Vinylphosphonium salt mediated reaction between alkyl propiolates and aminophenols or hydroxyphenols

Article abstract of DOI:10.1055/s-2006-950230

Addition of catechol to methyl propiolate or ethyl phenylpropiolate in the presence of Ph₃P leads to methyl 2-(1,3-benzodioxol-2-yl)acetate or 3-(1-phenylmethylidene)-1,4-benzodioxin-2-one. 2-Aminophenols react with alkyl propiolates in the pre

Full text of DOI:10.1055/s-2006-950230

PAPER
3243
Vinylphosphonium Salt Mediated Reaction between Alkyl Propiolates and
Aminophenols or Hydroxyphenols
V
inylpho
s
sphonium
s
Salt
M
ed
a
iated
R
eaction Yavari,* Sanaz Souri, Mehdi Sirouspour, Hoorieh Djahaniani
Chemistry Department, Tarbiat Modarres University, P. O. Box 14115-175, Tehran, Iran
Fax +98(21)88006544; E-mail: yavarisa@modares.ac.ir
Received 10 April 2006; revised 24 April 2006
CO2Me
Abstract: Addition of catechol to methyl propiolate or ethyl phen-
ylpropiolate in the presence of Ph3P leads to methyl 2-(1,3-benzo-
dioxol-2-yl)acetate or 3-(1-phenylmethylidene)-1,4-benzodioxin-
2-one. 2-Aminophenols react with alkyl propiolates in the presence
of Ph3P to produce a nearly 1:1 mixture of 3-methyl-2H-1,4-benz-
oxazin-2-one derivatives and methyl (E)-3-(2-aminophenoxy)-2-
propenoates.
OH
OH
O
O
+
PPh3
+
CO2Me
1
2
3
Scheme 1
Key words: alkyl propiolates, triphenylphosphine, hydroxylphe-
nol, aminophenol, benzodioxol, 2H-1,4-benzoxazin-2-one, O-viny-
lation
A possible mechanism for this transformation is proposed
in Scheme 2. It is conceivable that the initial event is the
formation of 1,3-dipolar intermediate 4 from Ph3P and the
acetylenic compound, which is subsequently protonated
by 2.7–10 Nucleophilic attack of the oxygen atom of the
conjugate base of 2 on the vinylphosphonium cation 5
then produces the 1,3-dipolar intermediate 6, which is
converted to 3, by elimination of Ph3P and cyclization (see
Scheme 2).
Vinyl ethers of alcohols and phenols are well established
monomers, building blocks and auxiliaries in organic syn-
thesis, steadily expanding their scope of application.1–3
The O-alkylated phenols have numerous industrial appli-
cations, particularly in the production of dyes and agro-
chemicals.3–6 Recently, we described6 a convenient
method for preparation of alkyl 2-arylacrylates and alkyl
3-aryloxypropenoates by nucleophilic conjugate addition
of phenols to alkyl propiolates in the presence of triphen-
ylphosphine (Ph3P). In this paper, we wish to extend that
methodology using bifunctional reagents such as ami-
nophenols and hydroxyphenols.
When the same reaction was carried out with ethyl phen-
ylpropiolate (7), 3-(1-phenylmethylidene)-1,4-benzo-
dioxin-2-one 8 was obtained (Scheme 3).
The plausible mechanism proposed for formation of prod-
uct 8 is similar to that shown in Scheme 2, except for the
addition of the conjugate base of 2 to the vinylphosphoni-
um cation, which leads to ylide 9. The intermediate 9 is
converted to the 1,3-dipolar species 10 by [1,3]-H+ shift.
Next, intermediate 10 is converted to 8 via the vinyl ether
11 by elimination of Ph3P and ethanol (see Scheme 4).
The reaction of catechol (2) with methyl propiolate (1) in
the presence of Ph3P was carried out in dichloromethane.
The colorless oil separated from the reaction mixture was
identified as methyl 2-(1,3-benzodioxol-2-yl)acetate (3;
Scheme 1).
The reaction of 2-aminophenol (12) with 1 in the presence
of Ph3P was carried out in dichloromethane. Two products
were isolated from the reaction mixture and identified as
_
H
H
O
2
CO2Me
+
CO2Me
CO2Me
+
PPh3
+
+
1
Ph3P
Ph3P
_
_
OH
H
5
4
O
O
CO2Me
3
+
PPh3
OH
OH
6
Scheme 2
SYNTHESIS 2006, No. 19, pp 3243–3249
x
x.
x
x
.
2
0
0
6
Advanced online publication: 05.09.2006
DOI: 10.1055/s-2006-950230; Art ID: P04306SS
© Georg Thieme Verlag Stuttgart · New York

3244
I. Yavari et al.
PAPER
CO2Et
give 5b. Then, addition of conjugate base of the OH-acid-
ic 12 to 5a or 5b produces 13a or 14a in nearly 1:1 ratio.
