A three-component reaction between trialkyl phosphites or triphenylphosphine, dimethyl acetylenedicarboxylate and N-aryl-3- hydroxynaphthalene-2-carboxamide

Article abstract of DOI:10.3184/030823407X272138

A three-component reaction between dimethyl acetylenedicarboxylate (DMAD) and trialkyl phosphites in the presence of N-aryl-3-hydroxynaphthalene-2- carboxamide leads to dialkyl 2-(dimethoxyphosphoryl)-3-[2-hydroxy-3- (arylcarbamyl)naphthalen-1-yl] succinate in excellent yields. A similar reaction with triphenylphosphine, instead of phosphites, produces dimethyl 2-[2-hydroxy-3-(arylcarbamoyl)naphthalen-1-yl]maleates. In the absence of triphenylphosphine or phosphite, DMAD adds to N-aryl-3-hydroxynaphthalene-2- carboxamide to produce alkyl 2-(alkoxycarbonylmethyl)-4-oxo-3-aryl-3,4-dihydro- 2H-naphtho[2,3-e][1,3]oxazine-2-carboxylates in good yields.

Full text of DOI:10.3184/030823407X272138

708 RESEARCH PAPER
DECEMBER, 708–712
JOURNAL OF CHEMICAL RESEARCH 2007
A three-component reaction between trialkyl phosphites or
triphenylphosphine, dimethyl acetylenedicarboxylate and
N-aryl-3-hydroxynaphthalene–2-carboxamide
Mohammad Anary-Abbasinejad*, Alireza Hassanabadi and Manouchehr Mazraeh-Seffid
Department of Chemistry, Islamic Azad University, Yazd Branch, P.O. Box 89195-155, Yazd, Iran
A three-component reaction between dimethyl acetylenedicarboxylate (DMAD) and trialkyl phosphites in the
presence of N-aryl-3-hydroxynaphthalene-2-carboxamide leads to dialkyl 2-(dimethoxyphosphoryl)-3-[2-hydroxy-
3-(arylcarbamyl)naphthalen-1-yl] succinate in excellent yields. A similar reaction with triphenylphosphine,
instead of phosphites, produces dimethyl 2-[2-hydroxy-3-(arylcarbamoyl)naphthalen-1-yl]maleates. In the absence
of triphenylphosphine or phosphite, DMAD adds to N-aryl-3-hydroxynaphthalene-2-carboxamide to produce alkyl
2-(alkoxycarbonylmethyl)-4-oxo-3-aryl-3,4-dihydro-2H-naphtho[2,3-e][1,3]oxazine-2-carboxylates in good yields.
Keywords: dimethyl acetylenedicarboxylate, thialkyl phosphites; N-aryl-3-hydroxynaphthalene-2-carboxamide, stereoselective
synthesis, triphenylphosphine
The nucleophilic addition of trialkyl phosphites to electron-
deficient triple bonds leads to a highly reactive zwitterionic
intermediate, which may be trapped by various electrophiles.
There have been many studies on the reactions between
trivalent phosphorus nucleophiles and unsaturated carbonyl
compounds in the presence of a proton source such as an
alcohol.1 The reaction of trimethyl phosphite with dimethyl
acetylenedicarboxylate (DMAD) in the presence of alcohols
is reported to produce phosphite ylide derivatives which are
stable at low temperatures, but converted to phosphonate
derivatives by warming or by treatment with water.2
The reaction of trimethyl phosphite with DMAD in the presence
of 2-naphthol has been reported to afford stable dimethyl
oxa-2,5-phosphaphenanthrene derivatives in good yields.3
In continuation of our previous work on three-component
reactionsbetweentrivalentphosphorusnucleophiles, acetylenic
esters and organic acidic compounds,4-8 we report herein the
results of our study on the reaction between acetylenic esters
and trialkyl phosphites or triphenylphosphine in the presence
of N-aryl-3-hydroxynaphthalene-2-carboxamides.
The 1H NMR spectrum of 4a exhibits two sharp lines
at d = 3.61 and 3.93 ppm for the protons of two methoxy
groups. Two methoxy groups of phosphoryl moiety are
diastereotopic and appear as two doublets at 3.37 and
1
3.45 ppm (3JHP = 11HZ). The H NMR spectrum of 4a also
exhibits signals for vicinal methine protons at d = 4.23
and 5.49 ppm as two sets of doublet of doublets, with
3
3
2JHP = 21 HZ, JHP = 6 HZ and JHH = 11 HZ. The vicinal
proton–proton coupling constants can be obtained from the
Karplus equation.9,10 Typically, Jgauche varies between 1.5 and
5 HZ and Janti between 10 and 14 HZ. Observation of
3JHH = 11 HZ for vicinal protons in compound 4a indicates
an anti arrangement for these centres. Since compound 4a
possesses two stereogenic centres, two diastereomers with
anti HCCH arrangements are possible (Scheme 2). The
3
three-bond carbon–phosphorus coupling, JCP, depends on
configuration, as expected, transoid couplings being larger
3
than cisoid ones.11 The observation for JCP of 19 HZ for the
ester carbonyl carbon, is in agreement with the (2R, 3S)-4a and
its mirror image (2S, 3R)-4a geometries. The NMR spectra
of compounds 4b–f also show only (2R, 3R) isomer and its
enantiomer.
