Документ взят из кэша поисковой машины. Адрес оригинального документа : http://chem.msu.ru/rus/events/orgolymp06/zad2-123.pdf Дата изменения: Tue Apr 25 20:30:12 2006 Дата индексирования: Sun Apr 10 16:43:22 2016 Кодировка: Поисковые слова: m 80

V ­

.1 6

1. , :
O O N2 OCH3 N CH3

Br

CH3CN 200C, K2CO3 2 days

A

, . . - , = 120; ­ C12H14N2O4;
1 (270 MHz, DMSO): 2.14 (s, 3H) 2.31 (s, 3H) 2.54 (s, 3H) 3.96 (s, 3H) 4.45 (s, 2H) 1 (270 MHz, CDCl3): 1.96 (s, 3H) 2.15 (s, 3H) 2.17* (s, 3H) 2.31* (s, 3H) 2.48 (s, 3H) 2.53* (s, 3H) 3.92 (s, 3H) 4.00* (s,3H) 4.30 (s, 2H) 5.30* (s, 1H) ~11* (s, 1H) 13C (270 MHz, CDCl3): 18.26 27.55 32.03 49.34 53.78 132.33 137.05 139.84 160.47 163.32 190.01 200.67

* - , . 13


V ­

.2 6

· 2. (BTMA Br3-) :

t-B u A C21H26BrO

OMe

BTMA Br3MeOH

C17H15BrO B, 92%

, ((MeOH) 107-108), 1 (270 MHz, CDCl3): 2.80-3.10 (m, 8H), 3.93 (s, 3H), 6.68 (s, 1H), 7.05-7.15 (m, 3H).


V ­

.3 6

3. , - (1-3), :
CH3 Ar OH CH3
3

HCl, EtOH

?

CH
1 2 3
4: C16H21N, IR(CHCl3):
1

Ar - 2,6- -
= 64-66,

, 24 85 C, 1 , 3
[]20D = 248.8o (EtOAc),
13

4 5 6

68% 88% 91%

o

3384 cm-1 C NMR (CDCl3, 100 MHz): 20.46, 21.03, 23.61 (CH2), 26.23 (CH2), 27.29, 44.63 (CH2), 46.41, 52.79 (q), 63.93 (q), 72.53 (q), 109.74, 118.08, 123.44, 127.43, 128.33 (q), 151.97 (q)

H NMR (CDCl3, 400 MHz): 0.94 (3H,s), 0.99 (3H, s), 1.20 (3H, s), 1.29 (1H, ddd, J = 12.5, 8.9, 5.5 Hz), 1.37 (1H, d, J = 12.5 Hz), 1.71 (1H, ddd, J = 12.3, 9.2, 2.8 Hz), 1.84-1.94 (2H, m), 2.01 (1H, m), 2.47 (1H, ddd, 12.5, 3.2, 3.2 Hz), 6.34 (1H, dd, J = 7.7, 7.7 Hz), 6.58 (1H, d, J = 7.7 Hz), 7.0-7.06 (2H, m).


V ­
5: C16H21N, IR(CHCl3):
1

.4 6

= 58-61,
-1 13

[]20D = -1.1o (EtOAc), C NMR (CDCl3, 100 MHz): 16.94, 18.66, 21.87, 23.54, 34.85, 42.47, 48.76, 50.93 (q), 54.92, 56.61 (q), 97.52 (q), 102.33 (q), 102.47 (q), 120.12 (q), 128.83, 157.40 (q), 160.01 (q).

1596, 1254, 1099, 1082 cm

H NMR (CDCl3, 400 MHz): 1.00 (1H, ddd, J = 12.1, 7.0, 4.3, 2.6 Hz), 1.12 (1H, ddd, J = 12.2, 12.2, 4.8 Hz), 1.24 (1H, dd, J = 10.4, 1.6 Hz), 1.28 (3H, s), 130 (3H, s), 1.355 (3H, s), 1.38 (dddd, J = 12.6, 12.6, 4.4, 4.4 Hz), 1.57-1.65 (2H, m), 2.16 (1H, br d, J = 4.6 Hz), 3.78 (3H, s), 6.36 (1H, d, J = 8.8 Hz), 6.38 (1H, d, J = 8.2 Hz), 7.06 (1H, dd, J = 8.8, 8.2 Hz).


V ­
6: C17H22, , IR(CHCl3):
1

.5 6

2959, 1290 cm-1
13

H NMR (CDCl3, 400 MHz): 0.76 (3H, s), 0.82* (3H, s), 0.84 (1H, ddd, J = 1.1, 1.1, 1.1 Hz), 0.86* (3H, s), 0.92 (3H, s), 1.05* (3H, s), 1.11* (1H, ddd, J = 1.1, 1.1, 1.1 Hz), 1.19 (3H, s), 1.26* (1H, dd, J = 10.4, 1.2 Hz), 1.28 (1H, dd, J = 10.6, 1.3 Hz), 1.37 (1H, ddd, J = 10.6, 1.3, 1.2 Hz), 1.43* (1H, ddd, J = 10.6, 1.4, 1.4) Hz), 1.57-1.60 (1H, m, both isomers), 1.84 (1H, ddd, J = 10.6, 1.6, 1.6 Hz), 1.93 (1H, br d, J = 9.4 Hz), 1.95* (1H, ddd, J = 10.7, 1.6, 1.6 Hz), 2.01* (1H, br d, J = 10.6 Hz), 2.38 (3H, s), 2.39* (3H, s), 7.06-7.29 (4H, m, both isomers).

C NMR (CDCl3, 100 MHz): 15.03*, 15.75, 20.43, 20.63*, 21.84, 22.07, 22.34* (q), 22.90*, 25.15 (q), 25.96*, 26.44* (q), 26.95, 32.02*, 32.68, 37.95, 38.06 (q), 38.46*, 40.23*, 42.27, 43.33*, 48.54 (q), 48.98* (q), 124.66, 124.99*, 125.98, 126.09*, 130.18*, 130.59, 133.62, 134.68*, 134.92 (q), 135.99* (q), 139.45* (q), 139.92 (q).

* - minor isomer