nitroalkanes to the functional acetates 3 and 4 in basic medium, leads to the cyclic nitroesters 5 and nitronitriles 6. These derivatives are easily converted via the Nef reaction to the corresponding γ-ketoestesrs 7 and γ-k

Full text of DOI:10.1081/SCC-120023510

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Synthesis of 5- and 6-Acyl-1-cyano and -1-
ethoxycarbonyl Cycloalkenes
Houda Kraïem a , Taoufik Turki a & Prof. Hassen Amri a
a Laboratoire de Chimie Organique et Organométallique , Faculté des Sciences , Campus
Universitaire , Tunis, Tunisia
Published online: 17 Aug 2006.
To cite this article: Houda Kraïem , Taoufik Turki & Prof. Hassen Amri (2003) Synthesis of 5- and 6-Acyl-1-cyano and -1-
ethoxycarbonyl Cycloalkenes, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:18, 3261-3269, DOI: 10.1081/SCC-120023510
To link to this article: http://dx.doi.org/10.1081/SCC-120023510
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 18, pp. 3261–3269, 2003
Synthesis of 5- and 6-Acyl-1-cyano and
-1-ethoxycarbonyl Cycloalkenes
*
Houda Kraıem, Taoufik Turki, and Hassen Amri
Laboratoire de Chimie Organique et Organometallique,
Faculte des Sciences, Campus Universitaire,
Tunis, Tunisia
ABSTRACT
Conjugated addition of primary nitroalkanes to the functional acet-
ates 3 and 4 in basic medium, leads to the cyclic nitroesters 5 and
nitronitriles 6. These derivatives are easily converted via the Nef
reaction to the corresponding g-ketoestesrs 7 and g-ketonitriles 8 in
good yields.
Key Words: Functional cycloalkenols; Nitroalkanes; Conjugated
addition.
*Correspondence: Prof. H. Amri, Laboratoire de Chimie Organique et
Organometallique, Faculte des Sciences, Campus Universitaire 2092, Tunis,
Tunisia; Fax: 216-71 885008; E-mail: hassen.amri@fst.rnu.tn.
3261
DOI: 10.1081/SCC-120023510
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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3262
Kraıem, Turki, and Amri
The five and six membered ring synthesis of functional cycloalkenols
has been achieved by the Wittig–Horner reaction on aliphatic 1,4- and
1,5-dialdehydes, stable in water, in heterogeneous medium in the presence
of potassium carbonates as base.[1] The electrophilic behavior of
cycloalkenols 1 and 2 and their derivatives (Sch. 1) toward various organo-
metallic reagents provided 1,4-addition products as well as the substi-
tution of OZ group, where both served as precursors in the synthesis of
natural products.[2–5]
In continuation to our interest in the synthesis of some functionalized
molecules, we report here the electrophilic reactivity of the allylic acetates
3 and 4 toward nitroalkanes anions to obtain the corresponding com-
pounds which are considered as a potential intermediates in organic
synthesis, where it is very well known that nitro groups can be converted
into various functional groups such as carbonyl which is was well docu-
mented.[6–10] Conjugate addition of nitroalkanes to a,b-unsaturated
carbonyl compounds, provides a convenient method for preparing the
corresponding nitro compound.[11–14]
In the present work we showed that, the substitution reaction of
functional allyl acetate with nitroalkanes can be carried out not only in
the case of acyclic molecules,[15,16] but also with cyclic acetates. Indeed
the condensation reaction of nitroalkanes under basic conditions with the
allyl acetates 3 and 4 provided, via a SN20substitution, cyclo nitroesters 5
and nitronitriles 6 (Sch. 2). However, appropriate solvents and bases were
chosen according to the nature of the group A and the size of the ring, as
described in Table 1.
Due to the existence of two asymmetric centers in the molecules of
cycloalkanes nitroesters 5 and nitronitriles 6, a mixture of two diastereo-
isomers (a,a0-d,d0) was obtained in each case and which were confirmed
1
by chromatography, H NMR and 13C spectra.
The transformation of cyclic nitroesters 5 and nitronitriles 6 into
cyclic g-ketoesters 7 and g-ketonitriles 8 was achieved by using Nef
reaction, an appropriate method for further transformation of 5 and 6 by
addition of their nitronate anions to a methanolic solution of concentrated
Scheme 1.

