Notes
,5-Bis(h yd r oxyp h en ylm eth yl)-2-m eth ylcyclop en ta n -1-
J . Org. Chem., Vol. 61, No. 6, 1996 2235
2
3.46 (s, OH), 2.53 (m, 1H), 1.20-1.75 (m, 7H), 0.95 (d, J ) 6.7,
1
13
on e: H NMR δ 7.31-7.33 (m, 10H), 4.82 (s, 1H), 4.70 (d, J )
3H); C NMR δ 216.33, 159.45, 134.05, 127.84, 113.54, 73.58,
9
0
1
2
,0, 1H), 4.61 (br s, 1H), 2.28-2.70 (m, 2H), 1.16-1.67 (m, 4H),
56.27, 54.89, 42.89, 35.07, 29.49, 20.22, 15.30; IR (neat) 3414,
1
3
-1
•+
.81 (s, 3H); C NMR δ 225.72, 141.31, 140.71, 128.33, 128.04,
27.90, 127.12, 126.57, 76.85, 75.82, 56.72, 54.39, 26.88, 22.42,
0.36; IR (neat) 3462, 2968, 2872, 1718 cm-1; MS, m/z 310 (M ).
2934, 1694, 1612, 1514 cm ; MS, m/z 248 (M ); HMRS calcd
for 248.1412, found 248.1417. Anal. Calcd for
: C, 72.55; H, 8.12. Found: C, 72.29; H, 8.17.
-(1′-Hyd r oxyp r op yl)-2-m et h ylcycloh exa n -1-on e (15a ).
C
15
H
3
20
O
3
•+
C
15
H
20
O
Anal. Calcd for C20
H, 7.18.
22 3
H O : C, 77.39; H, 7.14. Found: C, 77.54;
2
1
Threo isomer: H NMR δ 3.63 (dt, J ) 3.9,10.0, 1H), 3.29 (dd,
2
-(Hyd r oxy(p-n itr op h en yl)m eth yl)-2-m eth ylcycloh exa n -
J ) 1.3,3.9, OH), 2.20-2.60 (m, 2H), 1.20-2.00 (m, 10H), 1.14
1
1
(
(
2
2
-on e (11a ). Erythro isomer: Mp 149-151 °C. H NMR δ 7.56
13
(
3
2
s, 3H), 1.03 (t, J ) 7.2, 3H); C NMR δ 218.18, 76.44, 52.36,
d, J ) 8.0, 2H), 7.36 (d, J ) 8.0, 2H), 5.08 (d, J ) 3.9, 1H), 3.24
8.66, 35.92, 27.06, 22.70, 20.63, 16.53, 10.98; IR (neat) 3742,
1
3
d, J ) 3.9, OH), 1.20-2.60 (m, 8H), 1.03 (s, 3H); C NMR δ
-1
•+
938, 1698, 1458 cm ; MS, m/z 170 (M ). Anal. Calcd for
: C, 70.55; H, 10.66. Found: C, 70.45; H, 10.38.
-(1′-Hyd r oxyp r op yl)-6-m et h ylcycloh exa n -1-on e (16a ).
17.21, 144.84, 132.29, 131.28, 128.71, 76.43, 53.44, 39.08, 31.02,
10 18 2
C H O
-1
6.45, 21.25, 20.31; IR (neat) 3508, 2938, 1692, 1510, 1344 cm
.
2
1
Threo isomer: Mp 118-120 °C. H NMR δ 8.01 (d, J ) 5.0,
The crude material was a 42:28:28:2 diastereoisomeric mixture.
