PAPER
1-Bromoundecyl Acetate (2e)31
A Direct, Straightforward Conversion of Methoxymethyl Ethers into Acetates
303
13
1
C NMR (CDCl ): d = 171.2 (C-9), 144.9 (C-5), 109.9 (C-12), 62.0
3
IR (film): n = 2927, 2854, 1741, 1465, 1365, 1240, 1037, 1012, 943,
(C-8), 52.4 (C-2), 41.1 (C-1), 32.3 (C-7), 28.9 (C-4), 28.1 (C-6),
23.2 (C-11), 21.1 (C-10), 19.1 (C-3).
-
1.
7
23, 644, 605 cm
1
+
H NMR (CDCl ): d = 4.02 (t, J = 6.3Hz, 2 H, CH OAc), 3.38 (t,
MS (EI): m/z (%) = 136 (M - AcOH, 2), 121 (24), 93 (45), 68
3
2
J = 6.9 Hz, 2 H, CH Br), 2.02 (s, 3 H, OCOCH ), 1.82 (m, 2 H,
(100), 67 (88), 43 (91).
2
3
CH CH Br), 1.57 (m, 2 H, CH CH OAc), 1.25 (br, 18 H, 9 CH ).
2
2
2
2
2
1
-Acetoxymethyloxyundecane (3a)
1
3
C NMR (CDCl ): d = 171.21 (CO), 70.59 (CH OAc), 34.02,
IR (CHCl ): n = 2955, 2925, 2854, 1747, 1465, 1365, 1240, 1040
cm .
3
2
3
-
1
3
2.79, 30.90, 29.41, 29.29, 29.18, 28.71, 28.55, 28.12, 25.86, 21.00
(
OCOCH3).
1
H NMR (CDCl ): d = 5.26 (s, 2 H, OCH O), 3.61 (t, J = 6.6 Hz, 2
3
2
Hexadec-11-ynyl Acetate (2f)32
H, CH OCH O), 2.09 (s, 3 H, OCOCH ), 1.57 (m, 2 H,
2
2
3
IR (film): n = 2954, 2929, 2856, 1741, 1465, 1365, 1238, 1039
CH CH OCH O), 1.46-1.10 (br, 16 H, 8 CH ), 0.87 (t, J = 6.6 Hz,
2
2
2
2
-
1
cm .
3 H, CH CH ).
3 2
1
13C NMR (CDCl ): d = 170.6 (CO), 89.1 (OCH O), 70.7
H NMR (CDCl ): d = 4.02 (t, J = 6.6 Hz, 2 H, CH OAc), 2.11 (m,
3
2
3
2
4
H, CH C≡CCH ), 2.01 (s, 3 H, OCOCH ), 1.58 (m, 2H,
(CH OCH O), 31.9, 29.6, 29.5, 29.4, 29.2, 25.9, 22.7, 21.1
2 2
2
2
3
CH CH OAc), 1.2-1.5 (br, 20 H, 10 CH ), 0.87 (t, J = 7.2 Hz, 3 H,
(OCOCH ), 14.1 (CH ).
2
2
2
3 3
CH ).
+
3
MS (EI): m/z (%) = 185 (M - OCOCH , 2), 57 (49), 43 (100).
3
1
3
C NMR (CDCl ): d = 171.23 (CO), 80.15 (C≡C), 64.62
2 3
3
Anal. Calc. for C H O : C, 68.81; H, 11.55. Found: C, 68.84; H,
1
4
28
3
(
CH OCOCH ), 31.24, 29.42, 29.40, 29.21, 29.12, 29.09, 28.79,
1
1.44.
2
8.57, 25.87, 21,90, 20.99 (OCOCH ), 18.71, 18.41, 13.60 (CH )
3 3
1
-Acetoxymethyloxyundec-10-ene (3d)
ppm.
IR (CHCl ): n = 3076, 2927, 2856, 1745, 1641 1367, 1234, 1012
Z)-Tetradec-9-enyl Acetate (2g)27
3
(
-1
cm .
IR (film): n = 3004, 2927, 2856, 1743, 1465, 1365, 1240, 1039, 723
1
-
1
H NMR (CDCl ): d = 5.80 (m, 1 H, CH =CH), 5.25 (s, 2 H,
3 2
cm .
OCH O), 4.94 (m, 2 H, CH =CH), 3.60 (t, J = 6.6 Hz, 2 H,
1
2
2
H NMR (CDCl ): d = 5.31 (m, 2 H, CH=CH), 4.02 (t, J = 6.9 Hz,
3
CH OCH O), 2.08 (s, 3 H, OCOCH ), 2.03 (m, 2 H, CH =CHCH ),
2
2
3
2
2
2
H, CH OAc), 2.01 (s, 3 H, OCOCH ), 1.99 (m, 4 H,
2
3
1
.58 (m, 2 H, CH CH OCH O), 1.5-1.2 (br, 12 H, 6 CH ).
2
2
2
2
CH CH=CHCH ), 1.57 (m, 2 H, CH CH OAc), 1.28 (br, 16 H, 8
2
2
2
2
1
3
C NMR (CDCl ): d = 170.6 (CO), 139.1 (CH =CH), 114.1
2 2 2 2
CH ), 0.87 (t, J = 7.2 Hz, 3 H, CH ).
