10 α -Hydroxy- β -isomorphine, a by-product of the synthesis of 10 α -hydroxymorphine

Abstract  

A new compound was isolated from the reaction mixture after O-demethylation of 6-O-acetyl-10α-acetoxycodeine with boron tribromide. The structure of this compound, 10α-hydroxy-β-isomorphine, was elucidated by spectral data, and its spatial arrangement was deduced from an NOE experiment. Capillary zone electrophoresis was used for separation of morphine and its 10-hydroxy analogues.     

Hydroacridines XXI [1]. 13C NMR Spectroscopic Investigation of the Stereoselectivities of Quaternizations of N-Alkyl Derivatives of (4aα,8aβ,9aβ,10aα)- and (4aα,8aα,9aβ,10aα)-Tetradecahydroacridine

Summary.  The stereoselectivities of the quaternization reactions of (4aα,8aβ,9aβ,10aα)- and (4aα,8aα,9aβ,10aα)-tetradecahydro-10-methylacridine with methyl- and ethyl iodide as well as those of (4aα,8aβ,9aβ,10aα)- and (4aα,8aα,9aβ,10aα)-10-ethyl-tetradecahydroacridine with methyl iodide were investigated using ¹³C NMR spectroscopy including ¹³C-labelling where appropriate. The methylations of both N-methyl amines occur by predominant (60% and 75%, respectively) equatorial approach, their ethylations occur sterospecifically by equatorial approach, and the methylations of the N-ethyl amines occur by highly stereoselective (> 90%) axial approach of the quaternizing reagent. Received October 27, 1999. Accepted November 22, 1999     

Unusual oxidation reactions of 7α-methyl- and 7α-phenylcholest-5-ene-3β,7β-diol

Summary Ozonation of 7-methyl (or 7-phenyl) cholest-5-ene-3,7-diol 3-TBDMS ether afforded the corresponding 5,6-epoxy derivatives. The same product was formed byMCPBA oxidation. The reaction of 7-phenylcholest-5-ene-3,7-diol with CrO₃ yielded 3,7-dioxo-6,7-seco-7-phenylcholest-4-ene-5-carboxaldehyde. An analogous B-seco aldehyde was obtained from 7-methylcholest-5-ene-3,7-diol in addition to 7-methylcholesta-4,6-dien-3-one.Jones oxidation of 7-phenylcholest-5-ene-3,7-diol or B-seco-aldehyde gave 3,7-dioxo-6,7-seco-7-phenylcholest-4-en-6-oic acid isolated as its methyl ester upon treatment with diazomethane.

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Ungewöhnliche Oxidation von 7-Methyl- und 7-Phenylcholest-3-en-3,7-diol

Zusammenfassung Ozonolyse von 7-Methyl- bzw. 7-Phenyl-cholest-3-en-3,7-diol-3-TBDMS-ether ergab die entsprechenden 5,6-Epoxy-Derivate.MCPBA-Oxidation führte zum gleichen Ergebnis. Bei der Reaktion von 7-Phenyl-cholest-5-en-3,7-diol mit CrO₃ wurde 3,7-Dioxo-6,7-seco-7-phenyl-cholest-4-en-5-carbaldehyd gebildet. Einen analogen B-seco-Aldehyd erhält man neben 7-Methyl-cholesta-4,6-dien-3-on auch aus 7-Methyl-cholest-5-en-3,7-diol. DurchJones-Oxidation von 7-Phenyl-cholest-5-en-3,7-diol oder B-seco-Aldehyd erhält man 3,7-Dioxo-6,7-seco-7-phenylcholest-4-en-6-carbonsäure, die nach Behandlung mit Diazomethan als ihr Methylester isoliert wurde.

     

Synthesis of Novel 17α-Eethynyl-5-androstene-3β, 7β, 17β-triol (HE3286)Derivatives

以脱氢表雄酮为原料,经羟基乙酰化,羰基亚乙二氧基化,CrO3/3,5-二甲基吡啶氧化,硼氢化钠还原,脱17-位亚乙二氧基,脱3-位乙酰基,用叔丁基二甲基氯硅烷(TBDMSC1)保护3,7-OH,17-位环氧化,17-位开环,脱TBDMSC1保护等十步反应合成了四个新型的17α-乙炔基-5-雄甾烯-3β,7β,17β-三醇(HE3286)衍生物,其结构经1H NMR和MS表征.     

