Journal of the Korean Chemical Society

2010, Vol. 54, No. 4

Printed in the Republic of Korea
DOI 10.5012/jkcs.2010.54.4.437

[1,3] Oxazine 유도체 합성을 위한 효율적인 One-Pot 합성

Suryakant B. Sapkal, Kiran F. Shelke, Bapurao B. Shingate, and Murlidhar S. Shingare*
Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad-431004, M.S. India
(접수 2010. 3. 23; 수정 2010. 5. 4; 게재확정 2010. 5. 12)

An Efficient One-Pot Strategies for the Synthesis of [1,3] Oxazine Derivatives

Suryakant B. Sapkal, Kiran F. Shelke, Bapurao B. Shingate, and Murlidhar S. Shingare*
Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad-431004, M.S. India
*
E-mail: prof_msshingare@rediffmail.com
(Received March 23, 2010; Revised May 4, 2010; Accepted May 12, 2010)

요약. 수용액 속에서 NaHSO4, TBAB (phase transfer catalyst), ionic liquid (IL) (1-butyl-3-methyl imidazolium hydrogen sul-
phate [bmim]HSO4)를 사용하여, formalin, β-naphthol, aromatic amines을 반응시켜서 대응하는 2,3-dihydro-2-phenyl-1H-
naphtho-[1,2-e] [1,3] oxazine 유도체를 합성할 수 있는 보다 친환경적이고, 수율이 좋고, 크로마토그래피 분리 방법을 사용하
지 않는 합성 방법을 개발하였다.
주제어: [1,3] Oxazine 유도체, One-pot 전략, Cyclocondensation, Ionic liquid, Grinding

ABSTRACT. Sodium hydrogen sulphate (NaHSO4), n-tetra butyl ammonium bromide (TBAB) as a phase transfer catalyst
(PTC) in water, and 1-butyl-3-methyl imidazolium hydrogen sulphate [bmim]HSO4 as ionic liquid (IL) has been used as a mild
reaction promoter for the cyclocondensation of formalin, β-naphthol and aromatic amines to afford respective 2,3-dihydro-2-
phenyl-1H-naphtho-[1,2-e] [1,3] oxazine derivatives. The present protocols are greener, high yielding and involved the non-
chromatographic isolation procedure.
Keywords: [1,3] Oxazine derivatives, One-pot strategies, Cyclocondensation, Ionic liquid, Grinding

INTRODUCTION intermediates as well as in the synthesis of various drug

sources, reported in a few classical methods using dry me-
Heterocyclic compounds occur very widely in nature and thanolic ammonia,10 ammonium acetate,11 Cu(OAc)2/ZnCl2,12
are essential to the human life. Among a large variety of under basic condition,13 Au(I) complex,14 2-azadienes with
heterocyclic compounds, 1,3-oxazine containing moiety alkynes,15 Bu4NF/EtI,16 and p-TsCl, DMAP/CH2Cl2.17 But,
possesses wide synthetic utility as a useful intermediate for there have only been a few reports for the synthesis of 2,3-
the variety of functional group interconversions.1-3 Recently, dihydro-2-phenyl-1H-naphtho-[1,2-e] [1,3] oxazine deri-
1,3-oxazine ring system has been used for the photo induced vatives from formalin, 2-naphthol and aromatic amines.18
opening and thermal closing.4 Furthermore, they can be used However, most of the reactions require exotic reaction con-
as intermediates in the synthesis of N-substituted amino dition, low product yield, longer reaction time and tedious
alcohols (Betti base) or in enantioselective synthesis of chiral work-up procedure. Therefore in search of better alternatives,
amines.5 we have paid attention to find a convenient and efficient
In recent years, 1,3-oxazine heterocycles have been evalu- methods on the basis of green approach over reported methods
ated for the varied biological properties such as analgesic, for the synthesis of [1,3] oxazine derivatives.
anticonvulsant, antitubercular, antibacterial, anticancer acti- The best tools used to combine economic aspects with the
vity6 and shows high activity against a variety of HIV-1 environmental ones is the multicomponent reaction strategy;
mutant strain.7 In addition, naphthoxazine derivatives have this process consists of only one synthetic step which is
exhibited therapeutic potential for the treatment of Parkin- carried out without isolating of any intermediate, this reduces
son’s disease.8 The tautomeric character of 1,3-O,N-hetero- time and saving money, energy and raw materials.19 Now a
cycles offers a great number of synthetic possibilities.9 day’s chemist has attracted much attention toward the green
Realizing the importance of 1,3-oxazine derivatives as an and clean approach whilst using non-toxic reagents, solvents

