Condensation of 2- and 4-fluorobenzaldehydes with vinyl ethers derived from amino alcohols

Article abstract of DOI:10.1134/S1070428011120074

2- and 4-Fluorobenzaldehydes reacted with amino alcohol vinyl ethers to give Schiff bases, oxazolidines, and imidazolidines containing a vinyloxy group. The products attract interest as potential biologically active compounds.

Full text of DOI:10.1134/S1070428011120074

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 12, pp. 1817–1822. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © B.F. Kukharev, V.K. Stankevich, E.Kh. Sadykov, G.R. Klimenko, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47,
No. 12, pp. 1780–1785.
Dedicated to Full Member of the Russian Academy of Sciences
M.G. Voronkov on his 90th anniversary
Condensation of 2- and 4- Fluorobenzaldehydes with Vinyl
Ethers Derived from Amino Alcohols
B. F. Kukharev†, V. K. Stankevich, E. Kh. Sadykov, and G. R. Klimenko
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: irk_inst_chem@irioch.irk.ru
Received May 30, 2011
Abstract—2- and 4-Fluorobenzaldehydes reacted with amino alcohol vinyl ethers to give Schiff bases, oxaz-
olidines, and imidazolidines containing a vinyloxy group. The products attract interest as potential biologically
active compounds.
DOI: 10.1134/S1070428011120074
Condensation products of carbonyl compounds
with vinyl ethers derived from amino alcohols possess
diverse biological activity [1]; biological activity is
also intrinsic to organofluorine compounds [2]. There-
fore, fluorine-containing carbonyl compounds and
amino alcohol vinyl ethers could give rise to biologi-
cally active compounds. Aimakov et al. [3] previously
reported on the condensation of 4-fluorobenzaldehyde
with 2-vinyloxyethanamine [3].
imines [4], Schiff bases IIIa–IIId were assigned E
configuration at the double C=N bond.
In the condensation of aldehydes Ia and Ib with
1-amino-3-(2-vinyloxyethoxy)propan-2-ol (IV) con-
taining a hydroxy group in the β-position with respect
to primary amino group, Schiff bases Va and Vb were
formed together with stereoisomeric oxazolidines VIa,
VIb and VIIa, VIIb (Scheme 2). The overall yield of
the condensation products was 75–78%.
In the present work we examined condensation of
2- and 4-fluorobenzaldehydes Ia and Ib with various
amino alcohol vinyl ethers. The reactions were carried
out by keeping equimolar mixtures of the reactants in
diethyl ether in the presence of anhydrous potassium
carbonate at room temperature over a period of 20 h.
The reaction of aldehydes Ia and Ib with vinyloxyal-
kanamines IIa and IIb gave 82–87% of Schiff bases
IIIa–IIId (Scheme 1). The 1H and 13C NMR spectra of
compounds IIIa–IIId contained only one signal from
the N=CH proton and carbon atom (δ 8.26–8.64 ppm,
δC 154.78–161.49 ppm), indicating formation of
a single isomer. By analogy with known aliphatic
All condensation products displayed in the IR spec-
tra strong absorption bands in the regions 1641–1647
(C=N) and 1042–1295 cm–1 (O–C–N in the oxazoli-
1
dine ring) [5]. In the H NMR spectrum of product
mixture Va/VIa/VIIa we observed one signal from
N=CH proton (δ 8.62 ppm) and two signals from
NCHO protons (δ 5.80 and 5.63 ppm) with an intensity
ratio of 1.0:0.08:0.1. The corresponding signals in
1
the H NMR spectrum of mixture Vb/VIb/VIIb were
located at δ 8.27, 5.66, and 5.34 ppm, and their inten-
sity ratio was 1.0:0.05:0.08. Our results are consistent
with the known data according to which tautomeric
equilibrium imino alcohol–oxazolidine for imino alco-
Scheme 1.
CH2
CHO
O
( )n
N
NH2
+
F
F
( )n
O
H2C
Ia, Ib
IIa, IIb
IIIa–IIId
I, 2-F (a), 4-F (b); II, n = 1 (a), 2 (b); III, 2-F, n = 1 (a), 2 (b); 4-F, n = 1 (c), 2 (d).
†
Deceased.
1817

KUKHAREV et al.
1818
Scheme 2.
CH2
OH
O
N
O
O
Ia, Ib
+
F
O
NH2
O
OH
H2C
IV
Va, Vb
O
2(4)-FC6H4
2(4)-FC6H4
+
+
O
O
O
O
CH2
CH2
HN
HN
VIa, VIb
VIIa, VIIb
2-F (a), 4-F (b).
Scheme 3.
OH
H
N
Ia, Ib
+
O
O
Me
H2C
VIII
O
O
2(4)-FC6H4
2(4)-FC6H4
O
O
O
+
O
CH2
CH2
N
N
Me
Me
IXa, IXb
Xa, Xb
2-F (a), 4-F (b).
hols obtained from amino alcohols and aromatic
aldehydes is usually displaced toward the open-chain
structure [6]. Furthermore, it was reported that N-aryl-
1,3-oxazolidines containing a substituent in the 5-posi-
tion exist mainly as cis isomers [7]. Therefore, more
upfield signals from the NCHO protons were assigned
to cis isomers VIIa and VIIb.
Chemical shifts of some protons and carbon nuclei in
oxazolidines VI and VII were not determined because
of overlap of the corresponding signals by stronger
signals of Schiff bases V.
