Macromolecules
Article
6
7
8
.24 (dd, 1H, J = 8.4, 2.4 Hz), 6.44 (t, 1H, J = 7 Hz), 6.49 (d, 2H, J =
.6 Hz), 6.54−6.57 (m, 2H), 7.95 (dd, 1H, J = 8.8, 2.8 Hz, ArNO ),
2
1
3
.03 (d, 1H, J = 2.4 Hz, ArNO ), 8.56 (broad, 2H, OH). C NMR
2
(
100 MHz, DMSO-d ): δ 42.4 (CH ), 111.5, 112.6, 113.8, 115.4,
6 2
1
1
16.0, 116.1, 124.2, 124.5, 126.9, 128.5, 129.2, 140.1, 141.6, 146.8,
49.4, 162.0. (c) NH -H(PAM) P was synthesized by reducing
2
2
NO -H(PAM) P (10 g, 27.3 mmol) in the presence of tin(II) chloride
2
2
dihydrate (30.9 g, 136.9 mmol) at 85 °C for 2 h in ethanol (150 mL).
After cooling the reaction mixture, the pH of the solution was changed
to 8.5 by adding saturated Na CO solution. The obtained white pre-
2
3
cipitate was suction filtered, and the amino compound was extracted
using ethyl acetate and washed (first with distilled water, followed by
brine and distilled water again). The solvent was dried over anhydrous
sodium sulfate and evaporated off. The brown oily crude compound
was purified by column chromatography by eluting with hexane:ethyl
(
150 mL), stirring at 60 °C. The yellow homogeneous solution was
suddenly turned to orange-red powdery suspension, confirming the
imine formation. The heating was continued further for 4 h to ensure
the completion of reaction and then cooled. (b) To this NaBH4
acetate (50:50), which resulted in a brown powder (yield: 4.4 g,
1
13.18 mmol, 48%). H NMR (400 MHz, DMSO-d ): δ 3.91 (d, 2H,
6
J = 6 Hz, CH ), 4.04 (d, 2H, J = 5.6 Hz, CH ), 4.26 (s, 2H, NH ), 5.11
2
2
2
(
2.82 g, 74.7 mmol) was added portionwise over a period of 15 min
(t, 1H, J = 5.6 Hz, NH), 5.79 (t, 1H, J = 6 Hz, NH), 6.23 (dd, 2H, J =
8.74, 2.8 Hz), 6.42−6.47 (m, 3H), 6.51−6.54 (m, 4H), 6.99 (t, 2H, J =
7.8 Hz), 8.38 and 8.45 (s, overlapped, 2H, OH). 13C NMR (100 MHz,
DMSO-d ): δ 42.4 (CH ), 43.8 (CH ), 111.8, 112.7, 113.8, 114.2, 115.2,
116.0, 116.1, 126.7, 127.0, 129.3, 141.1, 142.5, 146.5, 146.6, 149.5.
Synthesis of 3′-Phenyl-2,3′,4,4′-tetrahydro-2′H-3,6′-
bibenzo[e][1,3]oxazine (Dibenzoxazine, BZ2). HPAMP (10 g,
46.49 mmol), aniline (4.32 g, 46.49 mmol), paraformaldehyde (4.6 g,
153.42 mmol), and chloroform (100 mL) were taken in a round-
at RT; when the reduction was completed (∼15 min), the red
suspension became homogeneous. Then distilled water was added
(
(
100 mL), and the compound was extracted with dichloromethane
3 × 100 mL). The organic layers were combined, washed again with
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2
2
distilled water (3 × 100 mL), and dried over anhydrous sodium
sulfate. The solvent was concentrated to yield yellow crystals of
1
NO -PAMP (yield: 27.5 g, 112.6 mmol, 75%). H NMR (400 MHz,
2
DMSO-d ): δ 4.21 (s, 2H, CH ), 6.2 (broad, 1H, NH), 6.47−6.53
6
2
(
8
m, 3H), 6.95−7.03 (m, 3H), 7.98 (dd, 1H, J = 8.8, 2.8 Hz, ArNO ),
bottomed flask fitted with a condenser and guard tube (CaCl ), and
2
2
13
.05 (d, 1H, J = 2.8 Hz, ArNO ), 11.23 (broad, 1H, OH). C NMR
the contents were refluxed. The completion of reaction was monitored
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1
(
100 MHz, DMSO-d ): δ 41.3 (CH ), 112.6, 115.6, 116.6, 124.1,
by H NMR and confirmed after 48 h by almost disappearance of
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2
1
24.7, 128.1, 129.5, 140.1, 148.8, 162.1. (c) In a 500 mL round-bottomed
triazine signal at 4.82 ppm. The reaction mixture was cooled, and the
solvent was evaporated off. The crude compound was purified by flash
column chromatography using hexane:ethyl acetate (20:1) mixture
as eluent and then recrystallized from hexane:ethyl acetate (20:1).
White needlelike crystals obtained (yield: 4.7 g, 13.65 mmol, 30%);
flask equipped with a reflux condenser and a guard tube, NO -PAMP
2
(
25 g, 102.4 mmol), tin(II) chloride dihydrate (115.5 g, 512.1 mmol),
and ethanol (250 mL) were combined and heated at 85 °C for 2 h.
