Investigation of the Structures of the Product Ions Produced via self-CI of Acetone

TheacetoneselfCImassspectrumAcetoneselfCImassspectrumisgiveninTable1.Table1.MajorproductionsandtheirrelativeabundanceofacetoneselfCIMSTheformationofionatmlZ73AnotherproductionintheselfCIMSofacetoneistheionatm/z73.InselfCIMSofacetone-d6,thecounterpartistheionatInjz82.InselfCIMSofthemixtureofacetoneandacetone-d6inaratioofl:l,thecorrespondingionsaretheionsatInlz73,76,79and82.TheirCIDreactionresultsarelistedinTable2.Table2.TheCIDMSoftheionatIn/z73andanalogsOnthebasisofthedatainTab…     

Synthesis of 2-Arylbenzofuran: Confirmation of the Structure of Gnetifolin A

GnethelinAu'asisolatedfromGnetumparvghlium(Warb.)C.Y.Chengb}'Lietal.'ItSstructUrextasproPosedpre\'iousl}'as2-(3.5allhydroxT4-methomphen}l)-3-methony-5-hydrox3-benLzofiiran(l).Aner9'nthesisofset1eralanalogsofStrUctUre(l),theStrUCtUrofGnetjfolinAseemstobenustakenanduasrerisedas2K3-5allhydrOny4-methomphenyl)4-methoxy-5-hvdrowtenzofuran(2).=Inordertoconfirmthisrer4ndmCtUranddevelopaversahlewtehcrouteforthe9-nthesisofGnetjfolinAandanalogs,2T-edSyl4-methoxy-5-hydrotwllZofuran(3)u'asselec…     

Synthesis of affinity column of phosphatidylinositol-3,4-diphosphate

Phosphatidylinositol polyphosphates (PIPx) are related with tyrosine kinase activation, cell proliferation and carcinogenesis. In order to investigate the action mechanism of PIPx, it is desirable to synthesize affinity column of PI-3,4-P2, which is expected to be able to isolate the binding proteins of PI-3,4-P2. Thyramine reacted with CH-Sepharose 4B giving column 13. The p-amino group of 3'-(1',2'-distearoyl-glyceryl)-1-(2-p-aminobenzyl)-3,4-di-O-phosphoryl-myo-inosityl phosphate (12) was diazotized, then diazo-coupled with column 13 to give PI-3,4-P2 affinity column 14. This PI-3,4-P2 affinity column is an effective tool to pick up binding proteins of PI-3,4-P2.     

Synthesis of New Cyclic Phosphate of Arylglyoxylonitrile Oximeand Their Diastereomers

Aspartofourinterestintheemergenceofnewcompoundsinthetieldofagrocllemicalsmanut'acttlring.wehavesynthesizedaseriesofstructurallyrelatedcompoundsbelongingtothet\\'Ofollowingfamiliesf1.3.2-dioxaphosphorinane-2-oneandoximeester'.Thec}'clicphosphateintroducedinourtargetmoleculecouldserveasbothanewcarrierandanactivepal-tofthemolecule.trails-2-chloro-2-oxo-4-phenyl-51.3.2-dioxaphosphorinaneI).,II7s-liseasily'obtainedbyrefluxinga1llixtureofl,3-propandiolsandPOCI;illdichloromethene--.Thereactionofir…     

Synthesis and Determination of Standard Molar Enthalpies of Formation for Complexes of Rare Earth Isothiocyanates with Glycine

Four solid complexes of rare earth isothiocyanates with glycine were synthesized. They were characterized by chemical analysis, elemental analysis, Infrared spectra, X-ray powder diffraction and TO-DSC analysis. Their chemical formulae were proved to be RE(NCS)2.Gly .H2O, where RE is La, Ce, Pr or Nd. The integral heats of solution of RE(NCS)3.3Gly. H2O in water, of RE(NCS)2. 7H2O in aqueous glycine solution and of glycine in water have been measured calorimetricaliy at 298. 15K. By means of a thermochemical cycle suggested in this paper, the standard molar enthalpies of formation for RE(NCS)2. 3Gly.H2O(c) were obtained and their lattice energies were calculated.     