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Functional Cycloalkenols
3263
Scheme 2.
Table 1. Synthesis of cycloalkenic nitroesters 5 and 60 nitronitriles.
ProductA
n
R
Base (equiv.)/solventTime (h)
Yield (%)
5a,a0
5b,b0
5c,c0
5d,d0
6a,a0
6b,b0
6c,c0
6d,d0
CO2Et1
CO2Et1
CO2Et2
CO2Et2
CN
Me
Et DBU (1)/THF
DBU (1)/THF
8
59
60
6
Me DBU (1.5)/THF
Et DBU (1.5)/THF
8
55
6
58
1
1
2
2
Me
EtNaOH (2)/THF
NaOH (2)/THF
96
58
CN
CN
72
53
Me DBU (1)/CH3CN
EtDBU (1)/CH 3CN
18
12
66
80
CN
Scheme 3.
sulfuric acid at À50ꢀC, leading to the pure cyclic g-ketoesters 7 and
g-ketonitriles 8 (Sch. 3).
In conclusion, we showed that the reaction of nitroalkanes with
alicyclic acetates of type 3 and 4 in basic medium provides an easy way
to synthesize a new family of cycloalkenic nitroesters 5 and nitronitriles 6
which can be converted via the Nef reaction in highly acidic medium and
at low temperature, to the corresponding cycloalkenic g-ketoesters 7 and
g-ketonitriles 8.

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3264
Kraıem, Turki, and Amri
Table 2. Synthesis of cycloalkenic g-ketoesters and g-ketonitriles.
ProductN
A
R
Yield (%)
38
7a
7b
7c
7d
8a
8b
8c
8d
1
1
2
2
1
1
2
2
CO2EtMe
CO2EtEt 33
CO2EtMe
CO2Me
CN
30
Et35
Me
Et
72
80
55
CN
CN
Me
Et
CN
68
EXPERIMENTAL
Synthesis of Cyclopentenic and Cyclohexenic
Nitroesters 5a,a0-d,d0
General procedure. To a solution of cyclic allyl acetate 3 (A¼CO2Et,
n ¼ 1) or 4 (A¼CO2Et, n ¼ 2) (5 mmol) in THF (15 mL) and suitable
amount nitroalkane, DBU was added at room temperature (Table 1).
After stirring for an appropriate time, the solvent was removed to give
an oil which was purified by column chromatography on silica gel
(EtOAc/hexane, 3:7).
5-(1-Nitroethyl) cyclopent-1-ene carboxylic acid ethyl ester 5a,a0. IR
(CHCl3, ꢀ cmÀ1): 1705 (C¼O); 1631 (C¼C); 1547 (C-NO2). 1H NMR
(300 MHz, CDCl3): 6.97, 6.87 (2m, 2H); 5.18 (m, 2H); 4.23 (2q, 4H,
J ¼ 7.2 Hz, J ¼ 7.2 Hz); 3.88, 3.40 (2m, 2H); 2.53, 2.47 (2m, 4H); 2.20,
2.04 (2m, 4H); 1.55, 1.33 (2dd, 6H, J ¼ 6.9 Hz, J ¼ 1.5 Hz); 1.32, 1.31 (2t,
6H, J ¼ 7.2 Hz, J ¼ 7.2 Hz). 13C NMR (75 MHz, CDCl3): 164.4, 164.0
(C¼O); 147.5, 146.2 (C¼CH); 135.0, 134.8 (C¼CH); 82.8, 82.7
(CHNO2); 60.5, 60.4 (CO2CH2CH3); 48.3, 48.0 (CHCHNO2); 32.2,
31.3 (CH2CH¼C); 23.9, 23.8 (CH2CH2CH¼); 16.7, 12.1 (CH3CHNO2);
14.1 (CO2CH2CH3). MS, m/z: 166 (18, 51); 137 (22, 16); 120 (41, 100); 93
þ
(100, 74); 29 (31, 25); exactmass M 213.2345 (Calcd. for C10H15NO4
213.2336).
