Ultrasound synthesis of diaryl ethers
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 8, August, 2015
1973
ried out in an S10H Elmasonic bath (Elma Schmidbauer Gmbh,
Germany).
Found (%): C, 62.57; H, 4.34; N, 12.19; O, 20.87. C12H10N O .
2 3
Calculated (%): C, 62.60; H, 4.38; N, 12.17; O, 20.85.
Diaryl ethers (general procedure). i. A mixture of compound
2,2ꢀBis[4ꢀ(4ꢀnitrophenoxy)phenyl]hexafluoropropane (3а).
2
a,b (6 mmol), 4а—d (6 mmol), and K CO (9 mmol or 18 mmol
The yield was 95% (ii), m.p. 162—163 С (Ref. 12: 161—162 С).
2
3
+
for 5с) in DMSO (25 mL) was stirred for 5 h (for 5а), 4 h (for 5b
and 5d), 4.35 h (for 5с), and 8 h (for 5f) at 80 С. After cooling,
the mixture was poured into water, filtered, dried, and recrystalꢀ
lized from alcohol.
ii. A mixture of compound 2a—c (6 mmol), 4а—e (6 mmol),
or 1 (3 mmol) and K CO (9 mmol or 18 mmol for 5с) in DMSO
Found: m/z 579.0993 [M + H] . C27H16F N O . Calculated:
6
2
6
1
М = 579.0991. H NMR (DMSOꢀd ), : 7.25 (m, 8 H, H(3´),
6
Н(3´), Н(5´), Н(5´), Н(2), Н(2), Н(6), Н(6)); 7.48 (d, 4 H,
H(2´), Н(2´), Н(6´), Н(6´), J = 8.3 Hz); 8.31 (d, 4 H, H(3),
Н(3), Н(5), Н(5), J = 8.7 Hz). Found (%): C, 56.10; H, 2.83;
F, 19.72; N, 4.88; O, 16.61. C27H16F N O . Calculated (%):
2
3
6
2
6
(
(
25 mL) was subjected to ultrasound irradiation at 80 С for 1 h
for 3a,b, 5а—d), 6 h (for 5е), and 2 h (for 3c, 5f). After cooling,
C, 56.06; H, 2.79; F, 19.71; N, 4.84; O, 16.60.
2,2ꢀBis[4ꢀ(3ꢀaminoꢀ4ꢀnitrophenoxy)phenyl]hexafluoropropꢀ
ane (3b). The yield was 92% (ii), m.p. 182—184 С. Found: m/z
the mixture was poured into water, filtered, dried, and recrystalꢀ
lized from alcohol.
+
609.1212 [M + H] . C27H18F N O . Calculated: М = 609.1209.
6
4
6
1
1
ꢀNitroꢀ4ꢀphenoxybenzene (5а). The yield was 88% (i) or
H NMR (DMSOꢀd ), : 6.28 (dd, 2 Н, Н(6), Н(6), J = 1.3 Hz,
6
9
2
7% (ii), m.p. 55—57 С (Ref. 8: 54—56 С ). Found: m/z
J = 8.2 Hz); 6.37 (d, 2 Н, Н(2), Н(2), J = 1.5 Hz); 7.23 (d, 4 H,
H(3´), Н(3´), Н(5´), Н(5´)); 7.46 (d, 4 H, H(2´), Н(2´), Н(6´),
+
16.0665 [M + H] . C12H NO . Calculated: М = 216.0661.
9
3
1
H NMR (DMSOꢀd ), : 7.12 (d, 2 Н, H(2´), Н(6´), J = 8.4 Hz);
Н(6´), J = 8.4 Hz); 7.50 (s, 4 H, 2 NH ); 8.10 (d, 2 Н, Н(5),
6
2
13
7
.19 (d, 2 H, H(3), Н(5), J = 8.4 Hz); 7.31 (t, 1 H, H(4´), J = 8.5 Hz);
Н(5), J = 8.8 Hz). С NMR (DMSOꢀd ), : 63.33 (septet,
6
7
.52 (t, 2 H, H(3´), Н(5´), J = 8.5 Hz); 8.26 (d, 2 H, H(2),
С(2), J = 28.0 Hz); 104.49 (С(2), C(2)); 104.56 (С(6), C(6));
107.07 (С(3), C(3)); 120.02 (С(3´), C(3´), С(5´), C(5´)); 123.91
(q, С(1), С(3), J = 296 Hz); 126.74 (С(5), C(5)); 128.26 (С(1´),
C(1´)), 131.72 (С(2´), C(2´), С(6´), C(6´)); 148.17 (С(4),
C(4)); 155.28 (С(4´), C(4´)); 161.89 (С(1), C(1)). 1 F NMR
Н(6), J = 9.0 Hz). Found (%): C, 67.02; H, 4.26; N, 6.53;
O, 22.32. C12H NO . Calculated (%): C, 66.97; H, 4.22;
N, 6.51; O, 22.30.
