A new conjugated addition of trialkyl phosphites and alkylidenephosphoranes to 3-ω-azideoacetyl coumarin synthesis of some 1,2,3,4-triazaphospholes, triazoles, and azido-coumarin derivatives

Article abstract of DOI:10.1002/jhet.743

A new and efficient conjugate addition of trimethyl and triethyl phosphites to 3-ω-azidoacetylcoumarin (1) has been studied. The reaction proceeded smoothly at r.t. furnishing 1,2,3,4-triazaphosphole coumarin derivatives 4a,b in ～75% yields. Linear substi

Full text of DOI:10.1002/jhet.743

1258
A New Conjugated Addition of Trialkyl Phosphites and
Alkylidenephosphoranes to 3-x-Azideoacetyl Coumarin Synthesis
of Some 1,2,3,4-Triazaphospholes, Triazoles, and
Azido-Coumarin Derivatives
Vol 48
Ashraf A. Sediek,a Abeer A. Shaddy,b and Wafaa M. Abdoub*
aChemistry Department, Faculty of Sciences and Arts, Al-Kamil Branch,
King Abdulaziz University, Jeddah, Saudi Arabia
bChemical Industries Division, National Research Centre, D-12622, Dokki, Cairo, Egypt
*E-mail: wabdou@link.net
Received October 15, 2010
DOI 10.1002/jhet.743
Published online 27 July 2011 in Wiley Online Library (wileyonlinelibrary.com).
A new and efficient conjugate addition of trimethyl and triethyl phosphites to 3-x-azidoacetylcou-
marin (1) has been studied. The reaction proceeded smoothly at r.t. furnishing 1,2,3,4-triazaphosphole
coumarin derivatives 4a,b in ꢀ75% yields. Linear substituted triazoles 10a,b were also obtained from
the reactions of 1 with a-keto ylides, acetyl- and benzoylmethylene triphenylphosphoranes. Contrary to
these results, Wittig reaction was occurred when 1 was allowed to react with a-alkoxycarbonylmethy-
lene- and cyanomethylenetriphenylphosphoranes 7c–e as well as with methylidene- and benzylidenetri-
phenylphosphoranes 8a,b resulting in the formation of the corresponding olefins either as an
intermediate 14b or as final products 11a–c.
J. Heterocyclic Chem., 48, 1258 (2011).
INTRODUCTION
RESULTS AND DISCUSSION
A considerable number of naturally occurring cou-
marins such as Muttalongin, Usthol, and 2,3-Auraptin
were found to have strong antimicrobial and anti-
cancer activities [1]. Also, coumarin dyes recently
have found great interests because of their high poten-
tial in dye laser to achieve tunable blue-green light
and are also used in enzyme determination; photobio-
logical energy transfer processes fluorescent probe
technique; and fluorescence whiteners in detergent
products [2].
The azide 1 reacted smoothly with trimethyl- 2a and
triethyl phosphite 2b in absolute methylene chloride at
room temperature and yielded, in each case, the tauto-
meric structure 4a,b
4Aa,b in ꢁ 75% yield. Com-
pound 4 can be viewed as derived from ring closure of
the phosphazide 3, initially formed [15,16] with con-
comitant extrusion of the appropriate alcohol moiety.
Further rearrangement through alkyl group shift led to
the triazaphosphole products 4a,b (Scheme 1).
Compounds 4a,b showed 31P-NMR chemical shifts
around d 11.4 ppm confirming the presence of NAPAC
linkage in a phosphole moiety and readily eliminate any
formation of phosphates for which a signal at dp ¼ 6
2–4 ppm would be expected. The IR spectrum of 4a
revealed the presence of absorption bands at 1722
(C¼¼O, lactone), 1633 (C¼¼O, acetyl), 1265 (P¼¼O,
free), and at 1055 (PAOACH3) cmꢂ1. Moreover, the
strong azide frequency present in the IR spectrum of 1
at 2093 cmꢂ1 was absent in the IR spectra of 4. In the
In continuation with our research program directed to-
ward the utility of trivalent and pentavalent phosphorus
reagents in synthesis of pharmaceuticals [3–12], we
extend our precedent work on coumarins and relevant
phosphor derivatives [13,14] to elaborate more novel
coumarin derivatives of expecting pharmacological
potenc. The methodology involved application of tri-
alkyl phosphites and alkylidenephosphoranes to 3-azido-
acetylcoumarin (1).