The Preparation and Application of two New Types of Oxazaborolidines

Stereoselectivereductionoftheprochiralketonesisoneofthemostactivelystudiedareasinasymmetricsynthesis.Inthiscontext,oxazaborolidinecatalysedreductionhasemergedasoneofthemostprominentmethodology'.(is,Zs)-2-amino-l-(4-nitrophenyl)-propane-l,3-diolIisaby-productinthechloramphenicolmanufacture.Inthispaped,wereporttheresultsofthecatalyticasy-mmetricreductionofacetophenoneswithboraneinthepresenceofchiralligandart-singfrom1.Thepreparationofligand2isscheduledand3canbeproducedfrom12.The10%mol.of2or3rea…     

Synthesis of Novel Isoxazole-contained Analogues of Losartan

Losartan 1 (Dup-753) is a nonpeptide angiotensin II receptor (type AT1) antagonist discovered by Duncia, J.V. et al. 1 in 1990 and its potassium salt (cozaar) has been marketed as an antihypertensive since 1995 2. 1 2 Starting from Dup-753, a great number of structural related compounds have been prepared by several laboratories and several antihypertensive drugs have been developed3. In order to find new and more active compounds, a novel type of Losartan analogues 2 was designed and syn…     

Synthesis of O-Glycosides of Heteroatom Aroyl-Substituted Heterocyclic Ketene Aminals

Asweknow,carbohydratesplayanimportantroleinnature,especiaIlyasrecogniti0ndeterminantinhost-pathogeninteractionsorinceIl-cellinteractions.Theref0re,stereo-controlledglucosylationhasbecomeone0ftheimportantt0picsinorganicsynthesis]'2.HeterocyclicketeneaminaIsareimportantintermediatesforthesynthesis0fawidevarietyofnewheterocyclesandfusedheterocycles,someofwhichhavehighbiologicalactivity'.IthasbeenrepoFtedthatbenzoyl-substitutedheterocyclicketeneaminalscanreactwith2usingmercuriccyanideascatalystt…     

Study of Intramolecular Cyclization of N-styryl-oxo-cinnamides (Ⅱ)

lnthepreviouspaper',wereportedtheintramolecularcyclizationsofamide4anditscis-eneisomerinanattempttosynthesizehomoclausenamideandzetaclausenamide2.Inordertostudytherelationshipbetweenthestereochemistryandtheilltramolecularcyclizationofthisseriesofcompounds,theamides5(cis-oxirane,trans-ene)and8(cis-oxirane,cis-ene)wereprepared,andtheirintramolecularcyclizationswerereportedinthispaper.Theamide5withm.p.152.O-l54.O"CwasobtainedfromDarzen'scondensationofcompound3withPhCHOinMeOHatl5-2OoCwithMeO…     

Kinetics of tautomerization of 1,3,4,7-tetramethylisoindole

The kinetics of transformation of 1,3,4,7-tetramethylisoindole(1)to 1,3,4,7-tetramethyl-1H-isoindole(2)in water or in deuterium oxide at various pH or pD at 25℃ were measuredspectrophotometricalty.The results indicated that the transformation of 1 to 2 could be promotedby acid and base.From the solvent isotope effects and the fact that the 1-position of isoindole nucleusis electron-rich,the mechanism of this transformation is suggested.     

3 D-QSAR Analysis of Agonists of nAChRs： Epibatidine Analogues

A 3 D-QSAR about nAChRs agonists epibatidine analogues was performed using theCoMFA and CoMSIA. The correlation coefficients were R2cv = 0.546, R2cv = 0.907 in CoMFA andR2cv = 0.655, R2,~ = 0.962 in CoMSIA of the final model. The prediction using the final models tothe test set was r2 = 0.675 in CoMFA and r2 = 0.462 in CoMSIA. This model will be useful in thedesign of novel compounds with high affinity.     

Preparation of Polystryenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

The polystyrenylphosphonous acid (PSPA) of low polymerization degress was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, therer are 2 or 3 serives of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH(C6H5)]n-PO2H2 respectively.     

2D NMR Investigation of Dynamic Equilibrium of Tautomers of Gossypol

Gossypol was obtained as an yellow platelike crystal with m.p. 210-214o . In CDCl3 there were three tautomers of gossypol: I aldehyde, II lactol,III ketal , in equilibrium .Their total H 1 NMR spectra were assigned by means of 1D and 2D NMR techniques including 1H-1H cosy , DEPT , HMQC (1H Detected Heteronuclear Multiple Quantum Coherence) and HMBC (1H Detected Heteronuclear Multiple Bond Connectivity) experiments . This paper first reported that we took use of the 2D NMR t…     

Syntheses and Characterization of Heterocyclic Compounds of Zirconium ( Ⅳ )

