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1.
Reaction of the amines (CF3)2NX (X=Cl,Br) with norbornadiene either in solvent (CH2Cl2) at ?78 °C in the dark or in the vapour phase at 20 °C in daylight gives a mixture of 3-halogeno-5-(-bistrifluoromethylamino)nortricyclene (, -and , -isomers) and -5-(-bistrifluoromethylamino)- -7-halogenonorbornene in quantitative yield formed halonium ion addition to the diene. The reaction of the amine (CF3)2NBr in solvent Me2O or Et2O at ?78 °C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene (, - and , -isomers) and the amine (CF3)2NR (R=Me, Et) in high yield. 相似文献
2.
Synthesis and properties of C5H5(CO)2Mn-N2H4-Cr(CC)5, C5H5(CO)2Mn-N2H2-Cr(CO)5 and C5H5(CO)2Mn-N2-Cr(CO)5 are reported. , and constitute the first series of heteronuclear complexes in which N2, N2H2 and N2H4 are bound to identical metal centers. and are obtained by reacting C5H5Mn(CO)2N2H4 respectively with Cr(CO)5THF, by oxidation of . disproportionates by addition of base yielding and H2. The IR Spectrum of allows the assignment of five normal vibrations of the diazene ligand; in the IR spectrum of the deuterated analogue all six normal vibrations can be assigned. The 1H-NMR spectrum of yields the coupling constant of protons on NN double bonds for the first time; the value of 3JHH 23,5 Hz points to a trans structure of . 相似文献
3.
A sequence of formylation followed by a carbene insertion reaction has led to the stepwise introduction of additional ethano bridges into 4,5,7,8- tetramethyl [22](1,4)cyclophane (), providing syntheses of 5,7,8-trimethyl- [23](l,2,4)cyclophane (), a mixture of 5,8-dimethyl[24(1,2,4,5)cyclophane () and 5,7-dimethyl[24(1,2,3,5)cyclophane (, and-4-methyl[25](1,2,3,4,5)-cyclophane (). This route to completes a formal eight-step synthesis of [26](1,2,3,4,5,6)cyclophane (, superphane) with an overall yield of 17%. A Birch reduction of readily gave 12,15-dihydro-5,7,8-trimethyl[23](1,2,4)-cyclophane () in 85% yield. 相似文献
4.
The structure of [Pt2Cl(CO) (μ-Ph2PCH2PPh2)2] [PF6] was determined by -ray methods and refined to = 0.082, using diffractometric intensities of 5646 independent reflections. The crystals are monoclinic, space group 21/, = 12.919(3), = 15.576(6), = 25.151(5)Å, β = 94.82(3)°, = 4. They are built of octahedral hexafluorophosphate anions and dinuclear platinum(I) cations. The latter contain PtCl and PtCO fragments linked to one another by a PtPt σ-bond and by two bridging bis(diphenylphosphino)methane ligands. The platinum atoms are in square planar environments and the dihedral angle between the two coordination planes is 40.1°. Selected bond lengths are: PtPt 2.620(1), PtCl 2.384(5), PtC 1.89(3) and PtP 2.291(5) – 2.308(5)Å. 相似文献
5.
R.J. Bertino B.A.W. Coller G.B. Deacon I.K. Johnson 《Journal of fluorine chemistry》1975,5(4):335-357
The lithium polyfluorobenzenesulphinates, Li O2SR (R = C6F5, -HC6F4, -HC6F4, or -HC6F4), and the dilithium tetrafluorobenzenedisulphinates, - and -(LiO2S)2C6F4, have been prepared by reaction of the appropriate polyfluoroaryllithium compounds with sulphur dioxide. All compounds were isolated as hydrates and gave the corresponding -benzylthiouronium salts on treatment with -benzylthiouronium chloride. From reactions of the lithium sulphinates with suitable mercuric salts in water, generally at room temperature, the derivatives RHgX (R = C6F5, X = Cl, Br, CH3CO2, or PhSO2; R = -HC6F4, X = Cl, Br, or CH3CO2; R = -HC6F4, X = Cl or Br; R = -HC6F4, X = Cl), -(XHg)2C6F4 (X = Cl, Br, or CH3CO2), and -(XHg)2C6X4 (X = Cl or Br) have been prepared. Similarly, the bispolyfluorophenylmercurials R2Hg (R = C6F5, -HC6F4, or -HC6F4) have been prepared from the corresponding lithium sulphinates and either mercuric salts or polyfluorophenylmercuric halides in aqueous -butanol. A possible mechanism for the sulphur dioxide elimination reactions is discussed. 相似文献
6.
C. Glidewell G.S. Harris H.D. Holden D.C. Liles J.S. McKechnie 《Journal of fluorine chemistry》1981,18(2):143-154
Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1–40%) in the absence of glass readily gives triphenylarsine difluoride. When the reaction with dilute (1%) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO·HBF4. Crystals of this compound are monoclinic, 21/, = 12.926(4), = 17.819(6), = 14.994(4) Å, β = 98.97(3)°, Z = 4. The structure contains cations [(Ph3AsO)2H]+ in which O is 2.44(2)Å, and anions BF4?. 相似文献
7.