Similar pathways can be proposed for formation of 13b–f
and 14b–f.
O
O
O
2
PPh3
+
+
CHPh
Ph
The structures of compounds 13a–f and 14a–f were deter-
mined on the basis of their elemental analyses, mass spec-
tra, 1H and 13C NMR and IR spectroscopic data.
8
7
Scheme 3
3
Observation of two characteristic doublets with JHH of
about 12 Hz in the 1H NMR spectra of 14a–f is consistent
with O-vinylation of the aromatic ring and formation of
alkyl (E)-aryloxy propenoates (14a–f). The 13C NMR
spectra of 13a–f and 14a–f show distinct resonances in
agreement with the proposed structures.
3-methyl-2H-1,4-benzoxazin-2-one (13a) and methyl
(E)-3-(2-aminophenoxy)-2-propenoate
(14a;
see
Table 1).
A plausible mechanism for the formation of products 13a
and 14a is shown in Scheme 5. The reaction starts from
addition of Ph3P to the electron-deficient acetylenic ester
to form the zwitterionic intermediate 4,7–10 which is either
subsequently protonated by the OH-acid 12 to produce vi-
nylphosphonium cation 5a, or loses a methoxy group to
Under the same reaction conditions given for catechol,
two products were isolated from the reaction mixture of
resorcinol or hydroquinone with alkyl propiolates in the
presence of Ph3P (see Table 2). When 3- or 4-aminophe-
Ph
Ph
OH
2
CO2Et
+
CO2Et
7
Ph3P +
+
+
Ph3P
_
Ph3P
–
O
H
_
O
OH
O
OH
_
_
Ph3P
CO2Et
CHPh
EtOH
CO2Et
Ph
CO2Et
Ph
8
+
_
PPh3
PPh3
O
O
10
11
9
Scheme 4
O
O
O
O
O
[1,3]-H shift
CO2Me
NH2
N
H
CH2
N
CH3
13a
14a
O
O
Ph3P
..
NH2
CO2Me
1
– PPh3
_
O
O
H
CO2Me
O
–
CO2Me
+
NH2
_
+
PPh3
+
C=C-PPh3
Ph3P
NH2
4
12
– MeOH
12
_
O
H
+
+
CHCO2Me
5a
+ MeO–
Ph3P-CH=C=C=O
+
Ph3P
NH2
5b
Scheme 5
Synthesis 2006, No. 19, 3243–3249 © Thieme Stuttgart · New York

PAPER
Vinylphosphonium Salt Mediated Reaction
3245
Table 1 Reaction of Alkyl Propiolates with 2-Aminophenols in the Presence of Triphenylphosphine
Entry
1
Aminophenol
Alkyl propiolate
Products
O
O
O
CO2Me
O
CO2Me
CO2Et
1
N
NH2
13a (50%)
14a (40%)
2
3
4
5
6
7
OH
CO2Et
O
O
4b
NH2
N
NH2
13a (50%)
12
14b (40%)
–
Ph
CO2Et
O
O
7
N
CH2Ph
O
13b (75%)
CO2Et
O
N
O
N
OH
O
CO2Et
4b
4b
4b
4b
NH2
OH
Cl
Cl
Cl
NH2
O
13c (40%)
15
Cl
14c (45%)
CO2Et
CO2Et
CO2Et
Cl
O
O
Cl
CO2Et
CO2Et
CO2Et
NH2
OH
NH2
13d (70%)
13e (55%)
13f (65%)
16
17
18
14d (30%)
14e (40%)
14f (30%)
O
O
N
O
N
NH2
OH
NH2
O
O
NH2
NH2
column chromatography (Merck 230–400 mesh) using n-hexane–
EtOAc (4:1) as eluent to give the product.
nol was treated with ethyl propiolate in the presence of
Ph3P only the O-vinylation products were obtained
(Table 2).
Methyl 2-(1,3-Benzodioxol-2-yl)acetate (3)
The presented reactions provide simple entries to the syn-
thesis of methyl 2-(1,3-benzodioxol-2-yl)acetate (3), 3-
alkyl-2H-1,4-benzoxazin-2-one derivatives 13a–f, and
alkyl (E)-3-(aminophenoxy)-2-propenoates 14a–f, 27,
and 28 of potential synthetic interest.
Yield: 0.06 g (20%); colorless oil.
IR (KBr): 1732 (C=O), 1224 (CO) cm–1.
1H NMR: d = 3.0 (d, 3JHH = 5.2 Hz, 2 H, CH2), 3.77 (s, 3 H, OCH3),
6.5 (t, 3JHH = 5.2 Hz, 1 H, CH), 6.83 (m, 2 H, 2 × CH), 7.3 (m, 2 H,
2 × CH).
13C NMR: d = 40.1 (CH2), 52.1 (OCH3), 107.5 (OCHO), 121.7
(CH), 128.7 (CH), 133.8 (C), 168.7 (C=O).
