تفاعل #1689228

ord-3d7e0f7e5dd74e4e89a17582d1ed9158

معادلة التفاعل

COC(=C1C2CC3CC(C2)CC1C3)c1ccc2cc(O)ccc2c1
6-hydroxy-2-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidene-methyl)naphthalene
c1ccc2ccccc2c1
naphthalene
COc1cc(CO)c([N+](=O)[O-])cc1OC
4,5-dimethoxy 2-nitrobenzyl alcohol
COC(=C1C2CC3CC(C2)CC1C3)c1cccc(O)c1
1-hydroxy-3-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidenemethyl)benzene
COP(=O)(Cl)Cl
methyl dichlorophosphate
COC(=C1C2CC3CC(C2)CC1C3)c1cccc(OP(=O)([O-])OCc2cc(OC)c(OC)cc2[N+](=O)[O-])c1.c1cc[nH+]cc1
pyridinium 4,5-dimethoxy-2-nitrobenzyl 3-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidenemethyl)phenyl phosphate

المذيبات

ظروف التفاعل

الظروف التفصيلية
See reaction.notes.procedure_details.

الإجراء التجريبي

The procedure for the preparation of 6-hydroxy-2-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidene-methyl)naphthalene (Edwards, B., Sparks, A., Voyta, J. C., Strong, R., Murphy, O., Bronstein, I., J. Org. Chem., 55, 6225-6229 (1990) and (U.S. Pat. No. 5,538,847, issued Jul. 23, 1996)), was followed to prepare both the naphthalene and benzene derivatives (Scheme 4). Subsequent phosphorylation of 1-hydroxy-3-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidenemethyl)benzene with methyl dichlorophosphate in pyridine and coupling with 4,5-dimethoxy 2-nitrobenzyl alcohol in pyridine (Rubinstein, M., Patchornik, A., Tetrahedron 31, 2107-2110 (1975)) afforded pyridinium 4,5-dimethoxy-2-nitrobenzyl 3-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidenemethyl)phenyl phosphate, which, upon ion exchange to the triethylamine salt, provided compound 9a in Scheme 4. Oxidation afforded 4,5-dimethoxy-2-nitrobenzyl (4-methoxyspiro[1,2-dioxetane-3,2'-tricyclo[3.3.1.13,7 ]decan]-3-yl)phenyl phosphate as the triethylamine salt (compound 10a in Scheme 4) [see Edwards et al., J. Org. Chem., 55, 6225-6229 (1990)]. Similarly, phosphorylation of 1-hydroxy-3-(methoxytricyclo[3.3.1.13,7 ]dec-2-ylidenemethyl)benzene with methyl dichlorophosphate in pyridine and coupling with 2-nitrobenzyl alcohol in pyridine followed by ion exchange to TEA salt and subsequent oxidation afforded triethylammonium 2-nitrobenzyl (4-methoxyspiro[1,2-dioxetane-3,2'-tricyclo[3.3.1.13,7 ]decan]-3-yl)phenyl phosphate.

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US05981207uspto-grants-1999_11