Replacement of the primary amino group in amino
alcohol IV by secondary amino group makes the
formation of Schiff bases impossible. Therefore, the
condensation of 1-methylamino-3-(2-vinyloxyethoxy)-
propan-2-ol (VIII) with aldehydes Ia and Ib gave
mixtures of trans/cis-isomeric oxazolidines IXa/Xa
and IXb/Xb in an overall yield of 67–69% (Scheme 3).
The formation of two stereoisomers in each case
The structure of compounds Va, Vb, VIa, VIb,
VIIa, and VIIb was also confirmed by the 13C NMR
spectra which contained the following signals:
3
156.45 d (C=N, JCF = 4.6 Hz, Va), 88.16 d (OCHN,
3
3JCF = 3.4 Hz, VIIa), 88.25 d (OCHN, JCF = 2.0 Hz,
1
follows from the presence in the H and 13C NMR
VIa), 161.64 (C=N, Vb), 92.15 (OCHN, VIIb), 93.16
(OCHN, VIb). The OCHN signals were assigned to
trans and cis isomers on the basis of their intensities.
spectra of signals from the OCHN proton and carbon
atom of each stereoisomer, δ, δC, ppm: IXa, 5.06,
Scheme 4.
H
N
H
N
O
CH2
N
Ia, Ib
+
F
O
NH2
H2C
XI
XIIa, XIIb
HN
N
+
O
CH2
2(4)-FC6H4
XIIIa, XIIIb
2-F (a), 4-F (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

CONDENSATION OF 2- AND 4- FLUOROBENZALDEHYDES WITH VINYL ETHERS
1819
91.63; Xa, 5.10, 91.08; IXb, 4.62, 98.07; Xb, 4.57,
97.47. Also, well resolved multiplets belonging to the
5-H proton were observed. The chemical shifts of the
OC5H proton and carbon nucleus were as follows, δ,
δC, ppm: IXa, 4.33–4.38, 74.90; Xa, 4.48–4.54, 76.07;
IXb, 4.44–4.51, 74.64; Xb, 4.29–4.35, 75.78. Signals
from all other protons of both stereoisomers were par-
tially or completely overlapped by each other. There-
fore, the ratio of stereoisomers was estimated from
the intensity of the OCH and NCHO protons; it was
1:0.92 for Xa/IXa and 1:0.91 for Xb/IXb. All proton
and carbon signals were assigned assuming predomi-
nant formation of the cis isomer (see above).
IV, VIII, and XI (general procedure). A mixture of
0.05 mol of fluorobenzaldehyde Ia or Ib and 0.11 mol
of amine IIa, IIb, IV, VIII, or XI in 50 ml of diethyl
ether was kept for 20 h over anhydrous potassium car-
bonate. The solvent was distilled off, and the residue
was subjected to fractional distillation under reduced
pressure.
N-[(E)-(2-Fluorophenyl)methylidene]-2-(vinyl-
oxy)ethanamine (IIIa). Yield 86%, bp 82–83°C
(3 mm), nD20 = 1.5263. IR spectrum, ν, cm–1: 3117,
3083, 3044, 2929, 2896, 2850, 2759, 1644, 1615,
1583, 1485, 1459, 1386, 1371, 1344, 1321, 1300,
1280, 1233, 1200, 1152, 1100, 1085, 1032, 1005, 984,
962, 912, 863, 817, 802, 760, 702, 621, 537, 460.
By condensation of fluorobenzaldehydes Ia and Ib
with N-(2-vinyloxyethyl)ethane-1,2-diamine (XI) we
obtained mixtures of products containing Schiff bases
XIIa, XIIb and imidazolidines XIIIa, XIIIb
(Scheme 4). The presence of Schiff bases XIIa and
XIIb in the product mixtures was confirmed by IR
absorption bands at 1640–1646 cm–1 (νC=N). The
3
1H NMR spectrum, δ, ppm: 3.92 t (2H, NCH2, J =
5.3 Hz), 3.99–4.05 m (3H, CH2O, cis-CH2=), 4.24 d.d
2
3
(1H, trans-CH2=, J = 1.7, Jtrans = 14.4 Hz), 6.49 d.d
3
(1H, =CHO, Jcis = 6.8, 3Jtrans = 14.4 Hz), 7.06–7.11 m
(5′-H), 7.16–7.20 m (3′-H), 7.38–7.43 m (4′-H), 7.97–
8.01 m (6′-H), 8.64 s (1H, CH=N). 13C NMR spec-
trum, δC, ppm: 60.55 s (CH2N), 67.28 s (CH2O),
86.72 s (=CH2), 115.69 d (C3′, 2JCF = 21.5 Hz), 123.68 d
13
1H and C NMR spectra of compounds XII and XIII
contained signals from proton and carbon nucleus in
the N=CH (δ 8.30–8.60, δC 155.44–155.86 ppm) or
NCHN group (δ 4.10–4.65, δC 76.26–82.79 ppm). The
product ratio was 0.92 :1 (XIIa/XIIIa) and 1.15:1
(XIIb/XIIIb). Appreciable difference in the ratio of
the linear and cyclic condensation products of 2- and
4-fluorobenzaldehydes is likely to be related to differ-
ent electrophilicities of the C=N carbon atom (due to
the presence of a fluorophenyl substituent), which is
known to considerably affect the formation of cyclic
structure [8].
