New systems for classical nitrosohalogenation of alkenes 1. Reactions of alkenes with ethyl nitrite in the presence of phosphorus halides and thionyl chloride

Article abstract of DOI:10.1007/s11172-006-0088-3

Studies of nitrosation of norbornene and norbornadiene derivatives and dimethyl tricyclo[4.2.2.0^2,5]deca-3,7-diene-9,10-cis-endo- dicarboxylate demonstrated that nitrosation of alkenes with EtONO-PHal ₃, EtONO-POHal₃ (Hal = Cl or Br), and EtONO-SOCl ₂ systems can afford nitroso halides in high yields without the formation of by-products (ketones and oximes). The reactions with 5-substituted norbornenes are nonregioselective. The trans dimer of endo-5-trifluoromethyl- cis-exo-2-chloro-3-nitrosobicyclo[2.2.1]heptane was studied by X-ray diffraction.

Full text of DOI:10.1007/s11172-006-0088-3

Russian Chemical Bulletin, International Edition, Vol. 54, No. 9, pp. 2133—2144, September, 2005
2133
New systems for classical nitrosohalogenation of alkenes
1. Reactions of alkenes with ethyl nitrite in the presence of phosphorus halides
and thionyl chloride*
O. B. Bondarenko, A. Yu. Gavrilova,ꢀ V. N. Tikhanushkina, and N. V. Zyk
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: gavrilova@org.chem.msu.ru
Studies of nitrosation of norbornene and norbornadiene derivatives and dimethyl
tricyclo[4.2.2.02,5]decaꢀ3,7ꢀdieneꢀ9,10ꢀcisꢀendoꢀdicarboxylate demonstrated that nitrosation
of alkenes with EtONO—PHal3, EtONO—POHal3 (Hal = Cl or Br), and EtONO—SOCl2
systems can afford nitroso halides in high yields without the formation of byꢀproducts (ketones
and oximes). The reactions with 5ꢀsubstituted norbornenes are nonregioselective. The
trans dimer of endoꢀ5ꢀtrifluoromethylꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane was
studied by Xꢀray diffraction.
Key words: ethyl nitrite, thionyl chloride, phosphorus(III) halides, phosphorus(V) oxohalides,
alkenes, dimers of nitroso halides, Xꢀray diffraction study.
Alkene nitrosochlorination products are successfully
used in organic synthesis, for example, for the construcꢀ
tion of various heterocycles (pyrazines,1 thiazoles,2 and
thiadiazines3) and in the original synthesis of cycloheptꢀ
4ꢀeneꢀ1ꢀcarboxylic acid.4 A search for new nitrosoꢀ
halogenating systems is a topical problem. Nitrosohaloꢀ
genation of unsaturated substrates can be performed acꢀ
cording to the following two main procedures: the direct
reaction with nitrosyl halides5—8 or the reaction with niꢀ
trosyl halides generated in situ by activation of alkyl niꢀ
trites with protic acids.6—12 However, both reactions afꢀ
ford halo ketones or halo oximes as byꢀproducts or even
the major products.
white crystals, which is characteristic of dimers of nitroso
compounds (Scheme 1, Table 1).
Scheme 1
R = H (1, 3a,b), COOMe (2, 4a,b); Hal = Cl (3a, 4a), Br (3b, 4b)
Reagents i. PCl3, PBr3, SOCl2, POCl3, or POBr3.
Results and Discussion
The highest yields were achieved at the PHal3 : olefin
molar ratio of 1 : 2. The reaction was completed in 30 min.
The reaction with POHal3 requires a longer time for
completion (48 h; POHal3 : olefin = 1 : 1; see Table 1).
The compositions and structures of the reaction prodꢀ
Earlier,13 we have developed a new procedure for
nitrosobromination of olefins by their reactions with ethyl
nitrite in the presence of phosphorus tribromide. In the
present study, we examined the possibility of activation of
ethyl nitrite with PHal3, POHal3 (Hal = Cl or Br),
and SOCl2. Compounds 1 and 2 of the norbornene seꢀ
ries afford cisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]hepꢀ
tane (3a), cisꢀexoꢀ2ꢀbromoꢀ3ꢀnitrosobicyclo[2.2.1]hepꢀ
tane (3b), cisꢀendoꢀ5,6ꢀdi(methoxycarbonyl)ꢀcisꢀexoꢀ
2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane (4a), and
cisꢀendoꢀ5,6ꢀdi(methoxycarbonyl)ꢀcisꢀexoꢀ2ꢀbromoꢀ3ꢀ
nitrosobicyclo[2.2.1]heptane (4b) in preparative yields as
1
ucts were established by H and 13C NMR spectroscopy
(Tables 2 and 3, respectively), IR spectroscopy, and elꢀ
emental analysis (Table 4). The coupling constants in
1
the H NMR spectra of compounds 3 and 4 (J3,2
=
6.5—7.1 Hz) correspond to the cisꢀdiꢀexo arrangement of
the substituents.14
In reactions with "effectively strong" electrophiles,15
alkenes of the norbornadiene series are prone to skeletal
rearrangements and are characterized by homoallylic asꢀ
sistance of the second double bond involved in stabilizaꢀ
tion of the intermediate carbocation. To obtain additional
* Dedicated to Academician N. S. Zefirov on the occasion of his
70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2070—2080, September, 2005.
1066ꢀ5285/05/5409ꢀ2133 © 2005 Springer Science+Business Media, Inc.