Elemental analyses for C, H, and N were performed using a Heraeus
CHN-O-Rapid analyzer. Melting points were measured on an Elec-
trothermal 9100 apparatus. IR spectra were measured on a Shimad-
zu IR-460 spectrometer. 1H NMR and 13C NMR spectra were
measured with a Bruker DRX-500 Avance instrument with CDCl3
as solvent at 500.1 MHz and 125.7 MHz, respectively. Mass spectra
were recorded on a Finnigan-Matt 8430 mass spectrometer operat-
ing at an ionization potential of 70 eV. Alkyl propiolates, hydroxy-
phenols, aminophenols, and Ph3P were obtained from Fluka and
were used without further purification.
MS: m/z (%) = 195 (5) [M+ + 1], 194 (10) [M+], 163 (15), 110 (100),
57 (20).
Anal. Calcd for C10H10O4 (194.1): C, 61.85; H, 5.19. Found: C,
61.80; H, 5.20.
3-(1-Phenylmethylidene)-1,4-benzodioxin-2-one (8)
Yield: 0.26 g (55%); white solid; mp 109–110 °C.
IR (KBr): 1731 (C=O), 1632, 1487, 1358, 1286, 1180 (CO) cm–1.
1H NMR: d = 7.01 (m, 1 H, CH), 7.10 (m, 2 H, 2 × CH), 7.12 (s, 1
H, CH), 7.17 (m, 1 H, CH), 7.36 (m, 2 H, CH), 7.41 (m, 1 H, 2 ×
CH), 7.82 (m, 2 H, 2 × CH).
13C NMR: d = 116.2 (CH), 117.4 (CH), 119.1 (CH), 123.8 (CH),
125.4 (CH), 128.7 (CH), 129.6 (CH), 130.7 (CH), 132.6 (C), 136.0
(C), 139.3 (C), 139.5 (C), 162.0 (C).
Preparation of Compounds 3, 8, 13, and 14; General Procedure
To a stirred solution of the phenol derivative (2 mmol) and the alkyl
propiolate (2 mmol) in CH2Cl2 (10 mL) was added dropwise at –10
°C over 10 min Ph3P (2 mmol). The reaction mixture was then al-
lowed to warm to r.t. and stand for 24 h. The solvent was removed
under reduced pressure and the residue was separated by silica gel
Synthesis 2006, No. 19, 3243–3249 © Thieme Stuttgart · New York

3246
I. Yavari et al.
PAPER
Table 2 O-Vinylation of Resorcinol, Hydroquinone, 1,3-Diaminobenzene, and 1,4-Diaminobenzene with Alkyl Propiolates in the Presence
of Triphenylphosphine
Entry
1
Hydroxyphenol
Products
CO2Me
OH
CO2Me
O
O
OH
CO2Me
O
OH
19
23 (50%)
24 (40%)
2
OH
CO2Me
CO2Me
O
O
OH
O
OH
20
CO2Me
CO2Et
26 (30%)
25 (60%)
3
4
–
OH
O
NH2
NH2
21
27 (60%)
–
OH
CO2Me
O
NH2
NH2
22
28 (80%)
MS: m/z (%) = 239 (3) [M+ + 1], 238 (8) [M+], 210 (9), 147 (21),
MS: m/z (%) = 238 (6) [M+ + 1], 237 (8) [M+], 146 (51), 91 (100),
132 (37), 130 (40), 91 (100), 44 (52).
44 (12).
Anal. Calcd for C15H10O3 (238.2): C, 75.62; H, 4.23. Found: C,
75.60; H, 4.26.
Anal. Calcd for C15H11NO2 (237.2): C, 75.94; H, 4.67; N, 5.90.
Found: C, 76.00; H, 4.50; N, 5.75.
3-Methyl-2H-1,4-benzoxazine-2-one (13a)
Yield: 0.16 g (50%); white solid; mp 97–98 °C.
6-Chloro-3-methyl-2H-1,4-benzoxazin-2-one (13c)
Yield: 0.14 g (40%); yellow oil.
IR (KBr): 1718 (C=O), 1087 (CO) cm–1.
IR (KBr): 1732 (C=O), 1218, 1115 cm–1.
1H NMR: d = 2.60 (s, 3 H, CH3), 7.31 (d, 3JHH = 8.2 Hz, 1 H, CH),
7.37 (t, 3JHH = 7.2 Hz, 1 H, CH), 7.50 (t, 3JHH = 7.2 Hz, 1 H, CH),
7.70 (d, 3JHH = 7.4 Hz, 1 H, CH).
13C NMR: d = 21.3 (CH3), 116.4 (CH), 125.4 (CH), 128.6 (CH),
131.1 (CH), 132.0 (CN), 146.6 (CO), 153.2 (N=C), 155.1 (C=O).
MS: m/z (%) = 162 (3) [M+ + 1], 161 (6) [M+], 146 (50), 120 (5),
118 (20), 76 (15).
