10.1002/chem.201903385
Chemistry - A European Journal
FULL PAPER
an excess of solid potassium carbonate (2.76 g, 20.0 mmol) was added.
J = 17.4 Hz, 2 H, H2C(4)), 4.05 (s, 5 H, Fc), 4.23–4.25 (m, 2 H, Fc), 4.34–
4.37 (m, 2 H, Fc), 6.11, 6.50 (AB system, J = 15.7 Hz, 2 H, 2 =CH), 7.33–
7.42, 7.64–7.66, 7.70–7.74 (3 m, 6 H, 2 H, 2 H, Ph) ppm. 13C NMR (CDCl3,
151 MHz): = 23.5 (t, C(4)), 67.1, 67.5, 69.2*, 69.3* (4 d, Fc), 81.1 (s, Fc),
87.0 (s, C(6)), 125.6, 125.9, 126.9, 128.54, 128.55, 128.6, 129.8, 131.9 (8
d, Ph, =CH), 136.0, 140.3 (2 s, Ph), 151.7 (s, C(3)) ppm; *signal with higher
intensity. IR: = 3086m, 2888m, 1654m, 1588m, 1446m, 1399m, 1224m,
969s, 887m, 754s, 693vs cm–1. HRMS (ESI-TOF): m/z [M + H]+ calcd for
C27H24FeNOS: 466.0928; found: 466.0929.
To the resulting suspension,
a freshly prepared solution of the
corresponding ´thiochalcone fraction´ 2/4 (1.00 mmol) in dry
dichloromethane (2 mL) was added dropwise at room temperature, and
stirring was continued until the characteristic color of the starting
thiocarbonyl precursors faded. After completion of the reaction (confirmed
by TLC) the precipitated inorganic materials were filtered off, washed with
dichloromethane (2 4 mL), and the solvents were removed under
reduced pressure. In all experiments the mass recovery was high (>90%),
and the ratio of products 11 and 14 identified in the crude mixtures and
collected in Table 1 was established based on the registered 1H NMR
spectra. The residue obtained thereafter was purified by column
chromatography (SiO2, petroleum ether/dichloromethane 7:3, gradient
(E)-3,6-Diphenyl-6-[2-(furan-2-yl)vinyl]-4H-1,5,2-oxathiazine
(11f):
reaction time: 60 min; yield: 145 mg (42%); pale yellow crystals, m. p. 131–
133 °C (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.41, 3.62 (AB system,
J = 17.4 Hz, 2 H, H2C(4)), 6.29 (dbr, J ≈ 3.3 Hz, 1 H, Fur), 6.36 (dd, J = 1.8,
3.3 Hz, 1 H, Fur), 6.47, 6.52 (AB system, J = 15.8 Hz, 2 H, =CH), 7.32–
7.41, 7.60–7.62, 7.70–7.73 (3 m, 7 H, 2 H, 2 H, Ph, Fur) ppm. 13C NMR
(CDCl3, 151 MHz): = 23.4 (t, C(4)), 86.6 (s, C(6)), 110.1, 111.5, 120.9,
125.7, 126.8, 127.3, 128.62, 128.63, 128.64, 129.8 (10 d, Ph, Fur, =CH),
136.0, 139.9 (2 s, Ph), 142.7 (d, Fur), 151.4 (s, C(3)), 152.1 (s, Fur) ppm.
IR: = 2905m, 2887m, 1573m, 1485m, 1444m, 1388m, 1246m, 1228m,
1088m, 989s, 954s, 822m, 733s, 688vs, 679vs cm–1. MS (ESI): m/z (%) =
370 (18, [M + Na]+), 348 (100, [M + H]+). Anal. Calcd for C21H17NO2S
(347.43): C 72.60, H 4.93, N 4.03, S 9.23; found: C 72.67, H 5.04, N 4.06,
S 9.30.
1:1) and the product was recrystallized from
ether/dichloromethane mixture to give the corresponding 4H-1,5,2-
oxathiazine derivative 11 and/or product 14 as crystalline materials.
a
petroleum
(E)-3,6-Diphenyl-6-styryl-4H-1,5,2-oxathiazine (11a):[22] the product
was obtained in improved yield by a modified general protocol, running the
reaction at 0 °C for 20 h; yield: 161 mg (45%); colorless crystals, m. p.
139–140 °C (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.42, 3.62 (AB
system, J = 17.4 Hz, 2 H, H2C(4)), 6.52, 6.75 (AB system, J = 15.9 Hz, 2
H, 2 =CH), 7.24–7.42, 7.60–7.63, 7.72–7.75 (3 m, 11 H, 2 H, 2 H, Ph) ppm.
For further characterization see ref. 22.