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Bondarenko et al.
Table 1. Yields of nitrosohalogenation products
data on the reaction mechanism and the nature of the
reagents under study, we thoroughly analyzed the comꢀ
positions of the products prepared by the reaction of
norbornadiene 5 with EtONO—PHal3 systems. In addiꢀ
tion to nitroso halides 6, we isolated small amounts and
identified dihalides 7a,b, 8a,b, and 9 and chloro nitrates
7c and 8c (Scheme 2). Under the same conditions, the
reactions of benzonorbornadienes 10 and 11 afforded
nitroso halides 12a and 13a,b, chloro nitrates 14a and
15a, and dibromide 15b (Scheme 3).
Olefin
Lewis
acid
Product
Yield
(%)
1
PCl3
3а
70
10
65
77
60
76
70
72
43
68
79
60
54
68
30
86
70
61
41
53a
23b
76
59
56
POCl3
SOCl2
PBr3
POBr3
PCl3
3b
4a
2
5
SOCl2
PBr3
POBr3
PCl3
4b
Scheme 3
6a
SOCl2
PBr3
6b
POBr3
PCl3
POCl3
SOCl2
PCl3
10
11
12a
13a
13b
PBr3
POBr3
PCl3
SOCl2
PCl3
16
17
22
18 + 20
19 + 21
23a
SOCl2
PBr3
23b
a 18 : 20 ≈ 1 : 1.
b 19 : 21 ≈ 1 : 1.
Comꢀ
R
Hal
X
Comꢀ
R
Hal
X
pound
pound
Scheme 2
10
11
12a
13a
OMe
H
OMe
H
—
—
Cl
Cl
—
—
—
—
13b
14a
15a
15b
H
OMe
H
Br
Cl
Cl
Br
—
ONO2
ONO2
Br
H
Reagents: i. POCl3 (SOCl2 or POBr3).
The physicochemical characteristics of compounds 7a,
8a, and 15a are consistent with the published data.16—18
The presence of a double bond in product 9 is evidenced
by a signal for the olefinic protons at δ 6.20 in the 1H NMR
spectrum. The conclusion about the rearranged character
of compound 9 was made based on the multiplicity of the
signal for the proton H(2)Br (δ 3.76). This signals appears
as a doublet of doublets of doublets with two vicinal couꢀ
pling constants (J2,3endo = 8.0 Hz and J2,3exo = 4.0 Hz)
and a W coupling constant with the proton antiꢀH(7)Br
(J2,7 = 1.3 Hz).
Dibromides 7b and 8b with nortricyclane structures
were isolated and characterized as a mixture. The assignꢀ
ment of the chemical shifts of the protons at the substituꢀ
ents was made based on the criteria proposed in the
study.19 The 13C NMR spectra of compounds 7b and 8b
correspond to those recorded earlier.20
Comꢀ
pound
Hal
Cl
Br
Cl
Br
X
Comꢀ
pound
Hal
X
6a
6b
7a
7b
—
—
Cl
Br
7c
8a
8b
8c
Cl
Cl
Br
Cl
ONO2
Cl
Br
ONO2

Reactions of alkenes with ethyl nitrite
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2135
Scheme 4
The functional compositions of nitrates 7c, 8c, 14a,
and 15a were determined by IR spectroscopy21 and were
confirmed by elemental analysis (see Table 4). Chloro
nitrates 7c and 8c were isolated and characterized as a
mixture. To establish the structures
of these compounds, we examined
the possibility of the formation of
the following three isomers: 7c, 8c,
2 NOBr
2 NO + Br2
2 NO + Cl2
2 NO2
2 NOCl
2 NO + O2
NOCl + NO2
NO2Cl + NO
and hypothetical structure 7d.
The chemical shifts of the proꢀ
tons at the substituents were calcuꢀ
In spite of the fact that nitrosochlorination has long
been in use, there is no general agreement as to its mechaꢀ
nism. Hence, it was of interest to study the influence of
electronꢀwithdrawing groups at position 5 of norbornene
on the regioꢀ and stereoselectivity of the reaction. We
examined 5ꢀtrifluoromethylbicyclo[2.2.1]heptꢀ2ꢀene*
(16) and endoꢀ5ꢀnitrobicyclo[2.2.1]heptꢀ2ꢀene (17) as
model substrates. In both cases, two regioisomers in a
ratio of approximately 1 : 1 were isolated (Scheme 5, see
Table 1).
lated by the equation δ3 = δ0 + ∆s +
∆de, where δ3 is the chemical shift of the proton of the
HCCl or HCONO2 group in a 3,5ꢀdisubstituted
nortricyclane, δ0 is the chemical shift of the proton at the
C(3) atom in the 3ꢀnortricyclane system (δ0(HCCl) =
3.85 0.03 and δ0(HCONO2) = 4.77), ∆s is the change in
the chemical shift of the proton due to the presence of a
substituent at position 5 (endo or exo) (for HCCl and
HCONO2, ∆s = 0.0), and ∆de is the deshielding effect of
an endo substituent at position 5 (∆de(HCCl) = 0.76 0.07
and ∆de(HCONO2) ≈ 0.6).19 A comparison of the calcuꢀ
lated data with the experimental results (Table 5) led us to
conclude that the reaction affords exoꢀ3ꢀchloroꢀendoꢀ5ꢀ
nitroxytricyclo[2.2.1.02,6]heptane (7c) and exoꢀ3ꢀchloroꢀ
exoꢀ5ꢀnitroxytricyclo[2.2.1.02,6]heptane (8c).
Scheme 5
The fact that the formation of nitrates 14a and 15a is
accompanied by a rearrangement is evidenced by the presꢀ
ence of two vicinal coupling constants of the proton
HC(2)O with the protons of the adjacent methylene group,
viz., 2 H(3), (J2,3endo = 7.5 Hz and J2,3exo = 3.5 and 3.7 Hz
R = CF3 (16, 18, 19), NO2 (17, 19, 21)
i. EtONO, PCl3 (or SOCl2).
1
for 14a and 15a, respectively) in the H NMR spectra of
these compounds. The endo arrangement of the proton
HC(2)O is confirmed by the presence of a longꢀrange W
coupling constant J2,7anti = 1.0 Hz (Table 6, see Ref. 14).
Consequently, neither the Wagner—Meerwein rearꢀ
rangement nor homoallylic assistance products of the secꢀ
ond double bond, nor the conjugated addition product
involving an ester group as the nucleophile, were present
among the resulting nitroso halides. These results are conꢀ
sistent with the published data5—12 on the addition of
nitrosyl chloride to such alkenes and suggest that the reꢀ
action is accompanied by the in situ generation of nitrosyl
halides, which react with olefins.
The formation of byꢀproducts under the conditions of
nitrosohalogenation of olefins used in the present study is
apparently attributed to the reaction of alkenes with traces
of halides and nitryl chloride generated as a result of
partial decomposition of nitrosyl halides (Scheme 4).24,25
However, the yields of compounds 7—9, 14, and 15
are so low (see Experimental) that their formation does
not impair the synthetic importance of this method. Beꢀ
sides, the use of Lewis acids (aprotic acids) for the activaꢀ
tion of ethyl nitrite prevents the formation of ketones and
oximes.
The dimer of endoꢀ5ꢀtrifluoromethylꢀcisꢀexoꢀ2ꢀ
chloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane (18) was isolated
in individual form by recrystallization from CHCl3. Howꢀ
ever, we failed to purify the dimer of endoꢀ6ꢀtrifluoroꢀ
methylꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane
(20), which remained in the mother liquor, from an imꢀ
purity of compound 18 by recrystallization. The strucꢀ
tures of these compounds were established based on the
analysis of the chemical shifts in the 1H NMR spectrum.
In particular, the signal for the proton HC(3)N in prodꢀ
uct 18 is shifted downfield by δ 0.47 compared to the
signal for the proton HC(3)N in compound 20 due to the
deshielding effect of the trifluoromethyl group.
Xꢀray diffraction study of compound 18 confirmed
the assignment of the signals. The overall view of the
molecule and the atomic numbering scheme** are shown
in Fig. 1. The bond lengths and bond angles calculated
* The reaction was carried out with a mixture of isomers in an
exo : endo ratio of 1 : 3. We failed to isolate and characterize
isomers obtained from 5ꢀexoꢀtrifluoromethylnorbornene.
** The atomic numbering scheme does not correspond to the
IUPAC nomenclature.

