1
4-Methoxy-4,15-retro-deoxyretinol (11). HPLC
R
T
=
Notes and references
9
(
.7 min, 16% (330 nm), kmax/nm 331, 347, 365, %III/II 51; m/z
EI) 300 (M , 100%, base peak), 268 (15, M − CH
1
2
3
F. H. Carr and E. A. Price, Biochem. J., 1926, 20, 497–501.
T. Moore, Vitamin A, Elsevier, Amsterdam, 1957.
+
3
OH).
U. Schwieter, G. Englert, N. Rigassi and W. Vetter, Pure Appl. Chem.,
969, 20, 365–420.
T. S. Sorensen, J. Am. Chem. Soc., 1965, 87, 5075–5084.
1
4-Ethoxy-4,15-retro-deoxyretinol. HPLC R
T
= 10.5 min, 7%
1
+
(
1
330 nm), kmax/nm 333, 349, 367, %III/II 48; m/z (EI) 314 (M ,
00%, base peak), 284 (10), 268 (12, M − EtOH), 260 (16).
Anhydroretinol (4). HPLC R
max/nm 349, 367, 385, %III/II 63; m/z (EI) 268 (M , 100%, base
4
5 T. S. Sorensen, in Carbonium Ions Vol 2: Methods of Formation and
Major Types, ed. G. A. Olah and P. von R. Schleyer, Wiley-Interscience,
New York, 1970, pp. 807-835.
T
= 11.7 min, 21% (330 nm),
+
k
6 A. Wassermann, J. Chem. Soc., 1959, 979–982.
7
8
9
N. C. Deno, C. U. Pittman, Jr. and J. O. Turner, J. Am. Chem. Soc.,
peak).
1
965, 87, 2153–2157.
W. V. Bush and L. Zechmeister, J. Am. Chem. Soc., 1958, 80, 2991–
999.
Dimer mixture. HPLC R
max/nm 305–323; m/z (EI) 536 (M , 16%), 268 (100, base peak).
T
= 36–39 min, 14% (330 nm),
2
+
k
P. E. Blatz and D. L. Pippert, J. Am. Chem. Soc., 1968, 90, 1296–
1300.
◦
c) Sodium methoxide at −15 C. Retinol (1, 5.0 mg,
1
0 P. E. Blatz, N. Baumgartner, V. Balasubramaniyan, P. Balasubra-
maniyan and E. Stedman, Photochem. Photobiol., 1971, 14, 531–549.
0
.017 mmol) was dissolved in chloroform (5.0 mL) immersed in
a dry ice–ethylene glycol bath to keep the solution at the desired
temperature. Trifluoromethanesulfonic acid (10 lL), dissolved in
chloroform (2.0 mL) and cooled to −15 C, was added, causing
11 P. E. Blatz and A. Estrada, Anal. Chem., 1972, 44, 570–573.
1
2 B. F. Lutnaes, L. Bru a˚ s, G. Kildahl-Andersen, J. Krane and S. Liaaen-
Jensen, Org. Biomol. Chem., 2003, 1, 4064–4072.
◦
1
3 F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, John
an immediate colour change to dark blue. The reaction mixture
was quenched with sodium methoxide in methanol (1.0 mL, 30%)
solution kept at the same temperature after 10 min, and regained its
yellow colour after a few seconds. The pigments were transferred
to hexane and washed with water and aqueous, saturated NaCl
solution. After evaporation of solvents, the crude product mixture
was redissolved in tert-butyl methyl ether and analysed by HPLC,
and subsequently separated in two fractions by preparative HPLC.
Wiley & Sons, New York, 5th edn, 1988, pp. 396–397.
14 A. C. Buchanan III, R. Livingston, A. S. Dworkin and G. P. Smith,
J. Phys. Chem., 1980, 84, 423–427.
1
1
5 K. Bobrowski and P. K. Das, J. Phys. Chem., 1985, 89, 5079–5085.
6 Q.-X. Guo, T. Ren, B. Li, J. Wang, Y.-C. Liu, T.-C. Tu and J.-R. Dong,
Chin. J. Chem., 1994, 12, 66–72.
1
1
7 G. Kildahl-Andersen, T. A. Konovalova, A. L. Focsan, L. D. Kispert,
T. Anthonsen and S. Liaaen-Jensen, unpublished work.
8 G. Englert, in Carotenoids, ed. G. Britton, H. Pfander and S. Liaaen-
Jensen, Birkh a¨ user, Basel, 1995, vol. 1B: Spectroscopy, pp. 147–260.