It is reasonable to assume that compounds 4 result from
the initial addition of trimethyl phosphite to DMAD and
subsequent protonation of the 1:1 adduct by N-aryl-3-
hydroxynaphthalene–2-carboxamide 3 (Scheme 3). Then,
Reaction of DMAD with trimethyl (or triethyl or tributyl)
phosphite in the presence of N-phenyl (or 2-methylphenyl)
(3-hydroxynaphthalene-2-carboxamide leads to dialkyl 2-
(dimethoxyphosphoryl)-3-[2-hydroxy-3-(arylcarbamyl)
naphthalen-1-yl] succinates in excellent yields (Scheme 1).
PO(OR)2
H3CO2C
CO2CH3
OH
OH
O
H
N
P(OR)3
H3CO2C
CO2CH3
+
+
H
N
Acetone, r.t.
Ar
Ar
O
3
4
1
2
Yield*(%)
93
4
a
R
Me
Ar
Ph
b
Ph
Ph
Et
89
91
c
Bu
d
e
f
2-Me-C6H4
2-Me-C6H4
Me
Et
95
93
2-Me-C6H4
Bu
90
*Isolated yield
Scheme 1
* Correspondent. E-mail: mohammadanary@yahoo.com
PAPER: 07/4899

JOURNAL OF CHEMICAL RESEARCH 2007 709
1
CO2CH3
H
The H NMR spectrum of 10a exhibits three sharp lines at
d = 3.74, 3.83 and 6.44 ppm for the protons of two methoxy
groups and olefinic proton, respectively. Two single signals
are observed at 10.17 and 12.33 ppm that disappeared
after addition of a few drops of D2O to d6-DMSO solution
of compound 10a. These signals are related to OH and NH
protons. Aromatic protons resonate between 7.21 and 8.75
ppm as multiplets. The chemical shift of 6.44 ppm of the
olefinic proton in the 1H NMR spectrum of compound 10a is
consistent with the E-geometry of the carbon–carbon double
bond.13 13C NMR spectra of compound 10a shows 21 distinct
signals, which is consistent with the proposed structure.
It is reasonable to assume that compound 10 results from
the initial addition of triphenylphosphine 2 to acetylenic ester
9 and subsequent protonation of the 1:1 adduct by N-aryl-3-
hydroxynaphthalene–2-carboxamide 3 (Scheme 5). Then, the
positively charged ion 11 is attacked by the anion 6 to form ylide
12 that loses triphenylphosphine to produce compound 10.
When acetylenic ester 9 was treated with N-aryl 3-
hydroxynaphthalene-2-carboxamide 3 in the absence of
triphenylphospline the addition product alkyl 2-(alkoxy-
CO2CH3
(CH3O)2OP
H
H
H
PO(OCH3)2
H3CO2C
CO2CH3
OH
OH
H
H
O
N
N
Ar
O
Ar
(2S, 3R)-4a
(2R, 3S)-4a
Scheme 2
the positively charged ion 5 is attacked by the anion 6 to
form ylide 7 that then tautomerises and is hydrolysed to
phosphonate 4.
The reaction of acetylenic ester 9 with triphenylphosphine (8)
in the presence of N-aryl 3-hydroxynaphthalene-2-carboxamide
3 leads to dialkyl 2-[2-hydroxy-3-(arylcarbamoyl)naphthalen-
1-yl]but-2-enedioate 10 in excellent yields (Scheme 4).
+
P(OR')3
P(OR')3
CO2CH3
P(OR')3
H3CO2C
CO2CH3
H3CO2C
H3CO2C
CO2CH3
OH
H
5
H
_
O
O
OH2
4
_
R'OH
H
O
H
O
N
N
H
N
Ar
Ar
8
Ar
O
6
7
Scheme 3
H
RCO2
CO2R
OH
P(Ph)3
OH
8
H
N
+
H
N
Ar
Ar
RCO2
C
C
CO2R
O
O
9
10
3
R
10
Ar
Yield*(%)
a
b
c
Ph
Ph
Me
Et
92
90
Me
90
89
Me-C6H4
Me-C6H4
d
Et
*isolated yields
Scheme 4
+
P(Ph)3
+
+
P(Ph)3
P(Ph)3
RO2C
_
H
_
CO2R
RO2C
RO2C
CO2R
CO2R
H
11
H
_
OH
N
_
O
O
P(Ph)3
10
H
O
H
O
N
H
O
N
Ar
Ar
Ar
6
13
12
Scheme 5
PAPER: 07/4899

710 JOURNAL OF CHEMICAL RESEARCH 2007
CO2R
O
OH
O
RO2C
CO2R
+
H
N
CO2R
Ar
Acetone, r.t.