C
V
2011 HeteroCorporation

November 2011 A New Conjugated Addition of Trialkyl Phosphites and Alkylidenephosphoranes
1259
Scheme 1
1H-NMR [17] spectrum of 4a (CDCl3), the 4’-H of cou-
marin was observed as a singlet at d 8.68 ppm. A dou-
stabilized Wittig reagents: i- a-ketomethylene-7a,b,
ii- alkoxycarbonyl-methylene-7c,d, iii- cyanomethylene-
triphenylphosphorane 7e; and two active ylides: i- meth-
ylidene- (8a) and benzylidenetriphenylphosphorane (8b).
When the azide 1 was treated with acetylmethylene-
7a or benzoylmethylenetriphenyl-phosphorane (7b) in
tetrahydrofuran (THF) at room temperature for 24 h,
1,2,3-triazoloactyl-coumarins 10a,b were formed in
ꢀ74% yield. Triphenylphosphine oxide (TPPO) was
also isolated from the reaction medium. The triazole
structure 10 was deduced from analytical and spectro-
scopic data. In the IR spectrum of 10a, the lactone car-
bonyl was observed at 1721 and that of the 3-acetyl car-
3
blet (3H, JP-H ¼ 8.8 Hz) was observed at d 3.66 due to
OCH3 protons attached to the phosphorus atom. A dou-
3
blet (3H, JP-H ¼ 8.3 Hz) was observed at d 3.27
assigned to the CH3 protons linked to the 3-N in the tri-
azaphosphole ring. The singlet due to the methylene
protons linked to the azide group present in the pmr
spectrum of 1 at d 4.73 ppm was absent in the spectrum
2
of 4a. Instead, a doublet (1H, JP-H ¼ 23.4 Hz) was dis-
played at d 5.16 due to 5-H (4a). Remarkably, the struc-
ture 4Aa (Scheme 1) cannot be overlooked since a weak
broad signal was displayed at 3339 cmꢂ1 in the IR spec-
trum assigned to an NH group; this signal appeared at d
11.42 (br) in its pmr spectrum. It is noteworthy that the
position of N-(H) hydrogen atom in triazoles such as
structure 4 has been the subject of contradictory discus-
sion [18] . Furthermore, the 31P-NMR chemical shifts;
the presence of 5-H as a doublet of high coupling con-
stant and 4’-H coumarin singlet, and the lack of a sin-
glet due to the methylene group in the pmr spectrum, as
well as the absence of the azido group in its ir spectrum,
1
bonyl group observed at 1685 cmꢂ1. In its H-NMR, the
protons of methylene group were observed downfield as
a singlet at d 5.37 ppm.
As depicted in Scheme 2, a 1,3-dipolar addition of
the azide 1 on the P¼¼C bond of the ylide 7a,b followed
by elimination of TPPO from the cyclic intermediate 9
afforded N-1-substituted-5-methyl (or 5-phenyl)-1,2,3-
triazoles 10a,b [19–23] . The formation of the triazoles
from treating 1 with 7a,b adequately demonstrates the
regiochemistry [23] of the reaction that leads to the
exclusive formation of 1,5- instead of 1,4-disubstituted
triazoles. Furthermore, the formation of 10 through ei-
ther a two step addition, via the intermediate 9, or a
confirm the assigned structures 4 4A and rule out
other alternative structures like 5 and 6.
