Further insight into the reactivity of oxazinones toward phosphorus reagents

Article abstract of DOI:10.1081/SCC-200036592

A series of quinoline derivates has been obtained from the reaction of 3-phenyl-2,4-benzoxazin-1-one (1) with alkylidenephosphoranes. With ester ylides 3a,b, the reaction affords hydroxyquinolines 8a,b and new stable phosphorus ylide 9, whereas with keto ylides 3c,d, quinolinones 12a,b, hydroxyindoles 10a,b and benzoazepines 14a,b are obtained. 1 reacts with allyl-4, methyl-5a and ethyltriphenylphosphonium bromides 5b in the presence of LiH to afford 2-hydrophenyloxazolo[1,2-a]-4-hydroxyquinoline (16) from the first reaction whereas alkoxyquinolines 21a,b and hydroxyazepines 22a,b are obtained from 5a,b.

Full text of DOI:10.1081/SCC-200036592

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Further Insight into the
Reactivity of Oxazinones
Toward Phosphorus Reagents
Wafaa M. Abdou a , Azza A. Kamel a & Maha D.
Khidre a
a Department of Pesticide Chemistry , National
Research Centre , Dokki, D‐12622, Cairo, Egypt
Published online: 10 Jan 2011.
To cite this article: Wafaa M. Abdou , Azza A. Kamel & Maha D. Khidre (2004)
Further Insight into the Reactivity of Oxazinones Toward Phosphorus Reagents,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 34:22, 4119-4134, DOI: 10.1081/SCC-200036592
To link to this article: http://dx.doi.org/10.1081/SCC-200036592
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 22, pp. 4119–4134, 2004
Further Insight into the Reactivity of
Oxazinones Toward Phosphorus Reagents
*
Wafaa M. Abdou, Azza A. Kamel, and Maha D. Khidre
Department of Pesticide Chemistry, National Research Centre,
Dokki, Cairo, Egypt
ABSTRACT
A series of quinoline derivates has been obtained from the reaction of
3-phenyl-2,4-benzoxazin-1-one (1) with alkylidenephosphoranes. With
ester ylides 3a,b, the reaction affords hydroxyquinolines 8a,b and new
stable phosphorus ylide 9, whereas with keto ylides 3c,d, quinolinones
12a,b, hydroxyindoles 10a,b and benzoazepines 14a,b are obtained.
1 reacts with allyl-4, methyl-5a and ethyltriphenylphosphonium bromides
5b in the presence of LiH to afford 2-hydrophenyloxazolo[1,2-a]-
4-hydroxyquinoline (16) from the first reaction whereas alkoxyquinolines
21a,b and hydroxyazepines 22a,b are obtained from 5a,b.
Key Words: 2,4-Oxazin-1-one; Quinolines; Azepines; Resonance-
stabilized; Unsaturated and active alkylidenephosphoranes; Intramole-
cular Wittig reaction.
*
Correspondence: Wafaa M. Abdou, Department of Pesticide Chemistry, National
Research Centre, Dokki D-12622, Cairo, Egypt; E-mail: wabdou@intouch.com.
4119
DOI: 10.1081/SCC-200036592
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

4120
Abdou, Kamel, and Khidre
INTRODUCTION
2,4-[1,2], and 2,3-benzoxazinones[3,4] have been shown to be versatile syn-
thons for introducing nucleophilic amine substituent into heterocyclic nucleus
and preparing new pyrimidine derivatives. Subsequently, we reported that
4-(4-methylphenyl)-2,3-benzoxazin-1-one (2) undergoes an insertion reaction
when exposed to phosphonium ylides giving isoquinolines as the major pro-
ducts.[5] In contrast, ring contraction was observed when 2 or the structurally
related, 3-phenyl-2,4-benzoxain-1-one (1) was allowed to react with trialkyl
phosphites, yielding phosphono substituted-isoindoles (or indoles).[6] These
intriguing transformations led us to apply ylide chemistry to 2,4-benzoxazi-
none 1, available from heating the benzoylanthranilic acid in excess acetic
anhydride.[1b] Furthermore, new quinoline-or indole chemistry would be of
potential interest to biochemistry and pharmaceutical chemistry.
RESULTS AND DISCUSSION
2,4-Benzoxazin-1-one 1 on treatment with one equivalent of methoxycar-
bonylmethylenetriphenylphosphorane (3a) in refluxing toluene, the reaction
was very slow and has been accelerated by using a catalytic amount of
benzoic acid as a protonating catalyst in the reaction medium. The success
of this procedure is attributable to the protonation of the carbonyl group,
making it more electrophilic and, therefore, more susceptible to nucleophilic
attack by the ylide 3. The product mixture was then subjected to column
chromatography to give methyl 4-hydroxy-2-phenylquinoline-3-carboxylate