1H NMR: d = 2.44 (s, 3 H, CH3), 7.05 (s, 1 H, CH), 7.13 (d, 3JHH
=
8.1 Hz, 1 H, CH), 7.55 (d, 3JHH = 8.1 Hz, 1 H, CH).
13C NMR: d = 21.5 (CH3), 116.4 (CH), 126.4 (CH), 128.1 (CH),
128.5 (CCl), 129.1 (CN), 146.4 (CO), 153.4 (C), 153.7 (C=O).
MS: m/z (%) = 196 (7) [M+], 181 (23), 168 (34), 141 (63), 55 (100).
Anal. Calcd for C9H6ClNO2 (195.6): C, 55.26; H, 3.09; N, 7.16.
Found: C, 55.21; H, 3.00; N, 7.25.
Anal. Calcd for C9H7NO2 (161.2): C, 67.08; H, 4.38; N, 8.69.
Found: C, 67.18; H, 4.30; N, 8.73.
7-Chloro-3-methyl-2H-1,4-benzoxazin-2-one (13d)
Yield: 0.26 g (70%); yellow solid; mp 55 °C.
3-Benzyl-2H-1,4-benzoxazin-2-one (13b)
Yield: 0.34 g (75%); pale yellow solid; mp 116–118 °C.
IR (KBr): 1732 (C=O), 1052 (CO) cm–1.
IR (KBr): 1728 (C=O), 1187, 1113 cm–1.
1H NMR: d = 2.56 (s, 3 H, CH3), 7.30 (d, 3JHH = 5.0 Hz, 1 H, CH),
7.33 (s, 1 H, CH), 7.71 (d, 3JHH = 5.0 Hz, 1 H, CH).
1H NMR: d = 4.20 (s, 2 H, CH2), 7.25 (d, 3JHH = 7.1 Hz, 2 H, 2 ×
13C NMR: d = 29.7 (CH3), 116.7 (CH), 125.9 (CH), 129.5 (CH),
132.2 (C), 132.3 (C), 133.6 (C), 133.8 (C), 155.1 (C=O).
MS: m/z (%) = 196 (9) [M+], 181 (27), 168 (41), 141 (53), 55 (100).
CH), 7.31 (d, 3JHH = 7.8 Hz, 1 H, CH), 7.34 (d, 3JHH = 7.8 Hz, 1 H,
CH), 7.40–7.47 (m, 4 H, 4 × CH), 7.74 (dd, 3JHH = 7.9 Hz, JHH
=
4
1.3 Hz, 1 H, CH).
13C NMR: d = 40.6 (CH2), 125.4 (CH), 127.1 (CH), 128.6 (CH),
129.1 (CH), 129.6 (CH), 130.8 (CH), 131.3 (CH), 132.3 (C), 135.5
(C), 146.6 (C), 152.8 (C), 156.3 (C=O).
Anal. Calcd for C9H6ClNO2 (195.6): C, 55.26; H, 3.09; N, 7.16.
Found: C, 55.21; H, 3.10; N, 7.34.
Synthesis 2006, No. 19, 3243–3249 © Thieme Stuttgart · New York

PAPER
Vinylphosphonium Salt Mediated Reaction
3247
3,6-Dimethyl-2H-1,4-benzoxazine-2-one (13e)
Yield: 0.18 g (55%); yellow crystal; mp 139–143 °C.
IR (KBr): 3270 (NH2), 1698 (C=O), 1633, 1490, 1192 (CO), 1115
cm–1.
IR (KBr): 1725 (C=O), 1095 (CO) cm–1.
1H NMR: d = 1.27 (t, 3JHH = 7.1 Hz, 3 H, CH3), 4.16 (br s, 2 H, NH2),
4.17 (q, 3JHH = 7.1 Hz, 2 H, CH2), 5.51 (d, 3JHH = 12.2 Hz, 1 H, CH),
6.71 (dd, 3JHH = 8.5 Hz, 4JHH = 2.4 Hz, 1 H, CH), 6.79 (d, 4JHH = 2.4
Hz, 1 H, CH), 6.86 (d, 3JHH = 8.5 Hz, 1 H), 7.68 (d, 3JHH = 12.2 Hz,
1 H).
13C NMR: d = 14.3 (CH3), 60.2 (CH2), 102.2 (CH), 116.4 (CH),
118.6 (CH), 119.6 (CH), 131.1 (CN), 138.2 (CCl), 141.3 (CO),
159.1 (CH), 166.9 (C=O).
1H NMR: d = 2.42 (s, 3 H, CH3), 2.55 (s, 3 H, CH3), 7.16 (d, 3JHH
=
3
8.2 Hz, 1 H, CH), 7.26 (d, JHH = 8.2 Hz, 1 H, CH), 7.32 (s, 1 H,
CH).