Major isomer: H NMR δ 3.62 (m, 1H), 3.44 (d, J ) 4.4, OH),
2
(
1
3
H), 7.36 (d, J ) 5.0, 2H), 4.95 (s, 1H), 4.21 (s, OH), 1.20-2.60
1
1
3
m, 8H), 1.11 (s, 3H); C NMR δ 218.12, 146.71, 133.81, 128.78,
2
3
3
1
1
.35 (m, 2H), 2.05 (m, 2H), 1.90-1.25 (m, 6H), 0.96 (d, J ) 6.4,
H), 0.92 (t, J ) 7.4, 3H); 13C NMR δ 216.21, 72.21, 55.30, 45.77,
6.65, 31.24, 26.03, 24.81, 13.67, 9.33; IR (neat) 3528, 2934, 1698,
22.50, 76.43, 52.41, 38.73, 36.63, 27.06, 20.38, 15.84; IR (neat)
-
1
•+
510, 2910, 1689, 1516, 1346 cm ; MS, m/z 263 (M ); HMRS
N 263.1158, found 263.1158. Anal. Calcd for
N: C, 63.87; H, 6.51; N, 5.32. Found: C, 63.70; H, 6.47;
calcd for C14
17 4
H O
-
1
•+
452 cm ; MS, m/z 152 (M ); HMRS calcd for C10
18 2
H O
14 17 4
C H O
70.1307, found 170.1292. Anal. Calcd for C10 : C, 70.55;
18 2
H O
N, 5.35.
-(Hyd r oxy(p-n itr op h en yl)m eth yl)-6-m eth ylcycloh exa n -
H, 10.66. Found: C, 70.31; H, 10.40. The second and third
isomers were collected together : 3.66 (m, 1H), 3.32 (d, J ) 2.7,
.5H, OH), 2.94 (d, J ) 2.7, 0.5H, OH), 2.45 (m, 2H), 1.90 (m,
H), 1.20-1.70 (m, 6H), 1.12 (d, J ) 1.5, 1.5H), 1.10 (d, J ) 1.7,
.5H), 0.95 (t, J ) 8.6, 1.5H), 0.94 (t, J ) 8.3, 1.5H).
2
1
1
-on e (12a ). Trans erythro isomer: Mp 124-126 °C. H NMR
0
2
1
δ 8.10 (d, J ) 7.7, 2H), 7.45 (d, J ) 7.7, 2H), 4.82 (dd, J ) 2.8,
9
7
7
2
, 1H), 3.41 (d, J ) 2.8, OH), 1.05-2.50 (m, 8H), 1.00 (d, J )
13
.9, 3H); C NMR δ 216.92, 148.70, 127.73, 127.19, 123.32,
2
-(1′-Hydr oxy-3′-m eth ylbu t-2′-en yl)-6-m eth ylcycloh exan -
3.69, 57.18, 46.07, 31.62, 24.67, 20.26, 14.03; IR (neat) 3516,
1
-
1
1-on e (17a ). Major isomer (55%): H NMR δ 5.06 (m, 1H), 4.46
942, 1702, 1514, 1352 cm . Cis threo isomer: Mp 134-136
1
(m, 1H), 3.50 (d, 1H), 2.25-2.45 (m, 2H), 1.6-2.1 (m, 4H), 1.67
°
C. H NMR δ 8.07 (d, J ) 7.7, 2H), 7.41 (d, J ) 7.7, 2H), 5.34
(
d, J ) 1.0, 3H), 1.61 (d, J ) 1.1, 3H), 1.1-1.4 (m, 2H), 0.96 (d,
(
s, 1H), 3.35 (s, OH), 1.05-2.50 (m, 8H), 0.94 (d, J ) 7.6, 3H);
13
1
3
J ) 6.4, 3H); C NMR δ 216.88, 136.43, 124.58, 68.39, 56.53,
C NMR δ 223.77, 149.52, 127.21, 126.60, 123.32, 70.43, 53.41,
4
5.98, 37.13, 31.41, 25.73, 24.94, 18.42, 14.05; IR (neat) 3508,
4
6.06, 32.94, 24.67, 19.21, 16.47; IR (neat) 3484, 2936, 1702,
-1
-
1
2932, 1696 cm . Anal. Calcd for C12
Found: C, 73.57; H, 10.32. Minor isomer (45%): H NMR δ 5.05
m, 1H), 4.57 (m, 1H), 2.86 (m, 1H), 2.59 (m, 1H), 2.42 (m, 1H),
1.72 (d, J ) 1.3, 3H), 1.67 (d, J ) 1.3, 3H), 1.4-2.0 (m, 6H),
.10 (d, J ) 7.0, 3H); 13C NMR δ 217.81, 137.01, 125.18, 68.48,
53.99, 44.04, 34.31, 29.61, 25.78, 20.30, 18.45, 15.93; IR (neat)
20 2
H O : C, 73.43; H, 10.27.