Next, the study has been extended to investigate the
interaction of the azide compound 1 with three types of
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1260
A. A. Sediek, A. A. Shaddy, and W. M. Abdou
Vol 48
Scheme 2
Scheme 4
spectra, they showed the molecular ion peaks (Mþ %)
that displayed the expected fragmentations of the corre-
sponding spectrum. The most characteristic signals in
their 1H-NMR spectra are those of the methylene
concerted cycloaddition, via the transition state 9A, is
consistent with the observed result.
(CH2N3) and the methinic (¼¼CHY) protons, which
4
appeared as a doublet and a triplet each with JH-H
¼
In the contrary to the behavior of trialkyl phosphites
and a-keto ylides, the reactions of 1 with a-alkoxy car-
bonyl- and a-cyanomethylenetriphenylphosphoranes
(7c–e), performed under similar conditions, followed the
Wittig reaction, gave coumarin-azido-derivatives 11a–c
in ꢁ70% yields. Compounds 11a–c were obtained as Z-
isomers predominantly based of spectroscopic data and
due to steric demand of the transition states to form the
oxaphosphetane 9A (Scheme 3) [24–27] .
1.6 Hz at d 4.44–4.23 and 6.08–6.28, respectively. The
presence of (¼¼CHY) and (CH2N3) moieties were also
attested by signals at dc 112-98, and 55–52 ppm in 13C-
NMR spectra. These recorded data for the methine
(¼¼CH) and the methylene protons could readily elimi-
nate structure like 12, which would predict a doublet at
ꢀ3.5 and a triplet at ꢀ7.3 ppm.
Further extension of this study to other ylides,
application of methylidene- (8a) and benzylidene-triphe-
nylphosphorane (8b) to 1 was investigated. When dime-
thylformamide (DMF) solution of an equivalent amounts
of 1 and 8a, prepared in situ from its bromide salt 13a,
in the presence of aqueous LiOH was stirred at rt for 12
h, the reaction afforded the Wittig product 14a (80%),
on the basis of comparable spectroscopic arguments
(Scheme 4).
The spectroscopic data of compounds 11a-c are in
agreement with the assigned structure. In the EI mass
Scheme 3
On the other hand, the reaction of 1 with slight excess
(10%) of 8b (prepared in situ from its chloride salts,
13b) under the same conditions gave the benzylvinyl de-
rivative 15 (84%), which is an isomer of the Wittig
product 14b (Scheme 4).
In summary, the condensation of trialkyl phosphites
and alkylidenephosphoranes (resonance-stabilized- and
active ylides) with 3-azidoacetylcoumarin resulted in an
interesting spectrum of the reactivity. Furtherward, the
structural products (4a,b, 10a,b, 11a–c, 14a, and 15)
obtained from the four studied reactions, however, indi-
cated two positions in 1 that are susceptible to nucleo-
philic attack by the phosphorus reagents. The first
position relates to an attack at the azide group; this
addition was observed by trialkyl phosphites and a-keto
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

November 2011 A New Conjugated Addition of Trialkyl Phosphites and Alkylidenephosphoranes
1261
C13H12N3O5P (321.2): C, 48.61; H, 3.77; N, 13.08; P, 9.64.
Found: C, 48.68; H, 3.82; N, 13.15; P, 9.59.
ylides, which afforded, via 1:3-dipolar intermediates,
1,2,3,4-triazaphosphole and triazolylacetyl-coumarin
derivatives, respectively. The second site of attack is
concerned with the attack of the ylides 7c–e and 8a,b at
the acetyl carbonyl carbon group, which led to the re-
spective olefins.