13C NMR: d = 20.8 (CH3), 21.3 (CH3), 115.9 (CH), 131.4 (CH),
135.3 (CH), 137.1 (C), 137.2 (C), 144.5 (C), 153.5 (C), 154.9 (CO).
MS: m/z (%) = 176 (3) [M+ + 1], 175 (8) [M+], 160 (31), 120 (70),
91 (100), 55 (72).
MS: m/z (%) = 242 (9) [M+], 227 (16), 213 (31), 197 (70), 169 (64),
142 (100), 100 (52), 73 (21), 29 (15).
Anal. Calcd for C10H9NO2 (175.2): C, 68.56; H, 5.18; N, 8.00.
Found: C, 68.50; H, 5.23; N, 8.08.
Anal. Calcd for C11H12ClNO3 (241.7): C, 54.6; H, 5.0; N, 5.8.
Found: C, 54.2; H, 5.5; N, 5.16.
3,7-Dimethyl-2H-1,4-benzoxazin-2-one (13f)
Yield: 0.22 g (65%); pale yellow oil.
IR (KBr): 1719 (C=O), 1099 (CO) cm–1.
Ethyl (E)-3-Amino-5-chlorophenoxy-2-propenoate (14d)
Yield: 0.14 g (30%); yellow oil.
IR (KBr): 3275 (NH2), 1685 (C=O), 1490, 1281, 1198 cm–1.
1H NMR: d = 1.28 (t, 3JHH = 7.4 Hz, 3 H, CH3), 4.31 (q, 3JHH = 7.4
Hz, 2 H, CH2), 5.53 (q, 3JHH = 12.1 Hz, 1 H, CH), 6.66 (d, 3JHH = 7.9
Hz, 1 H, CH), 6.87 (d, 3JHH = 7.9 Hz, 1 H, CH), 6.94 (s, 1 H, CH),
7.69 (d, 3JHH = 12.1 Hz, 1 H, CH).
1H NMR: d = 2.44 (s, 3 H, CH3), 2.53 (s, 3 H, CH3), 7.0 (s, 1 H, CH),
7.13 (d, 3JHH = 7.5 Hz, 1 H, CH), 7.55 (d, 3JHH = 7.5 Hz, 1 H, CH).
13C NMR: d = 21.2 (CH3), 21.5 (CH3), 116.4 (CH), 126.4 (CH),
128.1 (C), 129.1 (CH), 141.6 (C), 146.4 (C), 153.4 (C), 153.7 (CO).
MS: m/z (%) = 176 (4) [M+ + 1], 175 (9) [M+], 160 (43), 120 (65),
13C NMR: d = 14.3 (CH3), 60.5 (CH2), 102.5 (CH), 117.1 (CH),
122.8 (CH), 128.7 (CH), 136.1 (CCl), 142.7 (CN), 152.0 (CO),
158.8 (CH), 167.9 (C=O).
MS: m/z (%) = 242 (7) [M+], 227 (31), 213 (22), 197 (65), 169 (69),
142 (100), 100 (64), 73 (27), 29 (18).
91 (100), 55 (59).
Anal. Calcd for C10H9NO2 (175.2): C, 68.56; H, 5.18; N, 8.00.
Found: C, 68.50; H, 5.20; N, 8.34.
Methyl (E)-3-(2-Aminophenoxy)-2-propenoate (14a)
Yield: 0.14 g (40%); yellow oil.
IR (KBr): 3270 (NH2), 1697 (C=O), 1192 (CO) cm–1.
Anal. Calcd for C11H12ClNO3 (241.7): C, 54.67; H, 5.00; N, 5.80.
Found: C, 54.61; H, 5.08; N, 5.47.
1H NMR: d = 3.73 (s, 3 H, Me), 3.90 (br s, 2 H, NH2), 5.60 (d,
3JHH = 12.2 Hz, 1 H, CH), 6.73 (t, 3JHH = 6.6 Hz, 1 H, CH), 6.78 (d,
3JHH = 7.9 Hz, 1 H, CH), 6.93 (d, 3JHH = 7.9 Hz, 1 H, CH), 7.02 (t,
3JHH = 6.6 Hz, 1 H, CH), 7.78 (d, 3JHH = 12.2 Hz, 1 H, CH).
Ethyl (E)-3-(2-Amino-4-methylphenoxy)-2-propenoate (14e)
Yield: 0.16 g (40%); yellow oil.
IR (KBr): 3267 (NH2), 1119 (CO), 1699 (C=O) cm–1.
13C NMR: d = 51.3 (CH3), 101.2 (CH), 116.6 (CH), 118.6 (CH),
120.7 (CH), 126.0 (CH), 141.5 (C), 143.2 (C), 159.9 (CH), 170.6
(C=O).
MS: m/z (%) = 194 (4) [M+ + 1], 193 (8) [M+], 178 (19), 162 (42),
134 (60), 107 (100), 92 (51), 86 (39), 60 (42).