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Bondarenko et al.

Reactions of alkenes with ethyl nitrite
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2137

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Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Bondarenko et al.
Table 3. 13C NMR spectra of the compounds synthesized (in CDCl3)
Comꢀ
pound
δ (JC,F/Hz)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
3a
45.4
46.1
49.1
49.5
50.5
51.1
15.1
15.6
14.9
15.1
13.6
14.9
49.2
52.5
53.0
49.8
53.4
51.0
45.9
62.5
54.0
58.4
49.7
57.9
49.0
18.8
19.4
19.5
22.0
22.4
21.8
58.9
59.7
50.6
83.6
83.9
55.5
61.5
73.9
73.6
69.4
68.9
69.8
69.5
62.7
53.7
61.0
60.7
51.1
59.5
73.4
71.7
71.4
31.4
31.6
36.5
68.2
39.1
39.7
42.0
42.5
46.1
46.4
43.9
44.0
40.2
43.9
44.2
40.5
46.2
46.7
46.7
45.7
49.2
45.1
40.6
26.3
27.1
45.4
46.0
138.1
138.4
63.6
54.3
87.5
60.7
51.1
83.7
148.8
144.6
145.0
—
26.0
26.4
45.1
45.2
137.9
137.5
21.6
22.2
16.5
22.0
22.4
17.4
148.3
144.4
144.2
—
35.3
35.8
36.7
37.3
44.3
44.8
29.3
29.2
28.2
27.6
30.2
27.7
43.1
46.2
47.1
65.67
65.5
56.4
36.8
3b
4aa
4bb
6a
6b
7ac
7bd
7ce
8ac
8bd
8ce
12a f,g
13a f,h
13b f,i
14a f,j
15a f,k
15b f,l
18m
139.5
142.9
42.1
144.5
143.5
27.1
(J = 3.2) (J = 2.4) (J = 27) (J = 2.4)
19n
20m
44.7
46.5
60.9
61.4
68.1
73.3
45.6
39.5
84.4
27.4
30.8
42.7
35.7o
37.2
(J = 3.1)
50.6
(J = 29)
83.1
21n
56.6
72.5
39.6
31.2
36.4o
a 51.9, 52.2 (OCH3); 170.9, 171.3 (C=O).
b 51.86, 52.2 (OCH3); 170.9, 171.4 (C=O).
c In a mixture of isomers 7a and 8a.
d In a mixture of isomers 7b and 8b; the spectrum is consistent with the published data.20
e In a mixture of isomers 7c and 8c.
f The atomic numbering scheme does not correspond to the IUPAC nomenclature and is
presented in Scheme 3.
g 57.2, 57.6 (OCH3); 113.8, 114.4, 133.7, 134.7 (Carom) (in CDCl3 + CF3COOH).
h 122.2, 122.5, 127.4, 127.6 (Carom).
i 122.2, 122.5, 127.5, 127.7 (Carom).
j 55.9, 56.0 (OCH3), 110.55, 111.35 (Carom).
k 121.9, 122.6, 127.5, 128.1 (Carom).
l 121.3, 121.7, 127.2, 127.8 (Carom).
m 127.2 (CF3, JC,F = 276 Hz).
n In a mixture of isomers 19 and 21; the assignment of the chemical shifts was made using
an additive scheme accounting for the α, β, and γ effects of the substituents.22,23
o A precise assignment is absent.
from the Xꢀray diffraction data (Table 7) demonstrate
that the CN(O)—N(O)C fragment is planar. The C—N
bond length in the dimer (1.480(3) Å) is similar to the
C—N bond length in amines (1.47 Å), whereas the N—N
bond (1.313(3) Å) is intermediate between single and
double bonds. The N—O bond length is 1.263(2) Å.
Therefore, the bond lengths and bond angles in the
CN(O)—N(O)C fragment are typical of diazene dioxides
and agree well with the data for the transꢀdimer of
2ꢀchloroꢀ2ꢀmethylꢀ3ꢀnitrosobutane.26 The C—Cl bond
length (1.795(3) Å) is only slightly larger than the stanꢀ
dard value (1.78 Å). A decrease in the C(5)—C(8) bond
length to 1.485(4) Å due to the influence of the electroneꢀ
gative substituents (F(1), F(2), and F(3)) has been obꢀ
served earlier in 5ꢀtrifluoromethylnorbornane derivaꢀ
tives.27
Compounds 19 and 21 were isolated and characterꢀ
ized as a mixture. Due to the difference in solubility of the
1
isomers in CHCl3, the H NMR spectrum of compound
19 as the main component of the mixture could be reꢀ
corded. The signal for the proton H(1) of this isomer is
observed at higher field (δ 2.62) than the signal for the