(E)-6-(4-Bromostyryl)-3,6-diphenyl-4H-1,5,2-oxathiazine
(11b):
(E)-3,6-Diphenyl-6-[2-(thien-2-yl)vinyl]-4H-1,5,2-oxathiazine
(11g):
reaction time: 90 min; yield: 145 mg (33%); colorless crystals, m. p. 196–
198 °C (EtOAc) (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.40, 3.60 (AB
system, J = 17.5 Hz, 2 H, H2C(4)), 6.50, 6.67 (AB system, J = 15.9 Hz, 2
H, 2 =CH), 7.24–7.46, 7.59–7.62, 7.70–7.73 (3 m, 10 H, 2 H, 2 H, Ph, Ar)
ppm. 13C NMR (CDCl3, 151 MHz): = 23.3 (t, C(4)), 86.7 (s, C(6)), 122.3
(s, CBr), 125.7, 126.9, 128.4, 128.66, 128.71*, 129.8, 129.9, 131.6, 131.8
(9 d, Ph, Ar, =CH), 134.6, 135.9, 139.8 (3 s, Ph, Ar), 152.3 (s, C(3)) ppm;
* signal with higher intensity. IR: = 3053m, 3026m, 2914m, 1524m,
1476m, 1444m, 1368m, 1248m, 1245m, 1220m, 1197m, 951s, 918s,
836m, 758s, 745s, 711s, 693vs cm–1. MS (ESI): m/z (%) = 437 (6, [M +
H]+), 223 (48), 149 (100). Anal. Calcd for C23H18BrNOS (436.37): C 63.31,
H 4.16, N 3.21, S 7.35; found: C 63.11, H 4.20, N 3.17, S 7.23.
reaction time: 30 min; yield: 145 mg (40%); pale yellow crystals, m. p. 151–
152 °C (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.41, 3.61 (AB system,
J = 17.4 Hz, 2 H, H2C(4)), 6.35, 6.84 (AB system, J = 15.7 Hz, 2 H, =CH),
6.95 (dd, J = 3.6, 5.1 Hz, 1 H, Thie), 6.99 (dbr, J ≈ 3.6 Hz, 1 H, Thie), 7.20
(dbr, J ≈ 5.1 Hz, 1 H, Thie), 7.32–7.42, 7.60–7.62, 7.70–7.73 (3 m, 6 H, 2
H, 2 H, Ph) ppm. 13C NMR (CDCl3, 151 MHz): = 23.4 (t, C(4)), 86.7 (s,
C(6)), 125.4, 125.8, 126.3, 126.9, 127.3, 127.5, 128.3, 128.64, 128.66,
128.69, 129.9 (11 d, Ph, Thie, =CH), 136.0, 139.9, 140.6 (3 s, Ph, Thie),
152.3 (s, C(3)) ppm. IR: = 2955m, 2927m, 2901m, 2847m, 1591m,
1493m, 1485m, 1444s, 1389m, 1276m, 1223m, 1197m, 1078m, 954s,
946s, 923s, 873m, 850m, 753s, 709s, 698vs, 689vs cm–1. MS (ESI): m/z
(%) = 386 (12, [M + Na]+), 364 (100, [M + H]+). Anal. Calcd for C21H17NOS2
(363.49): C 69.39, H 4.71, N 3.85, S 17.64; found: C 69.41, H 4.73, N 3.86,
S 17.53.
(E)-3,6-Diphenyl-6-(4-methoxystyryl)-4H-1,5,2-oxathiazine
(11c):
reaction time: 60 min; yield: 110 mg (28%); pale orange crystals, m. p.
159–160 °C (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.40, 3.61 (AB
system, J = 17.5 Hz, 2 H, H2C(4)), 3.80 (s, 3 H, OMe), 6.37, 6.66 (AB
system, J = 15.9 Hz, 2 H, 2 =CH), 6.82–6.86, 7.32–7.42, 7.59–7.62, 7.70–
7.73 (4 m, 2 H, 8 H, 2 H, 2 H, Ph, Ar) ppm. 13C NMR (CDCl3, 151 MHz):
= 23.5 (t, C(4)), 55.3 (q, OMe), 87.0 (s, C(6)), 114.0, 125.7, 126.6, 126.9,
128.2 (5 d, Ar), 128.3 (s, Ar), 128.56, 128.60*, 129.8, 132.5 (4 d, Ar, =CH),
136.0, 140.1 (2 s, Ar), 151.9 (s, C(3)), 159.8 (s, COMe) ppm; *signal with
higher intensity. IR: = 3068m, 2931m, 2855m, 1605m, 1515s, 1455m,
1367s, 1193m, 1053m, 933s, 858s, 793vs, 698s cm–1. HRMS (ESI-TOF):
m/z [M + H]+ calcd for C24H22NO2S: 388.1371; found: 388.1373.
(E)-6-Ferrocenyl-3-phenyl-6-styryl-4H-1,5,2-oxathiazine
(11h):
reaction time: 24 h; yield: 240 mg (52%); beige crystals, m. p. 81–82 °C.