5-(1-Nitropropyl) cyclopent-1-ene carboxylic acid ethyl ester 5 b,b0. IR
1
(CHCl3 ꢀ cmÀ1): 1705 (C¼O); 1630 (C¼C); 1547 (C-NO2). H NMR
(300 MHz, CDCl3): 6.96, 6.85 (2m, 2H); 5.01 (m, 2H); 4.23 (2q, 4H,
J ¼ 7.2 Hz, J ¼ 7.2 Hz); 3.69, 3.40 (2m, 2H); 2.44 (m, 4H); 2.12 (m, 4H);
1.74 (m, 4H); 1.32, 1.31 (2t, 6H, J ¼ 7.2 Hz, J ¼ 7.2 Hz); 0.99, 0.96 (2t, 6H,
J ¼ 7.4 Hz, J ¼ 7.4 Hz). 13C NMR (75 MHz, CDCl3): 164.3, 164.0 (C¼O);

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Functional Cycloalkenols
3265
147.5, 146.4 (C¼CH); 135.0, 134.9 (C¼CH); 90.5, 89.9 (CHNO2); 60.4,
60.3 (CO2CH2CH3); 48.3, 48.2 (CHCHNO2); 32.1, 31.5 (CH2CH¼C);
24.6, 23.6 (CH2CH2CH¼); 20.3 (CH2CHNO2); 14.1 (CO2CH2CH3);
10.8, 10.5 (CH3CH2CHNO2). MS, m/z: 180 (38, 17); 151 (30, 41); 134
(100, 54); 107 (37, 75); 79 (42, 100); 29 (40, 99); exactmass M þ 227.2614
(Calcd. for C11H17NO4 227.2631).
6-(1-Nitroethyl) cyclohex-1-ene carboxylic acid ethyl ester 5c,c0. IR
1
(CHCl3, ꢀ cmÀ1): 1702 (C¼O); 1643 (C¼C); 1549 (C-NO2). H NMR
(300 MHz, CDCl3): 7.12, 7.06 (2t, 2H, J ¼ 4 Hz, J ¼ 4 Hz); 5.05, 4.85
(2qt, 2H, J ¼ 6.6 Hz, J ¼ 6.6 Hz); 4.14 (2q, 4H, J ¼ 7.0 Hz, J ¼ 7 Hz);
3.36, 3.08 (2m, 2H); 2.14 (m, 4H); 1.60–1.47 (m, 8H); 1.43, 1.32 (2d,
6H, J ¼ 7.0 Hz, J ¼ 7.0 Hz); 1.24, 1.22 (2t, 6H, J ¼ 7.0 Hz, J ¼ 7.0 Hz).
13C NMR (75 MHz, CDCl3): 167.0, 166.3 (C¼O); 143.8, 143.2
(C¼CH); 129.5, 129.4 (C¼CH); 84.3, 84.0 (CHNO2); 60.9, 60.6
(CO2CH2CH3); 37.3, 37.2 (CHCHNO2); 25.3, 25.5 (CH2CH¼C); 22.6,
22.5 (CH2CH2CH¼); 18.3, 18.4 (CH2CH2CH); 16.8, 17.5 (NO2CHCH3)
14.1, 14.0 (CO2CH2CH3). MS, m/z: 18þ0 (44,100); 152 (47,55); 107 (76,85);
79 (100,86); 29 (40,28); exactmass M 227.2620 (Calcd. for C11H17NO4
227.2625).
6-(1-Nitropropyl) cyclohex-1-ene carboxylic acid ethyl ester 5d,d0. IR
1
(CHCl3, ꢀ cmÀ1): 1713 (C¼O); 1632 (C¼C); 1555 (C-NO2). H NMR
(300 MHz, CDCl3): 7.09, 7.15 (2m, 2H); 4.82, 4.71 (2m, 2H); 4.23 (2q,
4H, J ¼ 6.9 Hz, J ¼ 6.9 Hz); 3.32, 3.18 (2m, 2H); 2.00–2.30 (m, 8H);
1.45–1.85 (m, 8H); 1.32, 1.30 (2t, 6H, J ¼ 6.9 Hz, J ¼ 6.9 Hz); 0.93, 0.92
(2t, 6H, J ¼ 7.0 Hz, J ¼ 7.2 Hz). 13C NMR (75 MHz, CDCl3): 166.7, 166.8
(C¼O); 143.3, 143.2 (C¼CH); 129.5, 129.6 (C¼CH); 92.1, 91.4 (CHNO2);
60.6 (CO2CH2CH3); 37.1, 36.3 (CHCHNO2); 25.2, 25.3 (CH2CH¼C);
24.2, 23.4 (CH2CH2CH¼); 23.0, 22.0 (CH2CHNO2); 18.3, 17.40
(CH2CH2CH); 14.1, 14.0 (CO2CH2CH3) 11.2, 10.7 (NO2CHCH2CH3).