1H NMR: d = 1.28 (t, 3JHH = 7.2 Hz, 3 H, CH3), 2.24 (s, 3 H, CH3),
4.16 (q, 3JHH = 7.2 Hz, 2 H, CH2), 3.86 (br s, 2 H, NH2), 5.46 (d,
3JHH = 12.2 Hz, 1 H, CH), 6.53 (d, 3JHH = 7.8 Hz, 1 H, CH), 6.59 (s,
1 H, CH), 6.81 (d, 3JHH = 7.8 Hz, 1 H, CH), 7.72 (d, 3JHH = 12.2 Hz,
1 H, CH).
13C NMR: d = 14.3 (CH3), 29.7 (CH3), 60.0 (CH2), 101.2 (CH),
117.2 (CH), 118.7 (CH), 119.4 (CH), 135.9 (C), 137.1 (C), 140.1
(C), 160.1 (CH), 167.2 (CO).
Anal. Calcd for C10H11NO3 (193.2): C, 62.17; H, 5.74; N, 7.25.
Found: C, 62.25; H, 5.38; N, 7.40.
MS: m/z (%) = 221 (7) [M+], 192 (41), 148 (29), 130 (12), 121 (72),
100 (39), 91 (100).
Ethyl (E)-3-(2-Aminophenoxy)-2-propenoate (14b)
Yield: 0.16 g (40%); yellow oil.
IR (KBr): 3265 (NH2), 1696 (C=O), 1117 (CO) cm–1.
1H NMR: d = 1.31 (t, 3JHH = 7.1 Hz, 3 H, CH3), 3.9 (br s, 2 H, NH2),
4.20 (q, 3JHH = 7.1 Hz, 2 H, CH2), 5.53 (d, 3JHH = 12.1 Hz, 1 H, CH),
6.70 (t, 3JHH = 7.7 Hz, 1 H, CH), 6.81 (d, 3JHH = 8.0 Hz, 1 H, CH),
6.90 (d, 3JHH = 8.0 Hz, 1 H, CH), 7.01 (t, 3JHH = 7.7 Hz, 1 H, CH),
7.78 (d, 3JHH = 12.1 Hz, 1 H, CH).
Anal. Calcd for C12H15NO3 (221.2): C, 65.14; H, 6.83; N, 6.33.
Found: C, 65.20; H, 6.54; N, 6.19.
Ethyl (E)-3-(2-Amino-5-methylphenoxy)-2-propenoate (14f)
Yield: 0.12 g (30%); yellow oil.
IR (KBr): 3260 (NH2), 1697 (C=O), 1633, 1587, 1169 (CO) cm–1.
13C NMR: d = 14.3 (CH3), 60.1 (CH2), 101.6 (CH), 116.6 (CH),
118.7 (CH), 118.8 (CH), 125.9 (CH), 137.5 (C), 143.7 (C), 159.7
(CH), 169.8 (C=O).
1H NMR: d = 1.27 (t, 3JHH = 7.1 Hz, 3 H, CH3), 2.24 (s, 3 H, CH3),
4.16 (q, 3JHH = 7.1 Hz, 2 H, CH2), 5.49 (d, 3JHH = 12.2 Hz, 1 H, CH),
6.68 (d, 3JHH = 7.9 Hz, 1 H, CH), 6.75 (s, 1 H, CH), 6.8 (d, 3JHH
7.9 Hz, 1 H, CH), 7.74 (d, 3JHH = 12.2 Hz, 1 H, CH).
=
MS: m/z (%) = 208 (4) [M+ + 1], 207 (9) [M+], 178 (21), 162 (37),
13C NMR: d = 14.0 (CH3), 20.4 (CH3), 60.0 (CH2), 101.4 (CH),
116.6 (CH), 119.2 (CH), 126.4 (CH), 128.5 (C), 134.7 (C), 142.7
(C), 159.8 (CH), 167.2 (CO).
MS: m/z (%) = 221 (6) [M+], 192 (34), 148 (42), 130 (21), 121 (70),
100 (46), 91 (100).
134 (82), 107 (100), 100 (37), 92 (44), 74 (29), 45 (31).
Anal. Calcd for C11H13NO3 (207.2): C, 63.76; H, 6.32; N, 6.76.
Found: C, 63.71; H, 6.37; N, 6.64.
Ethyl (E)-3-(2-Amino-4-chlorophenoxy)-2-propenoate (14c)
Yield: 0.20 g (45%); yellow oil.
Anal. Calcd for C12H15NO3 (221.3): C, 65.14; H, 6.83; N, 6.33.
Found: C, 65.24; H, 6.73; N, 6.25.