N
Ar
O
14
9
3
14
a
b
R
Me
Ar
Ph
Yield*(%)
92
87
93
Ph
Et
c
2-Me-C6H4
Me
d
2-Me-C6H4
Et
90
*Isolated yield
Scheme 6
RCO2
CO2R
RCO2
O
9
H
CO2R
14
H
OH
N
Ar
H
N
O
Ar
O
3
Scheme 7
Avance spectrometer at solutions in d6-DMSO using TMS as internal
standard or 85% H3PO4 as external standard. The chemicals used in
this work purchased from fluka (Buchs, Switzerland) and were used
without further purification.
carbonylmethyl)-4-oxo-3-aryl-3,4-dihydro-2H-naphtho[2,3-
e][1,3]oxazine-2-carboxylate 14 was obtained in good yield
(Scheme 6).
The 1H NMR spectrum of 14a exhibits two sharp lines at d
= 3.74 and 3.83 ppm for the protons of two methoxy groups.
The methylene protons resonate at 3.28 ppm as an AB-quartet
(d1 = 3.24, d2 = 3.32, 2JHH = 16 Hz). Aromatic protons resonate
between 7.21 and 8.75 ppm as multiplets. The IR spectrum of
compound 14a does not show the stretching absorption bonds
related to OH or NH bonds.
Dimethyl 2-(dimethoxyphosphoryl)-3-[2-hydroxy-3-(phenylcarbamoyl)
naphthalen-1-yl]succinate (4a)
General procedure for preparation of compounds 4a–f
To
a
magnetically stirred solution of 0.53
g N-phenyl-3-
hydroxynaphthalene–2-carboxamide
3
(2 mmol) and 0.28
g
DMAD (2 mmol) in 10,ml acetone was added a mixture of 0.25 g
trimethyl phosphite 1 (2 mmol) in 2 ml acetone at room temperature.
The reaction mixture was then allowed to stir for 24 h. The solvent
was evaporated at reduced pressure. The residue was precipitated in
a solution of diethyl ether–hexane. The solid was filtered and washed
with diethyl ether to give the pure product.
Compound 14 is probably produced by the addition of N-
aryl 3-hydroxynaphthalene-2-carboxamide 3 to ecetylenic
ester 9 as shown in Scheme 7.
In summary functionalised phosphonates may be prepared
by a simple, one-pot, three-component reaction between
DMAD, aryl 3-hydroxynaphthalene–2-carboxamides, and
trialkyl phosphites. The addition reaction between acetylenic
esters and N-aryl-3-hydroxynaphthalene-2-carboxamides
catalysed by triphenylphosphine produces dialkyl 2-[2-
hydroxy-3-(arylcarbamoyl)naphthalen-1-yl]-but-2-enedioates
in good yields. In the absence of triphenylphosphine N-aryl-3-
hydroxynaphthalene-2-carboxamides add to acetylenic esters
to produce alkyl 2-(alkoxycarbonylmethyl)-4-oxo-3-aryl-
3,4-dihydro-2H-naphtho[2,3-e][1,3]oxazine-2-carboxylates
in excellent yields. The present method carries the advantage
that the reaction is performed under neutral conditions and
starting materials can be mixed without any activation or
modification.
White powder, yield 0.96 g (93%), m.p. 177–180°C, IR (KBr) (νmax
cm-1): 3245 OH and NH), 1727 (C=O, ester), 1642 (C=O, amide).
Analyses:Calcd. forC25H26NO9P:C, 58.25;H, 5.08;N, 2.72%. Found:
C, 58.34; H, 4.93; N,2.80. MS (m/z,%): 515 (5). 1H NMR (500 MHz,
3
d6-DMSO): d 3.37 and 3.45 (6 H, 2d, JHP = 11 Hz, 2 POCH3),
2
3.61 and 3.93 (6 H, 2 s, 2 OCH3), 4.70 (1 H, dd, JHP = 21 Hz,
3
3
3JHH = 11 HZ, CH), 5.33 (1 H, dd, JHP = 6 Hz, JHH = 11 HZ, CH),
7.16–8.15 (10 H, m, aromatic),). 9.09 and 12.66 (2 H, 2 s,NH and OH).
2
13C NMR (125.8 MHz, d6-DMSO–Me4Si): d 41.95 (d, Jcp = 2 HZ,
1
P–C–C), 43.95 (d, Jcp = 131 HZ, P-C), 53.17 and 53.28 (2 OCH3),
66.32 and 66.58 (2 d, 2Jcp = 7 HZ, 2 POCH3), 116.21, 116.77, 123.04,
123.83, 125.86, 127.40, 129.16, 130.26, 135.76 and 156.55 (naphthol
moiety), 121.89, 122.81, 129.30, 137.34 (phenyl moiety), 169.00
(C=O), 170.43 (d, 2JCP = 6 HZ, C=O), 173.49 (d, 3JCP = 21 HZ, C=O).
31P NMR (202.5 MHz, d6-DMSO): d 19.94.
