PleaseRd So Cn oA t da vd aj un s ct ems argins
DOI: 10.1039/C5RA14214H
Journal Name
ARTICLE
1
result in tris- and tetra-p-aminophenylmethane, respectively. 1257, 1240, 1116, 1030, 995, and 950; H-NMR (500 MHz, CDCl3,
Synthetic strategies are detailed below. ppm): 0.94 (CH ,t), 1.35 [(CH )n, m], 1.85, 2.07 (CH CH=, m), 2.59
CH Ar, t), 2.89 [CH (CH=) , m], 4.55 (s, ArCH N–), 5.05 (–CH=CH–,
dd), 5.30-5.40 (m, CH=, CH =CH–, –OCH N–,–HC=CH ), 6.60(ArH, s),
3
2
2
(
2
2
2
2
4
,4',4''-methanetriyltrianiline
TrisAPM)]. To a solution of pararosaniline hydrochloride (0.50 g,
.54 mmol) prepared in ethanol (40 mL), sodium borohydride (0.53
[Tris-p-aminophenylmethane
2
2
2
1
3
(
6
.72(ArH, d), 6.93 (ArH, m), 7.15 (ArH, d), 7.27 (ArH, m); C-NMR
125 MHz, CDCl , ppm): 50.38 (ArCH N–), 79.47 (–OCH N–); LC-MS
ESI Interface-positive ions) [C-a] : 415.2818, 416.2944, 417.2975,
1
(
(
3
2
2
+.
g, 14.00 mmol) was added in two lots with continuous stirring in an
ice bath. Reaction continued till complete dissolution of sodium
borohydride accompanied by a color change from deep pink to
yellow. Reaction was quenched with addition of water (75 mL) and
4
4
18.3100, 419.3131, 420.3256 (monoene: 419.3188, diene:
17.3032, triene: 415.2875).
a
yellow precipitate of Tris-APM was obtained after simple bis(4-(7-alkyl-2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane (C-
-1
filtration. Yield 84 %. FTIR-ATR (diamond crystal/cm ): 3336, 3203, ddm). The preparation method is similar to that of C-a except that
1
3
029, 1608, 1507, 1267, 815, 770; H-NMR (500 MHz, CDCl
3
, δ ratio of reactants used: cardanol (5.00 g, 16.61 mmols),
ppm): 6.88 (d, 6H, ArH), 6.60 (d, 6H, ArH), 5.24 (s, Ar C-H), 3.56 (br, paraformaldehyde
(1.00
g,
33.32
mmol),
4,4′-
3
+
s, 6H,–NH
2
); LC-MS (ESI Interface-positive ions): [M+H] 290.1651 diaminodiphenylmethane (1.65 g, 8.30 mmol) and reaction was
o
(290.1613).
heated at a temperature of 90 C for 4h. C-ddm was obtained as
orange coloured sticky solid. Yield 85%; FTIR-ATR (diamond
-
1
tetrakis(4-nitrophenyl)methane
[Tetra-p-nitrophenylmethane
crystal/cm ): 3007, 2920, 2851,1614, 1575, 1513, 1466, 1365, 1276,
1
(TNPM)].Tetraphenylmethane (2.00 g, 6.24 mmol) was added to
1
225, 1111, 1086, 1015, 971, 986, and 942. H-NMR (500 MHz,
mixture of fuming nitric acid (11 mL), glacial acetic acid (6.8 mL) and
CDCl δ ppm): 0.94 (CH ,t), 1.35 [(CH )n, m], 1.85, 2.07 (CH CH=, m),
3,
3
2
2
o
acetic anhydride (3.8 mL) at -40 C with vigorous stirring. The
2
.59 (CH
2
Ar, t), 2.89 [CH
2
(CH=)
2
, m], 3.83 (s, Ar-CH
2
-Ar), 4.55 (s,
resultant mixture was stirred for 5h and filtered to give yellow solid
which was washed with water, dried and re-crystallized using
tetrahydrofuran to give TNPM as yellow crystals. Yield 82%; FTIR-
2 2 2
ArCH N–), 5.05 (–CH=CH–, dd), 5.40 (m, CH=, CH =CH–, –OCH N–, –
1
3
HC=CH ), 6.60-7.23 (m, ArH); C-NMR (125 MHz, CDCl , ppm): 40.37
2
3
(
ArCH
2
Ar), 50.36 (ArCH
2
+
N–), 79.77 (–OCH
2
N–); LC-MS (ESI Interface-
-1
.
ATR (diamond crystal/cm ): 3070, 3100, 1605, 1591, 1519, 1493,
positive ions) [C-ddm] :843.5606, 845.5762, 846.5799, 847.5912,
1
1
347, 840, 757, 744, 711. H-NMR (500 MHz, CDCl
H, Ar-H), 7.41 (d, 8H, Ar-H).