2
4
(C1′, JCF = 9.2 Hz), 124.26 d (C5′, JCF = 3.45 Hz),
127.79 d (C6′, JCF = 2.7 Hz), 132.28 d (C4′, JCF
=
=
3
3
3
8.8 Hz), 151.73 s (OCH=), 156.40 d (C=N, JCF
4.6 Hz), 162.24 d (C2′, JCF = 252.3 Hz). Found, %:
C 68.46; H 6.22; F 9.71; N 7.29. C11H12FNO. Calculat-
ed, %: C 68.38; H 6.26; F 9.83; N 7.25.
1
N-[(E)-(2-Fluorophenyl)methylidene]-3-(vinyl-
oxy)propan-1-amine (IIIb). Yield 87%, bp 105–
110°C (4 mm), nD20 = 1.5192. IR spectrum, ν, cm–1:
3117, 3083, 3044, 2937, 2891, 2846, 2759, 1642,
1615, 1582, 1485, 1459, 1380, 1341, 1321, 1300,
1280, 1234, 1197, 1152, 1099, 1075, 1029, 1006, 991,
967, 919, 887, 854, 808, 760, 701, 635, 621, 562, 537,
1
In the H NMR spectra of all compounds synthe-
sized in this work, signals from protons in the vinyloxy
group appeared as three doublets of doublets at δ 3.95–
3.99 (cis-CH=C), 4.12–4.18 (trans-CH=C), and 6.42–
1
2
3
496. H NMR spectrum, δ, ppm: 2.06 q (2H,
6.47 ppm (OCH=C); J = 1.7–1.9, Jcis = 6.2–6.8,
3
3
3Jtrans = 14.0–14.3 Hz; the C NMR spectra contained
13
CH2CH2CH2, J = 6.6 Hz), 3.76 d.t (2H, NCH2, J =
4
3
6.6, J = 1.1 Hz), 3.81 t (2H, CH2O, J = 6.6 Hz),
4.00 d.d (1H, cis-CH2=, J = 1.9, Jcis = 6.7 Hz),
4.21 d.d (1H, trans-CH2=, J = 1.9, Jtrans = 14.3 Hz),
signals at δC 86.38–86.55 (=CH) and 151.49–
151.63 ppm (OCH=).
2
3
2
3
3
3
6.46 d.d (1H, =CHO, Jcis = 6.7, Jtrans = 14.3 Hz),
7.06–7.11 m (5′-H), 7.16–7.20 m (3′-H), 7.37–7.43 m
(4′-H), 7.95–8.00 m (6′-H), 8.59 s (1H, CH=N).
13C NMR spectrum, δC, ppm: 30.22 s (CH2), 58.12 s
(CH2N), 65.51 s (CH2O), 86.42 s (=CH2), 115.66 d
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded at
26°C on a Bruker DPX-400 spectrometer at 400.13
and 100.62 MHz, respectively, using CDCl3 as solvent
and hexamethyldisiloxane as internal reference. The IR
spectra were obtained on a Bruker Vertex-70 spectrom-
eter from thin films.
2
2
(C3′, JCF = 21.1 Hz), 123.80 d (C1′, JCF = 9.2 Hz),
124.22 d (C5′, JCF = 2.7 Hz), 127.63 d (C6′, JCF
=
4
3
2.7 Hz), 132.03 d (C4′, JCF = 8.4 Hz), 151.76 s
(OCH=), 154.78 d (C=N, 3JCF = 4.6 Hz), 162.12 d (C2′,
1JCF = 252.3 Hz). Found, %: C 69.50; H 6.86; F 9.10;
3
Condensation of 2- and 4-fluorobenzaldehydes
Ia and Ib with amino alcohol vinyl ethers IIa, IIb,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

KUKHAREV et al.
1820
N 6.72. C12H14FNO. Calculated, %: C 69.55; H 6.81;
F 9.17; N 6.76.
bp 162–165°C (2 mm), nD20 = 1.5268. IR spectrum, ν,
cm–1: 3422, 3117, 3083, 3044, 2919, 2895, 1641, 1614,
1583, 1485, 1459, 1381, 1361, 1322, 1300, 1279,
1234, 1202, 1136, 1100, 1042, 967, 842, 822, 807,
762, 723, 680, 632, 537, 507, 468. 1H NMR spectrum,
δ, ppm: Va: 2.95 br.s (1H, OH), 3.55–3.86 m (8H,
NCH2, CH2O), 4.00 d.d (1H, cis-CH2=, 2J = 2.1, 3Jcis =
6.7 Hz), 4.08–4.15 m (1H, CHOH), 4.19 d.d (1H,
N-[(E)-(4-Fluorophenyl)methylidene]-2-(vinyl-
oxy)ethanamine (IIIc). Yield 83%, bp 88–90°C
(2 mm), nD20 = 1.5242; published data [3]: bp 118–
120°C (2.5 mm), nD20 = 1.5270. IR spectrum, ν, cm–1:
3117, 3073, 3056, 3041, 2930, 2875, 2849, 1654,
1647, 1617, 1602, 1509, 1475, 1460, 1441, 1416,
1386, 1370, 1342, 1322, 1295, 1231, 1199, 1152,
1094, 1084, 1035, 1004, 1012, 984, 964, 936, 912,
864, 837, 821, 787, 713, 702, 636, 608, 599, 578, 532,
2
3
trans-CH2=, J = 2.1, Jtrans = 14.3 Hz), 6.47 d.d (1H,
=CHO, 3Jcis = 6.7, 3Jtrans = 14.3 Hz), 7.05 m (1H, 5′-H),
7.15 t (1H, 3′-H, 3J = 7.6 Hz), 7.36–7.42 m (1H, 4′-H),
4
3
1
7.95 d.t (1H, 6′-H, J = 1.7, J = 7.5 Hz), 8.62 s (1H,
CH=N); VIa/VIIa: 2.14 s (2H, NH), 3.05–3.80 m (8H,
NCH2, CH2O), 3.98–4.01 m (2H, cis-CH2=), 4.09–
4.18 m (4H, trans-CH2=, NCH2CHO), 5.63 s and
5.80 s (1H each, NCHO), 6.46 m (2H, =CHO); 7.02–
7.27 m, 7.49 t, 7.55–7.65 m, 7.85 t (8H, Harom).