Dimethyl 2-(diethoxyphosphoryl)-3-[2-hydroxy-3-(phenylcarbamoyl)
naphthalen-1-yl]succinate (4b): White powder, yield 0.97 g (89%),
m.p. 185–188°C, IR (KBr) (νmax cm-1): 3255(OH),1729 (C=O,
ester),1643 (C=O, amide). Analyses: Calcd. for C27H30NO9P:
C, 59.67; H, 5.56; N, 2.58%. Found: C, 59.72; H, 5.48; N, 2.60.
Experimental
1
Melting points were determined with an electrothermal 9100
apparatus. Elemental analyses were performed using a Heraeus CHN-
O-Rapid analyser. Mass spectra were recorded on a FINNIGAN-
MAT 8430 mass spectrometer operating at an ionisation potential of
70 eV. IR spectra were recorded on a Shimadzu IR-470 spectrometer.
1H, 13C, and 31P NMR spectra were recorded on Bruker DRX-500
MS (m/z,%): 543 (11). H NMR (500 MHz, d6-DMSO): d 0.87 and
0.93 (6 H, t, 2 CH3), 3.71–3.76(4 H, m, 2 POCH2), 3.50 and 3.82
(6 H, 2 s, 2 OCH3), 4.54 (1 H, dd, 2JHP = 21 Hz, 3JHH = 11 HZ, CH),
3
3
5.21 (1 H, dd, JHP = 6 Hz, JHH = 11 HZ, CH), 7.13–8.57 (10 H, m,
aromatic), 9.91 and 12.43 (2 H, 2 s, NH and OH). 13C NMR (125.8
MHz, d6-DMSO-Me4Si): d 16.08 and 16.22 (2 CH3), 41.93 (d, Jcp
2
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JOURNAL OF CHEMICAL RESEARCH 2007 711
1
= 2 HZ, P–C–C), 43.78 (d, Jcp = 131 HZ, P-C), 53.28 and 53.60 (2
General procedure for preparation of compounds 10a–d
OCH3), 61.73 and 62.38 (2 d, 2Jcp = 7 HZ, 2 POCH2), 116.27, 117.77,
123.33, 123.80, 125.52, 127.46, 129.43, 130.76, 136.06 and 156.09
(naphthol moiety), 121.80, 122.77, 129.54, 137.31 (phenyl moiety),
169.27(C=O), 170.16(d, 2JCP = 6 HZ, C=O), 173.03 (d, 3JCP = 21 HZ,
C=O). 31P NMR (202.5 MHz, d6-DMSO): d 19.80.
Dimethyl 2-[2-hydroxy-3-(phenylcarbamoyl)naphthalen-1-yl]-but-
2-enedioate (10a): To a magnetically stirred solution of 0.53 g of
phenyl (3-hydroxynaphthalene)–2-carboxamide (2 mmol) and 0.28 g
of DMAD (2 mmol) in 10 ml acetone was added a mixture of 0.53 g
triphenylphosphine (2 mmol) in 2 ml acetone at room temperature.
The reaction mixture was then allowed to stir for 24 h. The solvent
was evaporated at reduced pressure. The residue was precipitated in
a solution of diethyl ether-hexane. The solid was filtered and washed
with diethyl ether to give the pure product.
Dimethyl 2-(dibutoxyphosphoryl)-3-[2-hydroxy-3-(phenylcarbamoyl)
naphthalen-1-yl]succinate (4c): White powder, yield 1.12 g (91%),
m.p. 190–193°C, IR (KBr) (νmax cm-1): 3250 (OH),1724 (C=O, ester),
1641 (C=O, amide). Analyses: Calcd. for C31H38NO9P: C, 62.10; H,
6.39; N, 2.34%. Found: C, 62.18; H, 6.30; N, 2.42. MS (m/z,%): 599
(7). 1H NMR (500 MHz, d6-DMSO): d 0.83 (6 H, t, 2 CH3), 0.93
(4 H, sextet, 2 CH2), 1.32(4 H, quintet, 2 CH2), 3.71–3.86 (4 H, m,
2 POCH2), 3.60 and 3.92 (6 H, 2 s, 2 OCH3), 4.72 (1 H, dd, 2JHP = 21 Hz,
Yellow powder, yield 92%, m.p. 179–181°C, IR (KBr) (νmax cm-1):
3305 OH), 1722 (C=O, ester), 1692 (C=O, amide). MS (m/z,%): 405
(7). 1H NMR (500 MHz, d, CDCl3): 3.74 and 3.83 (6 H, 2 s, 2 OCH3),
6.44 (1 H, s, CH), 7.21–8.75 (10 H, m, aromatic),). 10.17 and 12.33
(2 H, 2 s, NH and OH). 13C NMR (125.8 MHz, d, CDCl3): 51.78
and 52.06 (2 OCH3), 130.17 (C), 139.20 (C), 117.21, 118.01, 124.46,
125.44, 127.24, 129.87, 129.95, 130.46, 135.40 and 155.09 (naphthol
moiety), 122.00, 123.91, 129.21, 138.09 (phenyl moiety), 165.77
(C=O), 167.12 (C=O), 169.08 (C=O). Anal. Calcd. for C23H19NO6:
C, 68.14; H, 4.72; N, 3.46%. Found: C, 68.5; H, 4.45; N,3.65%.