MS, m/z: 194 þ(68,43); 165 (42,100); 148 (100,58); 121 (54,82); 29 (34,16);
exactmass M 241.2847 (Calcd. for C12H19NO4 241.2833).
Synthesis of Cyclopentenic Nitronitriles 6a,a0-b,b0
Typical procedure. To a mixture of cyclic allyl acetate 3 (A¼CN,
n ¼ 1) (5 mmol) and nitroalkane (20 mmol) dissolved in THF (25 mL),
ꢀ
cooled at0 C with an ice-bath, was added a solution of NaOH (18 mL,
0.6 N). After the addition was complete, the mixture was stirred at 50ꢀC
for the appropriate time given in Table 1. The mixture was diluted with
H2O and extracted with ether (3 ꢁ 30 mL). The combined organic layers
were washed with brine and dried over anhydrous MgSO4. The solvent

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3266
Kraıem, Turki, and Amri
was removed to leave an oil which was purified by column chromatogra-
phy on silica gel (EtOAc/hexane, 2:8).
5-(1-Nitroethyl) cyclopent-1-ene carbonitrile 6a,a0. IR (CHCl3,
1
ꢀ cmÀ1): 2223 (CꢂN); 1642 (C¼C); 1552 (C-NO2). H NMR (300 MHz,
CDCl3): 6.86 (m, 2H); 4.78 (m, 2H); 3.70, 3.41 (2m, 2H); 2.6 (m, 4H);
2.17, 1.93 (2m, 4H); 1.68, 1.54 (2d, 6H, J ¼ 6.9 Hz, J ¼ 6.7 Hz). 13C NMR
(75 MHz, CDCl3): 152.6, 152.5 (C¼CH); 115.5, 114.9 (C¼CH); 113.9,
113.6 (CꢂN); 83.7, 82.9 (CHNO2); 50.7, 49.8 (CHCHNO2); 32.8, 32.0
(CH2CH¼C); 24.8, 23.8 (CH2CH2CH¼); 16.8, 13.7 (CH3CHNO2). MS,
þ
m/z: 119 (69,100); 93 (100,68); 92 (74,71); 65 (51,49); exactmass M
166.1844 (Calcd. for C8H10N2O2 166.1829).
5-(1-Nitropropyl) cyclopent-1-ene carbonitrile 6b,b0. IR (CHCl3,
1
ꢀ cmÀ1): 2223 (CꢂN); 1641 (C¼C); 1552 (C-NO2). H NMR (300 MHz,
CDCl3): 6.84 (m, 2H); 4.58 (m, 2H); 3.52, 3.40 (2m, 2H); 2.56 (m, 4H);
2.18 (m, 4H); 1.98 (m, 4H); 1.01 (t, 6H, J ¼ 7.4 Hz, J ¼ 7.4 Hz). 13C NMR
(75 MHz, CDCl3): 152.7, 152.6 (C¼CH); 115.6, 115.2 (C¼CH); 114.0,
113.2 (CꢂN); 91.0, 90.8 (CHNO2); 49.8, 49.4 (CHCHNO2); 32.6, 32.1
(CH2CH¼C); 25.1, 24.8 (CH2CH2CH¼); 22.8 (CH2CHNO2); 10.2, 10.þ1
(CH3CH2). MS, m/z: 133 (13); 104 (7); 92 (100); 65 (22); exactmass M
180.2018 (Calcd. for C9H12N2O2 180.2023).
Synthesis of Cyclohexenic Nitronitriles 6c,c0-d,d0
Typical procedure: DBU (5 mmol) was added at room temperature
to a solution of nitroalkane (5 mmol) and acetate 4 (A¼CN, n ¼ 2) in
acetonitrile (25 mL). The solution was stirred for the time mentioned in
Table 1. After evaporation of the solvent the residue was purified by
chromatography (EtOAc/hexane, 2:8) giving the pure product 6c,c0-d,d0.