Reactivity of Oxazinones Toward Phosphorus Reagents
4121
(8a, 44%) and the phosphonium ylide 9 (28%). Hydroxyquinoline 8a was
identical in all aspects with material previously obtained from the reaction
of 2-[(benzylidene)amino]benzonitrile with ester ylide 3a.[7] A similar treat-
ment of 1 with ethoxy analogue 3b gave the ylide 9 (24%) together with
the known[7,8] hydroxyquinoline 8b (40%) (Scheme 1). Product 9 exhibited
a carbonyl band (C(4)55O) at 1740 cm21 in its IR spectrum, compared to
1680 cm21 for the corresponding band (C(1)55O) in 1.[2b] Other bands
appeared at 1655 cm21(C(2)55O), 1635 cm21 (N-COPh) and at 1556 cm21
(C55P). Its 13C NMR spectrum displayed a signal, among others, at d 134.2
attributed to C-P-ipso. The phosphonium ylide 9 failed to undergo the
Wittig reaction with aldehydes and was not affected by refluxing with
alcoholic potassium hydroxide solution. This latter behavior is inconsistent
Scheme 1.

4122
Abdou, Kamel, and Khidre
with the behavior of phosphonium ylide derived from 2,3-benzoxazinone 2
and benzoylmethylenetriphenylphosphorane (3d).[5] This presumably reflects
the extra stabilization (compared to 3) afforded by the other two carbonyl
groups and the conjugation possible in the resonance forms.[9] Accordingly,
its 31P NMR spectrum has positive chemical shift at dP ¼ 24.64 ppm
(vs. 85% H3PO4), which indicates a high contribution of the zwitterionic phos-
phorus betaine structure.[10]
A reasonable mechanism of condensation of 1 with ester ylides 3a,b
involves an initial attack[1–5] of the ylide carbon in 3a or 3b onto the
C(1)55O group, with subsequent ring opening of 1 to afford 7a,b via the inter-
mediates 6. Under thermal conditions and in the presence of a protonating
agent the zwitterion 7 is presumably formed. Further intramolecular Wittig
reaction and prototropic rearrangement produce the products 8a,b, with
concomitant elimination of triphenylphosphine oxide. On the other hand,
rearrangement of 7a,b to 7Aa,b followed by intramolecular cyclization
would lead to the final ylide 9 accompanied with the loss of the appropriate
alcohol moiety (Scheme 1).
By treatment of 1 with 2 equiv. of acetonyl- (3c) or benzoylmethylenetri-
phenylphosphorane (3d) in a way analogous to that described for 3a,b, a
mixture of 10a, 12a, and 14a (or 10b, 12b, and 14b) was obtained. Com-
pounds 10, 12, and 14 were obtained in essentially the same ratio regardless
whether 1 or 2 equivalents of 3c,d were used.
The structure of 2-acetyl-3-methyl-5-hydroxy-N-benzoylbenzoazepine
1
has been assigned to 14a (20%) on the base of analytical, IR, H, and 13C
NMR and mass spectral data. The seven membered heterocycle is well
supported by the presence in the 13C NMR spectrum of the signals 18.9
(3-C-CH3), 26.7 (2-C-COCH3), 141.5 (2-C-COCH3), 158.6 (5-C-OH) and
206.3 (C(O)Me). Also for N-benzoyl-2-methyl-4-oxo-quinoline (12a, 32%),
and N-benzoyl-2-acetyl-3-hydroxyindole (10a, 18%) analytical and spectral
data are consistent with the given structures (cf. Tables 1–3). Fused
substituted-azepines had been previously[5] observed through the reaction of
2 with 3c. Obviously, the expected zwitterion intermediates 7c,d initially
formed give, by electrocyclic ring closure and proton rearrangement, either
to 10a and 10b via elimination of triphenylphosphine (Scheme 2, i), or to
12a and 12b via extrusion of triphenylphosphine oxide (Scheme 2, ii).[11]
On the other hand, the formation of the azepines 14a and 14b is readily
explained if it is proposed that the anionic intermediates 7c,d undergo
Wittig olefination with a second ylide species 3c (or 3d) to give 13, which
leads to 14a (or 14b) via elimination of Ph3P and prototropic rearrangement
(Scheme 2, iii).
When a mixture of compound 1 and allyltriphenylphosphonium bromide
(4) in dimethylformamide (DMF) was treated with lithium hydride (LiH), the