1
604, 1520, 1346 cm . Cis erythro isomer: Mp 118-120 °C.
1
1
H NMR δ 8.09 (d, J ) 7.8, 2H), 7.43 (d, J ) 7.8, 2H), 5.12 (d, J
3.6, 1H), 4.05 (d, J ) 3.6, OH), 1.05-2.50 (m, 8H), 0.98 (d, J
(
)
)
1
3
7.4, 3H); C NMR δ 215.81, 147.11, 128.76, 127.20, 122.55,
1
7
2
1
4
0
1
3
6.06, 53.00, 44.83, 31.00, 26.33, 20.26, 19.46; IR (neat) 3504,
-
1
912, 1690, 1522, 1346 cm
. Trans threo isomer: Mp 153-
-
1
1
3516, 2936, 1700 cm
.
55 °C. H NMR δ 8.18 (d, J ) 8.9, 2H), 7.48 (d, J ) 8.9, 2H),
.88 (d, J ) 6.8, 1H), 3.31 (d, J ) 6.8, OH), 1.05-2.50 (m, 9H),
.99 (d, J ) 7.1, 3H); 13C NMR δ 218.11, 149.19, 128.34, 127.19,
24.10, 74.39, 57.85, 46.73, 32.24, 25.30, 20.26, 16.88; IR (neat)
1-h yd r oxy-5-m eth yl-1-p h en ylh exa n -3-on e (20): 1H NMR
δ 5.30 (m, 5H), 5.11 (m, 1H), 3.52 (br s, 1H), 2.75 (m, 2H), 2.27
(m, 2H), 2.12 (m, 1H), 0.88 (d, J ) 6.5, 6H); 13C NMR δ 211.18,
142.86, 128.41, 127.51, 125.57, 69.79, 52.54, 51.45, 24.39, 22.45;
-
1
•+
390, 2932, 1708, 1606, 1522, 1346 cm ; MS, m/z 263 (M );
N 263.1158, found 263.1162. Anal.
N: C, 63.87; H, 6.51; N, 5.32. Found: C,
3.48; H, 6.49; N, 5.23.
-(H yd r oxy(p -m et h oxyp h en yl)m et h yl)-2-m et h ylcyclo-
-
1
HMRS calcd for C14
Calcd for C14
H
17
O
4
18 2
IR (neat) 3448, 2958, 1704 cm ; HMRS calcd for C13H O
H
17
O
4
206.1307, found 206.1309. Anal. Calcd for C13
H
18
O
2
: C, 75.69;
6
H, 8.79. Found: C, 75.43; H, 8.91.
2
5-Meth yl-1-p h en ylh ex-1-en -3-on e (21):
1
H NMR δ 7.51 (d,
1
h exa n -1-on e (13a ). Erythro isomer: H NMR δ 7.13 (d, J )
J ) 16, 1H), 7.37 (m, 5H), 6.71 (d, J ) 16.1, 1H), 2.50 (m, 2H),
8
3
.6, 2H), 6.76 (d, J ) 8.6, 2H), 4.95 (d, J ) 2.0, 1H), 3.71 (s, 3H),
2.21 (m, 1H), 0.95 (d, J ) 6.6, 6H); 13C NMR δ 200.22, 142.28,
.20 (d, J ) 2.0, OH), 1.15-2.50 (m, 8H), 0.95 (s, 3H); 13C NMR
134.49, 130.31, 128.85, 128.17, 126.76, 126.49, 49.83, 25.15,
δ 217.86, 158.77, 131.96, 118.95, 112.81, 76.50, 54.08, 53.52,
22.63; IR (neat) 2958, 1688, 1652, 1608 cm-1; MS, m/z 188 (M•+),
3
1
2
9.30, 31.13, 24.98, 21.37, 20.42; IR (neat) 3466, 2936, 1694,
146, 131, 103, 77. Anal. Calcd for C13H16O: C, 82.94; H, 8.57.