The reaction mixture was then cooled, and the pH of the solution was
−1
changed to 8.5 by adding saturated Na CO3 solution. The white
precipitate thus obtained was suction filtered, which resulted in a white
cake and the amino compound was extracted using ethyl acetate
mp 122.7 °C. IR (solid) υ/cm : 1219 and 1032 (C−O−C), 1160
2
(C−N−C), 923, 934, and 971 (out-of-plane C−H stretch of benzene
1
attached to oxazine). H NMR (400 MHz, CDCl ): δ 4.51 and 4.55 (s,
3
(
(
400 mL). The organic layer was then washed with distilled water
2 × 250 mL), followed by brine, and then once again with distilled
4H, Ar−CH −N), 5.24 and 5.26 (s, 4H, O−CH −N), 6.69 (d, 1H, J =
2
2
8.4 Hz), 6.78 (d, 2H, J = 7.6 Hz), 6.84−6.91 (m, 3H), 6.96 (d, 1H, J =
13
water. The solvent was dried over sodium sulfate and evaporated
7.6 Hz), 7.05−7.11 (m, 3H), 7.21−7.24 (m, 2H). C NMR
(100 MHz, CDCl ): δ 50.7 and 51.1 (Ar−CH −N), 79.4 and 80.5
under reduced pressure to obtain light brown crystals (yield: 18 g,
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2
1
84 mmol, 82%). H NMR (400 MHz, DMSO-d ): δ 4.04 (d, 2H, J =
(O−CH −N), 117.05, 117.3, 117.6, 118.3, 119.6, 120.93, 120.97,
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Hz, CH ), 4.31 (s, 2H, NH ), 5.86 (t, 1H, J = 5.8 Hz, NH), 6.26
2
2
121.3, 121.5, 126.8, 127.9, 129.3, 142.5, 148.5, 149.6, 154.4. Anal.
Calcd for C H N O : C, 76.72; H, 5.85; N, 8.13. Found: C, 76.84;
(
dd, 1H, J = 8.2, 2.4 Hz), 6.44−6.52 (m, 5H), 6.99 (t, 2H, J = 7.8 Hz),
22
20
2
2
8
1
.43 (s, 1H, OH). 13C NMR (100 MHz, DMSO-d ): δ 42.1(CH ),
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2
H, 5.81; N, 8.04.
12.6, 113.7, 114.8, 115.9, 116.0, 126.6, 129.2, 141.2, 146.2, 149.5.
Synthesis of 4-Amino-2-(((4-hydroxy-3-((phenylamino)-
Synthesis of 3″-Phenyl-2,2′,3″,4,4′,4″-hexahydro-2″H-
3,6′:3′,6″-terbenzo[e][1,3]oxazine (Tribenzoxazine, BZ3). A
methyl)phenyl)amino)methyl)phenol (NH -H(PAM) P). NO -H-
2
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2
mixture of HPAMP (5 g, 23.24 mmol), NH -PAMP (4.97 g,
2
(
PAM) P was synthesized (a) by reacting 5-nitrosalicylaldehyde (7.8 g,
2
23.24 mmol), paraformaldehyde (3.06 g, 102.2 mmol), and chloro-
form (50 mL) was refluxed for 48 h and cooled, and the solvent was
evaporated off. The crude product was purified by column chroma-
tography using eluent hexane:ethyl acetate (70:30) mixture and then
recrystallized from hexane:ethyl acetate (1:1), which resulted in white
shiny solid crystals (yield: 3.9 g, 8.17 mmol, 35%); mp 140−143.5 °C.
−1
IR (solid) υ/cm : 1211 and 1024 (C−O−C), 1152 (C−N−C), 904,
9
34, and 960 (out-of-plane C−H stretch of benzene attached to
1
oxazine). H NMR (400 MHz, CDCl ): δ 4.45, 4.52, and 4.54 (s, 6H,
3
Ar−CH −N), 5.17, 5.25, and 5.27 (s, 6H, O−CH −N), 6.69 (dd, 2H,
2
2
J = 8.8, 2.8 Hz), 6.75 (t, 2H, J = 3.2 Hz), 6.78 (d, 1H, J = 8.4 Hz),
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.85−6.92 (m, 4H), 6.97 (d, 1H, J = 7.2 Hz), 7.05−7.12 (m, 3H),
13
.21−7.24 (m, 2H). C NMR (100 MHz, CDCl ): δ 50.6, 51.1, and
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4
6.7 mmol) and NH -PAMP (10 g, 46.7 mmol) in ethanol (100 mL)
51.3 (Ar−CH −N), 79.4, 80.4, and 80.5 (O−CH −N), 117.0, 117.30,
2
2
2
at 60 °C for 4 h. (b) Then, after cooling the reaction mixture, an
excess amount of NaBH (1.76 g, 46.7 mmol) was added and stirred
for 15 min. Distilled water was added; the yellow precipitate thus
obtained was extracted with CH Cl and washed with distilled water
and dried over sodium sulfate. The solvent was concentrated to afford
yellow crystals (yield: 12.4 g, 33.9 mmol, 72%). H NMR (400 MHz,
DMSO-d ): δ 4.08 (d, 4H, J = 15.2 Hz, CH ), 5.83 (broad, 2H, NH),
117.37, 117.6, 118.3, 119.6, 119.7, 120.92, 120.98, 121.31, 121.35,
121.4, 126.8, 127.9, 129.3, 142.5, 142.6, 148.5, 149.60, 149.67, 154.4.
Anal. Calcd for C H N O : C, 75.45; H, 5.70; N, 8.80. Found: C,
4
30
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2
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75.50; H, 5.62; N, 8.67.
Synthesis of 3‴-Phenyl-2,2′,2″,3‴,4,4′,4″,4‴-octahydro-
2‴H-3,6′:3′,6″:3″,6‴-quaterbenzo[e][1,3]oxazine (Tetraben-
zoxazine, BZ4). A mixture of HPAMP (2 g, 9.29 mmol),
1
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2
J
Macromolecules XXXX, XXX, XXX−XXX