3-[(4-Ethoxy-3-ethyl-4-oxido-4,5-dihydro-3H-1,2,3,4-triaza-
phosphol-5-yl)-carbonyl]-2H-chromen-2-one (4b) This was
obtained as yellow needles, 0.9 g (74%); mp 132–134ꢃC
(cyclohexane); IR: mmax NH 3384 (4Ab), 2C¼¼O 1722, 1638,
1
P¼¼O, free 1258, 1088 (PAOAC) cmꢂ1; H-NMR (DMSO6): d
Finally, the synthesized heterocyclic phosphole sys-
tem 4a,b that included a phosphorus linked to a nitrogen
atom are of great interest because this system is com-
1.03–1.31 (2dt (m), 6H, NC.CH3 and POC.CH3), 3.99 (dq,
3
3
3JH-H ¼ 6.4, JP-H ¼ 4.8 Hz, 2H, NCH2), 4.09 (dq, JH-H
¼
3
2
6.4, JP-H ¼ 4.8 Hz, 2H, POCH2), 5.09 (d, JP-H ¼ 23.4 Hz,
1H, 5-H, 4b), 7.35 (t, JH-H ¼ 7.4 Hz, 2H, 6’H and 7’H), 7.57
(d, JH-H ¼ 7.8 Hz, 2H, 5’H and 8’H), 8.64 (s, 1H, 4’H), 11.14
mon to
molecules.
a
diverse array of important biological
ppm (br, 1H, NH, 4Ab); 13C-NMR (DMSO6): d 177.6 (d, JP-
2
¼ 5.8 Hz, C¼¼O), 158.8 (C¼¼O, lactone), 154.7 (9’-C), 147.8
C
(4’C), 134.7, 130.6, 126.4, 118.3, 117.6 (7’-C, 8’-C, 5’-C, 6’-
1
3
C, 10’-C), 136 (d, JP-C ¼139 Hz, 5-C-P, 4Ab), 120.4 (d, JP-
EXPERIMENTAL
1
¼ 4.4 Hz, 3’-C), 67.4 (d, JP-C ¼ 144 Hz, 5-C-P), 62.5 (d,
C
2JP-C ¼ 7.5 Hz, POCH2), 44.1(d, JP-C ¼ 7 Hz, N-CH2), 19.6
2
General: Melting points were determined with open capil-
lary tube on an Electrothermal (variable heater) melting point
apparatus and were uncorrected. IR spectra were recorded on a
Perkin–Elmer spectrophotometer model 297 using KBr disc.
NMR spectra were measured with a JEOL E.C.A-500 MHz
3
3
(d, JP-C ¼ 5.8 Hz, POC.CH3), 14.4 ppm (d, JP-C ¼ 5.8 Hz,,
NAC.CH3); 31P-NMR (DMSO6): d 10.8 ppm; ms: m/z (ei):
351 [mþ þ 2, 26%], 349 (74) [mþ], 320 (17), 291 (37),
263(100), 252 (71), 227 (83), 213 (20), 188 (13), 173(53), 170
(15), 77 (18); Anal. Calcd. for C15H16N3O5P (349.3): C,
51.58; H, 4.62; N, 12.03; P, 8.87. Found: C, 51.65; H, 4.57;
N, 12.11; P, 8.91.
1
(13C: 125.7 MHz, H: 500 MHz, 31P: 202.4 MHz) spectrome-
ter. 31P-NMR spectra were recorded with H3PO4 (85%) as
external reference. 1H- and 13C-NMR spectra were recorded
with trimethylsilane as internal standard in CDCl3 or DMSO-
d6. Chemical shifts (d) are given in ppm. The mass spectra
were performed at 70 eV on an MS-50 Kratos (A.E.I.) spec-
trometer provided with a data system. The appropriate precau-
tions in handling moisture-sensitive compounds were observed.
Materials and reagents were purchased from Aldrich Company.
The substrate, 3-azidoacetycoumarin 1 was prepared according
to the reported method [15] .
Reaction of 1 withketomethylenetriphenyphosphorane-
s7a,b. Preparation of compounds 10a and 10b. A mixture of
azide 1 (0.8 g, 3.5 mmol) and acetyl- 7a (1.3 g, 3.5 mmol) or
benzoylmethylenetriphenylphosphorane (7b) (1.1 g, 3.5 mmol)
in 30 mL of dry tetrahydrofuran (THF) was stirred at rt for 24
h. After removing the solvent, the residue was chromato-
graphed on silica gel to afford the triazoles 10a or 10b. Tri-
phenylphosphine oxide (Ph3PO) was also isolated.