Synthesis and molecular structure study of 3-methoxy-7α-methyl-6-oxa-9β,14β-estra-1,3,5(10)-trien-17-one in solution

It was established by NMR spectroscopy that the catalytic hydrogenation of 3-methoxy-7α-methyl-6-oxa-14β-estra-1,3,5(10),8-tetraen-17-one leads to the formation of 3-methoxy-7α-methyl-6-oxa-9β,14β-estra-1,3,5(10)-trien-17-one, the structure of which was investigated in solution. The corresponding analog with a free hydroxyl group at the position 3 possesses an antiradical activity at the absence of uterotropic effect.     

STRUCTURE OF 19-NOR-9β-METHYL-10α-2β,3α,16α,20,25-PENTAHYDROXY-Δ~5-LANOSTADIENE-11,22-DIONE-25-ACETATE,C_(32)H_(50)0_8

<正> Mr=562.8, monoclinic, P21, a=13.099(7), b=7.954(4), c=15.446(8)A, Z=2, V=1453(1)A3, Dx=1.29 Mgm-3, λ(MoKα)=0.71069A, μ=(MoKα)=1.0 cm-1, F(000)= 612, room temperature, R=0.072 for 1726 reflections. The structure was solved by random start direct method.The steroid nucleus of the title compound has a bowed conformation, with ring junction configurations being A/B QUASI-TRANS, B/C CIS, C/D TRANS. Ring A and C are in the chair conformation, while ring B and C are in the half-chair confomation. The configurations of the substituents on the steroid nucleus are the same as those reported in the literature.     

Possible conformations of the seven-membered rings and relative stabilities of 1β,5α,6β,7α(H)- and 1α,5α,6β,7α(H)-guai-11(13)-en-6,12-olides

A calculation has been made by the method of molecular mechanics, using the MM2 program, of a number of stereomeres of 1,5,6,7(H)- and 1,5,6,7(H)-guai-11(13)-en-6,12-olides. The possibilities of the adoption by the seven-membered ring of particular conformations according to the type of its linkage with the 5-membered carbocycle have been considered. Questions of the influence of the orientation of the Me groups on the degree of distortion of the conformation of the seven-membered ring from the ideal and the relative stabilities of the various conformers are discussed.A. N. Nesmeyanov Institute of Organometallic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 198–203, March–April, 1991.     

Synthesis of quercetin 3-O-β-d-apiofuranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)]-β-d-glucopyranoside

A concise method to construct a unique 2,6-branched trisaccharide was established by regioselective glycosylation of three free hydroxyl groups on a 3-O-protected glucose moiety, and successfully used in the synthesis of quercetin 3-O-β-d-apiofuranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)]-β-d-glucopyranoside, a flavonol O-glycoside isolated from glandless cotton seeds which showed notable antidepressant activities.     

TiCl4 – an Effective Catalyst for Transformation of Betulin Into A-Neo-3-Isopropyl-19β,28-Epoxy-18α-Olean-9(10)-Ene

Chemistry of Natural Compounds -     

A Facile Synthesis of 3-Oxo-7αH-eudesma-4-ene-9β, 12-diol

3-Oxo-7αH-eudesma-4-en-9β,12-diol1awasfirstisolatedfromCassinauncatabyKingetal.,anditsstructurewasdeterminedbyhighfieldNMRtechniques;however,theabsoluteconfigurationofC-llremainedunsolved.RecentlyPedroetalreportedthefirsttotalsynthesisof(llS)-3-oxo-7aH-eudesma-4-en-95,l21bfromartemisin2inl3steps'.Herein,wereportafacileprocedureforsynthesisofC-llisomericdiolsandthestereochemistryofnaturaldiol.Oursyntheticrouteisshownasbelow:a)ref5,36%;b)Vilsmeierreagent.30%H202,CH2Cl2.-20"C,lh.62%,c)i.…     

Synthesis of (24R)-3β,5,14α-trihydroxy-5α-stigmast-7-en-6-one 3-benzoate

An ecdysteroid analog has been synthesized from -sitosterol.Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus', 220141, Belarus', Minsk, ul. Akad. Kuprevich, 5/2. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 488–491, July–August, 1999.     

A Facile Synthesis of (-)-5_αH,7β,10_α-Eudesmane-3,1 1-diene

ＡＦａｃｉｌｅＳｙｎｔｈｅｓｉｓｏｆ（－）－５_αＨ，７β，１０_α－Ｅｕｄｅｓｍａｎｅ－３，１１－ｄｉｅｎｅ￥ＮｉｎｇＺＯＵ；ＤｏｎｇＬｉａｎｇＣＨＥＮＧ；ＸｉｎＦｕＰＡＮ；ＹａｏＺｕＣＨＥＮ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，Ｌａｎｚｈｏ...     