6-(1-Nitroethyl) cyclohex-1-ene carbonitrile 6c,c0. IR (CHCl3, ꢀ cmÀ1):
1
2217 (CꢂN); 1631 (C¼C); 1552 (C-NO2). H NMR (300 MHz, CDCl3):
6.85 (t, 2H, J ¼ 4 Hz, J ¼ 4 Hz); 4.85 (qt, 2H, J ¼ 6.2 Hz, J ¼ 6.2 Hz); 3.25,
2.80 (2m, 2H); 2.23 (m, 4H) 1.86, 1.73 (2m, 4H), 1.52 (m, 4H); 1.70, 1.54
(2d, 6H, J ¼ 7 Hz, J ¼ 7 Hz). 13C NMR (75 MHz, CDCl3): 149.8, 149.4
(C¼CH); 118.6, 117.4 (C¼CH); 112.4, 112.0 (CꢂN); 83.9, 82.4
(CHNO2); 39.9, 39.3 (CHCHNO2); 25.8, 25.7 (CH2CH¼C); 22.6, 21.3
(CH2CH2CH¼); 19.4, 18.2 (CH2CH2CH), 16.2, 12.7 (CH3CHNO2). MS,
þ
m/z: 133 (70); 118 (63); 106 (66); 92 (100), 79 (58); exactmass M
180.2041 (Calcd. for C9H12N2O2 180.2034).
6-(1-Nitropropyl) cyclohex-1-ene carbonitrile 6d,d0. IR (CHCl3,
1
ꢀ cmÀ1): 2217 (CꢂN); 1631 (C¼C); 1552 (C-NO2). H NMR (300 MHz,
CDCl3): 6.84 (m, 2H); 4.60 (m, 2H); 3.06, 2.80 (2m, 2H); 1.90–2.28

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Functional Cycloalkenols
3267
(m, 8H); 1.83–1.53 (m, 8H); 1.03, 1.02 (2t, 6H, J ¼ 7.3 Hz, J ¼ 7.3 Hz).
13C NMR (75 MHz, CDCl3): 149.8, 149.8 (C¼CH); 112.2, 112.1
(C¼CH); 118.8, 117.6 (CꢂN); 91.5, 91.1 (CHNO2); 39.4, 38.1
(CHCHNO2); 25.8, 25.7 (CH2CH¼C); 24.6 (CH2CH2CH¼); 22.6, 21.3
(CH2CHNO2; 19.2, 17.9 (CH2CH2CH); 11.2, 10.4 (CH3CH2). MS, m/z:
147 (48); 132 (33); 106 (68), 79 (100).
Synthesis of Cycloalkenic Ketoesters and Ketonitriles 7,8a–d
Typical procedure. To a solution of MeOH (15 mL) and Na
(15 mmol), was added the nitro derivative 5 or 6 (5 mmol) to obtain the
corresponding nitronate. After stirring for 1h, a mixture of MeOH
(15 mL) and concentrated H2SO4 (3 mL) was added at À50ꢀC. After
1 h, H2O (30 mL) was added and the solution was concentrated in
order to partially remove MeOH. The mixture was extracted with
CH2Cl2 (3 ꢁ 30 mL), washed with 1% NaOH (10 mL), brine (10 mL)
and dried (MgSO4). The solventwas evaporated under reduced pressure
to obtain a crude product, which was purified by chromatography
(EtOAc/hexane, 2:8).
5-Acetyl cyclopent-1-ene carboxylic acid ethyl ester 7a. IR (CHCl3,
1
ꢀ cmÀ1): 1710 (C¼O); 1631 (C¼C). H NMR (300 MHz, CDCl3): 6.97
(m, 1H); 4.18 (q, 2H, J ¼ 7.2 Hz); 3.90 (m, 1H); 2,60 (m,2H); 2.23 (s,
3H); 2.00, 2.28 (2m, 2H); 1.27 (t, 3H, J ¼ 7.2 Hz). 13C NMR (75 MHz,
CDCl3): 206.6 (CH3C¼O); 164.2 (CO2C2H5); 146.6 (CH¼C); 135.8
(CH¼C); 60.4 (CO2CH2CH3); 56.5 (CHCOCH3); 32.5 (CH2CH¼C);
28.8 (CH3C¼O); 27.7 (CH2CH2CH¼); 14 (CO2CH2CH3). MS, m/z:
þ
182 (Mþ., 5); 140 (76); 112 (47); 67 (88); 43 (100); exactmass M
182.2217 (Calcd. for C10H14O3 182.2209).