3-[(5-Methyl-1H-1,2,3-triazol-1-yl)acetyl]-2H-chromen-2-
one (10a). This was obtained as yellow crystals, 705 mg
(75%); mp 158–160ꢃC (MeCN); IR: mmax 2C¼¼O 1721, 1685
Reaction of 3-azidoacetylcoumarin (1) withtrialkylphos-
phites 2a,b. Preparation of compounds 4a and 4b. To a so-
lution of 0.8 g (3.5 mmol) of the azide 1 in 25 mL of absolute
CH2Cl2 at 0ꢃC, 3.5 mmol of freshly distilled trimethyl- 2a or
triethyl phosphite 2b were added dropwise with stirring. After
the addition was complete, the reaction mixture was stirred at
room temperature for 6 h, and the solvent was evaporated to
dryness. The residue was washed several times with light pe-
troleum (40–608C) and crystallized from the proper solvent to
give 4a or 4b, respectively.
cmꢂ1
;
1H-NMR (DMSO6): d 2.38 (d, JH-H ¼ 2.3 Hz, 3H, 5-
C.CH3), 5.37 (s, 2H, C(O)CH2), 7.34 (d, JH-H ¼ 7.4 Hz, 2H,
6’-H and 7’-H), 7.55 (d, JH-H ¼ 7.8 Hz, 2H, 5’-H and 8’-H),
7.58 (q, JH-H ¼ 2.3 Hz, 1H, 4-H), 8.65 ppm (s, 1H, 4’-H);
13C-NMR (DMSO6): d 187.4 (C¼¼O, acetyl), 161.2 (2’-C¼¼O),
154.7 (9’-C), 148.7 (4’-C), 142.8 (5-C), 138.3 (4-C), 134.3,
131.5, 126.4, 118.7, 114.2 (7’-C, 8’-C, 5’-C, 6’-C, 10’-C),
121.6 (3’-C), 53.8 (CH2, acetyl), 13.3 ppm (5-CACH3); ms:
m/z (EI): 270 (27) [Mþ þ 1], 269 (22) [Mþ], 254 (26), 237
(100), 188 (63), 172 (53), 170 (15), 145 (18), 77 (16). Anal.
Calcd. for C14H11N3O3 (269.3): C, 62.45; H, 4.12; N, 15.61.
Found: C, 62.52; H, 4.06; N, 15.64.
3-[(4-Methoxy-3-methyl-4-oxido-4,5-dihydro-3>H-1,2,3,4-
triazaphosphol-5-yl)-carbonyl]-2H-chomen-2-one (4a). This
was obtained as straw yellow needles, 863 mg (77%); mp
170–1728C (cyclohexane); IR: mmax NH 3339 (4Aa), 2C¼¼O
1
1722, 1633, P¼¼O, free 1265, 1055 (PAOAC) cmꢂ1; H-NMR
3
3
(DMSO6): d 3.27 (d, JP-H ¼ 8.3 Hz, 3H, NCH3), 3.66 (d, JP-H
3-[(5-Phenyl-1H-1,2,3-triazol-1-yl)acetyl]-2H-chromen-2-
one (10b). This was obtained as yellow crystals, 855 mg
2
¼ 8.8 Hz, 3H, POCH3), 5.16 (d, JP-H ¼ 23.4 Hz, 1H, 5-H, 4a),
(74%); mp 186–188ꢃC (MeCN); IR: mmax 2C¼¼O 1720, 1680
7.32 (t, JH-H ¼ 7.4 Hz, 2H, 6’-H and 7’-H), 7.52 (d, JH-H ¼ 7.8
Hz, 2H, 5’-H and 8’-H), 8.68 (s, 1H, 4’-H), 11.42 ppm (br, 1H,