3
, δ ppm): 8.22 (d,
8
8
48.5952, 849.6063, 850.6104 (monoene: 850.6376, diene:
46.6063, triene: 842.5750).
8
4
,4',4'',4'''-methanetetrayltetraaniline
[Tetra-p-
tris(4-(7-alkyl-2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane (C-
trisapm). The preparation method is similar to that of C-a except
that ratio of reactants used: cardanol (1.56 g, 5.18 mmols),
paraformaldehyde (0.31 g, 10.36 mmol), Tris-APM (0.50 g, 1.72
aminophenylmethane (TAPM)]. To a solution of TNPM (1.40 g, 2.79
mmol) in tetrahydrofuran (35 mL), Pd/C (10% Pd, catalytic amount)
was added and the reaction mixture was purged with nitrogen
followed by hydrogen. Thereafter, the reaction mixture was stirred
under hydrogen pressure at room temperature for 3 days followed
by filtration over celite to remove Pd/C powder. The filtrate was
dried to give TAPM as white powder. Yield: 96%. FTIR-ATR (diamond
o
mmol) and reaction was heated at a temperature of 90 C for 5h. C-
trisapm was obtained as viscous brown oil. Yield 80%; FTIR-ATR
-
1
(
diamond crystal/cm ): 3007, 2923, 2852, 1657, 1610, 1508, 1256,
1
1
240, 1198, 1041, 1014, 990, and 960; H-NMR (500 MHz, CDCl δ
3,
-
1
1
crystal/cm ): 3400, 3161, 3022, 1608, 1507, 1267, 803. H-NMR
500 MHz, (CD SO, δ ppm): 6.67 (d, 8H, Ar-H), 6.38 (d, 8H, Ar-H),
ppm): 4.46 (s, Ar-CH
2
-N-), 5.32-5.38 (m, CH=, CH
C-H); C-NMR (125 MHz, CDCl , ppm): 50.32 (ArCH
CH), 79.52 (–OCH N–); LC-MS (ESI Interface-positive ions)
C-trisapm] : 1261.8551, 1262.8649, 1263.8689, 1264.8783,
2
=CH-, -OCH
2
N-,
1
3
(
3 2
)
HC=CH2, Ar
3
3
2
N–),
+
4.85 (s, 8H, -NH
2
); LC-MS (ESI Interface-positive ions): [M+H] :
5
4.5 (Ar
3
2
+.
381.2063 (381.2035).
[
1
1
265.8816, 1266.8904, 1267.8904, 1268.8966 (monoene:
267.9408, diene: 1261.8938, triene: 1255.8469).
Synthesis of cardanol based benzoxazine monomers. 7-alkyl-3-
phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (C-a). The monomer C-
2
4
a was prepared in reference to the procedure. In brief, a mixture
of cardanol (5.00 g, 16.61 mol), paraformaldehyde (1.00 g, 33. 22
tetrakis(4-(7-alkyl-2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane
C-tetraapm). The preparation method is similar to that of C-a
(
o
mmol), aniline (1.51 mL, 16.61 mmol) was gradually heated to 80 C
except that ratio of reactants used: cardanol (1.58 g, 5.25 mmols),
paraformaldehyde (0.41 g, 13.81 mmol), TAPM (0.50 g, 1.31 mmol)
o
and stirred for an hour, followed by heating at 90 C for 2h. The
o
reaction was indicated by evolution of water and colour changed
from yellow to red brown. On cooling, water (10 mL) was added
and organic layer was extracted with chloroform (20 mL). The
organic layers were combined and washed with NaOH (0.5 N,
was heated at 90 C for 8 h. C-tetraapm was obtained as a
gelatinous brown viscous solid. Yield 74%; FTIR-ATR (diamond
-1
crystal/cm ): 3007, 2921, 2851, 1657, 1607, 1503, 1256, 1240,
1
1
1
199, 1037, 1014, 990, and 960; H-NMR (500 MHz, CDCl
3
, δ ppm):
100mL) followed by washing with water (3 x 30 mL), dried over
.2-1.59 (m, aliphatic -CH2 protons), 4.46(s, Ar-CH -N-), 5.32-5.38
2
1
3
sodium sulphate and filtered. The solvent was removed under
reduced pressure to give C-a as a red oil. Yield 95%; FTIR-ATR
(
m, CH=, CH
NMR (125 MHz, CDCl
LC-MS(ESI Interface-positive ions) [C-tetraapm] :
2
=CH-, -OCH
2
N-, HC=CH
2
), 6.63-7.26 (m, 28 H, ArH); C-
N–), 79.22 (–OCH N–);
1619.1887,
3
, ppm): 49.86 (ArCH
2
2
-
1
+.
(
diamond crystal/cm ) 3008, 2926, 2854,1626, 1595, 1579, 1350,
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