The Zr-H bond of zirconocene hydridochloride was heterolyzed at room temperature by five compounds containing nitrogen and hydroxyl group to give Cp(Q)2ZrCl(1) (Cp = cyclopentadienyl and Q = 8-quinolinoyl ) , Cp (Q-Me )2ZrCl (2) , Cp(5,7-Br2Q)2ZrCl(3), Cp2(2-pyridoyl)ZrCl(4) , and Cp(2-aminoethanoyl)2ZrCl(5), which were characterized by elemental analysis, IR, and 1H NMR spectroscopy. The molecular structure of 1 was confirmed by X-ray diffraction determination. The crystal of 1 crystallized monoclinically, space group P21/n a= 0.9004(2), b=1.3961(2), c = 1. 6056(2) nm, β=99. 48(1)°? V=1. 9906 nm3, Z = 4, and Dc=1. 582 g/cm3. The coordination polyhedron around the Zr atom can be described as a distorted octahedron. The Zr-N bonds of 0. 2364(3) and 0. 2377(4) nm suggest that they are coordination bonds. The two planar 8-quinolinoyl groups as bidentate ligands chelate with Zr atom, forming a dihedral angle of 108. 4(1)°?     

The Studies of A New Type of Crystalline Antimonic Acid

A new type of crystalline antimonic acid Sb2O5 ·3H2O was synthesized. The composition, crystal structure, the equilibrium distribution coefficients for sodium and potassium ions and the ion-exchange capacity of this exchanger were determined. With this exchanger, sodium ions were removed from potassium chloride, and the content of sodium chloride was reduced from 3.24 % to 0.02% .Compared with other ion-exchange materials, the crystalline antimonic acid gives an unusual selectivity for potassium and sodium ions . The different compositions and properties of antimonic acid exchangers are obtained through different preparing conditions and its crystalline formula of Sb2O5 ·4H2O[2](C-SbA1) is currently accepted. This paper reports a new type of crystalline antimonic acid-Sb2O65·3H2O(C-SbA2), synthesized by an improved Kuzin's method[3]. Sodium ions are removed from potassium chloride with C-SbA2. The exchange efficiency is better than that of C-SbA1.     

Chiral Synthesis of the Key Intermediate of Diterpenoids

(-)-Methyl(4R,5SloR)-l4-methoxyPodocmpa-8,ll,l3-triene-l9-oate(I)isthekeyintermediateforsynthesesofditerpenoidssuchaskaurenoicacid(3),kaur-l6-en-l9-ol(4),monoginol(5)('),aswellasC,,-diterpenealkaloidssuchasveachine(6),garryine(7)andatisine(8)(=).TheracemicsynthesisofthisintermediatewasdonebyK.Morietar'),butthechiralsynthesishasnotbeenreported.Herewepresentthechiralsynthesisofthiskeyintermediatefrom(R)-(+)-2-methyl-2-(2'-nitrovinyl)-5-vaierolactone(2).2wassynthesizedaccordingtoliterattirmeth…     

CIDNP of Diecyl Peroxides Studies on the Kinetics of Decomposition of Diacyl Peiroxides Ⅷ in the Decomposition of Diacyl Peroxides

H CIDNP spectra recorded during the decomposition of aliphatic diacyl peroxides ((RCOO)2 R=n-C H (1),n-c5H11(2)) in ODCB in the presence of scavengers,such as I2C2H5I,(CH3)2CHI,and CH2=CHCH2 Br show multiplet effect for the scavenged products,RX(X=Br,I) and for disproportionation products,R-H.The reactionmechanism is discussed in terms of radical pair theory.     

A Convenient Method of Synthesis of Ferrocenylethynyl Ketones

It is well known that molecules possessing extensive conjugated π-electron systems exhibit large non-linear optical properties,[1,2] but the compounds of ferrocenylethynyl ketones have not been reported so far. We now reported preparation of some ferrocenylethyl ketones. These new ethynylketones containing ferrocenyl were prepared conveniently via coupling reaction catalyzed by PdCl2(PPh3)2/PdBzCl(PPh3)2-CuI from ferrocenylethyne and acyl chlorides. This coupling reaction proceeded smoothly in argon and free-water atmosphere at room temperature and gave coupling products in satisfactory yields. All products were characterized by 1H NMR, MS, IR and UV spectra.     

Syntheses of fluoroalkyl derivatives of two biologically active oligopeptides

Fluoroalkyl derivatives of two biologically active oligopeptides [ enkephalin,[(m-C2F4Cl)Tyr1]-Leu-enkephalin and [(m-COCF2Cl)Tyr2]-melanocyte-stimulating hormone releasing hormone have been synthesized.Studies on the activities of these peptides are underway.     

Semiconductor photoinduced cycloreversion of the dimer of methyl 2-naphthoate

The dimer of methyl 2-naphthoate (1) has been found to undergo efficient cyclorever-sion to its monomer, methyl naphtha)ene-2-carboxylate (2) on illuminated ZnO and TiO2 but not on CdS. An electron transfer and cation radical chain mechanism is proposed. Quantum yields, solvent effect, the role of oxygen, and the quenching of the reaction were investigated, and were consistent with the proposed mechanism.