1H NMR (CDCl3, 600 MHz): = 3.60, 3.67 (AB system, J = 17.3 Hz, 2 H,
H2C(4)), 4.27 (mc, 2 H, Fc), 4.31 (s, 5 H, Fc), 4.40–4.42, 4.46–4.48 (2 m,
1 H each, Fc), 6.51, 6.76 (AB system, J = 15.9 Hz, 2 H, 2 =CH), 7.27–7.30,
7.34–7.42, 7.44–7.47, 7.64–7.68 (4 m, 1 H, 5 H, 2 H, 2 H, Ph) ppm. 13C
NMR (CDCl3, 151 MHz): = 23.8 (t, C(4)), 66.9, 67.3, 68.5, 68.8, 69.4* (5
d, Fc), 84.8 (s, Fc), 88.6 (s, C(6)), 125.8, 126.8, 128.2, 128.3, 128.6, 128.7,
129.7, 131.2 (8 d, Ph, =CH), 135.9, 136.0 (2 s, Ph), 152.1 (s, C(3)) ppm; *
signal with higher intensity. IR: = 3058m, 3026m, 2926m, 1578m, 1456m,
1444m, 1313m, 1221m, 967s, 906s, 818m, 725s, 689vs cm–1. HRMS (ESI-
TOF): m/z [M + H]+ calcd for C27H24FeNOS: 466.0928; found: 466.0929.
(E)-3,6-Diphenyl-6-[2-(naphth-2-yl)vinyl]-4H-1,5,2-oxathiazine (11d):
reaction time: 60 min; yield: 150 mg (37%); colorless crystals, m. p. 171–
172 °C (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.43, 3.65 (AB system,
J = 17.5 Hz, 2 H, H2C(4)), 6.64, 6.90 (AB system, J = 15.9 Hz, 2 H, 2 =CH),
7.34–7.47, 7.59–7.64, 7.75–7.80 (3 m, 8 H, 3 H, 6 H, Ar) ppm. 13C NMR
(CDCl3, 151 MHz): = 23.4 (t, C(4)), 87.0 (s, C(6)), 123.6, 125.7, 126.3,
126.4, 127.0, 127.5, 127.7, 128.1, 128.3, 128.6, 128.67, 128.68, 129.3,
129.8, 133.0 (15 d, Ar, =CH), 133.1, 133.3, 133.4, 136.0, 140.0 (5 s, Ar),
152.2 (s, C(3)) ppm. IR: = 3054m, 2914m, 1582m, 1489m, 1443m,
1392m, 1222m, 1097m, 955s, 916s, 887m, 752s, 745s, 708s, 693vs,
689vs cm–1. HRMS (ESI-TOF): m/z [M + H]+ calcd for C27H22NOS:
408.1422; found: 408.1426.
(E)-6-Ferrocenyl-3-phenyl-6-[2-(thien-2-yl)vinyl]-4H-1,5,2-oxathiazine
(11i): reaction time: 24 h; yield: 260 mg (55%); beige crystals, m. p. 102–
1
104 °C. H NMR (CDCl3, 600 MHz): = 3.58, 3.68 (AB system, J = 17.3
Hz, 2 H, H2C(4)), 4.26 (mc, 2 H, Fc), 4.30 (s, 5 H, Fc), 4.40, 4.44 (2 sbr, 1
H each, Fc), 6.37, 6.88 (AB system, J = 15.6 Hz, 2 H, =CH), 6.98 (dd, J =
3.5, 4.9 Hz, 1 H, Thie), 7.01 (dbr, J ≈ 3.5 Hz, 1 H, Thie), 7.21 (dbr, J ≈ 4.9
Hz, 1 H, Thie), 7.39–7.42, 7.65–7.68 (2 m, 3 H, 2 H, Ph) ppm. 13C NMR
(CDCl3, 151 MHz): = 23.8 (t, C(4)), 66.9, 67.3, 68.6, 68.8, 69.4* (5 d, Fc),
84.5 (s, Fc), 88.4 (s, C(6)), 124.5, 124.9, 125.8, 127.0, 127.6, 127.9, 128.6,
129.8 (8 d, Ph, Thie, =CH), 136.0, 140.8 (2 s, Ph, Thie), 152.3 (s, C(3))
ppm; *signal with higher intensity. IR: = 3039m, 2957m, 2894m, 1493m,
1442m, 1378w, 1226m, 998s, 956s, 823m, 733s, 695s, 689vs cm–1. MS
(ESI): m/z (%) = 472 (100, [M + H]+). Anal. Calcd for C25H21FeNOS2
(E)-3,6-Diphenyl-6-[2-(ferrocenyl)vinyl]-4H-1,5,2-oxathiazine
(11e):
reaction time: 24 h; yield: 250 mg (54%); pale orange crystals, m. p. 155–
156 °C (decomp.). 1H NMR (CDCl3, 600 MHz): = 3.44, 3.46 (AB system,
9
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