9
3
9
1
ꢀChloroꢀ4ꢀ(4ꢀnitrophenoxy)benzene (5b). The yield was 89%
+
(
i) or 96% (ii), m.p. 77—78 С. Found: m/z 250.0275 [M + H] .
(DMSOꢀd ), : –63.73. Found (%): C, 53.38; H, 2.93; F, 18.71;
6
1
C12H ClNO . Calculated: М = 250.0271. H NMR (DMSOꢀd ),
N, 9.24; O, 15.75. C27H20F N O . Calculated (%): C, 53.30; H,
8
3
6
6
2
2
: 7.15 (d, 2 Н, Н(3), Н(5), J = 8.5 Hz); 7.24 (d, 2 Н, Н(2´),
Н(6´), J = 8.4 Hz); 7.54 (d, 2 Н, Н(2), Н(6), J = 8.7 Hz); 8.26
d, 2 Н, Н(3´), Н(5´), J = 8.7 Hz). Found (%): C, 57.76; H,
.25; Cl, 14.24; N, 5.63; O, 19.29. C12H ClNO . Calculated (%):
2.98; F, 18.73; N, 9.21; O, 15.78.
2,2ꢀBis[4ꢀ(2ꢀchloroꢀ4ꢀnitrophenoxy)phenyl]hexafluoropropꢀ
ane (3c). The yield was 97% (ii), m.p. 157—159 С. Found: m/z
(
3
+
647.0208 [M + H] . C27H14Cl F N O . Calculated: М = 647.0211.
8
3
2
6
2 6
1
C, 57.73; H, 3.23; Cl, 14.20; N, 5.61; O, 19.23.
ꢀ(4ꢀNitrophenoxy)benzoic acid (5c). The yield was 86% (i)
or 95% (ii), m.p. 238 С (Ref. 9: 236—237 С). Found: m/z
H NMR (DMSOꢀd ), : 7.27—7.33 (m, 6 H, H(3´), Н(3´),
6
4
Н(5´), Н(5´), Н(6), Н(6)); 7.47 (d, 4 H, H(2´), Н(2´), Н(6´),
Н(6´), J = 8.3 Hz); 8.24 (dd, 2 H, H(5), Н(5), J = 1.4 Hz,
J = 8.5 Hz); 8.52 (d, 4 H, H(3), Н(3), J = 1.5 Hz). С NMR
+
13
2
60.0563 [M + H] . C13H NO . Calculated: М = 260.0559.
9
5
1
H NMR (DMSOꢀd ), : 7.23—7.27 (m, 4 H, H(3), Н(5), Н(2´),
(DMSOꢀd ), : 63.84 (septet, С(2), J = 28.0 Hz); 119.13 (С(6),
6
6
Н(6´)); 8.05 (d, 2 H, H(2), Н(6), J = 8.8 Hz); 8.29 (d, 2 H,
H(3´), Н(5´), J = 9.2 Hz); 13.05 (s, 1 H, COOH). Found (%):
C, 60.22; H, 3.47; N, 5.45; O, 30.84. C13H NO . Calculated (%):
C(6)); 119.65 (С(3´), C(3´), С(5´), C(5´)); 123.82 (q, С(1),
С(3), J = 296 Hz); 124.62 (С(5), C(5)); 125.02 (С(3), C(3));
126.24 (С(2), C(2)); 128.51 (С(1´), C(1´)); 131.95 (С(2´),
C(2´), С(6´), C(6´)); 143.43 (С(4), C(4)); 155.43 (С(4´),
9
5
C, 60.24; H, 3.50; N, 5.40; O, 30.86.