1
m
ꢂ1; H-NMR (DMSO6): d 5.27 (s, 2H, C(O)CH2), 7.24–7.37
NH, 4Aa); 13C-NMR (DMSO6): d 177.4 (d, JP-C ¼ 5.8 Hz,
2
(m, 3H, H-Ph and H-Ar), 7.46–7.66 (m, 6H, H-Ph and H-Ar),
8.02 (s, 1H, 4-H), 8.53 ppm (s, 1H, 4’-H); 13C-NMR (DMSO6):
d 186.7, 160.4 (2C¼¼O), 154.7 (9’-C), 148.7 (4’-C), 142.8 (5-C),
)134.3 (4-C), 131.5, 130.5, 129.2, 126.4, 125.7, 123.6, 123.1,
122.6, 118.7, 114.2 (C-Ph and C-Ar), 121.6 (3’-C), 53.8 (CH2,
acetyl); ms: m/z (EI): 333 (36) [Mþ þ2], 331(100) [Mþ], 303
(92), 289 (78), 288 (51), (26), 237 (100), 188 (63), 172 (53), 170
(15), 145 (18), 77 (14). Anal. Calcd. for C19H13N3O3 (331.3): C,
68.88; H, 3.95; N, 12.68. Found: C, 68.85; H, 4.01; N, 12.62.
C¼¼O), 158.8 (C¼¼O, lactone), 153.3 (9’-C), 147.7 (4’C), 134.3,
131.5, 126.4, 118.7, 116.2 (7’-C, 8’C, 5’-C, 6’-C, 10’-C), 133
1
3
(d, JP-C ¼ 139 Hz, 5-C-P, 4Aa), 120.2 (d, JP-C ¼ 4.4 Hz, 3’-
1
2
C), 65.3 (d, JP-C ¼ 141 Hz, 5-C-P), 55.1 (d, JP-C ¼ 7.5 Hz,
POCH3), 28.8 ppm (d,2JP-C ¼ 7 Hz, N-CH3); 31P-NMR
(DMSO6): d 11.4 ppm; ms: m/z (EI): 323 [Mþ þ 2, 80 %], 321
[Mþ, 100%], 306 (16), 291 (31), 252 (83), 228 (33), 227 (24),
213 (19), 188 (18), 173(43), 170 (10), 77 (18). Anal. Calcd. for
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1262
A. A. Sediek, A. A. Shaddy, and W. M. Abdou
Vol 48
trated to 10 mL, diluted with 30 mL of dist H2O, acidified
with conc. HCl, and then extracted with two portions of ethyl
acetate. The AcOEt extracts were combined and washed with
50 mL of dist H2O and dried, and the solvents were evapo-
rated to dryness. The residue was purified by column chroma-
tography with n-hexane /AcOEt) as the eluents, whereupon
compounds 14a and 15, were obtained. Ph3PO was also
isolated.
Reaction of 1 with alkylidenetriphenyphosphoranes 7c–
e.Preparation of compounds 11a, 11b, and 11c. A mixture
of the azide 1 (0.8 g, 3.5 mmol) and 3.5 mmol of methoxycar-
bonyl- (7c), ethoxycarbonyl- (7d), or cyanomethylenetriphenyl-
phosphorane (7e) in 30 mL THF was stirred at r.t. for 24 h.
After removing the solvent, the residue was chromatographed
on silica gel to afford 11a, 11b, or 11c, respectively. Ph3PO
was also isolated.