5-Propionyl cyclopent-1-ene carboxylic acid ethyl ester 7b. IR (CHCl3,
ꢀ cmÀ1): 1710 (C¼O); 1631 (C¼C). 1H NMR (300 MHz, CDCl3): 6.95 (m,
1H); 4.15 (q, 2H, J ¼ 7.2 Hz); 3.92 (m, 1H); 2.64 (m, 2H); 2.52 (q, 2H,
J ¼ 6.9 Hz); 2.25, 1.94, (2m, 2H); 1.28 (t, 3H, J ¼ 7.2 Hz); 1.09 (t, 3H,
J ¼ 6.9 Hz). 13C NMR (75 MHz, CDCl3): 222.2 (CH3CH2C¼O); 164.2
(CO2C2H5); 146.4 (CH¼C); 135.6 (CH¼C); 60.3 (CO2CH2CH3); 55.4
(CHCOCH2); 35.2 (CH2C¼O); 28.1 (CH2CH2CH ¼); 14
(CO2CH2CH3); 7.6 (CH3CH2C¼O). MS, m/z: 196 (Mþꢃ, 4); 140 (33);
þ
111 (22); 57 (100); 29 (46); exactmass M
C11H16O3 196.2413).
6-Acetyl cyclohex-1-ene carboxylic acid ethyl ester 7c. IR (CHCl3,
196.2455 (Calcd. for
ꢀ
cmÀ1): 1707 (C¼O); 1651 (C¼C). H NMR (300 MHz, CDCl3): 7.20 (t,
1
1H, J ¼ 4.1 Hz); 4.17 (q, 2H, J ¼ 7.2 Hz); 3.61 (m, 1H); 2.25 (s, 3H); 2,23

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3268
Kraıem, Turki, and Amri
(m, 2H); 1.84 (m, 2H); 1.59 (m, 2H); 1.26 (t, 3H, J ¼ 7.2 Hz). 13C NMR
(75 MHz, CDCl3): 209.6 (CH3C¼O); 166.0 (CO2C2H5); 142.1 (CH¼C);
129.1 (CH¼C); 60.4 (CO2CH2CH3); 47.4 (CHCOCH3); 28.5 (CH2CH¼C);
25.7 (CH3C¼O); 25.0 (CH2CH2CH¼) 18.6 (CH2CH2CH); 14.1
(CO2CH2CH3). MS, m/z: 154 (100); 108 (53); 79 (53); 43 (52); exact
mass Mþ 196.2433 (Calcd. for C11H16O3 196.2446).
6-Propionyl cyclohex-1-ene carboxylic acid methyl ester 7d. IR
(CHCl3, ꢀ cmÀ1): 1708 (C¼O); 1650 (C¼C). 1H NMR (300 MHz,
CDCl3): 7.12 (t, 1H, J ¼ 4 Hz); 3.61 (s, 3H); 3.53 (m, 1H); 2,54 (q, 2H,
J ¼ 7.4 Hz); 2.17 (m, 2H); 1.77 (m, 2H), 1.51 (m, 2H); 1.03 (t, 3H,
J ¼ 7.2 Hz). 13C NMR (75 MHz, CDCl3): 212.0 (CH3CH2C¼O); 167.0
(CO2C2H5); 142.0 (CH¼C); 128.8 (CH¼C); 60.3 (CO2CH3); 51.4
(CHCOCH2); 46.5 (CH2CH¼O); 34.4 (CH2CH¼C); 25.2 (CH2CH2CH¼);
18.5 (CH2CH2CH); 7.7 (COCH2CH3). MS, m/z:þ164 (22); 140 (32); 108
(30); 79 (30); 57 (100); 29 (23); exactmass M
C12H18O3 210.2736).