Reactions of alkenes with ethyl nitrite
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2139
Table 4. Melting points, elemental analysis data, and IR spectra of the compounds synthesized
Comꢀ
pound
M.p./°C
(solvent)
Found
Calculated
Molecular
formula
IR,
ν/cm–1
(%)
C
H
N
3aa
156—158
(MeOH)
122—123
(MeOH)
167—168
(Et2O)
160
(MeOH)
164—165
(MeOH)
164
52.61
52.66
41.11
41.18
47.52
47.91
40.46
41.25
53.37
53.33
41.86
41.58
44.70
44.33
57.88
58.32
63.60
63.61
51.91
52.38
52.49
52.09
42.21
42.20
40.97
41.08
53.64
53.59
46.39
46.93
6.46
6.27
4.93
4.90
5.31
5.08
4.27
4.38
5.17
5.08
3.84
3.96
4.42
4.22
5.23
5.23
4.67
4.85
3.87
3.97
4.35
4.67
4.03
3.96
4.36
4.40
4.91
5.10
4.25
4.47
8.78
8.78
6.80
6.86
—
C7H10ClNO
C7H10BrNO
C11H14ClNO5
C11H14BrNO5
C7H8ClNO
1230
1230
3b
4ab
1740 (C=O), 1280,
1250, 1200
1730 (C=O); 1290,
1280, 1210
4b
4.09
4.38
8.87
8.89
7.14
6.93
—
6a
1250, 1220
6b
C7H8BrNO
1250, 1220
(MeOH)
—
7c + 8c
12ac
13a
C7H8ClNO3
C13H14ClNO3
C11H10ClNO
C11H10BrNO
C13H14ClNO5
C8H9ClF3NO
C7H9ClN2O3
C14H16ClNO5
C14H16BrNO5
1640, 1285,
870 (ONO2)
1250, 1220
165—166
(Et2O)
5.13
5.23
6.57
6.74
5.32
5.56
4.69
4.67
6.23
6.15
13.50
13.69
4.21
4.47
3.75
3.91
148—150
(MeOH)
140—141
(MeOH)
—
1280, 1270,
1255, 1215
1280, 1265, 1260,
1225, 1210
1640, 1270,
855 (ONO2), 1510
1280, 1250,
1165e
1550, 1380(NO2);
1235
13b
14a
18 + 20
19 + 21
23a
208—210d
(CHCl3)
150
(CHCl3)
172—175
(MeOH)
165
1750 (C=O);
1220, 1180
1750 (C=O);
1220, 1180
23b
(MeOH)
a Found (%): Cl, 21.75. C7H10ClNO. Calculated (%): Cl, 22.26.
b Found (%): Cl, 12.57. C11H14ClNO5. Calculated (%): Cl, 12.89.
c Found (%): Cl, 13.18. C13H14ClNO3. Calculated (%): Cl, 13.27.
d For isomer 18.
e The IR spectrum of a mixture of isomers 18 and 20 is identical with that of individual compound 18.
Table 5. Calculated and experimental chemical shifts for the
protons at the carbon atoms bearing substituents in nortricyclane
C(5)
C(3)
C(4)
C(5)
chloro nitrates
C(2)
C(1)
C(7)
Comꢀ
pound
δ
N
Calculated
H(3)
Found
F(3)
C(8)
C(6)
O
F(1)
H(5)
4.77
5.53 0.07
4.77
H(3)
H(5)
F(2)
7c
7d
8c
4.45 0.03
3.85
4.40
—
4.05
5.00
—
4.80
3.85
Fig. 1. Molecular structure of the dimer of endoꢀ5ꢀtrifluoroꢀ
methylꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane 18.
proton H(4) of isomer 21 (δ 3.12) due to the weaker
deshielding effect of the chlorine atom compared to the
NO group. This also accounts for the smaller chemical
shift of the proton H(1) of compound 21 (δ 2.98) comꢀ
pared to that of the proton H(4) of isomer 19 (δ 3.48).