Reactivity of Oxazinones Toward Phosphorus Reagents
4123
Table 1. Physical properties and IR spectra for products 9, 10a,b, 12a,b, 14a,b, 16,
21a,b, and 22a,b.
Product/
color
R1/R2
Mp (8C)/solvent
.300/AcOEt
Yield (%)
IR (KBr), n cm21
9/brown
—
ꢀ26
1740 (C(4)55O),
1655 (C(2)55O),
1635 (N-C55O),
1556 (C55P).
3350 (OH),
10a/orange R1 ¼ Me 132–134/
18
24
CHCl3 : CH2Cl2
(1 : 1, v/v)
172–174/acetone
1658 (C(O)Me),
1630 (C(O)Ph).
3355 (OH), 1660,
1632
10b/orange R1 ¼ Ph
(2 ꢀ C(O)Ph).
1738 (C(4)55O),
1625 (C(O)Ph).
1735 (C(4)55O),
1630 (C(O)Ph).
3355 (C(5)OH),
1658 (C(O)Me),
1640 (C(O)Ph).
3333 (C(5)OH),
1658,
12a/pale
yellow
R1 ¼ Me 109–111/cyclohexane
32
29
20
12b/pale
yellow
R1 ¼ Ph
131–132/CH2Cl2
14a/yellow R1 ¼ Me 164–166/EtOH
14b/brown
R1 ¼ Ph
184–186/EtOH
13
1640
(2 ꢀ C(O)Ph).
3442 (OH).
16/yellow
—
190–192/EtOH
96–98/ether
52
33
37
36
21a/yellow R2 ¼ H
1585 (C55N).
1585 (C55N).
3448, 3356 (OH
and NH).
21b/yellow R2 ¼ Me 84–86/pentane
22a/pale
yellow
R2 ¼ H
R2 ¼ Me 245–247/MeCN
170–172/MeCN
22b/pale
yellow
40
3455, 3348 (OH
and NH).
aSee the experimental section for further details.
unexpected 1-hydro-2-phenyloxazolo[1,2-a]-6-hydroxyquinoline (16) (52%)
was isolated according to Scheme 3. As with the reaction between 1 and 3,
addition of allyl ylide at C(1) position of 1 and ring opening followed
by cycloelimination sequence affords the product 16. A similar approach
is known[12] for the reaction of isatoic anhydride with carbanions. The
mechanism of this reaction as well as further reactions with similar oxazinones
is still under consideration.