Oligomeric Derivatives of 3α,7β-D Ihydroxy-5β-Cholan-24-Oic Acid (Ursodeoxycholic Acid)

The synthesis and pharmacological evaluation of Oligomeric and polymeric derivatives of drugs is receiving increasing attention by several groups ^1-9. Usually, in these derivatives, the drug moieties are linked to a proper oligomeric or polymeric matrix by means of covalent bonds of limited stability to biological environments. This may ensure a gradual release of the active principle after introduction into the body Fluids. Poly(oxyethyleneglycol)s, as matrices, appear to be particularly promising on this respect⁷.     

Study on the Total Synthesis of 3-Oxo-9β-Acetoxyilicic Acid─The Synthesis of 9β-Acetoxy-3(4),11(13)-Dien-5αH,7αH-12-Eudesmanoic Acid Methyl Ester

EudsmanetwCOInPOUnarewidlydistribUtedinthekingdomofplants.Becauseoftheirwide~ofbiologicalpropenies,~lyantif~cellgrowthinhiitoryandPlangrowthregUlatinactivihesl"'],eudesmandc~havbendIawinconsiderableattontion.IncounectionwithourlongtiIneffortinthesfi6ld.weareinteedintheSynthniOfanoveleudeSmanderivativ,3-oxo-99-aCetoWdcadd.,whichwasisofatalfrOmArtemiSiaPhaeolePisinl995tyTanetal'].ThCmoleculeisrathrmplexwithreSpeCttOstereochemsitry.Onthethen-carbonskeletonofthemolecule,therearefivcstCn…     

Ca9Y(PO4)7:Ce3+,Tb3+纳米荧光粉的制备及发光性能

采用水热法制备出Ca_9Y(PO4)7∶Ce~(3+),Tb~(3+)纳米荧光粉,通过XRD、SEM和荧光光谱等对样品进行了分析,研究在Ca_9Y(PO4)7基质中引入Ce~(3+),Tb~(3+)离子对发光性能的影响规律。研究发现因Tb~(3+)离子自身能量交叉驰豫的存在,使得单掺Tb~(3+)时,通过调节Tb~(3+)离子的浓度可以实现对发光颜色的控制。同时研究了Ce~(3+)-Tb~(3+)之间的能量传递为电多极相互作用的偶极-四极机制,Ce~(3+)-Tb~(3+)之间最大的能量传递效率为55.6%。Ca_9Y(PO4)7∶Ce~(3+),Tb~(3+)的发光颜色可以通过激活离子之间的能量传递和共发射得到可控调节。SEM分析表明荧光粉颗粒尺寸在100 nm左右,分散性好。     

Synthesis of 24-Methylene-cholest-5-ene-7-oxo-3β,19-diacetate

24-Methylenecholest-5-ene-7-oxo-3β,19-diacetate 5 was synthesized starting from stigmasterol via twelve step reactions in 4.1% overall yield. It can be served as a key intermediate for the synthesis of 24-methylenecholest-5-ene-3β,7β,19-mol 1, a naturally occuring polyhydroxylated sterol with potential biological activity.     

Nonsymmetrical iron bis(carborane) complexes (η-1-ButNH-1,7,9-C3B8H10)Fe(η-9-L-7,8-C2B9H10) (L = SMe2, NMe3)

Visible light irradiation of the benzene complex [(η-1-Bu^tNH-1,7,9-C₃B₈H₁₀)Fe(η-C₆H₆)]⁺ in the presence of the charge-compensated carborane anions [9-L-7,8-C₂B₉H₁₀]⁻ (L = SMe₂, NMe₃) affords ferracarboranes (η-1-Bu^tNH-1,7,9-C₃B₈H₁₀)Fe(η-9-L-7,8-C₂B₉H₁₀). Their structures were established by X-ray diffraction analysis.     

三缺位杂多阴离子α-A-PW9O349-的甲基硅衍生物(TBA)3[α-A-PW9O34(CH3SiO)3(CH3Si)]的合成和晶体结构

Reaction of the trivacant heteropolyanions α-A-PW₉O₃₄^9- with CH₃SiCl₃ leads to the formation of the organosilyl derivative (TBA)₃[α-A-PW₉O₃₄(CH₃SiO)₃(CH₃Si)]. The crystal X-ray diffraction analysis shows that the crystal belongs to orthorhombic with space group Pca2₁, M=3177.09 and the unit cell parameters: a=25.761(5)?,b=14.519(3)?,c=24.396(5)?.V=9124(3)?³,Z=4,D_c=2.225g·cm^-3,μ(MoKα)=11.438mm^-1,F(000)=5464,R=0.0561,R_w=0.0866. The anion consists of one α-A-PW₉O₃₄^9- anion linked by three CH₃SiO⁺ groups, which attached to the fourth CH₃Si through three Si-O-Si bridges.