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Bondarenko et al.
1
Table 6. H NMR spectra of compounds 12a, 13a,b, 14a, and 15a,b (in CDCl3)
Comꢀ
pound
δ (JH,H/Hz)
Н(1)
Н(2)
H(3)
H(4)
synꢀH(7)
antiꢀH(7)
12aa,b 3.74c
4.42 (dd, J2,3 = 6.7,
J2,7anti = 1.7)
4.43 (dd, J2,3 = 6.4,
J2,7anti = 1.6)
4.44 (dd, J2,3 = 6.7,
J2,7anti = 1.7)
4.92 (ddd, J2,3endo = 7.5,
4.96 (dd, J3,7anti = 1.4)
4.96 (br.d)
3.99
(d)
3.77
(br.s)
3.76
(s)
3.71
(m)
3.48
(m)
3.48
(m)
2.05 (dt, J7,7 = 10.0,
J7,1 = J7,4 = 1.6)
2.10 (dt, J7,7 = 9.9,
J7,1 ≈ J7,4 = 1.5)
2.58 (dt)
13аa,d 3.52
2.62 (dt,
J7,3 = 1.0)
2.67 (dt,
(br.s)
3.62
(s)
13ba,e
14aa,f
15aa,g
4.96 (dd, J3,2 = 6.7)
2.15 (d, J7,7 = 9.9)
J7,3 = 1.4)
3.96
exo: 2.49 (dt, J3,3 = 13.0, J3,4 = 3.5)
4.09 (t, J7,4 = 1.5)
(br.s) J2,3exo = 3.5, J2,7anti = 1.0) endo: 2.17 (dd, J3,3 = 13.0, J3,2 = 7.5)
3.72
4.89 (ddd, J2,3endo = 7.5,
exo: 2.50 (dt, J3,3 = 13.5, J3,4 = 3.7)
endo: 2.12 (dd, J3,3 = 13.5, J3,2 = 7.5)
exo: 2.84 (dt, J3,3 = 13.0, J3,4 = 4.0)
endo: 2.18 (dd)
4.09 (t, J7,4 = 1.5)
4.11 (t, J7,4 = 1.2)
(br.s) J2,3exo = 3.7, J2,7anti = 1.0)
15ba,h 3.72
3.77 (ddd, J2,3endo = 8.0,
J2,3exo = 4.0, J2,7 = 1.2)
(br.s)
a The atomic numbering scheme does not correspond to the IUPAC nomenclature and is presented in Scheme 3.
b Other signals: 3.74c and 3.80 (both s, 3 H each, CH3O); 6.65 (br.s, 2 H, Harom).
c The signals in the spectrum overlap.
d Other signals: 7.15 and 7.24 (both m, 2 H each, Harom).
e Other signals: 7.15 and 7.23 (both m, 2 H each, Harom).
f Other signals: 3.79 and 3.82 (both s, 3 H each, CH3O); 6.70 (d, 2 H, Harom, J = 2.0 Hz).
g Other signals: 7.15 and 7.20 (both m, 2 H each, Harom).
h Other signals: 7.20 and 7.28 (both m, 2 H each, Harom).
involved in stabilization of the resulting carbocation.29
However, the fact that the reaction with 5ꢀtrifluoromethylꢀ
substituted compound 16 produced two isomeric nitroso
chlorides in a ratio of 1 : 1 was unexpected.
Table 7. Selected interatomic distances (d) and bond angles (ω)
in compound 18
Bond
d/Å
Angle
ω/deg
We believe that high stereospecificity and the absence
of regioselectivity of the reactions with 5ꢀsubstituted
norbornenes either confirm the assumption that NOCl
adds to alkenes of the bicyclo[2.2.1]heptene series by cyꢀ
clic electron transfer in a fourꢀcenter transition state7 or
are a consequence of the fact that nitrosation, contrary to
typical electrophilic addition reactions, proceeds via a
π complex rather than via a σ intermediate.30
Nitrosohalogenation of diester 22, which is highly
prone to transannular crossꢀcyclizations,31 also afforded
exclusively cisꢀexoꢀaddition products to the double bond
of the cyclobutane ring (Scheme 6).
Cl—C(2)
F(1)—C(8)
F(2)—C(8)
F(3)—C(8)
O—N
N—N
N—C(1)
C(5)—C(8)
1.795(3)
1.338(3)
1.321(4)
1.340(3)
1.263(2)
1.313(3)
1.480(3)
1.485(4)
O—N—N
O—N—C(1)
N—N—C(1)
120.8(2)
122.95(17)
116.2(2)
111.14(17)
113.28(18)
106.1(3)
106.6(3)
105.8(3)
112.6(3)
114.2(3)
111.0(3)
N—C(1)—C(6)
N—C(1)—C(2)
F(2)—C(8)—F(1)
F(2)—C(8)—F(3)
F(1)—C(8)—F(3)
F(2)—C(8)—C(5)
F(1)—C(8)—C(5)
F(3)—C(8)—C(5)
The above assignments suggest that product 19 has the
structure of the dimer of endoꢀ5ꢀnitroꢀcisꢀexoꢀ2ꢀchloroꢀ
3ꢀnitrosobicyclo[2.2.1]heptane, and compound 21 has the
structure of the dimer of endoꢀ6ꢀnitroꢀcisꢀexoꢀ2ꢀchloroꢀ
3ꢀnitrosobicyclo[2.2.1]heptane.
Scheme 6
The fact that the reaction with 5ꢀnitrobicyꢀ
clo[2.2.1]heptꢀ2ꢀene 17 is nonregioselective can be acꢀ
counted for by the dual influence of the nitro group. On
the one hand, due to high electronegativity of the subꢀ
stituent, the electrophilic addition gives rise to a cation in
which the positive charge on the carbon atom is at the
maximum distance from this electronꢀwithdrawing subꢀ
stituent.28 On the other hand, the nitro group can be
Hal = Cl (a), Br (b)
i. EtONO, PCl3 (SOCl2 or PBr3).

