Chemistry of carbon compounds – Miscellaneous organic carbon compounds – C-metal
Patent
1980-03-05
1981-10-13
Rotman, Alan L.
Chemistry of carbon compounds
Miscellaneous organic carbon compounds
C-metal
2603405R, 560 56, 564172, 568327, 568649, C07D31770, C07C 6976, C07C 49337
Patent
active
042947634
ABSTRACT:
The present invention provides compounds having the structure: ##STR1## wherein R.sup.1 represents alkoxy or aralkoxy, R.sup.2 represents hydrogen, alkoxy, aralkoxy, alkyl, aralkyl, or R.sup.1 and R.sup.2 taken together represent the group --O--CH.sub.2 --O--, R.sup.3 represents hydrogen, alkyl, aralkyl, acyl or a protecting group, Y represents Cl, Br, I or a leaving group; and X represents Cl, Br or I.
The present invention also provides a process for preparation of compounds VI in a single step wherein X and Y are the same and represent Cl, Br, or I, and R.sup.3 is as previously defined except that in this instance, it does not represent a protecting group.
According to another aspect of the present invention there are provided compounds VII-a and VII-b having the structure: ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 are as previously defined, j is an integer having a value of 0 or 1, Z.sup.1 represents a non-reacting electron withdrawing group, and Z.sup.2 represents a non-reacting electron withdrawing group or hydrogen, R.sup.8 and R.sup.9 are the same or different and represent hydrogen, alkyl, aralkyl, alkoxy, or aralkoxy, and R.sup.7 represents hydrogen, alkyl, aralkyl or acyl. Compounds VII-a may be prepared from compounds VI through the use of the process of "insertion-cyclization" which is provided by another aspect of the present invention.
According to a further aspect of the present invention, compounds VII-a are converted into tetralone III-a shown below: ##STR3## wherein R.sup.1, R.sup.2, R.sup.3, Z.sup.1, Z.sup.2, R.sup.7, R.sup.8 and R.sup.9 are as previously defined. Certain of these compounds can, in turn, be readily converted into picropodophyllin and picrosikkimotoxin. The latter can be converted into known antineoplastic agents by known procedures.
REFERENCES:
patent: 3524844 (1970-08-01), Keller-Juslen
patent: 4122092 (1978-10-01), Kende et al.
Shamma, The Isoquinoline Alkaloids, Chemistry and Pharmacology 1972, Academic Press, pp. 42-45.
Hartwell et al., Fortschr. Chem. Organische Naturstoffe 15, p. 101.
McOmie, Protective Groups in Organic Chemistry Plenum Press, 1973, pp. 95-143.
March, Advanced Organic Chemistry, McGraw-Hill Book Co. p. 21.
Hergrueter et al. Tetrahedron Letters No. 48 pp. 4145-4148, 1977.
Parham et al., J. Org. Chem., vol. 43, No. 8, 1978 pp. 1606-1607.
Kraus et al., J. Org. Chem., 44, 2480-2482 (1979).
Bruwer et al., Tetrahedron Letters, 52, 4573-4574, 1977.
Parham et al., J. Org. Chem., vol. 41, 1184-1186, 2628-2633, 2704-2706 (1976).
Parham et al., J. Org. Chem., vol. 39, 2051-2053 (1974).
Wildeman et al., Tetrahedron Letters, 25, 2213-2216 (1978).
Gilman et al., J. Org. Chem., 30, 325-328 (1965).
Semmelhack et al., J.A.C.S., 97, 2507-2516 (1975).
Uyeo et al., Chem. Abst. 36, 4286g (1964).
Gensler et al., J. Am. Chem. Soc., 82, 1714-1727, 6074-6081 (1960).
Wagh et al., Indian J. Chem., 13, 882-885 (1975).
Campbell et al., J. Am. Chem. Soc., 75, 4681-4684, 1953.
Kuhn et al., Helv. Chim. Acta. 52, 944-947, 1969.
Curran Dennis P.
Feldstein Neil A.
Kende Andrew S.
King Margaret L.
Fan Jane T.
Rotman Alan L.
University of Rochester
LandOfFree
Intermediates for the production of picropodophyllin and related does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Intermediates for the production of picropodophyllin and related, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Intermediates for the production of picropodophyllin and related will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-930404