Diethyl 2-[2-hydroxy-3-(phenylcarbamoyl)naphthalen-1-yl]-but-
2-enedioate (10b): Yellow powder, yield 90%, m.p. 168–170°C,
IR (KBr) (νmax cm-1): 3390(OH), 1704 (C=O, ester), 1683 (C=O,
amide). MS (m/z,%): 433 (10). 1H NMR (500 MHz,,d, CDCl3): 1.24
and 1.35 (6 H, 2t, 2 CH3), 4.18 and 4.31(4 H, 2q, 2 OCH2), 6.42
(1 H, s, CH), 7.21–8.57 (10 H, m, aromatic), 10.17 and 12.31 (2 H,
2 s, NH and OH). 13C NMR (125.8 MHz, d, CDCl3): 13.71 and 13.94
(2 CH3), 61.02 and 61.26 (2 OCH2), 130.20 (C), 139.28 (C), 117.24,
118.26, 124.42, 125.42, 127.24, 129.78, 129.93, 130.39, 135.46 and
155.09 (naphthol moiety), 121.98, 124.00, 129.20, 138.12 (phenyl
moiety), 165.34(C=O), 166.64(C=O), 169.24 (C=O). Anal. Calcd.
for C25H23NO6: C, 69.27; H, 5.35; N, 3.23%. Found: C, 69.40; H,
5.25; N, 3.3%.
3JHH = 11 HZ, CH), 5.34 (1 H, dd, JHP = 6 Hz, JHH = 11 HZ, CH),
7.12–8.56 (10 H, m, aromatic), 9.06 and 12.64 (2 H, 2 s, NH and
OH). 13C NMR (125.8 MHz, d6-DMSO-Me4Si): d 13.94 and 14.02
3
3
3
(2 CH3), 18.87 and 18.96 (2CH2), 32.32 and 32.64 (2 d, JCP = 7 Hz,
2 CH2), 42.12 (d, 2Jcp = 2 HZ, P–C–C), 44.82 (d, 1Jcp = 131 HZ, P-C),
53.11 and 53.38 (2 OCH3), 66.53 and 66.91 (2 d, 2Jcp = 7 HZ, 2 POCH2),
116.22, 117.01, 123.27, 123.71, 125.78, 127.47, 129.04, 130.17, 135.86
and 156.61 (naphthol moiety), 121.50, 122.82, 129.29 and 137.39
(phenyl moiety), 169.01 (C=O), 170.16(d, 2JCP = 6 HZ, C=O), 172.92 (d,
3JCP = 21 HZ, C=O). 31P NMR (202.5 MHz, d6-DMSO): d 21.65.
Dimethyl 2-(dimethoxyphosphoryl)-3-[2-hydroxy-3-(2-methylphenyl-
carbamoyl)naphthalen-1-yl]succinate (4d): White powder, yield
1.03 g (95%), m.p. 194–197°C, IR (KBr) (νmax cm-1): 3200(OH),
1729(C=O, ester), 1641(C=O, amide). Analyses: Calcd. for
C26H28NO9P: C, 58.98; H, 5.33; N, 2.65%. Found: C, 59.45; H, 5.22;
N, 2.73. MS (m/z,%): 529 (6). 1H NMR (500 MHz, d6-DMSO): d 2.34
(3 H, s, CH3), 3.13 and 3.43 (6 H, 2d, 3JHP = 11 Hz, 2 POCH3), 3.60
and 3.90 (6 H, 2 s, 2 OCH3), 4.62 (1 H, dd, 2JHP = 21 Hz, 3JHH = 11 HZ,
3
3
CH), 5.32 (1 H, dd, JHP = 6 Hz, JHH = 11 HZ, CH), 7.17–8.21
(9 H, m, aromatic), 8.90 and 12.61 (2 H, 2 s, NH and OH). 13C NMR
(125.8 MHz, d6-DMSO–Me4Si): d 18.46 (CH3), 41.95 (d, 2Jcp = 2 HZ,
Dimethyl 2-[2-hydroxy-3-(2-methylphenylcarbamoyl)naphthalen-1-
yl]-but-2-enedioate (10c): Yellow powder, yield 90%, m.p. 163–165°C,
IR (KBr) (νmax cm-1): 3375 (OH), 1713 (C=O, ester), 1642 (C=O,
1
P–C–C), 43.95 (d, Jcp = 131 HZ, P–C), 53.17 and 53.28 (2 OCH3),
66.32 and 66.58 (2 d, 2Jcp = 7 HZ, 2 POCH3), 116.13, 117.14, 123.20,
124.08, 126.49, 127.47, 129.00, 130.36, 135.06 and 156.49 (naphthol
moiety), 127.34, 127.43, 129.21, 131.10, 133.31 and 135.89 (phenyl
moiety), 169.23 (C=O), 170.30 (d, 2JCP = 6 HZ, C=O), 173.31 (d, 3JCP
= 21 HZ, C=O). 31P NMR (202.5 MHz, d6-DMSO): d 20.71.