-437-
438 Suryakant B. Sapkal, Kiran F. Shelke, Bapurao B. Shingate, and Murlidhar S. Shingare

and catalysts.20 Therefore, we would like to perform some evaporator. The solid obtained was crystallized from ethanol
of the safer processes such as, use of ionic liquid, use of to get pure product.
phase transfer catalyst in water and grinding for the preferred Method B. A mixture of formalin (2 mmol), aromatic
reaction. amine (1 mmol), 2-naphthol and PTC (0.5 mmol) was stirred
One of the alternatives for organic solvents under inves- in water (10 mL) at room temperature upto the completion
tigation in organic transformations is an ionic liquid.21 The of reaction as monitored by TLC for appropriate time period.
use of ionic liquids as a solvent as well as catalyst is surpri- After completion of the reaction, further procedure was per-
singly effective because of non-inflammability, high tempera- formed as per method A.
ture tolerance, high solubility, non-volatile nature, negligible Method C. A mixture of formalin (2 mmol), aromatic
vapour pressure, recovery and reusability. In continuation amine (1 mmol), 2-naphthol and NaHSO4 (3 mmol) was
of our work on IL in search of benign methods for the syn- ground by pestle and mortar at room temperature for speci-
thesis of various organic compounds,22 herein, we would fied period of time as mentioned in Table 4. After comple-
like to report for first time, the selective and rapid synthesis tion of reaction, as monitored by TLC, the reaction mixture
of 1,3-oxazine derivatives in the presence of [bmim]HSO4 was poured on cold water. The solid thus obtained was fil-
acidic ionic liquid. On the other side of this method, one tered, dried and crystallized in ethanol to get pure product.
ideal alternative under examination as a greener solvent for
organic reaction is water.23 The use of water as a solvent/ Spectroscopic data of the products
reaction media is often surprisingly effective because of low 2,3-Dihydro-2-m-tolyl-1H-naphtho-[1,2-e][1,3] oxazine
cost, easy availability in abundant quantity, non-inflamm- (4c): IR (KBr, υmax/cm-1) 1029 (sym. C-O-C), 1231 (asym.
ability, non-toxic, ecofriendly, and easy product isolation C-O-C); 1H NMR (DMSO-d6, 400 MHz, δ ppm) 2.20 (q, 3H,
when product is solid. The introduction of PTC to the re- Ar-CH3), 4.90 (s, 2H, Ar-CH2-N-), 5.60 (s, 2H, -O-CH2-N-),
action in water has developed synthetic methodology and 6.70-7.80 (m, 10H, Ar-H); 13C NMR (DMSO-d6, 75 MHz,
made progress in approaching green chemistry. As far as δ ppm) 20.2, 50.1, 79.1, 113.2, 116.1, 117.4, 119.2, 120.5,