ꢀMethylꢀ4ꢀ(4ꢀnitrophenoxy)benzene (5d). The yield was
19
1
C(4´)); 156.80 (С(1), C(1)). F NMR (DMSOꢀd ), : –63.8.
6
9
2
0% (i) or 97% (ii), m.p. 65—67 С (Ref. 10: 65 С). Found: m/z
Found (%): C, 50.13; H, 2.19; Cl, 10.97; F, 17.60; N, 4.30;
+
30.0821 [M + H] . C13H11NO . Calculated: М = 230.0817.
O, 14.85. C27H14Cl F N O . Calculated (%): C, 50.10; H, 2.18;
3
2
6
2
6
1
H NMR (DMSOꢀd ), : 2.35 (s, 3 Н, Ме); 7.02 (d, 4 H, H(2),
Cl, 10.95; F, 17.61; N, 4.33; O, 14.83.
6
H(3), Н(5), Н(6), J = 8.4 Hz); 7.31 (d, 2 H, H(2´), Н(6´),
J = 8.6 Hz); 8.24 (d, 2 H, H(3´), Н(5´), J = 8.7 Hz). Found (%):
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 14ꢀ03ꢀ31727
mol_a).
C, 68.18; H, 4.80; N, 6.15; O, 20.92. C13H11NO . Calculatꢀ
3
ed (%): C, 68.11; H, 4.84; N, 6.11; O, 20.94.
1
ꢀNitroꢀ4ꢀ(4ꢀnitrophenoxy)benzene (5e). The yield was
+
5
7% (ii), m.p. 145—147 С. Found: m/z 261.0518 [M + H] .
C12H N O . Calculated: М = 261.0512. H NMR (DMSOꢀd ),
References
1
8
2
5
6
8
: 7.36 (d, 4 H, H(2), Н(6), Н(3´), Н(2´), Н(5´), J = 8.3 Hz);
.33 (d, 4 H, H(3), Н(5), Н(2´), Н(6´), J = 8.5 Hz). Found (%):
C, 55.44; H, 3.15; N, 10.79; O, 30.76. C12H N O . Calculatꢀ
1. P. E. Cassidy, T. M. Aminabhavi, J. M. Farley, J. Macromol.
Sci.: Rev. Macromol. Chem. Phys., 1989, С.29 (283), 365;
C.ꢀP. Yang, R.ꢀS. Chen, K.ꢀH. Chen, J. Polym. Sci., Part A:
Polym. Chem., 2003, 41, 922.
2. Y. S. Negi, YꢀI. Sijzuki, I. Kawamura, MꢀI. Kakimoto,
Y. Imai, J. Polym. Sci., Part A: Polym. Chem., 1996, 34, 1663;
S. Maji, S. Banerjee, J. Appl. Polym. Sci., 2008, 108, 1356;
M. Nechifor, J. Polym. Res., 2011, 18, 2477.
8
2
5
ed (%): C, 55.39; H, 3.10; N, 10.77; O, 30.74.
ꢀNitroꢀ5ꢀphenoxyaniline (5f). The yield was 79% (i) or 96%
ii), m.p. 145—147 С (Ref. 11: 146—148 С). Found: m/z
2
(
+
2
31.0774 [M + H] . C13H11NO . Calculated: М = 231.0770.
3
1
H NMR (DMSOꢀd ), : 6.28 (dd, 1 Н, Н(4), J = 1.5 Hz,
6
J = 8.5 Hz); 6.36 (d, 1 Н, Н(6), J = 1.5 Hz); 7.16 (d, 2 Н, H(2´),
Н(6´), J = 9.0 Hz); 7.28 (t, 1 Н, H(4´), J = 8.5 Hz); 7.44—7.52
3. W. E. Wright, US Pat. 5043478, 1991.
(
m, 4 Н, Н(3´), Н(5´), NH ); 8.10 (d, 1 Н, Н(3), J = 9.5 Hz).
4. R. J. Jones, M. K. O´Rell, J. M. Hom, US Pat. 420922, 1980.
2