13C NMR spectrum, δC, ppm: Va: 63.98 s (NCH2),
67.40 s (=CHOCH2), 69.93 (=CHOCH2CH2), 70.14 s
(OCH), 73.65 s (OCHCH2O), 86.90 s (=CH2),
521, 508, 420. H NMR spectrum, δ, ppm: 3.87 t (2H,
3
NCH2, J = 5.4 Hz), 3.97–4.04 m (3H, CH2O, cis-
2
3
CH2=), 4.23 d.d (1H, trans-CH23, J = 2.0, Jtrans
=
=
3
14.4 Hz), 6.48 d.d (1H, =CHO, Jcis = 6.8, Jtrans
14.4 Hz), 7.10 t (2H, 3′-H, 5′-H, J = 8.6 Hz), 7.70–
7.79 m (2H, 2′-H, 6′-H), 8.29 s (1H, CH=N). 13C NMR
spectrum, δC, ppm: 60.06 s (CH2N), 67.28 s (CH2O),
2
86.66 s (=CH2), 115.57 d (C3′, C5′, JCF = 21.9 Hz),
3
4
130.03 (C2′, C6′, JCF = 8.4 Hz), 132.29 d (C1′, JCF
=
2
2
115.84 d (C3′, JCF = 21.1 Hz), 124.36 d (C1′, JCF
=
2.3 Hz), 151.67 s (OCH=), 161.49 s (C=N), 162.26 d
3.4 Hz), 127.80 d (C5′, JCF = 2.3 Hz), 130.18 d (C6′,
4
1
(C4′, JCF = 250.7 Hz). Found, %: C 68.43; H 6.20;
3JCF = 4.5 Hz), 132.44 d (C4′, JCF = 8.8 Hz), 151.82 s
3
F 9.77; N 7.22. C11H12FNO. Calculated, %: C 68.38;
H 6.26; F 9.83; N 7.25.
(OCH=), 156.45 d (C=N, JCF = 4.6 Hz), 163.33 (C2′,
3
1JCF = 252.3 Hz); VIa/VIIa: 49.26 s and 49.84 s
(NCH2), 67.04 s and 67.24 s (=CHOCH2), 69.94 s and
70.02 s (=CHOCH2CH2), 73.19 s and 73.54 s (5-CH2),
75.02 s and 75.80 s (C5), 86.68 s and 86.86 s (=CH2),
88.16 d (C2, 3JCF = 3.4 Hz), 88.25 d (C2, 3JCF = 2.0 Hz),
N-[(E)-(4-Fluorophenyl)methylidene]-3-(vinyl-
oxy)propan-1-amine (IIId). Yield 82%, bp 113–
115°C (2 mm), nD20 = 1.5177. IR spectrum, ν, cm–1:
3117, 3073, 3041, 2949, 2932, 2874, 2845, 1649, 1616,
1509, 1471, 1457, 1416, 1379, 1339, 1321, 1295,
1231, 1196, 1152, 1093, 1075, 1026, 1011, 992, 971,
923, 888, 860, 835, 822, 797, 713, 702, 636, 619, 600,
577, 523, 514, 386. 1H NMR spectrum, δ, ppm: 2.07 q
115.52 d and 116.58 d (C3′, JCF = 21.1 Hz), 124.04 d
2
(C5′, JCF = 3.5 Hz), 124.24 d (C5′, JCF = 3.5 Hz),
4
4
1
1
160.63 d (C2′, JCF = 248.0 Hz), 160.71 d (C2′, JCF
=
248.4 Hz). Found, %: C 62.83; H 6.89; F 7.18; N 5.12.
C14H18FNO3. Calculated, %: C 62.91; H 6.79; F 7.11;
N 5.24.