4124
Abdou, Kamel, and Khidre

Reactivity of Oxazinones Toward Phosphorus Reagents
4125

4126
Abdou, Kamel, and Khidre

Reactivity of Oxazinones Toward Phosphorus Reagents
4127
Table 3. NMRa spectral data for products 9, 10a,b, 12a,b, 14a,b, 16, 21a,b and 22a,b.
Cmpd
1H NMR (CDCl3), d (ppm)
7.12–8.21 (m, H-Ph).
13C NMR (CDCl3), d (ppm)
9b
121.3, 124.5, 124.7, 126.4, 127.2,
127.9, 129.1, 129.6, 131.5,
132.2 (C55C, Ph), 134.2
(d, 1JCP ¼ 104, 3-C-P, ipso),
172.8 (C(1)55O), 183.3 (C55O,
benzoyl).
10a
2.44 (s, 3H, C(O)CH3), 7.24–7.83
(m, 9H, H-Ph), 11.85 (s, 1H, OH,
D2O - exchang.).
26.8 (COCH3), 120.6, 121.5,
122.6, 122.8, 124.3, 124.6,
131.79, 133.2 (C55C, Phc),
127.9 (C-9), 136.3 (2-C), 148.9
(8-C), 154.5 (3-C-OH), 187.2
(C(O)Ph), 202.8 (C(O)Me).
134.3 (2-C), 156.7 (3-C), 174.7,
181.3 (2 ꢀ C(O)Ph).
10b
12a
7.23–8.18 (m, 14H, H-Ph), 11.95
(s, 1H, OH, D2O - exchang.).
2.14 (s, 3H, 2-C-CH3), 6.38 (s, 1H,
3-CH), 7.22–8.15 (m, 9H, H-Ph).
19.2 (CH3), 133.7 (3-C), 143.1
(2-C), 172.4 (4-C55O)), 176.2
(C(O)Ph).
12b
14a
6.27 (s, 1H, 3-CH), 7.09–8.19
(m, 14H, H-Ph).
131.0 (3-C), 147.1 (2-C), 168.2
(4-C55O), 178.2 (C(O)Ph).
18.9 (3-C-CH3), 26.7 (C(O)CH3),
116.7 (4-C), 141.5 (2-C), 158.1
(5-C-OH), 175.6 (C(O)Ph),
206.3 (C(O)CH3).
2.13, 2.25 (2s, 2 ꢀ 3H, 2 ꢀ CH3),
6.18 (s, 1H, 4-CH), 7.25–7.88
(m, 9H, H-Ph), 14.82 (s (br), 1H,
5-C-OH, D2O - exchang.).
14b
16
6.11 (s, 1H, 4-CH), 6.97–8.27
(m, 19H, H-Ph), 14.82 (s (br), 1H,
5-C-OH, D2O - exchang.).
113.2 (4-C), 141.6 (2-C), 156.2
(5-C-OH), 172.7, 178.8
(2 ꢀ C(O)Ph).
4.22 (2-C-H), 6.26 (s, 1H, 4-CH),
6.55 (s, 1H, 5-CH), 7.27–7.87
(m, 9H, H-Ph), 14.82 (s (br), 1H,
6-C-OH, D2O - exchang.).
51.5 (2-C0), 114.6 (5-C), 120.2,
121.1, 122.4, 122.8, 124.5,
124.2, 133.2, 133.7 (C55C, Ph),
144.8 (4-C0), 153.6 (50-C),
158.6 (6-C).
21a
3.72 (s, 3H, OCH3), 6.31 (s, 1H,
3-CH), 7.18–7.82 (m, 9H, H-Ph).
54.7 (OCH3), 111.4 (3-C), 119.8,
121.2, 122.3, 122.8, 124.6,
126.4, 132.4, 133.4 (C55C, Ph),
127.6 (10-C), 149.4 (9-C),
154.7 (2-C), 158.3 (4-C).
(continued)