Methyl (2Z)-4-azido-3-(2-oxo-2H-chromen-3-yl)but-2-enoate
(11a). This was obtained as yellow crystals, 657 mg (66%);
mp 165–167ꢃC (CHCl3); IR: mmax C-N3 2112, C¼¼O (lactone)
3-[1-(Azidomethyl)vinyl]-2H-chromen-2-one (14a). This was
obtained as yellow leaflets, 635 mg (80%); mp 173–175ꢃC (ac-
etone); IR: mmax CAN3 2106, C¼¼O (lactone) 1720, C¼¼C (exo-
1721, C¼¼O (ester)1713, C¼¼C (exocyclic) 1611 cmꢂ1
;
1H-
1
cyclic) 1618 cmꢂ1; H-NMR (DMSO6): d 4.02 (t, JH-H ¼ 2.2
4
NMR (DMSO6): d 3.73 (s, 3H, OCH3), 4.23 (d, JH-H ¼ 1.6
Hz, 2H, H2CN3), 5.45, 5.66 (2t(br), 2 ꢄ 1H, ¼¼CH2), 7.28 (t,
JH-H ¼ 7.4 Hz, 2H, 6’-H and 7’-H), 7.54 (d, JH-H ¼ 7.8 Hz,
2H, 5’-H and 8’-H), 8.43 ppm (s, 1H, 4’-H); 13C-NMR
(DMSO6): d 156.2 (2’-C¼¼O), 154.2 (9’-C), 139.7 (C¼¼CH2),
132.3, 129.5, 128.4, 126.4, 118.7, 117.2 (7’-C, 4’-C, 5’-C, 6’-
C, 8’-C, 10’-C), 120.4 (3’-C), 114.2 (C¼¼CH2), 60.2 ppm
(H2CAN3); ms: m/z (EI): 228 (11) [Mþþ1], 227 (16) [Mþ],
185 (44), 167 (48), 149 (100), 99 (65), 77 (28); Anal. Calcd
for C12H9N3O2 (227.2): C, 63.43; H, 3.99; N, 18.49. Found:
C, 63.51; H, 3.96; N, 18.43.
4
Hz, 2H, H2C-N3), 6.28 [t, JH-H ¼ 1.6 Hz, 1H, ¼¼CHC(O)],
7.34 (t, JH-H ¼ 7.4 Hz, 2H, 6’-H and 7’-H), 7.56 (d, JH-H
¼
7.8 Hz, 2H, 5’-H and 8’-H), 8.45 ppm (s, 1H, 4’-H); 13C-
NMR (DMSO6): d 162.5, 161.8 (2C¼¼O), 153.7 (9’-C), 146.7
(3’-CAC¼¼), 141.7 (4’-C), 133.3, 126.4, 125.6, 118.7, 114.2
(7’-C, 8’-C, 5’-C, 6’-C, 10’-C), 113.2 (3’-C), 112.8
[¼¼CHC(O)], 56.5 (H2C-N3), 52.6 ppm (OCH3, ester); ms: m/z
(EI): 286 (9) [Mþ þ 1], 285 (17) [Mþ], 254 (11), 243 (100),
225 (32), 198 (28), 171 (43), 170 (19), 142 (10), 114 (8).
Anal. Calcd for C14H11N3O4 (285.3): C, 58.95; H, 3.89; N,
14.73. Found: C, 59.01; H, 3.84; N, 14.67.
3-[(E,Z)-2-Azido-1-benzylvinyl]-2H-chromen-2-one (15).
This was obtained as yellow leaflets, 890 mg (84%); mp 198–
200ꢃC (CHCl3, mixture of isomers E and Z, 50:50); IR: mmax
CAN3 2108, C¼¼O (lactone) 1721, C¼¼C (exocyclic) 1617
Ethyl (2Z)-4-azido-3-(2-oxo-2H-chromen-3-yl)but-2-enoate
(11b). This was obtained as yellow leaflets, 710 mg (68%);
mp 128–130ꢃC (cyclohexane); IR: mmax N3 2102, C¼¼O (lac-
cmꢂ1
;
1H-NMR (DMSO6): E isomer: d 3.38 (d, 2H, JH-H
¼
tone) 1720, C¼¼O (ester) 1714, C¼¼C (exocyclic) 1608 cmꢂ1
;
2.1 Hz, CH2), 7.18 (t, JH-H ¼ 2.1 Hz, 1H, ¼¼CHN3), 7.24–7.38
(m, 3H, H-Ph and H-Ar, E, Z), 7.45–7.67 (m, 6H, H-Ph and
H-Ar, E, Z), 8.46, 8.54 ppm (2s, 2 ꢄ 1H, 4’-H, E, Z); Z iso-
mer: d 3.47 (d, 2H, JH-H ¼ 2.2 Hz, CH2), 7.23 (t, JH-H ¼ 2.2
Hz, 1H, ¼¼CHN3); ms: m/z (EI): 304 (13) [Mþþ1], 303 (21)
[Mþ], 275 (100), 256 (77), 210 (21), 149 (44), 137 (36), 111
(13), 77 (58); Anal. Calcd for C18H13N3O2 (303.3): C, 71.28;
H, 4.32; N, 13.85. Found: C, 71.33; H, 4.37; N, 13.90.