we know, PTC is widely used in chemical reaction since it 124.7, 125.8, 126.1, 126.8, 127.9, 129.7, 130.4, 147.2, 148.1,
offers high yield with reduced cycle time, reduced or non 149.2, 150.4; MS: m/z 276.2 (m+1); Elemental analysis:
added solvent, mild reaction condition, enhanced environ- C19H17NO Calcd.: C: 82.88%; H: 6.22%; N: 5.09%; Found:
mental performance and sometime better selectivity.24 C: 82.71%, H: 6.29%, N: 5.06%.
Furthermore, the solid state reaction by grinding has many 2,3-Dihydro-2-(3-methoxyphenyl)-1H-naphtho[1,2-e]
advantages such as reduced pollution, low costs, simplicity [1,3] oxazine (4j): IR (KBr, υmax/cm-1) 1029 (sym. C-O-C),
in process, handling and there is no need for the use of 1211 (asym. C-O-C); 1H NMR (DMSO-d6, 400 MHz, δ ppm)
harmful organic solvents. These factors are beneficial to 3.54 (s, 3H, -OCH3), 4.70 (s, 2H, Ar-CH2-N-), 5.50 (s, 2H,
industry as well as to environment. Therefore solid state re- -O-CH2-N-), 6.11-7.53 (m, 10H, Ar-H); 13C NMR (DMSO-
actions or solvent free reactions are one of the most impor- d6, 75 MHz, δ ppm) 49.1, 53.4, 79.2, 112.1, 114.5, 115.8,
tant synthesis techniques in green chemistry. Various solvent 117.3, 118.2, 120.9, 124.5, 125.6, 125.9, 126.5, 127.5, 130.3,
free reactions were found to occur by hand grinding in 133.2, 146.7, 148.9, 151.1; MS: m/z 292.2 (m+1); Elemental
mortar and pestle.25 analysis: C19H17NO2 Calcd.: C: 78.33%; H: 5.88%; N: 4.81%;
Found: C: 78.21%, H: 5.78%, N: 4.90%.
EXPERIMENTAL 2,3-Dihydro-2-(4-methoxyphenyl)-1H-naphtho[1,2-e]
[1,3] oxazine (4k): IR (KBr, υmax/cm-1) 1019 (sym. C-O-C),
General procedures for compounds 4(a-n) 1228 (asym. C-O-C); 1H NMR (DMSO-d6, 400 MHz, δ ppm)
Method A. A mixture of formalin (2 mmol), aromatic 3.62 (s, 3H, -OCH3), 4.87 (s, 2H, Ar-CH2-N-), 5.40 (s, 2H,
amine (1 mmol), 2-naphthol (1 mmol) in [bmim]HSO4 (5 -O-CH2-N-), 6.77-7.82 (m, 10H, Ar-H); 13C NMR (DMSO-
mol %) at 60 oC was stirred for specified time period as d6, 75 MHz, δ ppm) 48.2, 52.2, 80.1, 111.2, 113.2, 115.6,
shown in Table 4. The progress of reaction was monitored 117.4, 119.5, 121.1, 124.2, 125.7, 125.9, 126.8, 127.2, 130.1,
on TLC. Upon completion of reaction, the reaction mixture 132.3, 146.8, 148.6, 150.1; MS: m/z 292.2 (m+1); Elemental
was extracted with ethyl acetate (2 × 20 mL) leaving behind analysis: C19H17NO2 Calcd.: C: 78.33%; H: 5.88%; N: 4.81%;
[bmim]HSO4, organic layer was washed by brine (2 × 10 mL) Found: C: 78.45%, H: 5.90%, N: 4.72%.
solution and dried over anhydrous sodium sulphate. The 2-(2-ethoxyphenyl)-2,3-dihydro-1H-naphtho[1,2-e][1,3]
organic layer was evaporated under reduced pressure in Rota oxazine (4l): IR (KBr, υmax/cm-1) 1021 (sym. C-O-C), 1234