3
3
(3H, CH2, J = 6.6 Hz), 3.71 t.d (2H, NCH2, J = 6.6,
4J = 0.7 Hz), 3.79 t (2H, CH2O, J = 6.6 Hz), 3.99 d.d
3
2
3
(1H, cis-CH22=, J = 1.8, Jcis = 6.7 Hz), 4.20 d.d (1H,
1-[(E)-(4-Fluorophenyl)methylideneamino]-3-[2-
(vinyloxy)ethoxy]propan-2-ol (Vb) and 2-(4-fluoro-
phenyl)-5-[2-(vinyloxy)ethoxymethyl]-1,3-oxazoli-
dines VIb and VIIb (mixture of isomers). Yield 78%,
bp 160–162°C (2 mm), nD20 = 1.5253. IR spectrum, ν,
cm–1: 3423, 3117, 3073, 2921, 2876, 1647, 1619, 1510,
1453, 1417, 1377, 1360, 1322, 1295, 1231, 1153,
1136, 1094, 1042, 974, 867, 836, 789, 714, 680, 637,
3
trans-CH2=, J = 1.8, Jtrans = 14.4 Hz), 6.48 d.d (1H,
3
3
=CHO, Jcis = 6.7, Jtrans = 14.4 Hz), 7.09 t (2H, 3′-H,
3
5′-H, J = 8.6 Hz), 7.68–7.76 m (2H, 2′-H, 5′-H),
8.26 s (1H, CH=N). 13C NMR spectrum, δC, ppm:
30.15 s (CH2), 57.55 s (CH2N), 65.40 s (CH2O),
2
86.36 s (=CH2), 115.50 d (C3′, C5′, JCF = 21.9 Hz),
3
129.80 d (C2′, C6′, JCF = 8.8 Hz), 151.69 s (OCH=),
132.45 d (C1′, 4JCF = 2.3 Hz), 159.88 s (C=N), 164.11 d
1
607, 575, 519. H NMR spectrum, δ, ppm: Vb:
1
(C4′, JCF = 250.3 Hz). Found, %: C 69.60; H 6.78;
2.63 br.s (1H, OH), 3.54–3.86 m (8H, NCH2, CH2O),
4.00 d.d (1H, cis-CH2=, 2J = 2.1, 3Jcis = 6.8 Hz), 4.07–
F 9.09; N 6.80. C12H14FNO. Calculated, %: C 69.55;
H 6.81; F 9.17; N 6.76.
2
4.12 m (1H, CHOH), 4.18 d.d (1H, trans-CH2=, J =
3
1-[(E)-(2-Fluorophenyl)methylideneamino]-3-[2-
(vinyloxy)ethoxy]propan-2-ol (Va) and 2-(2-fluoro-
phenyl)-5-[2-(vinyloxy)ethoxymethyl]-1,3-oxazoli-
dines VIa and VIIa (mixture of isomers). Yield 75%,
2.1, 3Jtrans = 14.3 Hz), 6.47 d.d (1H, =CHO, Jcis = 6.8,
3
3Jtrans = 14.3 Hz), 7.07 t (2H, 3′-H, 5′-H, J = 8.6 Hz),
7.69–7.73 m (1H, 2′-H, 6′-H), 8.27 s (1H, CH=N);
VIb/VIIb: 2.63 br.s (2H, NH), 2.96–3.81 m (8H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

CONDENSATION OF 2- AND 4- FLUOROBENZALDEHYDES WITH VINYL ETHERS
1821
2
3
NCH2, CH2O), 3.99 d.d (2H, cis-CH2=, J = 2.2 Hz),
130.16 d (C4′, JCF = 7.7 Hz), 151.67 s (OCH=),
4.11–4.13 m (2H, 5-H), 4.15 d.d (2H, trans-CH2=, 2J =
2.2 Hz), 5.34 s and 5.56 s (1H each, 2-H), 6.41–6.51 m
(2H, =CHO); 6.98–7.05 m, 7.42–7.52 m, 7.63–7.68 m
161.39 d (C2′, JCF = 248.1 Hz); IXa: 37.74 s (NMe),
1
56.80 s (NCH2), 67.12 s (=CHOCH2), 69.70 s
(=CHOCH2CH2), 73.35 s (5-CH2), 74.90 s (C5),
13
3
(8H, Harom). C NMR spectrum, δC, ppm: Vb: 63.46 s
86.58 s (=CH2), 91.63 d (C2, JCF = 3.0 Hz), 115.19 d
2
4
(NCH2), 67.33 s and 69.89 s (=CHOCH2), 70.09 s
(C3′, JCF = 21.9 Hz), 124.15 d (C5′, JCF = 3.1 Hz),
(OCH), 73.59 s (5-CH2), 86.87 s (=CH2)3, 115.70 d (C3′,
125.61 d (C1′, JCF = 10.7 Hz), 128.84 d (C6′, JCF
=
2
3
C5′, JCF = 21.8 Hz), 130.13 (C2′, C6′, JCF = 8.4 Hz),
3.8 Hz), 130.16 d (C4′, JCF = 7.7 Hz), 151.65 s
2
3
132.32 d (C1′, JCF = 2.6 Hz), 151.78 s (OCH=),
(OCH=), 161.58 d (C2′, JCF = 248.4 Hz). Found, %:
3
1
161.64 s (C=N), 165.40 d (C4′, JCF = 251.1 Hz);
C 64.11; H 7.24; F 6.58; N 4.82. C15H20FNO3. Cal-
culated, %: C 64.04; H 7.17; F 6.75; N 4.98.
1
VIb/VIIb: 48.95 s and 49.69 s (NCH2), 63.13 s and
63.18 s (=CHOCH2), 67.39 s (5-CH2), 69.98 s and
70.72 s (=CHOCH2CH2), 73.19 s and 73.67 s (5-CH2),
2-(4-Fluorophenyl)-3-methyl-5-[2-(vinyloxy)-
ethoxymethyl]-1,3-oxazolidines IXb and Xb (mixture
of stereoisomers). Yield 69%, bp 165–167°C (3 mm),
nD20 = 1.5003. IR spectrum, ν, cm–1: 3117, 3072, 3054,
2927, 2872, 2796, 2702, 1636, 1607, 1511, 1471,
1456, 1430, 1418, 1375, 1338, 1322, 1293, 1232,
1203, 1170, 1133, 1095, 1075, 1058, 1014, 974, 947,
916, 860, 833, 794, 734, 701, 637, 616, 571, 536, 417.