Synthesis 2006, No. 19, 3243–3249 © Thieme Stuttgart · New York

3248
I. Yavari et al.
PAPER
Preparation of Compounds 23–28; General Procedure
13C NMR: d = 51.5 (CH3), 100.5 (CH), 116.4 (2 × CH), 119.5 (2 ×
To a solution of the hydroxyphenol (2 mmol) and the alkyl propi-
olate (4 mmol) in CH2Cl2 (10 mL) was added dropwise at –10 °C
over 10 min a solution of Ph3P (4 mmol) in CH2Cl2 (5 mL). The re-
action mixture was allowed to warm to r.t. and stand for 24 h. The
solvent was removed under reduced pressure and the residue was
separated by silica gel column chromatography (Merck 230–400
mesh) using n-hexane–EtOAc (4:1) as eluent to give the product.
CH), 149.2 (C), 153.6 (C), 161.1 (CH), 168.7 (C=O).
MS: m/z (%) = 194 (5) [M+], 179 (20), 135 (43), 108 (100), 86 (64),
59 (32), 31 (12).
Anal. Calcd for C10H10O4 (194.2): C, 61.85; H, 5.19. Found: C,
61.75; H, 5.30.
Ethyl (E)-3-(3-Aminophenoxy)-2-propenoate (27)
Yield: 0.24 g (60%); yellow oil.
IR (KBr): 3260 (NH2), 1698 (C=O), 1112 (CO) cm–1.
Methyl (E)-3-(3-{[(E)-3-Methoxy-3-oxo-1-propenyl]oxy}phen-
oxy)-2-propenoate (23)
Yield: 0.26 g (50%); colorless oil.
IR (KBr): 1697 (C=O), 1148 (CO) cm–1.
1H NMR: d = 1.28 (t, 3JHH = 7.1 Hz, 3 H, CH3), 3.78 (br s, 2 H, NH2),
4.18 (q, 3JHH = 7.1 Hz, 2 H, CH), 5.54 (d, 3JHH = 12.1 Hz, 1 H, CH),
6.33 (s, 1 H, CH), 6.44 (d, 3JHH = 7.8 Hz, 1 H, CH), 6.48 (d, 3JHH
=
=
1H NMR: d = 3.75 (s, 6 H, 2 × CH3), 5.63 (d, 3JHH = 12.1 Hz, 2 H,
7.8 Hz, 1 H, CH), 7.1 (t, 3JHH = 8.0 Hz, 1 H, CH), 7.76 (d, JHH
3
4
3
CH), 6.80 (t, JHH = 2.2 Hz, 1 H, CH), 6.91 (dd, JHH = 8.2 Hz,
4JHH = 2.2 Hz, 2 H, 2 × CH), 7.38 (t, 3JHH = 8.2 Hz, 1 H, CH), 7.70
(d, 3JHH = 12.1 Hz, 2 H, CH).
12.1 Hz, 1 H, CH).
13C NMR: d = 14.3 (CH3), 60.0 (CH2), 101.9 (CH), 104.6 (CH),
107.6 (CH), 111.6 (CH), 130.5 (CH), 148.7 (CN), 157.0 (CO),
159.0 (CH), 167.3 (CO).
MS: m/z (%) = 208 (4) [M+ + 1], 207 (11) [M+], 178 (29), 134 (45),
107 (100), 100 (65), 73 (24), 29 (12).
13C NMR: d = 51.4 (2 × CH3), 102.9 (2 × CH), 108.2 (CH), 114.1
(2 × CH), 131.1 (CH), 156.9 (2 × CH), 158.0 (2 × C), 167.3 (2 ×
C=O).
MS: m/z (%) = 279 (6) [M+ + 1], 278 (12) [M+], 150 (18), 108 (73),
57 (100).
Anal. Calcd for C11H13NO3 (207.2): C, 63.76; H, 6.32; N, 6.76.
Found: C, 63.70; H, 6.36; N, 6.81.
Anal. Calcd for C14H14O6 (278.3): C, 60.43; H, 5.07. Found: C,
60.54; H, 5.17.
Methyl (E)-3-(4-Aminophenoxy)-2-propenoate (28)
Yield: 0.3 g (80%); pale yellow solid; mp 55 °C.
IR (KBr): 3385 (NH2), 1728 (CO), 1162 (CO) cm–1.
Methyl (E)-3-(3-Hydroxyphenoxy)-2-propenoate (24)
Yield: 0.14 g (40%); yellow oil.
IR (KBr): 3365 (OH), 1676 (C=O), 1141 (CO) cm–1.
1H NMR: d = 3.68 (s, 3 H, CH3), 3.77 (s, 2 H, NH2), 5.42 (d, 3JHH
=
12.2 Hz, 1 H, CH), 6.61 (d, 3JHH = 8.7 Hz, 2 H, 2 × CH), 6.8 (d, 3JHH
1H NMR: d = 3.75 (s, 3 H, CH3), 5.59 (d, 3JHH = 12.2 Hz, 1 H, CH),
= 8.7 Hz, 2 H, 2 × CH), 7.71 (d, 3JHH = 12.2 Hz, 1 H, CH).