Journal of the Korean Chemical Society

 [1,3] Oxazine 유도체 합성을 위한 효율적인 One-Pot 합성 439

(asym. C-O-C); 1H NMR (DMSO-d6, 400 MHz, δ ppm) 1.29 Table 1. Screening of IL for the synthesis of [1,3] oxazines
(t, 3H, J = 14 Hz, -O-CH2-CH3), 3.96 (q, 2H, J = 14 Hz,
-O-CH2-CH3), 4.61 (s, 2H, Ar-CH2-N-), 5.40 (s, 2H, -O- NH2
OH
CH2-N-), 6.17-7.44 (m, 10H, Ar-H); 13C NMR (DMSO-d6, + HCHO+ IL, 60 oC N
O
75 MHz, δ ppm) 13.9, 48.8, 64.7, 81.5, 111.8, 114.7, 115.8,
117.5, 118.5, 121.2, 122.2, 124.5, 125.4, 125.7, 126.2, 127.4,
128.8, 133.2, 146.1, 149.3; MS: m/z 306.2 (m+1); Elemental 1 2 3 (a-n) 4 (a-n)

analysis: C20H19NO2 Calcd.: C: 78.66%; H: 6.27%; N: 4.59%;

Entry IL Time (h) Yield (%)a
Found: C: 78.48%, H: 6.37%, N: 4.67%.
2-(4-ethoxyphenyl)-2,3-dihydro-1H-naphtho[1,2-e][1,3] 1 [bmim]BF4 2 65
oxazine (4m): IR (KBr, υmax/cm-1) 1028 (sym. C-O-C), 1224 2 [bmim]PF6 2 40
3 [bmim]Cl 3 45
(asym. C-O-C); 1H NMR (DMSO-d6, 400 MHz, δ ppm) 1.20
4 [bnmim]Cl 2 60
(t, 3H, J = 14 Hz, -O-CH2-CH3), 3.90 (q, 2H, J = 14 Hz,
5 [emim]Br 2.5 40
-O-CH2-CH3), 4.90 (s, 2H, Ar-CH2-N-), 5.40 (s, 2H, -O-
6 [bmim]HSO4 0.5 90
CH2-N-), 6.80-7.80 (m, 10H, Ar-H); 13C NMR (DMSO-d6, a
Isolated yield
75 MHz, δ ppm) 14.6, 48.4, 65.1, 80.6, 112.6, 114.8, 115.9,
117.5, 119.7, 120.1, 123.4, 124.8, 125.4, 125.7, 126.5, 127.7,
129.8, 130.0, 147.2, 148.8; MS: m/z 306.2 (m+1); Elemental PF6, 1-butyl-3-dimethylimidazolium chloride [bmim]Cl,
analysis: C20H19NO2 Calcd.: C: 78.66%; H: 6.27%; N: 4.59%; 1-benzyl-3-methylimidazolium chloride [bnmim]Cl, 1-ethyl-
Found: C: 78.71%, H: 6.28%, N: 4.24%. 3-methylimidazolium bromide [emim]Br, and 1-butyl-3-
2-(4-fluorophenyl)-2,3-dihydro-1H-naphtho[1,2-e][1,3] methylimidazolium hydrogen sulphate [bmim]HSO4 for
oxazine (4n): IR (KBr, υmax/cm-1) 1026 (sym. C-O-C), 1245 the said reactants (Table 1).
(asym. C-O-C); 1H NMR (DMSO-d6, 400 MHz, δ ppm) 1.20 After these successful screening it has been found that
(t, 3H, J = 14 Hz, -O-CH2-CH3), 4.90 (s, 2H, Ar-CH2-N-), acidic IL [bmim]HSO4 5 mol % was the best promoter for
5.60 (s, 2H, -O-CH2-N-), 6.80-7.80 (m, 10H, Ar-H); 13C this reaction which gives 90% product yield within 30 min
NMR (DMSO-d6, 75 MHz, δ ppm) 49.2, 78.5, 112.2, 114.2, at 60 oC (Table 1, entry 6). Encouraged by this result, we
115.7, 116.1, 117.2, 118.2, 122.4, 123.1, 125.1, 125.6, 125.9, extended this condition for derivatization with substituted
127.5, 128.4, 130.4, 150.2, 151.8; MS: m/z 280.2 (m+1); anilines furnishing the respective 1,3-oxazine derivatives.
Elemental analysis: C18H14FNO Calcd.: C: 77.40%; H: These results are listed in Table 4. Also we have investigated
5.05%; N: 5.01%; Found: C: 77.87%, H: 5.14%, N: 5.15%. the reusability of this IL [bmim]HSO4 for 4a (Table 4, entry 1)
and observed that it was successfully recovered and reused
RESULTS AND DISCUSSION for three cycles affording 90, 89, 89% yield with no signi-
ficant loss of activity. The simple experimental and product
In continuation of our research to synthesize 1,3-oxazine isolation procedure combined with ease of recovery and reus-
derivatives11 and for developing benign methodologies for ability of IL is expected to the development of green strategy
various organic compounds22,26 encourage us to propose an for the synthesis of 2,3-dihydro-2-phenyl-1H-naphtho[1,2-e]
effective strategy by applying greener approach. For this [1,3] oxazine.
synthesis, we have condensed the 2-naphthol, formalin and Our next attempt was to perform the reaction in water
aniline as a representative substrates to synthesis respective under magnetic stirring at room temperature. We observed
1,3-oxazine. that even after 3 - 5 hr the starting materials were remained
Our initial investigation focused on the use of ionic liquid in heterogeneous form, they exist as a non-miscible mixture
as a solvent as well as catalyst for the synthesis of 1,3-oxazine like oil and water. Therefore, it has been undertaken, the use
by the condensation of said reactants. In search of an effi- of PTCs for this transformations (Table 2).
cient IL and the best experimental condition the preferred Consequently, we tested various PTCs such as tridecyl
reaction in the presence of IL at 60 oC has been considered. trimethyl ammonium bromide (TDTMAB), cetyl pyridinium
A variety of ILs was employed for this synthesis. After chloride (CPC), tetraethyl ammonium bromide (TEAB),
successful screening of different ionic liquids such as, sodium dodecyl sulphate (SDS) and tetra butyl ammonium
1-butyl-3-methylimidazolium tetrafluroborate [bmim]BF4, bromide (TBAB) to perform the preferred reaction. Accor-
1-butyl-3-methylimidazolium hexaflurophosphate [bmim] dingly, TDTMAB was applied for this reaction; the result