1H NMR spectrum, δ, ppm: Xb: 2.18 (1H, Me), 2.69–
2.73 m and 3.20–3.23 m (1H each, 4-H), 3.58–3.85 m
(6H, CH2O), 3.99 d.d (1H, cis-CH2=, J = 2.1, Jcis
6.8 Hz), 4.17 d.d (1H, trans-CH2=, J = 2.1, Jtrans
14.3 Hz), 4.29–4.35 m (1H, 5-H), 4.57 s (2-H),
6.48 d.d (1H, =CHO, Jcis = 6.8, Jtrans = 14.3 Hz),
7.04 t (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.39–7.45 m (2H,
2′-H, 6′-H); IXb: 2.19 (1H, Me), 2.47–2.52 m and
3.39–3.43 m (1H each, 4-H), 3.58–3.85 m (6H, CH2O),
3.99 d.d (1H, cis-CH2=, J = 2.1, Jcis = 6.8 Hz),
75.23 s and 75.61 s (C5), 86.33 s and 86.51 s (=CH2),
92.15 s and 93.16 s (C2), 115.14 d (C3′, C5′, JCF
=
2
21.2 Hz), 115.22 d (C3′, C5′, JCF = 21.5 Hz), 127.98 d
2
(C2′, C6′, JCF = 8.1 Hz), 128.25 d (C2′, C6′, JCF
=
3
3
8.4 Hz), 163.49 d (C4′, 1JCF = 246.7 Hz), 163.51 d (C4′,
1JCF = 246.9 Hz). Found, %: C 62.80; H 6.75; F 7.06;
N 5.27. C14H18FNO3. Calculated, %: C 62.91; H 6.79;
F 7.11; N 5.24.
2
3
=
=
2-(2-Fluorophenyl)-3-methyl-5-[2-(vinyloxy)-
ethoxymethyl]-1,3-oxazolidines IXa and Xa (mixture
of stereoisomers). Yield 67%, bp 142–144°C (2 mm),
nD20 = 1.5032. IR spectrum, ν, cm–1: 3117, 3069, 3049,
3021, 2926, 2873, 2807, 2739, 1636, 1618, 1590,
1491, 1457, 1422, 1392, 1365, 1339, 1322, 1297,
1276, 1235, 1203, 1181, 1169, 1133, 1099, 1074, 1057,
1022, 975, 948, 916, 845, 809, 761, 728, 702, 630,
2
3
3
3
3
2
3
2
3
1
4.18 d.d (1H, trans-CH2=, J = 2.1, Jtrans = 14.3 Hz),
4.44–4.51 m (1H, 5-H), 4.62 s (2-H), 6.48 d.d (1H,
=CHO, Jcis = 6.8, Jtrans = 14.3 Hz), 7.04 t (2H, 3′-H,
618, 550, 531, 489. H NMR spectrum, δ, ppm: Xa:
2.26 s (3H, Me), 2.52–2.57 m and 3.41–3.45 m (1H
each, 4-H), 3.61–3.85 m (6H, CH2O), 3.995 d.d (1H,
cis-CH2=, 2J = 1.9, 3Jcis = 6.8 Hz), 4.18 d.d (1H, trans-
3
3
3
5′-H, J = 8.7 Hz), 7.39–7.45 m (2H, 2′-H, 6′-H).
13C NMR spectrum, δC, ppm: Xb: 37.39 s (NMe),
56.83 s (NCH2), 67.12 s (CH2OCH=), 69.70 s
2
3
CH2=, J = 1.9, Jtrans = 14.3 Hz), 4.48–4.54 m (1H,
3
5-H), 5.10 s (2-H), 6.49 d.d (1H, =CHO, Jcis = 6.8,
(OCH2CH2O), 73.57 s (5-CH2), 75.78 s (C5), 86.58 s
3Jtrans = 14.3 Hz), 6.99–7.03 m (1H, 5′-H), 7.14 t (1H,
(=CH2), 97.47 s (C2), 115.04 d (C3′, C5′, JCF
=
2
3
3′-H, Jtrans = 7.5 Hz), 7.28–7.31 m (1H, 4′-H), 7.56–
7.62 m (1H, 6′-H); IXa: 2.26 s (3H, Me), 2.74–2.78 m
and 3.22–3.25 m (1H each, 4-H), 3.61–3.85 m (6H,
CH2O), 3.992 d.d (1H, cis-CH2=, J = 1.9, Jcis
6.8 Hz), 4.17 d.d (1H, trans-CH2=, J = 1.9, Jtrans
14.3 Hz), 4.33–4.38 m (1H, 5-H), 5.06 s (2-H),
6.49 d.d (1H, =CHO, Jcis = 6.8, Jtrans = 14.3 Hz),
6.99–7.03 m (1H, 5′-H), 7.14 t (1H, 3′-H, Jtrans
22.5 Hz), 129.58 d (C2′, C6′, JCF = 8.1 Hz), 134.37 s
(C1′), 151.64 s (OCH=), 163.51 d (C4′, 1JCF = 246.9 Hz);
IXb: 37.56 s (NMe), 57.27 s (NCH2), 67.27 s
(CH2OCH=), 69.90 s (OCH2CH2O), 72.68 s (5-CH2),
74.64 s (C5), 86.58 s (=CH2), 98.07 s (C2), 115.09 d
3
2
3
=
=
2
3
(C3′, C5′, JCF = 22.4 Hz), 129.58 d (C2′, C6′, JCF
=
2
3
3
3
8.1 Hz), 134.37 s (C1′), 151.67 s (OCH=), 163.51 d
3
=
(C4′, JCF = 246.9 Hz). Found, %: C 64.09; H 7.12;
1
7.5 Hz), 7.28–7.31 m (1H, 4′-H), 7.56–7.62 m (1H,
6′-H). 13C NMR spectrum, δC, ppm: Xa: 37.46 s
(NMe), 57.40 s (NCH2), 67.25 s (=CHOCH2), 69.92 s
(=CHOCH2CH2), 72.64 (5-CH2), 76.02 s (C5), 86.60 s
F 6.63; N 4.93. C15H20FNO3. Calculated, %: C 64.04;
H 7.17; F 6.75; N 4.98.
