9
814
T. Rosenau et al. / Tetrahedron 58 (2002) 9809–9815
5a 7a
1
8b
3
4
4
3
4
.4.2. 3-Bromo-propan-1,2-diol (13). H NMR: d 3.47 (m,
H, CH Br, CH OH), 3.69 (m, 1H, CH OH), 3.76 (CH),
.07 (s, 2H, OH). C NMR: d 34.5 (CH Br), 64.4
2
13.3; 13.7 ( C, C, C), 20.3 (OAc), 60.3 ( C), 70.5 ( C),
2
77.1 ( C), 119.3 ( C), 123.0 ( C), 126.1 ( C), 129.8 ( C),
4a
5
7
8
2
2
2
1
3
8a
6
147.5 ( C), 148.2 ( C), 169.2 (CO). Resonances of the
isoprenoid side chain are not given. Anal. calcd for
C H O Cl (523.20): C, 71.17; H, 9.83; Cl, 6.78. Found:
(
CH OH), 71.3 (CH).
2
3
1 51 4
1
4
b, 1H, OH), 3.69 (d, 4H, CH ), 4.07 (quint., 1H, CH).
.4.3. 1,3-Dichloro-propan-2-ol (14). H NMR: d 2.53 (s,
3
C, 71.08; H, 10.02.
1
C
2
NMR: d 45.9 (CH Cl), 71.0 (CH).
2
4.4.12. 3-Bromo-4-hydroxy-a-tocopheryl acetate (23).
1
H NMR: d 2.09 (s, 3H, CH ), 2.12 (s, 3H, CH ), 2.22 (s,
3
3
1
3
3
4
.4.4. 1-Bromo-3-chloro-propan-2-ol (15). H NMR: d
.23 (s, 1H, OH), 3.45 (dq, 2H, CH Br), 3.60 (m, 2H,
3H, CH ), 2.31 (s, 3H, CH CO), 4.32 (d, 1H, CH, J¼
3
3
4
3
13
2
CH OH), 4.10 (m, 1H, CH). C NMR: d 35.1 (CH Br),
6.1 Hz), 5.03 (t, 1H, CH, J¼6.1 Hz). C NMR: d 11.9;
2
1
3
5a
7a
8b
3
4
13.3; 13.4 ( C, C, C), 20.5 (OAc), 58.4 ( C), 71.2 ( C),
77.0 ( C), 119.5 ( C), 123.6 ( C), 125.6 ( C), 130.2 ( C),
2
2
2
4a
5
7
8
4
7.1 (CH Cl), 70.7 (CH).
2
8
a
6
1
47.7 ( C), 148.2 ( C), 169.4 (CO). Resonances of the
1
4
1
3
.4.5. 1,3-Dibromo-propan-2-ol (16). H NMR: d 3.14 (s,
1
isoprenoid side chain are not given. Anal. calcd for
C H O Br (567.64): C, 65.59; H, 9.06; Br, 14.08.
Found: C, 65.45; H, 8.92.
3
H, OH), 3.56 (d, 4H, CH ), 4.03 (m, 1H, CH). C NMR: d
2
31 51 4
5.4 (CH Br), 69.9 (CH).
2
1
18
4
3
5
.4.6. 5-Chloro-pentan-1,4-diol (17). H NMR: d 1.50 (m,
3
4.5. Synthesis of NMMO· OH
2
2
3
H, CH (1H), CH ), 1.69 (m, 1H, CH ), 3.41 (m, 1H,
2 2 2
5
1
CH Cl), 3.55 (m, 1H, CH Cl), 3.59 (t, 1H, CH OH), 4.11
2
Anhydrous NMMO was twice recrystallized from acetone
(HPLC quality), followed by recrystallization from dry
chloroform and drying in vacuo. The NMMO (52 mmol,
6.10 g) was dissolved in dry chloroform (50 ml) at rt, and
2
2
4
13
(
(
(
m, 1H, CHOH), 4.50 (s, b, 2H, OH). C NMR: d 29.4
1
3
2
5
CH ), 30.0 ( CH ), 47.9 ( CH Cl), 60.9 ( CH OH), 70.7
2
2
2
2
4
CHOH).
1
8
23
O-labeled water (40 mmol, 0.99 g, d¼1.110 g cm ) was
1
4
1
1
3
.4.7. 5-Bromo-pentan-1,4-diol (18). H NMR: d 1.35 (m,
3
added. The solution was concentrated to a volume of about
25 ml at a bath temperature of 408C, and cooled to rt. Dry
diethyl ether (20 ml) was added, upon which the mono-
hydrate crystallized. The mixture was kept at 2208C
3
2
H, CH (1H), 1.55 (m, 3H, CH (1H), CH ), 2.98 (m,
2
2
2
5
5
1
H, CH Br), 3.15 (m, 1H, CH Br), 3.62 (t, 1H, CH OH),
2
2
2
4
13
.72 (s, 2H, OH), 4.15 (m, 1H, CHOH). C NMR: d 30.1
3
2
5
1
(
(
CH ), 31.4 ( CH ), 38.4 ( CH Br), 61.5 ( CH OH), 69.9
2
overnight, the solids were collected by filtration and dried
18
2
2
2
4
CHOH).