Reactions of alkenes with ethyl nitrite
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2141
The structures of the reaction products were estabꢀ
lished by 1H and 13C NMR spectroscopy (Tables 8 and 9).
Analysis of the spectra and subsequent structural assignꢀ
ments were made taking into account the data on the
influence of substituents on the chemical shifts, the
1H—1H coupling constants, and the results of homoꢀ
nuclear selective double resonance and NOE experiments.
The presence of signals for olefinic protons in the
1H NMR spectra of nitroso halides 23a,b indicates that
the reaction is not accompanied by a rearrangement. The
signals for the protons in nitroso chloride 23a were asꢀ
signed with the use of NOE experiments. For example,
irradiation at the frequency of the signal for the proton
HC(4)N led to a change in the integral intensity of the
signals for the protons of the double bond (2.6%) and the
proton HC(3)Cl (9.1%). At the same time, irradiation of
the proton HC(3)Cl gave NOE on the protons of the
double bond (2.2%) and the proton HC(4)N (8.0%). This
is evidence for the cisꢀdiꢀexo arrangement of the substituꢀ
ents. In addition, irradiation at a frequency of the signal
of HC(4)N gave a signal at δ 3.12 (0.9%). Hence, this
signal was assigned to the proton H(6).
proton H(2) revealed the coupling constants of the proꢀ
ton H(2) with the proton HC(3)Cl (J = 3.9 Hz), the proton
H(5) (J = 10.0 Hz), and the proton H(1) (J = 3.9 Hz).
The assignment of the signals for the protons of nitroso
bromide 23b was made taking into account the results
obtained for product 23a. The following constants were
revealed for structure 23b using the double resonance
3
3
3
method: J4,5 = 5.4 Hz, J5,2 = 10.0 Hz, J5,6 = 3.0 Hz,
3
and J3,2 = 3.8 Hz. The constant J2,1 was also detected,
but its precise value could not be determined.
Spinꢀspin decoupling from the proton H(2) in nitroso
halides 23 simplifies the tripletꢀlike signal for HC(4)N to
a doublet of doublets, which is indicative of the presence
of a W coupling constant (4J2,4 ≤ 1 Hz).
The set of the coupling constants J2,3, J3,4, and J4,5 for
compounds 23a and 23b is characteristic of cisꢀexo deꢀ
rivatives of tricyclo[4.2.2.02.5]decꢀ7ꢀene.32,33 Hence, we
assigned the structures cisꢀendoꢀ9,10ꢀdi(methoxycarboꢀ
nyl)ꢀcisꢀexoꢀ3ꢀchloroꢀ4ꢀnitrosotricyclo[4.2.2.02,5]decꢀ7ꢀ
ene and cisꢀendoꢀ9,10ꢀdi(methoxycarbonyl)ꢀcisꢀexoꢀ3ꢀ
bromoꢀ4ꢀnitrosotricyclo[4.2.2.02,5]decꢀ7ꢀene to comꢀ
pounds 23a and 23b, respectively.
To determine coupling constants in the spectrum of
product 23a, we carried out additional NMR experiments
using the H—{1H} double resonance method. Spinꢀspin
decoupling from the proton H(5) revealed the couꢀ
pling constants of this proton with the proton HC(4)N
(J = 5.1 Hz), the proton H(2) (J = 10.0 Hz), and the
proton H(6) (J ≈ 3.0 Hz). Spinꢀspin decoupling from the
To summarize, nitrosohalogenation of olefins of the
norbornene and norbornadiene series and dimethyl triꢀ
cyclo[4.2.2.02,5]decaꢀ3,7ꢀdieneꢀ9,10ꢀcisꢀendoꢀdicarboxyꢀ
late was studied using EtONO—PHal3, EtONO—POHal3
(Hal = Cl or Br), and EtONO—SOCl2 systems. Nitroso
halides NOHal that were generated in these systems were
demonstrated to serve as nitrosating agents. Nitrosation
1
Table 8. H NMR spectra of compounds 23a,b in CDCl3 containing 10% of trifluoroacetic acid
Comꢀ
pound
δ (JH,H/Hz)
Н(1), m
3.26
Н(2)
Н(3), dd
Н(4), ddd
5.10b
Н(5), ddd
3.57
Н(6), m
3.12
23аа
23bс
2.75 (dt, J2,5 = 10.0,
J2,1 = 3.9)
2.90 (dm, J2,5 = 10.0)
4.22 (J3,4 = 7.4,
J3,2 = 3.9)
(J4,5 = 5.1, J4,2 ≈ 1.0) (J5,2 = 10.0, J5,6 ≈ 3.0)
5.15d
3.56
(J4,5 = 5.4, J4,2 ≈ 1.0) (J5,2 = 10.0, J5,6 ≈ 3.0)
3.28
4.30 (J3,4 = 7.8,
J3,2 = 3.8)
3.12
a Other signals: 3.00 (dd, H(10), J10,9 = 11.0 Hz, J10,6 = 1.6 Hz); 3.05 (d, H(9), J9,10 = 11.0 Hz); 3.66 and 3.67 (both s, 3 H each,
OCH3); 6.55 (t, 2 H, H(7), H(8), J = 3.4 Hz).
1
b As follows from the experiments with the use of the double resonance method. The signal in the H NMR spectrum appears as a
triplet with the coupling constant J = 6.1 Hz.
c Other signals: 3.00 (dd, H(10), J10,9 = 10.5 Hz, J10,6 = 1.7 Hz); 3.04 (dd, H(9), J9,10 = 10.5 Hz, J9,1 = 1.4 Hz); 3.66 and 3.67 (both s,
3 H each, OCH3); 6.55 (t, 2 H, H(7), H(8), J = 4.0 Hz).
1
d As follows from experiments with the use of the double resonance method. The signal in the H NMR spectrum appears as a triplet
with the coupling constant J = 6.4 Hz.
Table 9. 13C NMR spectra of compounds 23a,b (in CDCl3 with an admixture of CF3COOH)
Comꢀ
pound
δ
С(1)
С(2)
С(3)
С(4)
С(5)
С(6)
С(7), С(8)
С(9), С(10)
С=О
ОСН3
23a
23b
34.4
34.5
47.4
47.6
53.2
41.9
69.0
68.9
37.1
37.7
35.2
35.5
133.6, 133.0
133.5, 132.9
46.3, 46.1
46.2, 46.0
176.4
176.3
53.6
53.5