N-[(E)-(2-Fluorophenyl)methylidene]-N′-[2-
(vinyloxy)ethyl]ethane-1,2-diamine (XIIa) and
2-(2-fluorophenyl)-1-[2-(vinyloxy)ethyl]imidazoli-
dine (XIIIa) (mixture of isomers). Yield 83%, bp 115–
(=CH2), 91.08 d (C2, JCF = 3.0 Hz), 115.12 d (C3′,
3
2JCF = 21.5 Hz), 124.15 d (C5′, 4JCF = 3.1 Hz), 125.71 d
(C1′, JCF = 10.7 Hz), 129.04 d (C6′, JCF = 3.5 Hz),
2
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

KUKHAREV et al.
1822
118°C (2 mm), nD20 = 1.5251. IR spectrum, ν, cm–1:
3116, 3067, 3044, 2933, 2885, 2828, 1640, 1616,
1587, 1486, 1458, 1376, 1338, 1321, 1300, 1279,
1233, 1201, 1182, 1151, 1134, 1151, 1100, 1075, 1031,
999, 964, 947, 912, 890, 814, 760, 729, 701, 622, 601,
5.2 Hz), 3.97 d.d (1H, cis-CH2=, J = 1.9, Jcis
=
=
=
2
3
2
3
6.6 Hz), 4.16 d.d (1H, trans-CH2=, J = 1.8, Jtrans
3
3
14.3 Hz), 6.44 d.d (1H, =CHO, Jcis = 6.7, Jtrans
14.3 Hz), 7.07–7.12 m (2H, 3′-H, 5′-H), 7.46–7.75 m
(2H, 2′-H, 6′-H), 8.30 s (CH=N); XIIIb: 1.67 br.s (1H,
NH); 2.48–2.55 m, 2.78–2.84 m, 3.09–3.15 m, 3.25–
3.32 m, 3.43–3.48 m (6H, HNCH2CH2NCH2); 3.78
(2H, OCH2, 3J = 5.2 Hz), 3.95 d.d (1H, cis-CH2=, 2J =
1
558, 530, 470. H NMR spectrum, δ, ppm: XIIa:
3
1.80 br.s (1H, NH), 2.95 t (2H, NCH2CH2O, J =
5.2 Hz), 3.00 t (2H, =NCH2CH2N, 3J = 5.9 Hz), 3.72 t
3
3
(2H, =NCH2CH2N, J = 5.9 Hz), 3.78 t (2H, OCH2,
1.7, Jcis = 6.2 Hz), 4.10 s (1H, NCHN), 4.12 d.d (1H,
2
3
3J = 5.2 Hz), 3.99 d.d (1H, cis-CH2=, J = 1.9, Jcis
=
=
=
2
3
trans-CH2=, J = 1.8, Jtrans = 14.3 Hz), 6.42 d.d (1H,
2
3
=CHO, 3Jcis = 6.8, 3Jtrans = 14.1 Hz), 7.02–7.06 m (2H,
6.7 Hz), 4.18 d.d 1H, trans-CH2=, J = 1.9, Jtrans
14.0 Hz), 6.47 d.d (1H, =CHO, Jcis = 6.7, Jtrans
3
3
13
3′-H, 5′-H), 7.46–7.49 m (2H, 2′-H, 6′-H). C NMR
14.0 Hz), 7.02–7.10 m (1H, 5′-H), 7.14–7.19 m (1H,
spectrum, δC, ppm: XIIb: 48.41 s (=NCH2CH2N),
48.91 s (NCH2CH2O), 61.00 s (CH2N=), 67.20 s
(NCH2CH2O), 86.44 s (=CH2), 115.47 d (C3′, C5′,
3
3′-H), 7.37–7.42 m (1H, 4′-H) 7.99 t (1H, 6′-H, J =
7.4 Hz), 8.64 s (1H, CH=N); XIIIa: 1.80 br.s (1H,
NH); 2.51–2.61 m, 2.83–2.89 m, 3.11–3.19 m, 3.24–
3.32 m, and 3.42–3.48 m (6H, NCH2CH2NCH2); 3.81 t
(OCH2, 3J = 5.2 Hz), 3.97 d.d (1H, cis-CH2=, 2J = 1.9,
2
2JCF = 22.4 Hz), 129.85 d (C2′, C6′, J = 8.8 Hz),
132.31 d (C1′, 4J = 3.1 Hz), 151.59 s (OCH=), 160.48 s
(C=N), 164.03 d (C4′, 1JCF = 250.7 Hz); XIIIb: 44.70 s
(HNCH2CH2N), 51.17 s (NCH2CH2O), 53.21 s
(NCH2CH2NH), 66.86 s (OCH2), 82.79 s (NCHNH),
2
3Jcis = 6.8 Hz), 4.14 d.d (1H, trans-CH2=, J = 1.9,
3Jtrans = 14.2 Hz), 4.65 s (1H, 2-H), 6.43 d.d (1H,
=CHO, 3Jcis = 6.8, 3Jtrans = 14.2 Hz), 7.02–7.10 m (1H,
5′-H), 7.14–7.19 m (1H, 3′-H), 7.26–7.31 m (1H,
2
86.38 s (=CH2), 115.38 d (C3′, C5′, JCF = 22.4 Hz),
2
4
129.18 d (C2′, C6′, JCF = 8.1 Hz), 136.11 d (C1′, J =
3
13
2.2 Hz), 151.49 s (OCH=), 162.64 d (C4′, JCF
=
1
4′-H), 7.65 t (1H, 6′-H, J = 7.2 Hz). C NMR spec-
trum, δC, ppm: XIIa: 48.49 s (NCH2CH2O), 49.93 s
(=NCH2CH2NH), 61.54 s (=NCH2), 67.27 s (OCH2),
246.5 Hz). Found, %: C 64.94; H 6.65; F 8.43;
N 12.48. C12H15FN2O. Calculated, %: C 64.85; H 6.80;
F 8.55; N 12.60.