2010, Vol. 54, No. 4

440 Suryakant B. Sapkal, Kiran F. Shelke, Bapurao B. Shingate, and Murlidhar S. Shingare

Table 2. Selection of PTC for the synthesis of [1,3] oxazines. Table 3. Screening of suitable catalyst for synthesis of [1,3] oxazines.

NH2 NH2
OH OH
PTC/H2O, RT N N
+ HCHO + Catalyst, Grinding
+ HCHO +
O O

1 2 3 (a-n) 4 (a-n) 1 2 3 (a-n) 4 (a-n)

Entry PTC Time (h) Yield (%)a Entry Catalyst Time (min) Yield (%)a
1 TDTMAB 12 60 1 EPZ-10 35 45
2 CPC 15 45 2 EPZG 40 30
3 TEAB 11 70 3 SnCl2․H2O 30 65
4 SDS 17 40 4 FeCl3 30 60
5 TBAB 5 92 5 NaHSO4 7 89
a a
Isolated yield Isolated yield

showed that the reaction require longer time duration and the non-ammonium ion PTC like, SDS having amphiphilic
gave low yield 60% (Table 2, entry 1). properties, but we found that the time required was compara-
Further attempts were made by using other PTCs like tively very high 17 hr regarding product yield 40% (Table 2,
CPC, TEAB in water but we did not get appreciable % yield entry 4). In due course to prepare more derivatives with
within shorter reaction time (Table 2, entry 2, 3). Providen- aromatic amines having different substituents at various po-
tially, the target compound could be obtained by using TBAB sitions were reacted smoothly giving excellent product yield
due to the fact, which facilitates the migration of the reactants when subjected with TBAB in water at room temperature
in heterogeneous system from one phase into another phase as shown in Table 4.
effectively. Hence by using TBAB the reaction was com- Finally, attempts were made using grinding approach
pleted successfully within 5 hr that affords respective yield which is less hazardous to human health and environment.
92% (Table 2, entry 5). Even though, we have screened for In order to select an appropriate catalyst for the synthesis of

Table 4. Synthesis of 1,3-oxazine derivatives 4(a-n).

R

NH2
OH N
+ HCHO + R O

1 2 3 (a-n) 4 (a-n)
o
IL/60 C (Method A) PTC/H2O (Method B) Grinding (Method C)
Entry R a a a
M. P. (oC)
Time (min) Yield (%) Time (h) Yield (%) Time (min) Yield (%)
4a H 30 90 5 92 7 89 49-51b
4b 2-Me 35 92 4.5 92 7 90 56-58b
4c 3-Me 32 90 5 87 7 85 70-72
4d 4-Me 30 89 5 90 8 87 88-90b
b
4e 2-NO2 30 90 6 91 7 89 110-112
4f 3-NO2 32 91 5 90 7 90 129-131b
b
4g 4-NO2 29 89 5 89 7 87 165-167
4h 4-Br 29 92 4.5 90 6 90 115-117b
4i 2,4,6-tri Br 40 87 6 85 8 89 96-98b
4j 3-OMe 30 93 4 93 7 91 66-68
4k 4-OMe 35 91 4.5 88 6 87 78-80
4l 2-OEt 29 89 5 90 8 89 100-102
4m 4-OEt 30 90 5 91 7 90 69-71
4n 4-F 29 91 4.5 92 6 96 135-137
a b 1
Isolated yield. Reported in reference No. 18, other compounds are characterized with the help of Spectroscopic analysis (IR, H NMR, MS and
Elemental analysis).

Journal of the Korean Chemical Society

 [1,3] Oxazine 유도체 합성을 위한 효율적인 One-Pot 합성 441

1,3-oxazine by simply grinding method in mortar and pestle Commun. 2008, 38, 4125.
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