Dimer I. HPLC R
91, 303 sh; m/z (EI) 555 (20%, M + 1), 554 (M , 48), 431 (15),
65 (22), 351 (11), 285 (20), 269 (45), 268 (100, base peak).
Dimer II. HPLC R
m/z (EI) 555 (34%, M + 1), 554 (M , 81), 431 (44), 364 (20), 351
39), 285 (76), 269 (100, base peak), 268 (40).
T
= 17.6 min, 50% (280 nm), kmax/nm 281sh,
19 G. Englert, Helv. Chim. Acta, 1975, 58, 2367–2390.
+
20 H. Spiesecke and W. G. Schneider, Tetrahedron Lett., 1961, 3, 468–472.
2
3
2
1 B. F. Lutnaes, G. Kildahl-Andersen, J. Krane and S. Liaaen-Jensen,
J. Am. Chem. Soc., 2004, 126, 8981–8990.
T
= 18.8 min, 21% (280 nm), kmax/nm 289;
22 G. Kildahl-Andersen, B. F. Lutnaes, J. Krane and S. Liaaen-Jensen,
+
Org. Lett., 2003, 5, 2675–2678.
2
2
2
2
2
3 R. L. Christensen and B. E. Kohler, Photochem. Photobiol., 1973, 18,
(
2
93–301.
4 V. V. Konovalov and L. D. Kispert, J. Chem. Soc., Perkin Trans. 2, 1999,
901–909.
Reaction of Carr–Price product with sodium methoxide
5 H. Schmidbaur, R. Nowak, O. Steigelmann and G. M u¨ ller, Chem. Ber.,
1990, 123, 1221–1226.
Retinol (1, 10.0 mg, 0.035 mmol) was dissolved in chloroform
5.0 mL) at room temperature. SbCl (200 mg, 0.88 mmol) in chlo-
6 T. Probst, O. Steigelmann, J. Riede and H. Schmidbaur, Chem. Ber.,
(
3
1
991, 124, 1089–1093.
roform (2.0 mL) was added, causing an immediate colour change
to dark blue. The reaction mixture was quenched with sodium
methoxide in methanol (1.0 mL, 30%) after 30 s, and regained
its yellow colour. A few drops of N-ethyl diisopropylamine was
added, and the pigments transferred to hexane and washed with
water and aqueous, saturated NaCl solution. After evaporation of
solvents, the crude product mixture was redissolved in tert-butyl
methyl ether and analysed by HPLC, showing mainly formation of
7 P. J. Durrant and B. Durrant, Introduction to Advanced Inorganic
Chemistry, Longman, London, 2nd edn, 1970, pp. 778–779.
28 K. Bobrowski and P. K. Das, J. Phys. Chem., 1986, 90, 927–931.
2
9 W. Oroshnik, G. Karmas and A. D. Mebane, J. Am. Chem. Soc., 1952,
4, 3807–3813.
7
3
0 M. Casey, J. Leonard, B. Lygo and G. Procter, Advanced Practical
Organic Chemistry, Blackie, Glasgow, 1990, pp. 35–36.
31 G. Britton, in Carotenoids, ed. G. Britton, H. Pfander and S. Liaaen-
Jensen, Birkh a¨ user, Basel, 1995, vol. 1B: Spectroscopy, pp. 13–62.
3
2 S. W. Provencher, CONTIN (Version 2) Users manual, technical
report EMBL-DA07, Max-Planck-Institut Biophysikalische Chemie,
G o¨ ttingen, 1984.
dimers, vide supra (HPLC R
T
= 17.3 min, 21% (280 nm), kmax/nm
= 18.5 min, 11%, kmax/nm 287; R
6.6 min, 11%, kmax/nm 291; R
2
3
81sh, 291, 303 sh; R
T
T
=
3
3
3
3
3
3 N. C. Santos and M. A. R. B. Castanho, Biophys. J., 1996, 71, 1641–
T
= 37.7 min, 11%, kmax/nm 291).
◦
1650.
Reduction of the reaction temperature to −15 C gave similar
4 R. L. Lin, G. R. Waller, E. D. Mitchell, K. S. Yang and E. C. Nelson,
Anal. Biochem., 1970, 35, 435–441.
results.
5 R. Burger, C. Schorn and P. Bigler, J. Magn. Reson., 2001, 148, 88–
9
4.
Acknowledgements
6 E. M. Shantz, J. D. Cawley and N. D. Emtree, J. Am. Chem. Soc., 1943,
6
5, 901–906.
G. K.-A. was supported by a KOSK PhD fellowship from The
Research Council of Norway.
7 F. J. Petracek and L. Zechmeister, J. Am. Chem. Soc., 1956, 78, 3188–
3191.
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