4128
Abdou, Kamel, and Khidre
Table 3. Continued.
Cmpd
1H NMR (CDCl3), d (ppm)
13C NMR (CDCl3), d (ppm)
21b
0.99 (t, 3H, JHH ¼ 6.8, OC.CH3),
2.16 (s, 3H, 3-C-CH3), 4.08
(q, 2H, JHH ¼ 6.8, OCH2), 7.24–
8.18 (m, 9H, H-Ph).
16.7, 18.3 (2 ꢀ CH3), 60.8
(OCH2), 120.1, 121.1, 122.5,
122.8, 124.6, 126.1, 131.5,
133.4 (C55C, Ph), 127.9 (10-C),
129.1 (3-C), 149.2 (9-C), 152.6
(2-C), 157.2 (4-C).
22a
22b
7.36–8.26 (m, 11H, H-Ph & H-
Het), 9.66, 11.89 (2s (br),
2 ꢀ 1H, NH & OH).
110.8 (4-C), 118.3 (3-C), 119.7,
120.1, 121.5, 122.2, 124.3,
126.4, 132.5, 133.2 (C55C, Ph),
127.9 (C-11), 135.5 (2-C),
139.6 (10-C), 158.5 (5-C).
14.6, 18.2 (2 ꢀ CH3), 119.9,
120.8, 121.7, 122.4, 124.3,
126.6, 132.58, 133.3 (C55C,
Ph), 128.5 (4-C), 131.5 (3-C),
135.8 (2-C), 139.1 (10-C),
156.1 (5-C).
1.98, 2.14 (2s, 2 ꢀ 3H, 3-C & 4-C-
CH3), 7.27–8.01 (m, 9H, H-Ph),
9.66, 11.89 (2s (br), 2 ꢀ 1H, NH
& OH, D2O - exchang.).
aSee the experimental section for further details.
b31P NMR (CDCl3): dP 24.64 ppm.
cdC Compounds 10b, 12a,b, and 14a,b showed signals for (C55C, Ph), almost as com-
pound 10a.
Finally, the reaction of 1 with 2 equiv. of methyl- (5a) and ethyltriphenyl-
phosphonium bromide (5b) in DMF containing LiH afforded hydroxybenzoa-
zepines 22a,b (ꢀ38%) together with alkoxyquinolines 21a,b (ꢀ35%). Wittig
olefination of the initially formed 17a (or 17b) by a second phosphorus species
afforded the ylides 18a (or 18b). An electrocyclic ring closure of 18 afforded
19, which by subsequent formation of an oxirane 20 (and loss of Ph3P) and
proton migration could account for the formation of 21a,b. A parallel mech-
anism has been suggested,[5] by one of the referees, for similar alkoxyisoqui-
noline derivatives were obtained previously by treatment of 2,3-oxazinone 2
with salts 5a,b. Compounds 22a,b could reasonably be formed from 18 by
a cycloelimination reaction[5] (Scheme 4).
In summary, the present and the previous studies[5,6] have demonstrated a
range of reactivity of oxazinones 1 and 2 toward different types of phosphorus
ylides 5 as well as toward trialkyl phosphites and dialkyl phosphonates. The
divergent pathways have led to the construction of a variety of 5-, 6-, and
7-N-heterocycles, related to biologically active compounds based on the
known drug skeletons.

Reactivity of Oxazinones Toward Phosphorus Reagents
4129
Scheme 2.
EXPERIMENTAL
The melting points are uncorrected. The IR spectra were recorded on
a Perkin–Elmer spectrophotometer model 297 (Grating) using KBr discs.
1
The H and 13C NMR spectra were run in CDCl3 or d6-DMSO as solvents
on a Jeol-270 MHz instrument, using SiMe4 as an internal reference. The
31P NMR spectra were recorded relative to external H3PO4 (85%) with a
Varian CFT-20 instrument. The mass spectra were performed at 70 eV

4130
Abdou, Kamel, and Khidre
Scheme 3.
on a Shimadzu GCS-QP 1000 EX spectrometer provided with a data system.
The appropriate precautions in handling moisture-sensitive compounds were
observed. Solvents were dried by standard techniques. Light petroleum
refers to the fraction 40–608C.
Reaction of 3-Phenyl-2,4-benzoxazin-1-one (1) with
Ester Ylides 3a and 3b
(A) Preparation of Compounds 8a, 8b, and 9
A stirred solution of 1 g (4.48 mmol) of 1 and 5.8 mmol alkoxycarbonyl-
methylenetriphenylphosphorane 3a or 3b in 30 mL toluene containing 0.2 g
benzoic acid was heated under reflux for 55 hr. The volatile materials were
evaporated under reduced pressure and the residue was separated by column
chromatography on silica gel. Elution with n-hexane/CHCl3 (4:6, v/v)
yielded 4-hydroxyquinolines 8a or 8b.
Methyl 4-hydroxy-2-phenylquinoline-3-carboxylate (8a) was obtained
as pale yellow crystals (550 mg, 44%), mp 275–2778C from EtOH (Lit.[7]
m.p. 276–2788C).
,
Ethyl 4-hydroxy-2-phenylquinoline-3-carboxylate (8b) was obtained
as pale yellow needles (524 mg, 40%), mp 260–2618C from MeCN
(Lit.[7,8], m.p. 260–2628C).
Elution with n-hexane/CHCl3 (2:8, v/v) yielded the phosphonium ylide
9. Percentage yield, physical, and spectral data are listed in the Tables 1–3.