2
86.55 s (=CH2), 115.71 d (C3′, JCF = 21.1 Hz),
2
4
123.70 d (C1′, JCF = 9.2 Hz), 124.25 d (C5′, JCF
=
3.0 Hz), 127.64 d (C6′, JCF = 2.6 Hz), 132.18 d (C4′,
3JCF = 8.4 Hz), 151.72 s (OCH=), 155.44 d (CH=N,
3JCF = 4.1 Hz), 162.16 d (C2′, 2JCF = 252.3 Hz); XIIIa:
45.03 s (HNCH2), 51.51 (NCH2CH2O), 53.22
(HNCH2CH2N), 66.93 (CH2O), 76.26 (NCHN), 86.47
3
REFERENCES
1. Shostakovskii, M.F., Trofimov, B.A., Atavin, A.S., and
Lavrov, V.I., Usp. Khim., 1968, vol. 37, p. 2070; Kukha-
rev, B.F., Stankevich, V.K., and Klimenko, G.R., Usp.
Khim., 1995, vol. 64, p. 562.
2. Sheppard, W.A. and Sharts, C.M., Organic Fluorine
Chemistry, New York: W.A. Benjamin, 1969. Translated
under the title Organicheskaya khimiya ftora, Moscow:
Mir, 1972, p. 392.
(=CH2), 115.43 d (C3′, J = 21.9), 124.35 d (C5′, J =
2
4
3.1 Hz), 127.53 d (C1′, 3J = 11.90 Hz), 128.29 (C6′, 3J =
3.9 Hz), 129.63 (C4′, J = 8.0 Hz), 151.63 (OCH=),
3
2
161.69 d (C2′, JCF = 247.3 Hz). Found, %: C 64.71;
H 6.87; F 8.46; N 12.51. C12H15FN2O. Calculated, %:
C 64.85; H 6.80; F 8.55; N 12.60.
3. Aimakov, O.A., Erzhanov, K.B., and Mastryukova, T.A.,
Izv. Ross. Akad. Nauk, Ser. Khim., 1999, p. 1815.
N-[(E)-(4-Fluorophenyl)methylidene]-N′-[2-
(vinyloxy)ethyl]ethane-1,2-diamine (XIIb) and
2-(4-fluorophenyl)-1-[2-(vinyloxy)ethyl]imidazoli-
dine (XIIIb) (mixture of isomers). Yield 79%, bp 134–
138°C (2 mm), nD20 = 1.5245. IR spectrum, ν, cm–1:
3117, 3070, 3043, 2931, 2883, 2832, 1646, 1616,
1604, 1509, 1460, 1437, 1416, 1367, 1353, 1321,
1294, 1228, 1200, 1153, 1092, 1075, 1015, 999, 965,
947, 912, 835, 822, 786, 772, 714, 635, 599, 569, 543,
4. Potapov, V.M.,
Stereokhimiya
(Stereochemistry),
Moscow: Khimiya, 1988, p. 332.
5. Kazitsina, L.A. and Kupletskaya, N.B., Primenenie UF,
IK, YaMR spektroskopii v organicheskoi khimii (Applica-
tions of UV, IR, and NMR Spectroscopy in Organic
Chemistry), Moscow: Vysshaya Shkola, 1971.
6. Bergman, E.D., Chem. Rev., 1953, vol. 53, p. 309;
Fülöp, F., Pihlaja, K., Neuvonen, K., Bernath, G.,
Aragy, G., and Kalman, A., J. Org. Chem., 1993, vol. 58,
p. 1967.
1
519, 463. H NMR spectrum, δ, ppm: XIIb: 1.67 br.s
(1H, NH), 2.93 t (2H, NCH2CH2O, 3J = 5.2 Hz), 2.97 t
7. Beckett, A.H. and Jones, G.R., Tetrahedron, 1977,
vol. 33, p. 3313.
8. Valter, R.E., Usp. Khim., 1982, vol. 51, p. 1374.
3
(2H, =NCH2CH2N, J = 5.9 Hz), 3.72 t (2H,
3
3
=NCH2CH2N, J = 5.9 Hz), 3.74 t (2H, OCH2, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011