amide). MS (m/z,%): 419 (9). H NMR (500 MHz, d, CDCl3): 2.94
1
(3 H, s, CH3), 3.51 and 3.73 (6 H, 2 s, 2 OCH3), 6.45 (1 H, s, CH),
7.26–8.87 (9 H, m, aromatic), 10.11 and 12.41 (2 H, 2 s, NH and
OH). 13C NMR (125.8 MHz, d, CDCl3): 17.81(CH3), 51.45 and 52.59
(2 OCH3), 129.90 (C), 138.85 (C), 116.69, 117.26, 123.61, 123.99,
126.66, 127.26, 128.90, 130.94, 135.39 and 154.52 (naphthol moiety),
127.05, 127.17, 129.04, 131.40, 133.03 and 135.40 (phenyl moiety),
164.66 (C=O), 166.73(C=O), 169.52 (C=O).Anal. Calcd. for C24H21NO6:
C, 68.73; H, 5.05; N, 3.34%. Found: C, 68.9; H, 4.95; N, 3.4%.
Dimethyl2-(diethoxyphosphoryl)-3-[2-hydroxy-3-(2-methylphenyl-
carbamoyl)naphthalen-1-yl]succinate
(4e):
White
powder,
yield 1.05 g (93%), m.p. 175–178°C, IR (KBr) (νmax cm-1): 3195
(OH), 1725 (C=O, ester),1642 (C=O, amide). Analyses: Calcd. for
C28H32NO9P: C, 60.32; H, 5.79; N, 2.51%. Found: C, 60.48; H, 5.70;
N, 2.55. MS (m/z,%): 557 (9). 1H NMR (500 MHz, d6-DMSO):
d 0.96 and 1.11 (6 H, t, 2 CH3), 2.36 (3 H, s, CH3), 3.72–3.82 (4 H, m,
2 POCH2), 3.61 and 3.91 (6 H, 2 s, 2 OCH3), 4.62 (1 H, dd, 2JHP= 21 Hz,
Diethyl
2-[2-hydroxy-3-(2-methylphenylcarbamoyl)naphthalen-
1-yl]-but-2-enedioate (10d): Yellow powder, yield 89%, m.p. 154–
156°C, IR (KBr) (νmax cm-1): 3320(OH), 1719(C=O, ester), 1648(C=O,
1
amide). MS (m/z,%): 447 (6). H NMR (500 MHz, d, CDCl3): 0.99
3JHH = 11 HZ, CH), 5.34 (1 H, dd, JHP = 6 Hz, JHH = 11 HZ, CH),
7.15–8.72 (9 H, m, aromatic), 8.95 and 12.50 (2 H, 2 s, NH and
OH). 13C NMR (125.8 MHz, d6-DMSO-Me4Si): d 16.34 and 16.48
(2CH3),18.43(CH3),42.09(d,2Jcp=2HZ,P-C-C),44.23(d,1Jcp=131HZ,
and 1.28 (6 H, 2t, 2 CH3), 2.50 (3 H, s, CH3), 4.38 and 4.50 (4 H,
2q, 2 OCH2), 6.30 (1 H, s, CH), 7.17–8.52 (9 H, m, aromatic), 9.03
and 11.80 (2 H, 2 s, NH and OH). 13C NMR (125.8 MHz, d, CDCl3):
14.09 and 14.46 (2 CH3), 18.43 (CH3), 61.13 and 62.80 (2 OCH2),
131.04 (C), 140.42 (C), 117.02, 117.83, 122.86, 124.28, 125.25,
127.30, 129.54, 131.63, 135.60 and 154.00 (naphthol moiety), 126.37,
127.09, 129.69, 132.17, 134.84 and 138.11 (phenyl moiety), 165.13
(C=O), 166.68 (C=O), 168.66 (C=O). Anal. Calcd. for C26H25NO6: C,
69.79; H, 5.63; N, 3.13%. Found: C, 69.9; H, 5.5; N,3.2%.
3
3
2
P-C), 53.14 and 53.43 (2 OCH3), 62.66 and 62.88 (2 d, Jcp = 7 HZ,
2 POCH2), 116.29, 117.53, 123.69, 124.12, 126.10, 127.45, 129.70,
130.87, 135.01 and 156.40 (naphthol moiety), 127.17, 127.37, 130.13,
131.15, 133.62 and 136.08 (phenyl moiety), 169.12 (C=O), 170.49(d,
2JCP = 6 HZ, C=O), 173.17 (d, 3JCP = 21 HZ, C=O). 31P NMR (202.5
MHz, d6-DMSO): d 20.31.