6.59 (s, 1 H, CH), 6.62 (d, 3JHH = 8.1 Hz, 1 H, CH), 6.67 (d, 3JHH
8.1 Hz, 1 H, CH), 7.2 (t, 3JHH = 8.1 Hz, 1 H, CH), 7.80 (d, 3JHH
12.2 Hz, 1 H, CH).
=
=
13C NMR: d = 51.2 (CH3), 100.3 (CH), 115.9 (2 × CH), 119.3 (2 ×
CH), 143.9 (C), 148.2 (C), 160.9 (CH), 167.9 (C=O).
13C NMR: d = 51.5 (CH3), 101.8 (CH), 105.5 (CH), 109.8 (CH),
112.1 (CH), 130.6 (CH), 156.9 (CH), 157.3 (C), 159.1 (C), 168.1
(C=O).
MS: m/z (%) = 194 (8) [M+], 179 (23), 135 (51), 108 (100), 86 (72),
59 (21), 31 (18).
MS: m/z (%) = 194 (2) [M+ + 1], 193 (6) [M+], 178 (22), 162 (64),
134 (40), 107 (100), 86 (56), 59 (13), 31 (14).
Anal. Calcd for C10H11NO3 (193.2): C, 62.17; H, 5.74; N, 7.25.
Found: C, 62.27; H, 5.63; N, 7.31.
Anal. Calcd for C10H10O4 (194.2): C, 61.85; H, 5.19. Found: C,
61.80; H, 5.20.
References
(1) Wan, Z.; Jones, C. D.; Koenig, T. M.; Pu, Y. J.; Mitchell, D.
Tetrahedron Lett. 2003, 44, 8257.
(2) Gestoso, P.; Brisson, J. Polymer 2001, 42, 8415.
(3) Weissermel, K.; Arfe, H. J. Industrial Organic Chemistry,
3rd ed.; Wiley VCH: Weinheim, 1997, 358.
(4) Quin, L. D. A Guide to Organophosphorus Chemistry;
Wiley-Interscience: New York, 2000.
(5) (a) Zaitsev, A. B.; Vasil’tsov, A. M.; Schmidt, E. Y.;
Mikhaleva, A. I.; Morozova, L. V.; Afonin, A. V.; Ushakov,
I. A.; Trofimov, B. A. Tetrahedron 2002, 58, 10043.
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Methyl (E)-3-(4-{[(E)-3-Methoxy-3-oxo-1-propenyl]oxy}phe-
noxy)-2-propenoate (25)
Yield: 0.32 g (60%); white solid; mp 120–122 °C.
IR (KBr): 1705 (C=O), 1114 (CO) cm–1.
1H NMR: d = 3.71 (s, 6 H, 2 × OMe), 5.53 (d, 3JHH = 12.6 Hz, 2 H,
2 × CH), 7.06 (s, 4 H, CH), 7.73 (d, 3JHH = 12.6 Hz, 2 H, 2 × CH).
13C NMR: d = 51.3 (2 × CH3), 102.1 (2 × CH), 119.6 (4 × CH), 152.7
(2 × C), 159.0 (2 × CH), 167.4 (2 × C=O).
MS: m/z (%) = 279 (4) [M+ + 1], 278 (11) [M+], 150 (10), 108 (70),
57 (100).
(6) (a) Yavari, I.; Ramazani, A. Synth. Commun. 1997, 27,
1449. (b) Yavari, I.; Norouzi-Arasi, H. Phosphorus, Sulfur
Silicon 2002, 177, 87. (c) Yavari, I.; Souri, S.; Sirouspour,
M.; Djahaniani, H.; Nasiri, F. Synthesis 2005, 1761.
(7) Nair, V.; Rajesh, C.; Vinod, A. U.; Bindu, S.; Sreekanth, A.
R.; Mathess, J. S.; Balagopal, L. Acc. Chem. Res. 2003, 36,
899.
Anal. Calcd for C14H14O6 (278.3): C, 60.43; H, 5.07. Found: C,
60.37; H, 5.27.
Methyl (E)-3-(4-Hydroxyphenoxy)-2-propenoate (26)
Yield: 0.1 g (30%); yellow oil.
IR (KBr): 3365 (OH), 1688 (C=O) cm–1.
1H NMR: d = 3.74 (s, 3 H, CH3), 5.47 (d, 3JHH = 12.3 Hz, 1 H, CH),
6.83 (d, 3JHH = 8.8 Hz, 2 H, CH), 6.90 (d, 3JHH = 8.8 Hz, 2 H, CH),
7.71 (d, 3JHH = 12.3 Hz, 1 H, CH).
(8) Van Meervelt, L.; Vydzhak, R. N.; Brovarets, V. S.;
Mishchenko, N. I.; Drach, B. S. Tetrahedron 1994, 50, 1889.
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Vinylphosphonium Salt Mediated Reaction
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Synthesis 2006, No. 19, 3243–3249 © Thieme Stuttgart · New York