2142
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Bondarenko et al.
(determined from the intensity ratio of the signals in the 1H NMR
spectrum of the mixture; these data are consistent with the pubꢀ
lished data16,17); b) a mixture of exoꢀ3ꢀchloroꢀendoꢀ5ꢀnitroxyꢀ
tricyclo[2.2.1.02,6]heptane (7c) and exoꢀ3ꢀchloroꢀexoꢀ5ꢀnitroxyꢀ
tricyclo[2.2.1.02,6]heptane (8c) (Rf 0.85) in a yield of 0.05 g
(3.5%) as a transparent oil, 7c : 8c = 4 : 1 (1H NMR).
of alkenes with ethyl nitrite in the presence of phosꢀ
phorus(III) halides, phosphorus(V) oxohalides, or thionyl
chloride is a convenient procedure for the synthesis of
1,2ꢀnitrosyl halides, because the reactions proceed rather
selectively without the formation of ketones and oximes
as byꢀproducts.
Reaction of norbornadiene (5) with ethyl nitrite in the presꢀ
ence of PBr3. The product prepared by the reaction of norꢀ
bornadiene (0.60 g, 6.5 mmol) with ethyl nitrite (1.5 g, 20 mmol)
in CHCl3 (30 mL) and PBr3 (0.88 g, 3.25 mmol) in CHCl3
(15 mL) was recrystallized from MeOH and cisꢀexoꢀ2ꢀbromoꢀ3ꢀ
nitrosobicyclo[2.2.1]heptꢀ5ꢀene (6b) was obtained in a yield
of 0.79 g as white crystals. Preparative TLC (light petroꢀ
leum—EtOAc, 3 : 1) of the mother liquor afforded a) a mixture
of endoꢀ5ꢀexoꢀ3ꢀdibromotricyclo[2.2.1.02,6]heptane (7b) and
exoꢀ5ꢀexoꢀ3ꢀdibromotricyclo[2.2.1.02,6]heptane (8b) in a yield
of 0.12 g (7.3%) (Rf 0.72) as a paleꢀyellow oil, 7b : 8b = 3 : 1
(1H NMR, these data are consistent with the published data20);
b) exoꢀ5ꢀbromoꢀsynꢀ7ꢀbromobicyclo[2.2.1]heptꢀ2ꢀene (9)
(Rf 0.67) in a yield of 0.025 g (1.5%) as a paleꢀyellow oil.
Reaction of 3,6ꢀdimethoxybenzonorbornadiene (10) with ethyl
nitrite in the presence of PCl3. The product prepared by the
reaction of 3,6ꢀdimethoxybenzonorbornadiene (0.31 g,
1.5 mmol) with ethyl nitrite (0.40 g, 5.3 mmol) in CHCl3 (25 mL)
and PCl3 (0.105 g, 0.76 mmol) in CHCl3 (15 mL) was recrysꢀ
tallized from MeOH and 3,6ꢀdimethoxyꢀcisꢀexoꢀ10ꢀchloroꢀ
9ꢀnitrosotricyclo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (12a) was
obtained in a yield of 0.28 g as white crystals. Preparative
TLC (light petroleum—EtOAc, 3 : 1) of the mother liquor
afforded 3,6ꢀdimethoxyꢀexoꢀsynꢀ11ꢀchloroꢀ9ꢀnitroxytricyꢀ
clo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (14a) (Rf 0.65) in a yield
of 0.02 g (4.3%) as a transparent crystallizable oil.
Reaction of benzonorbornadiene (11) with ethyl nitrite in the
presence of PCl3. The product prepared by the reaction of
benzonorbornadiene 11 (0.66 g, 4.6 mmol) with ethyl nitrite
(1.20 g, 16.0 mmol) in CHCl3 (25 mL) and PCl3 (0.32 g,
2.3 mmol) in CHCl3 (20 mL) was recrystallized from MeOH
and cisꢀexoꢀ10ꢀchloroꢀ9ꢀnitrosotricyclo[6.2.1.02,7]undecaꢀ
2(7),3,5ꢀtriene (13a) was obtained in a yield of 0.67 g as white
crystals. Preparative TLC (light petroleum—EtOAc, 3 : 1) of
the mother liquor afforded exoꢀsynꢀ11ꢀchloroꢀ9ꢀnitroxytricyꢀ
clo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (15a) (Rf 0.57) in a yield
of 0.06 g (5.4%) as a paleꢀyellow oil.
Reaction of benzonorbornadiene (11) with ethyl nitrite in the
presence of PBr3. The product prepared by the reaction of
benzonorbornadiene 11 (0.525 g, 3.7 mmol) with ethyl niꢀ
trite (1.20 g, 16 mmol) in CHCl3 (25 mL) and PBr3 (0.5 g,
1.85 mmol) in CHCl3 (20 mL) was recrystallized from MeOH
and cisꢀexoꢀ10ꢀbromoꢀ9ꢀnitrosotricyclo[6.2.1.02,7]undecaꢀ
2(7),3,5ꢀtriene (13b) was obtained in a yield of 0.57 g as white
crystals. Preparative TLC (light petroleum—EtOAc, 3 : 1) of
the mother liquor afforded exoꢀ9ꢀbromoꢀsynꢀ11ꢀbromotricyꢀ
clo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (15b) (Rf 0.71) in a yield
of 0.142 g (13%) as a paleꢀyellow oil (the results are consistent
with the published data18).
Using the aboveꢀdescribed general procedure, endoꢀ5ꢀ
trifluoromethylꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane
(18) and endoꢀ6ꢀtrifluoromethylꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosoꢀ
bicyclo[2.2.1]heptane (20) were prepared from compound 16,
endoꢀ5ꢀnitroꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]hepꢀ
tane (19) and endoꢀ6ꢀnitroꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyꢀ
Experimental
The H and 13C NMR spectra were recorded on a Varian
1
VXRꢀ400 spectrometer (400 and 100 MHz, respectively) at 28 °C.
The chemical shifts are given on the δ scale relative to Me4Si as
the internal standard. The IR spectra were measured on URꢀ20
(in thin films or Nujol mulls) and Specord 75 IR (in Nujol
mulls) instruments. The melting points were determined in open
capillary tubes on a heating block and are uncorrected.
The solvents were purified according to standard proceꢀ
dures.14 Ethyl nitrite was synthesized according to a known proꢀ
cedure.34
Nitrosation of olefins with ethyl nitrite in the presence of
phosphorus(III) halides, phosphorus(V) oxohalides, and thionyl
chloride (general procedure). A solution of phosphorus(III) haꢀ
lide, thionyl chloride, or phosphorus(V) oxochloride in anhydrous
CH2Cl2 (or CHCl3) (olefin : PHal3 (or SOCl2) = 2 : 1, and
olefin : POHal3 = 1 : 1) was slowly added dropwise with stirring
to a solution of an olefin and ethyl nitrite (the olefin : ethyl
nitrite molar ratio ≈ 1 : 3) in the same solvent at –30 °C under
dry argon. The reaction mixture was stirred at this temperature
for 0.5 h, after which the mixture was slowly warmed to room
temperature (in the reactions with the use of POHal3, the temꢀ
perature was raised to 0 °C, and the mixture was stirred at this
temperature for 48 h). The solvent was distilled off, and the
product was purified by recrystallization from ethanol. The crysꢀ
tals were filtered off. The mother liquor was concentrated, and
the residue was separated by preparative TLC on Silufol plates.
The yields of the reaction products are given in Table 1. The
physicochemical characteristics of the products are listed in
Tables 2—4 and 6—9.
The reactions of norbornene 1 with EtONO—PCl3 (SOCl2
or POCl3) and EtONO—PBr3 (or POBr3) (see Table 1) gave cisꢀ
exoꢀ2ꢀchloroꢀ3ꢀnitrosobicyclo[2.2.1]heptane (3a) and cisꢀexoꢀ2ꢀ
bromoꢀ3ꢀnitrosobicyclo[2.2.1]heptane (3b), respectively.
The reactions of norbornene 2 with EtONO—PCl3 (or
SOCl2) and EtONO—PBr3 (or POBr3) produced cisꢀendoꢀ5,6ꢀ
di(methoxycarbonyl)ꢀcisꢀexoꢀ2ꢀchloroꢀ3ꢀnitrosobicyꢀ
clo[2.2.1]heptane (4a) and cisꢀendoꢀ5,6ꢀdi(methoxycarbonyl)ꢀ
cisꢀexoꢀ2ꢀbromoꢀ3ꢀnitrosobicyclo[2.2.1]heptane (4b), respecꢀ
tively.
Reaction of norbornadiene (5) with ethyl nitrite in the presꢀ
ence of PCl3. The product prepared by the reaction of norꢀ
bornadiene (0.70 g, 7.6 mmol) with ethyl nitrite (1.85 g,
24.7 mmol) in CHCl3 (30 mL) and PCl3 (0.525 g, 3.8 mmol) in
CHCl3 (15 mL) was recrystallized from MeOH and cisꢀexoꢀ2ꢀ
chloroꢀ3ꢀnitrosobicyclo[2.2.1]heptꢀ5ꢀene (6a) was obtained in a
yield of 0.81 g as white crystals. Preparative TLC (light petroꢀ
leum—EtOAc, 10 : 1) of the mother liquor afforded a) a mixture
of exoꢀ3ꢀendoꢀ5ꢀdichlorotricyclo[2.2.1.02,6]heptane (7a) and
exoꢀ3ꢀexoꢀ5ꢀdichlorotricyclo[2.2.1.02,6]heptane (8a) (Rf 0.90) in
a yield of 0.05 g (4%) as a transparent oil, 7a : 8a = 2.7 : 1