1H-NMR (DMSO6): d 1.23 (t, 3H, JH-H ¼ 6.8 Hz, OC.CH3),
4
4.08 (q, JH-H ¼ 6.8 Hz, 2H, OCH2, ester), 4.39 [d, 2H, JH-H
4
¼ 1.8 Hz, H2CAN], 6.08 [t, JH-H ¼ 1.8 Hz, 1H, ¼¼CHC(O)],
7.34 (t, JH-H ¼ 7.4 Hz, 2H, 6’-H and 7’-H), 7.56 (d, JH-H
¼
7.8 Hz, 2H, 5’-H and 8’-H), 8.42 ppm (s, 1H, 4’-H); 13C-
NMR (DMSO6): d 163.2, 162.6 (2C¼¼O), 152.8 (9’-C), 145.6
(3’-CAC¼¼), 140.1 (4’-C), 132.7, 127.1, 125.8, 118.8, 114.2
(7’-C, 8’-C, 5’-C, 6’-C, 10’-C), 113.7 (3’-C), 112.6
[¼¼CHC(O)], 62.6 (OCH2, 56.5 (H2CAN3), 15.6 ppm
(OC.CH3); ms: m/z (EI): 300 (11) [Mþþ1], 299 (22) [Mþ],
257 (100), 242 (18), 225 (35), 198 (25), 171 (16), 142 (10),
114 (8); Anal. Calcd for C15H13N3O4 (299.2): C, 60.20; H,
4.38; N, 14.04. Found: C, 60.27; H, 4.43; N, 14.13.
Acknowledgment. Financial support from the Egyptian Acad-
emy of Scientific Research and Technology is gratefully
acknowledged.
(2Z)-4-Azido-3-(2-oxo-2H-chromen-3-yl)but-2-enenitrile
(11c). This was obtained as yellow leaflets, 669 mg (76%); mp
148–150ꢃC (EtOH); IR: mmax CN 2216, N3 2102, C¼¼O (lac-
REFERENCES AND NOTES
1
tone) 1721, C¼¼C (exocyclic) 1607 cmꢂ1; H-NMR (DMSO6):
[1] Chimenti, F.; Bolasco, A.; Secci, D.; Bizzarri, B.; Chimenti,
P.; Granese, A.; Carradori, S.; Bishay, D. W.; Sayyed, S. M.; Abd El-
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4
4
d 4.44 (d, JH-H ¼ 2.1 Hz, 2H, H2C-N3), 6.26 (t, JH-H ¼ 2.1
Hz, 1H, ¼¼CHCN), 7.33 (t, JH-H ¼ 7.4 Hz, 2H, 6’-H and 7’-
H), 7.55 (d, JH-H ¼ 7.8 Hz, 2H, 5’-H and 8’-H), 8.45 ppm (s,
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114.2 (7’-C, 8’-C, 5’-C, 6’-C, 10’-C), 120.4 (3’-C), 115.6
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(11) [Mþþ1], 252 (16) [Mþ], 224 (77), 210 (48), 197 (100),
169 (85), 140 (42), 114 (13); Anal. Calcd for C13H8N4O2
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