Reactivity of Oxazinones Toward Phosphorus Reagents
4131
Scheme 4.
(B) Attempted Reaction of 9 with Aldehydes
The reaction of 9 with benzaldehyde and p-chlorobenzaldehyde was
investigated in dioxane and ethyl acetate at reflux temperatures for periods
as long as 48 hr. In all cases the starting material was recovered.
(C) Attempted Hydrolysis of 9
A mixture of 0.3 g of 9 and 20 mL alcoholic KOH (10%, aqu.) was heated
under reflux for 15 hr. The mixture was concentrated to its half, to give 216 mg

4132
Abdou, Kamel, and Khidre
(72%) of brown needles, shown to be identical with 9 (TLC, IR, and MS
spectra).
Reaction of 1 with Keto Ylides 3c,d
Preparation of Compounds 10a,b, 12a,b, and 14a,b
A solution of 8.96 mmol of acetylmethylenetriphenylphosphorane (3c) or
benzoylmethylenetriphenylphosphorane (3d) and 1 g (4.48 mmol) of 1 in
30mL toluene containing 0.2 g of benzoic acid was refluxed for 3 days. The
product mixture was worked up as described for the reactions of 3a,b. Further
separation by column chromatography using n-hexane-AcOEt yielded com-
pounds 12a (or 12b) (7:3, v/v), 10a (or 10b) (4:6, v/v), and 14a (or 14b) (3:7,
v/v) (cf. Tables 1–3). The reaction between equimolar amounts of 1 and 3c
(or 3d) under the same reaction conditions again afforded 12a (or 12b)
(ꢀ20%), 10a (or 10b) (ꢀ15%), and 14a (or 14b) (ꢀ13%) along with 1 (18%).
Reaction of 1 with Unsaturated Ylide 4
Preparation of Compound 16
To a slurry of 0.5 g LiH dispersion (60% in mineral oil) in 15 mL DMF
was added slowly 1 g (4.48 mmol) of 1 in 20 mL DMF. The reaction
mixture was stirred at r.t. until all hydrogen evolution had ceased (ꢀ1 hr),
and a solution of 1.7 g (4.5 mmol) of allyltriphenylphosphonium bromide
(4) in 15 mL DMF was added in one portion. The resulting mixture was
stirred at r.t. for 2 hr and then refluxed up. After the consumption of the start-
ing oxazinone (ꢀ16 hr) the reaction mixture was poured onto 400 mL of water
and extracted with two 200-mL portions of CHCl3 (2 ꢀ 100 mL). The com-
bined organic extracts were backwashed with 100 mL H2O, dried, and the
solvent was removed under reduced pressure. The residue was chromato-
graphed on silica gel, gradient eluting from 20% to 50% AcOEt in n-
hexane, yielded 16 (1:1, v/v) (cf. Tables 1–3).
Reaction of 1 with Phosphonium Bromides 5a,b
Preparation of 21a,b, and 22a,b
A solution of the appropriate salt 5a (3 g, 8.96 mmol) or 5b (3.2 g,
8.96 mmol) and 1 g (4.48 mmol) of 1 in 30 mL DMF was treated with 0.5 g

Reactivity of Oxazinones Toward Phosphorus Reagents
4133
(12 mmol) LiH in 10 mL DMF for 2 hr at r. t. and then was heated for 18 hr.
The mixture was worked up as described for the reaction of 4 and separated
by column chromatography using n-hexane-AcOEt to give products 21a,
21b (7:3, v/v) and 22a, 22b (4:6, v/v) (cf. Tables 1–3). The reaction
between equimolar amounts of 1 and 5a (or 5b) under the same reaction con-
ditions, again afforded 21a (or 21b) (ꢀ17%) and 22a (or 22b) (ꢀ24%) along
with 1 (ꢀ23%).
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benzoxazones). Preparation: reactions with water, ammonia, and
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Salvadori, G. Studies on the hydrolysis of 3,1-benzoxazin-4-ones.
J. Chem. Soc. B. 1971, 1105; (c) Mahmoud, M.M.; El-Hashash, M.A.
Some reactions with 4H-3,1-benzoxazin-4-one and some studies on the
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3,1-benzoxazin-4-one, 6-bromo-2-methyl-4H-3,1-benzoxazin-4-one and
2-benzyl-3-phenyl-4(3H)-quinazolinone. Egypt. J. Chem. 1979, 2, 115;
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Received in the UK April 21, 2004