Found: C, 82.79; H, 8.66.
-
1
1
512, 1248 cm . Threo isomer: H NMR δ 7.20 (d, J ) 8.3,
H), 6.72 (d, J ) 8.3, 2H), 4.85 (d, J ) 1.6, 1H), 4.07 (d, J ) 1.6,
1
,3-Bis(h yd r oxyp h en ylm et h yl)-4-m et h ylp en t a n -2-on e
1
3
OH), 3.65 (s, 3H), 1.00-2.50 (m, 8H), 0.87 (s, 3H); C NMR δ
1
(
22). Major isomer: H NMR δ 7.26 (m, 10H), 4.98 (m, 1H),
2
2
17.42, 158.68, 131.81, 126.84, 112.78, 76.16, 54.93, 53.41, 39.25,
6.10, 21.24, 20.33, 19.08; IR (neat) 3458, 2934, 1698, 1514, 1248
4
1
3
1
2
.87 (m, 1H), 3.50 (m, 2H), 2.70 (m, 1H), 2.62 (dd, J ) 9.5, 18.1,
H), 2.21 (dd, J ) 1.4, 18.1, 1H), 2.01 (m, 1H), 1.02 (d, J ) 6.7,
-
1
•+
cm ; MS, m/z 248 (M ); HMRS calcd for C15
H
20
O
3
248.1412,
13
H), 0.89 (d, J ) 6.5, 3H); C NMR δ 216.81, 142.46, 128.54,
found 248.1418. Anal. Calcd for C15
Found: C, 72.38; H, 8.27.
20 3
H O : C, 72.55; H, 8.12.
28.27, 127.63, 127.31, 125.61, 125.34, 72.99, 68.90, 65.06, 55.90,
-1
8.27, 20.91, 20.12; IR (neat) 3398, 2962, 1700 cm
. Anal.
2
-(H yd r oxy(p -m et h oxyp h en yl)m et h yl)-6-m et h ylcyclo-
Calcd for C20
24 3
H O : C, 76.89; H, 7.74. Found: C, 76.75; H, 7.81.
Minor isomer: H NMR δ 7.26 (m, 10H), 5.01 (m, 2H), 3.43 (m,
1
h exa n -1-on e (14a ). Cis threo isomer: Mp 138-140 °C.
NMR δ 7.15 (d, J ) 8.6, 2H), 6.81 (d, J ) 8.6, 2H), 4.66 (d, J )
H
1
2
1
3
1
1
H), 2.84 (m, 1H), 2.66 (dd, J ) 3.4, 17.2, 1H), 2.57 (dd, J ) 8.8,
7.2, 1H), 1.85 (m, 1H), 0.95 (d, J ) 6.8, 3H), 0.85 (d, J ) 6.7,
8
1
1
3
.7, 1H), 3.91 (s, OH), 3.71 (s, 3H), 2.50 (m, 2H), 2.02 (m, 1H),
.20-2.60 (m, 5H), 0.96 (d, J ) 6.4, 3H); 13C NMR δ 216.55,
59.02, 133.31, 128.00, 113.56, 77.79, 57.57, 55.08, 45.99, 37.06,
13
H); C NMR δ 216.51, 142.62, 142.16, 128.55, 128.34, 127.81,
27.49, 125.94, 125.61, 73.73, 69.97, 64.96, 55.77, 28.28, 21.21,
-1
1.74, 24.81, 14.17; IR (neat) 3526, 2928, 1696, 1612, 1452 cm
.
-1
9.42; IR (neat) 3400, 2962, 1701 cm
.
1
Trans threo isomer: Mp 124-126 °C. H NMR δ 7.08 (d, J )
8
.5, 2H), 6.69 (d, J ) 8.5, 2H), 4.69 (d, J ) 9.9, 1H), 3.60 (s, 3H),
J O951429P