Reactions of alkenes with ethyl nitrite
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2143
clo[2.2.1]heptane (21) were prepared from compound 17, and
cisꢀendoꢀ9,10ꢀdi(methoxycarbonyl)ꢀcisꢀexoꢀ3ꢀchloroꢀ4ꢀnitrosoꢀ
tricyclo[4.2.2.02,5]decꢀ7ꢀene (23a) and cisꢀendoꢀ9,10ꢀdi(methꢀ
oxycarbonyl)ꢀcisꢀexoꢀ3ꢀbromoꢀ4ꢀnitrosotricyclo[4.2.2.02,5]decꢀ
7ꢀene (23b) were prepared from compound 22.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
33347), the Foundation "Russian Universities" (Grant
05.03.046), and the Russian Academy of Sciences (Proꢀ
gram of the Chemistry and Materials Science Division
"Theoretical and Experimental Studies of the Nature of
Chemical Bonds and Mechanisms of Important Chemiꢀ
cal Reactions and Processes").
Xꢀray diffraction study of compound 18. Crystals suitable for
Xꢀray diffraction study were grown as colorless prisms of dimenꢀ
sions 0.50×0.35×0.25 mm by slow evaporation of a solution
in chloroform. Xꢀray diffraction data were collected on an
EnrafꢀNonius CADꢀ4 diffractometer (MoꢀKα radiation). The
structure was solved by direct methods and refined by the fullꢀ
matrix leastꢀsquares method against F2 with anisotropic disꢀ
placement parameters for nonhydrogen atoms. The hydrogen
atoms were located from difference Fourier maps and reꢀ
fined isotropically. All calculations were carried out using the
SHELXL97 program package.35 The atomic coordinates for the
structure of 18 and the complete tables of the bond lengths and
bond angles were deposited with the Cambridge Structural Daꢀ
tabase. Selected bond lengths and bond angles are given in
Table 7. Principal crystallographic data, details of Xꢀray data
collection, and characteristics of structure refinement are listed
in Table 10.
References
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Table 10. Crystallographic data, details of Xꢀray data collection,
and characteristics of structure refinement of compound 18
Parameter
Characteristic
Molecular formula
Molecular weight
Crystal system
Space group
Т/K
C8H9ClF3NO
227.61
Monoclinic
Р21/c
293(2)
λ/Å
a/Å
b/Å
c/Å
0.71073
6.572(10)
11.574(2)
12.726(3)
90
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J. Wiley and Sons, New York, 1972.
α/deg
β/deg
98.47(3)
90
957.4(3)
4
1.579
0.410
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γ/deg
V/Å3
Z
dcalc/g cm–3
µ/mm–1
F(000)
464
Scan range, θ/deg
Scanning mode
Ranges of indices
3.13—24.95
θ/2θ
–7 ≤ h ≤ 0,
–13 ≤ k ≤ 0,
–14 ≤ l ≤ 14
1138
Number of measured reflections
Number of reflections with I > 2σ(I )
Rint
1040
0.0142
Number of parameters in refinement
GOOF on F 2
164
1.058
R1/wR2 (I > 2σ(I ))
0.0276/0.0689
0.0276/0.0689
0.0045(15)
0.150/–0.150
R1/wR2 (based on all reflections)
Exctinction coefficient
Residual electron density,
max/min, е Å–3

2144
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Received May 19, 2005;
in revised form September 21, 2005