The crystal structure of 7α-[（R）-1-hydroxyl-1-methyl-3-（thien-2-yl）propyl]-6,14-endoethanotetrahydrothebaine （C29H37NO4S, Mr=495.66） has been determined by single-crystal X-ray diffraction analysis. The crystal...The crystal structure of 7α-[（R）-1-hydroxyl-1-methyl-3-（thien-2-yl）propyl]-6,14-endoethanotetrahydrothebaine （C29H37NO4S, Mr=495.66） has been determined by single-crystal X-ray diffraction analysis. The crystal belongs orthorhombic, space group P212121 with α=10.063（4）, b=12.571（5）, c=19.626（8）A°, V=2482.9（17）A°^3, Z=4, Dc=1.326 g/cm^3,μ=0.167 mm^-1, F（000）=1064, the final R=0.0537 and wR=0.0888. The C（7） substituent is l-hy-droxyl-1-methyl-3-（thienyl-2-）propyl group adopting R-configuration. The N-methyl group is located at the equatorial position as expected. The crystal structure shows the presence of intra- molecular hydrogen bonds, O（1）-H（1）…O（2）.展开更多
The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）...The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）-6,14- endoethano-6,7,8,14-tetrahydrothebaine （3） and a by-product 4 were isolated. The structure of 4 was elucidated by X-ray analysis. The Grignard reaction shows high degree of stereoselectivity according with Cram rule. The crystal structure of 4 indicates that dihydrofuran ring was opened to form a phenolic hydroxyl group and a three-membered ring structure. It maintains the main rigid structure of morphine and contains a C（6）-C（14） enthano bridge. The 1-hydroxyl-1-methyl-3-（thien-2-yl）propyl group at C（7） position adopted S-configuration.展开更多
Oripavine is the major alkaloid of Papaver orientale. It is an important intermediate in the biosynthesis of morphine alkaloids. Recently, new Papaver somniferum strains have been developed which accumulate thebaine a...Oripavine is the major alkaloid of Papaver orientale. It is an important intermediate in the biosynthesis of morphine alkaloids. Recently, new Papaver somniferum strains have been developed which accumulate thebaine and oripavine, but not morphine and codeine. Therefore, the chemistry of oripavine has been studied intensively to synthesize opioid pharmaceuticals such as oxymorphone, naloxone and buprenorphine.展开更多
The title compound, C25H24N2O2, a new rearrangement byproduct,has been found in the O-demethylation of 7a-o-amino pheny1-6, 14-endo-ethenotetrahydro thebaine. Its structure was determined by X-ray crystallography. Its...The title compound, C25H24N2O2, a new rearrangement byproduct,has been found in the O-demethylation of 7a-o-amino pheny1-6, 14-endo-ethenotetrahydro thebaine. Its structure was determined by X-ray crystallography. Its crystal isorthorhombic, space group P212121, Mr= 384. 48 with a= 9. 128(2), b= 11. 953 (3),c=17. 422(4) A, V= 1901 (1) A3, Dc= 1. 34 g/cm3, Z= 4, A(MoKa)=0. 71073A,μ= 0. 8 cm-1, F(000) = 816, R= 0. 048, Rw= 0. 051. The molecule is mainly a closedstructure except three extended legs. It consists of a lot of multi-membered rings suchas five- and six- membered rings.展开更多
基金The project was supported by the NNSFC (No. 30271492)
文摘The crystal structure of 7α-[（R）-1-hydroxyl-1-methyl-3-（thien-2-yl）propyl]-6,14-endoethanotetrahydrothebaine （C29H37NO4S, Mr=495.66） has been determined by single-crystal X-ray diffraction analysis. The crystal belongs orthorhombic, space group P212121 with α=10.063（4）, b=12.571（5）, c=19.626（8）A°, V=2482.9（17）A°^3, Z=4, Dc=1.326 g/cm^3,μ=0.167 mm^-1, F（000）=1064, the final R=0.0537 and wR=0.0888. The C（7） substituent is l-hy-droxyl-1-methyl-3-（thienyl-2-）propyl group adopting R-configuration. The N-methyl group is located at the equatorial position as expected. The crystal structure shows the presence of intra- molecular hydrogen bonds, O（1）-H（1）…O（2）.
基金Project supported by the National Natural Science Foundation of China （No. 30271492）
文摘The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）-6,14- endoethano-6,7,8,14-tetrahydrothebaine （3） and a by-product 4 were isolated. The structure of 4 was elucidated by X-ray analysis. The Grignard reaction shows high degree of stereoselectivity according with Cram rule. The crystal structure of 4 indicates that dihydrofuran ring was opened to form a phenolic hydroxyl group and a three-membered ring structure. It maintains the main rigid structure of morphine and contains a C（6）-C（14） enthano bridge. The 1-hydroxyl-1-methyl-3-（thien-2-yl）propyl group at C（7） position adopted S-configuration.
文摘Oripavine is the major alkaloid of Papaver orientale. It is an important intermediate in the biosynthesis of morphine alkaloids. Recently, new Papaver somniferum strains have been developed which accumulate thebaine and oripavine, but not morphine and codeine. Therefore, the chemistry of oripavine has been studied intensively to synthesize opioid pharmaceuticals such as oxymorphone, naloxone and buprenorphine.
文摘The title compound, C25H24N2O2, a new rearrangement byproduct,has been found in the O-demethylation of 7a-o-amino pheny1-6, 14-endo-ethenotetrahydro thebaine. Its structure was determined by X-ray crystallography. Its crystal isorthorhombic, space group P212121, Mr= 384. 48 with a= 9. 128(2), b= 11. 953 (3),c=17. 422(4) A, V= 1901 (1) A3, Dc= 1. 34 g/cm3, Z= 4, A(MoKa)=0. 71073A,μ= 0. 8 cm-1, F(000) = 816, R= 0. 048, Rw= 0. 051. The molecule is mainly a closedstructure except three extended legs. It consists of a lot of multi-membered rings suchas five- and six- membered rings.