3
2
2
3
(
(
(
CH =CH), 89.4 (OCH O), 70.6 (CH OCH O), 33.8
CH =CHCH ), 29.5, 29.5, 29.4, 29.3, 29.1, 28.9, 25.9, 21.0
OCOCH3).
1
3
C NMR (CDCl ): d = 171.24 (CO), 129.88 (CH=CH), 129.76
3
2
2
(
CH=CH), 64.62 (CH OCOCH ), 31.92, 29.68, 29.36, 29.19, 29.15,
2 3
2
8.56, 27.12, 26.88, 25.86, 22.31, 20.98 (OCOCH ), 13.96 (CH ).
3 3
+
MS (EI): m/z (%) = 153 (M - OCH OCOCH , 1), 97 (42), 55 (48),
Benzyl Acetate (2h)27
2
3
4
3 (100).
IR (film): n = 3089, 3066, 3035, 2956, 2894, 1953, 1741, 1498,
-
1
Anal. Calc. for C H O : C, 69.38; H, 10.81. Found: C, 69.39; H,
1
456, 1380, 1363, 1230, 1027, 750 cm .
14 26
3
1
0.98.
1
H NMR (CDCl ): d = 7.35 (s, 5 H, C H ), 5.10 (s, 2 H, C H CH ),
3
6
5
6
5
2
r-1-Acetoxymethyloxyethyl-1-methyl-c-2-isopropenylcyclobu-
tane (3j)
2
.09 (s, 3H, OCOCH ).
3
1
3
C NMR (CDCl ): d = 170.80 (CO), 135.87 (arom Cipso), 128.50
3
(
arom 2 C ), 128.19 (arom C , 2 C ), 66.24 (CH OCOCH ),
meta
ortho
para
2
3
2
0.94 (OCOCH3).
2
,5-Dimethoxybenzyl Acetate (2i)33
IR (film): n = 3001, 2950, 2912, 2837, 1741, 1595, 1502, 1463,
-
1
1
1
379, 1232, 1047, 806, 713 cm .
IR (film): n = 3080, 2950, 2931, 2867, 1745, 1647, 1367, 1228,
-1
H NMR (CDCl ): d = 6.91 (m, 1 Harom, H-6), 6.82 (d, J = 1.2 Hz, 2
1128, 1010, 939 cm .
3
Harom, H-3, 4), 5.14 (s, 2 H, C H CH ), 3.80 (s, 3 H, OCH ), 3.77 (s,
1
6
5
2
3
H NMR (CDCl ): d = 5.25 (s, 2 H, H-9), 4.83 (d, J = 1.5 Hz, 1 H,
3
3
H, OCH ), 2.11 (s, 3 H, OCOCH ).
3
3
H-13), 4.63 (br, 1 H, H-13), 3.64 (m, 2 H, H-8), 2.54 (t, J = 9.0 Hz,
1
3
C NMR (CDCl ): d = 170.90 (CO), 153.37 (C-5), 151.55 (C-2),
25.18 (C-1), 115.61 (C-3), 113.63 (C-4), 111.48 (C-6), 61.55
1 H, H-2), 2.09 (s, 3 H, H-11), 2.04-1.35 (m, 6 H, H-3,4,7), 1.66 (s,
3 H, H-6), 1.15 (s, 3 H, H-12).
3
1
(
(
CH OCOCH ), 55.98 (OCH ortho), 55.68 (OCH para), 20.99
CH3).
13
2
3
3
3
C NMR (CDCl ): d = 170.7 C-10) 144.9 (C-5), 109.8 (C-13), 89.4
3
(C-9), 67.8 (C-8), 52.4 (C-2), 41.1 (C-1), 33.3 (C-7), 29.1 (C-4),
r-1-Acetoxyethyl-1-methyl -c-2-isopropenylcyclobutane (Gran-
28.2 (C-6), 23.2 (C-12), 21.1 (C-11), 19.1 (C-3).
disol Acetate) (2j)34
+
MS (EI): m/z (%) = 167 (M - OCOCH , 1), 107 (34), 93 (36), 73
3
(
43), 69 (56), 68 (99), 67 (84), 43 (100).
1
,5,5-Trimethyl-4-oxabicyclo[4.2.0]octane (4j)35
-
1
IR (film): n = 3080, 2952, 2867, 1741, 1647, 1365, 1240, 887 cm .
1
H NMR (CDCl ): d = 4.83 (d, J = 1.5 Hz, 1 H, H-12), 4.64 (br, 1
3
H, H-12), 4.07 (m, 2 H, H-8), 2.56 (t, J = 9.3 Hz, 1 H, H-2), 2.03 (s,
IR (film): n = 2970, 2950, 2529, 2862, 1463, 1215, 1072, 918, 734
3
3
H, H-10), 2.01-1.35 (m, 6 H, H-3,4,7), 1.66 (s, 3 H, H-6), 1.17 (s,
H, H-11).
-
1
cm .
Synthesis 2000, No. 2, 300–304 ISSN 0039-7881 © Thieme Stuttgart · New York