210.2746 (Calcd. for
5-Acetyl cyclopent-1-ene carbonitrile 8a. IR (CHCl3, ꢀ cmÀ1): 2224
(CꢂN); 1717 (C¼O); 1612 (C¼C). 1H NMR (300 MHz, CDCl3): 6.84 (m,
1H); 3.87 (m, 1H); 2,61 (m,2H); 2.28 (s, 3H); 2.35, 2.17 (2m, 2H).
13C NMR (75 MHz, CDCl3): 205.6 (CH3C¼O); 152.1 (CH¼C); 115.6
(CH¼C); 112.9 (CꢂN); 58.7 (CHCOCH3); 32.6 (CH2CH¼C); 28.3
(CH3C¼O); 26.1 (CH2CH2CH¼). MS, m/z: 135 (Mþꢃ, 6); 92 (10); 43
þ
(100); exactmass M 135.1654 (Calcd. for C8H9NO 135.1635).
5-Propionyl cyclopent-1-ene carbonitrile 8b. IR (CHCl3, ꢀ cmÀ1): 2223
(CꢂN); 1717 (C¼O); 1611 (C¼C). 1H NMR (300 MHz, CDCl3): 6.84 (m,
1H); 3.87 (m, 1H); 2.65–2.57 (m, q, 4H, J ¼ 7.2 Hz); 2.3–2.12 (m, 2H);
1.10 (t, 2H, J ¼ 7.2 Hz). 13C NMR (75 MHz, CDCl3): 208.4
(CH3CH2C¼O); 152.1 (CH¼C); 115.7 (CH¼C); 113.2 (CꢂN); 57.9
(CHCOCH2); 34.7 (CH2C¼O); 32.8 (CH2CH¼C); 26.5 (CH2CH2CH¼);
7.3 (COCH2CH3). MS, m/z: 149 (Mþ., 2); 92 (9); 57 (100); 29 (39); exact
mass Mþ 149.1965 (Calcd. for C9H11NO 149.1924).
6-Acetyl cyclohex-1-ene carbonitrile 8c. IR (CHCl3, ꢀ cmÀ1): 2220
(CꢂN); 1715 (C¼O); 1633 (C¼C). 1H NMR (300 MHz, CDCl3): 6.84 (td,
1H, J ¼ 4 Hz, J ¼ 1.8 Hz); 3.37 (m, 1H); 2.28 (s, 3H); 2.24 (m, 2H); 1.91
(m, 2H); 1.65 (m, 2H). 13C NMR (75 MHz, CDCl3): 206.5 (CH3C¼O);
148.5 (CH¼C); 118.9 (CH¼C); 110.6 (CꢂN); 49.5 (CHCOCH3); 28.5
(CH2CH¼C); 25.7 (CH3C¼O); 24.5 (CH2CH2CH¼); 18.4 (CH2CH2CH).
þ
MS, m/z: 149 (Mþꢃ, 3); 106 (23); 43 (100); exactmass M
149.1944
(Calcd. for C9H11NO 149.1948).
6-Propionyl cyclohex-1-ene carbonitrile 8d. IR (CHCl3, ꢀ cmÀ1): 2220
(CꢂN); 1717 (C¼O); 1622 (C¼C). 1H NMR (300 MHz, CDCl3): 6.83 (td,
1H, J ¼ 4 Hz, J ¼ 1.5 Hz); 3.39 (m, 1H); 2,60 (q, 2H, J ¼ 7.3 Hz); 2.22 (m,

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Functional Cycloalkenols
3269
2H); 1.77, 1.65 (2m, 4H); 1.09 (t, 3H, J ¼ 7.3 Hz). 13C NMR (75 MHz,
CDCl3): 209.3 (CH3CH2C¼O); 148.2 (CH¼C); 118.9 (CH¼C);
48.6 (CHCOCH2); 34.6 (CH2CH¼O); 26.07 (CH2CH¼C); 24.5
(CH2CH2CH¼); 18.5 (CH2CH2CH);þ7.8 (COCH2CH3). MS, m/z: 106
(8); 57 (100); 29 (28); exactmass M 163.2241 (Calcd. for C10H13NO
163.2228).
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¨
Received in the USA November 12, 2002

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