in vacuo to give NMMO· OH (92%) in long, colorless
2
1
21
needles, mp 788C. H NMR (300 MHz, CDCl , 5 mg ml
3
2.70 (s, 2H, H O), 3.14 (dd, 2H, N–CH ), 3.26 (s, 3H,
2 2
N–CH ), 3.38 (dt, 2H, N–CH ), 3.78 (dd, 2H, O–CH ),
3 2 2
4.43 (dt, 2H, O–CH ,). C NMR: d 60.86 (N–CH ), 61.52
2
)
1
4
.4.8. 1-Chloro-decan-2-ol (19). H NMR: d 0.85 (t, 3H,
3
1
0
CH ), 1.25 (m, 10H, 5£CH ), 1.50 (m, 3H, CH (1H)),
3
2
2
4
3
1
13
CH ), 1.62 (m, 1H, CH (1H)), 3.38 (dd, 1H, CH Cl),
2
2
2
3
1
2
3.56 (dd, 1H, CH Cl), 4.04 (m, 1H, CHOH), 4.82 (s, 1H,
3
OH). C NMR: d 14.2, 22.2, 25.0, 29.4, 29.5, 29.7, 31.5
( CH ), 32.0, 47.9 ( CH Cl), 72.0 ( CHOH). Anal. calcd for
2 2
C H OCl (192.73): C, 62.32; H, 10.98; Cl, 18.40. Found:
(N–CH ), 65.72 (O–CH ).
2
2
2
1
3
1
2
1
0 21
C, 62.45; H, 11.09.
Acknowledgements
1
4
.4.9. 1-Bromo-decan-2-ol (20). H NMR: d 0.87 (t, 3H,
3
The financial support by the Austrian Fonds zur F o¨ rderung
der Wissenschaftlichen Forschung (FWF), project 14687, is
gratefully acknowledged. The authors would like to thank
Dr A. Hofinger and Dr J. R o¨ hrling, Institute of Chemistry
at the University of Agricultural Sciences Vienna, for
recording NMR spectra, as well as Dr T. Baldinger, Lenzing
A. G., and Dr P. Holubar, Institute of Microbiology at the
University of Agricultural Sciences, Vienna, for GC–MS
measurements.
1
0
CH ), 1.26 (m, 13H, 6£CH , CH (1H)), 1.52 (m, 1H,
3
2
2
3
1
1
CH (1H)), 2.97 (dd, 1H, CH Cl), 3.21 (dd, 1H, CH Cl),
2
2
2
2
13
3
2
7
5
.80 (s, 1H, OH), 4.18 (m, 1H, CHOH). C NMR: d 14.1,
3
1
2.2, 25.6, 29.1, 29.4, 29.7, 32.0, 33.1 ( CH ), 38.9 ( CH Br),
2
2
2
0.2 ( CHOH). Anal. calcd for C H OBr (237.18): C,
1
0.64; H, 8.92; Br, 33.69. Found: C, 50.78; H, 8.88.
0 21
4
.4.10. 2-Chloro-3,7,11,15-tetramethyl-hexadecan-1,3-
1
diol (21). H NMR: d 0.85 (m, 12H, 4£CH ), 1.04–1.62
3
3
(
1
(
m, 21H, 9£CH , 3£CH), 1.12 (s, 3H, C–CH ), 3.20 (s,
2
3
2
1
H, OH), 3.62 (t, 1H, CHCl), 3.67 (m, 1H, CH OH), 3.87
2
1
13
m, 1H, CH OH). C NMR: d 19.8, 19.9, 21.1, 22.6 (d.i.),
2
References
2
3
4.4, 24.5, 28.3, 31.0, 33.0, 36.7, 37.6, 37.7, 37.8, 39.2,
3
1
2
9.4, 60.7 ( CH OH), 66.9 ( CHCl), 74.2 ( C–OH). Anal.
2
1. See for instance: Godfrey, A. G.; Ganem, B. Tetrahedron Lett.
1990, 31, 4825. Suzuki, S.; Onishi, T.; Fujita, Y.; Misawa, H.;
Otera, J. Bull. Chem. Soc. Jpn 1986, 59, 3287.
calcd for C H O Cl (349.00): C, 68.83; H, 11.84; Cl,
2
0 41 2
1
0.16. Found: C, 68.59; H, 12.02.
2
. For a review see: Albini, A. Synthesis 1993, 263.
4
.4.11. 3-Chloro-4-hydroxy-a-tocopheryl acetate (22).
H NMR: d 2.08 (s, 3H, CH ), 2.11 (s, 3H, CH ), 2.20 (s,
3. Chanzy, H. J. Polym. Sci., Polym. Phys. Ed. 1980, 1137.
Today, NMMO is used to generate the Lyocell fiber type.
4. Rosenau, T.; Potthast, A.; Ebner, G.; Kosma, P. Synlett 1999,
5, 623.
1
3
3
3
3
3
6
H, CH ), 2.31 (s, 3H, CH CO), 4.48 (d, 1H, CH, J¼
3
3
4
3
13
.3 Hz), 5.05 (t, 1H, CH, J¼6.3 Hz). C NMR: d 12.0;