Dimethyl2-(dibutoxyphosphoryl)-3-[2-hydroxy-3-(2-methylphenyl-
General procedure for preparation of compounds 14a–d
carbamoyl)naphthalen-1-yl]succinate
(4f):
White
powder,
Dimethyl 2-(methoxycarbonylmethyl)-4-oxo-3-phenyl-3,4-dihydro-
2H-naphtho[2,3-e][1,3]oxazine-2-carboxylate (14a): A mixture of
0.53 g of N-phenyl-3-hydroxynaphthalene)–2-carboxamide (2 mmol)
and 0.28 g of DMAD (2 mmol) in 10 ml acetone was stirred at
room temperature for 24 h. The solvent was removed under reduced
pressure and the residue was purified by silica gel (Merck silica gel
60, 230–400 mesh) column chromatography using hexane-ethyl
acetate as eluent. The solvent was removed under reduced pressure
to afford the product.
yield 1.10 g (90%), m.p. 181–184°C, IR (KBr) (νmax cm-1): 3150
(OH), 1727 (C=O, ester), 1640 (C=O, amide). Analyses: Calcd. for
C32H40NO9P: C, 62.63; H, 6.57; N, 2.28%. Found: C, 62.70; H, 6.47;
N, 2.30. MS (m/z,%): 613 (8). 1H NMR (500 MHz, d6-DMSO): d 0.82
(6 H, t, 2 CH3), 0.91 (4 H, sextet, 2 CH2), 1.29 (4 H, quintet, 2 CH2),
2.35 (3 H, s, CH3), 3.70–3.78 (4 H, m, 2 POCH2), 3.60 and 3.89 (6 H,
2
3
2 s, 2 OCH3), 4.63 (1 H, dd, JHP = 21 Hz, JHH = 11 HZ, CH), 5.34
3
3
(1 H, dd, JHP = 6 Hz, JHH = 11 HZ, CH), 7.13–8.76 (9 H, m,
aromatic), 8.80 and 12.47 (2 H, 2 s, NH and OH). 13C NMR (125.8
MHz, d6-DMSO-Me4Si): d 13.96 and 14.00 (2 CH3), 18.46 (CH3),
18.85 and 18.93 (2CH2), 32.66 and 32.58 (2 d, 3JCP = 7 Hz, 2 CH2),
42.11 (d, 2Jcp = 2 HZ, P–C–C), 44.63 (d, 1Jcp = 131 HZ, P–C), 53.09
Yellow powder, yield 92%, m.p. 161–163°C, IR (KBr) (νmax cm-1):
3458(OH),1744(C=O,ester),1673(C=O,amide).MS(m/z,%):405(8).
1H NMR (500 MHz,,d, CDCl3): 3.28 (2 H, AB quartet, 2JHH = 16 HZ,
CH2), 3.42 and 3.72 (6 H, 2 s, 2 OCH3), 7.46–8.59 (11 H, m,
aromatic). 13C NMR (125.8 MHz, d, CDCl3): 42.84 (CH2), 52.37 and
53.92 (2 OCH3), 91.57 (C), 112.70, 118.48, 129.24, 129.47, 129.70,
129.98, 130.02, 131.24, 136.84 and 151.31(naphthol moiety), 125.69,
127.40, 130.85, 137.14 (phenyl moiety), 162.44 (C=O), 167.87
(C=O), 168.83 (C=O). Anal. Calcd. for C23H19NO6: C, 68.14; H,
4.72; N, 3.46%. Found: C, 68.3; H, 4.70; N, 3.5%.
2
and 53.42 (2 OCH3), 66.32 and 66.57 (2 d, Jcp = 7 HZ, 2 POCH2),
116.24, 117.50, 123.61, 124.08, 126.14, 127.47, 129.66, 130.83,
135.06 and 156.43 (naphthol moiety), 127.15, 127.38, 130.13,
131.13, 134.01 and 136.05 (phenyl moiety), 169.10 (C=O), 170.45(d,
2JCP = 6 HZ, C=O), 173.46 (d, 3JCP = 21 HZ, C=O). 31P NMR (202.5
MHz, d6-DMSO): d 21.37
PAPER: 07/4899

712 JOURNAL OF CHEMICAL RESEARCH 2007
Diethyl 2-(methoxycarbonylmethyl)-4-oxo-3-phenyl-3,4-dihydro-
2H-naphtho[2,3-e][1,3]oxazine-2-carboxylate (14b):Yellow powder,
yield 87%, m.p. 126–128°C, IR (KBr) (νmax cm-1): 3465 (OH), 1727
(C=O, ester),1673 (C=O, amide). MS (m/z,%): 433 (9). 1H NMR
(500 MHz, d, CDCl3): 1.05 and 1.11 (6 H, 2t, 2 CH3), 3.27 (2 H, AB
quartet, 2JHH = 16 HZ, CH2), 3.78–4.18 (4 H, m, 2 OCH2), 7.47–8.53
(11 H, m, aromatic). 13C NMR (125.8 MHz, d, CDCl3): 13.62 and
13.67 (2CH3), 42.38 (CH2), 60.93 and 62.75 (2 OCH2), 91.78 (C),
112.56, 119.21, 129.05, 129.23, 129.78, 129.92, 130.12, 131.43,
137.13 and 151.65(naphthol moiety), 125.71, 127.36, 131.64, 137.42
(phenyl moiety), 161.86 (C=O), 166.97 (C=O), 168.05 (C=O). Anal.
Calcd. for C25H23NO6: C, 69.27; H, 5.35; N, 3.23%. Found: C, 69.4;
H, 5.24; N, 3.3%.
(4 H, m, 2 OCH2), 7.29–8.62 (10 H, m, aromatic). 13C NMR (125.8
MHz, d, CDCl3): 14.26 and 14.30 (2CH3), 18.69 (CH3), 42.30 (CH2),
61.60 and 63.21 (2 OCH2), 91.81 (C), 112.76, 118.90, 125.65,
127.41, 129.58, 129.94, 130.02, 131.29, 137.16 and 151.88(naphthol
moiety), 127.21, 129.22, 130.83, 131.41, 136.16 and 138.04 (phenyl
moiety), 161.92 (C=O), 167.35 (C=O), 168.50 (C=O). Anal. Calcd.
for C26H25NO6: C, 69.79; H, 5.63; N, 3.13%. Found: C, 69.9; H, 5.6;
N, 3.2%.
Received 7 November 2007; accepted 17 December 2007
Paper 07/4899
doi: 10.3184/030823407X272138
Dimethyl2-(methoxycarbonylmethyl)-4-oxo-3-o-tolyl-3,4-dihydro-
2H-naphtho[2,3-e][1,3]oxazine-2-carboxylate (14c): Yellow powder,
yield 93%, m.p. 158–160°C, IR (KBr) (νmax cm-1): 3470 (OH), 1730
(C=O, ester), 1675(C=O, amide). MS (m/z,%): 419 (9). 1H NMR
(500 MHz, d, CDCl3): 2.84 (3 H, s, CH3), 3.30 (2 H, AB quartet, 2JHH
= 16 HZ, CH2), 3.36 and 3.71 (6 H, 2 s, 2 OCH3), 7.46–8.55 (10 H,
m, aromatic). 13C NMR (125.8 MHz, d, CDCl3): 17.90 (CH3), 42.40
(CH2), 60.95 and 62.77 (2 OCH3), 91.80 (C), 112.74, 119.21, 125.72,
126.81, 129.06, 129.95, 130.18, 131.36, 137.13 and 151.65(naphthol
moiety), 127.37, 129.25, 131.12, 131.66, 136.41 and 138.21 (phenyl
moiety), 161.61 (C=O), 168.06 (C=O), 169.04 (C=O). Anal. Calcd.
for C24H21NO6: C, 68.73; H, 5.05; N, 3.34%. Found: C, 68.8; H, 4.9;
N, 3.4%.
References
1
D.E.C. Corbridge, Phosphorus an Outline of the Chemistry Biochemistry
and Uses, 5th edn, Elsevier, Amsterdam, 1995.
2
A.W. Johnson, W.C. Kaska, A.O. Starzewski and D.A. Dixon, Ylides and
Imines of Phosphorus, John Wiley & Sons, 1993, pp.386-387.
I. Yavari and M. Anary-Abbasinejad, Org. Biomo.l Chem., 2003, 3, 560.
M. Anary-Abbasinejad and N. Ascarrian, J Chem Res., 2007, 11.
M. Anary-Abbasinejad, N. Rostami, A. Parhami and A. Hassanabadi,
J. Chem. Res., 2007, 257.
3
4
5
6
M. Anary-Abbasinejad, A. Hassanabadi and H. Anaraki-Ardakani,
J. Chem. Res., 2007, 455.
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8
M. Anary-Abbasinejad and A. Hassanabadi, J. Chem. Res., 2007, 475.
M. Anary-Abbasinejad, H. Anaraki-Ardakani, A. Dehghan,
A. Hassanabadi and M.R. Seyedmir, J. Chem. Res., 2007, in press.
M. Karplus, J. Am. Chem. Soc., 1963, 88, 2870.
Diethyl 2-(methoxycarbonylmethyl)-4-oxo-3-o-tolyl-3,4-dihydro-
2H-naphtho[2,3-e][1,3]oxazine-2-carboxylate
(14d):
Yellow
9
powder, yield 90%, m.p. 125–127°C, IR (KBr) (νmax cm-1): 3430
(OH), 1745 (C=O, ester), 1681 (C=O, amide). MS (m/z,%): 447 (6).
1H NMR (500 MHz,,d, CDCl3): 1.14 and 1.16 (6 H, 2t, 2 CH3), 2.34
(3 H, s, CH3), 3.10 (2 H, AB quartet, 2JHH = 16 HZ, CH2), 3.76–4.25
10 C.A.G. Haasnot, F.A.A.M. De Leeuww and C. Altona, Tetrahedron, 1980,
36, 2783.
11 E. Breitmaier and W. Voelter, Carbon-13 NMR Spectroscopy, 3rd edn,
VCH New York, 1990, p. 250.
PAPER: 07/4899