The diene reacted with CHCl3/aq. NaOH/PTC in CH2 Cl2 unexpectedly to give a mixture of the chlorination products and . Usual chlorination with Cl2 yielded similarly , , and dependent on the amount of Cl2. The formation of as well as the reaction of to give (besides ) shows an unusual Cl-Cl-interaction. 相似文献
8.
Optical absorption and emission spectra are reported for single crystals of the cubic elpasolite Cs2NaSmCl6. The variable temperature spectra obtained at high resolution are assigned using energies and relative intensities. Transitions from the ground level, 6H to cystal fi levels of 6H-, 6F-, 4G-, 4F,, 4I, and 6P, are located and characterized. Intensity calculations are reported for magnetic dipole allowed transitions. The dominance of vibronic intensity in 6H→6F - and 6P, transitions is accounted for qualitatively through the ligand polarization model involving quadrupole metal (Sm3+)-ligand (Cl?) interaction mechanisms. The Eu″(6H)→E′(6H) Eu′(6F) no-phonon transition is postulated to be pure electric quadrupole allowed. The ground state magnetic moment is determined to be very small from magnetic circular dichroism (MCD) spectra.This study has led to the assignment of nearly all of the crystal field levels in the visible and IR region for Cs2NaSmCl6. A total of 27 such levels were identified, 17 from no-phonon transitions and the rest from vibronic transitions. The magnetic dipole intensity calculated using intermediate coupling Oh wavefunctions along with a crystal field analysis of the splitting pattern was used in the assignment of the levels. Vibronic bands were observed for all transitions and their vibrational symmetries were tentatively assigned. MCD data were used to determine the magnet moment of the ground state. 相似文献
9.
HC(SO2F)3 has been prepared and characterized. It turned out to be a strong acid, comparable to mineral acids. In aqueous solution the salts of the type Cs+C(SO2F)3? are formed. The anion, as found by crystal structure analysis contains planar CS3 configuration.Quite in contrast to these findings HC(OSO2F)3 is not even soluble in water.Derivatives of HC(SO2F)3 have been prepared so far CH3C(SO2F)3 FC(SO2F)3 ClC(SO2F)3 BrC(SO2F)3 JC(SO2F)3The heavier halogen derivatives ( Cl, Br, J ) are oxidizing agents (‘positive halogen’).A mixture of and (HO)2TeF4 is obtained if HOTeF5 and Te(OH)6 are melted together. The mixture of the isomeres have been transfered into the corresponding silylesters - and (R3SiO)2TeF4, which could be separated by fractional crystallisation and distillation.Without conformational change the pure silylesters have been reacted back to pure - (HO)2TeF4 and - (HO)2TeF4 by means of anhydrous HF. Both and (HO)2TeF4 have been reacted with ClF to give - and - (ClO)2TeF4, yellow liquids. The latter react with elemental bromine to the rather unstable and (BrO)TeF4, red liquids.Starting with -(HO)2TeF4 and XeF2 a polimer Xenon compound of the formula All materials have been characterized by melting point and vapour pressure, 19 F - nmv spectroscopy, vibrational spectroscopy, and elemental analysis. 相似文献
10.
Janina Karolak-Wojciechowska Marian Mikołajczyk Andrzej Zatorski Katarzyna Kiec-Kononowicz Alfred Zejc 《Tetrahedron》1985,41(20):4593-4602
The crystal and molecular structures of the title isomeric compounds and , obtained by intramolecular N,S--dialkylation of 5,5-diphenyl-2-thiohydantoin with 1,2-dibro-moethane, have been determined from X-ray diffractometer data. 2,3-Dihydro-6,6-diphenylimidazo-[2,1-b]-thiazol-5(6H)-one crystallizes in space group P212121 with a=11.376(3), b=12,255(5), c=8.434(3) Å and Z=4. Crystals of , containing one molecule of benzene, are monoclinic,space group P21/c with a=11.539(6), b=10.242(3), c=16.353(5) Å, β=95.45(5)° and Z=4. In both cases a planar geometry of the two fused five-membered heterocyclic rings was found. The selected bond lengths in and , as well as those analogous imidazothiazinones and , were used to calculate EHOSE (Harmonic Oscillation Stabilization Energy). The problem of stability and chemical reactivity of compounds to is also discussed. 相似文献
11.
Oxidation of benzotropylium () fluoborate with Na2O2 and KO2 gives the benzotropones, and , as the major products with no naphthalene () or other ring contracted products formed. Oxidation with -chloroperoxybenzoic acid produces a small amount of naphthaldehydes ( and ) and even less naphthalene, a long with the benzotropones, while oxidation with H2O2 and -butyl peroxyacetate gives slightly more of the ring contracted naphthaldehydes than benzotropones, in addition to a small quantity of naphthalene. All reactions produce some 1,2-benzotropilidene () 相似文献
12.
Thermodynamic data have been obtained by calorimetric titration in benzene solution at 30° for reaction of organotin compounds with Lewis bases; data are reported for forty acid/base systems.Ph3SnCl forms adducts of low stability with pyridine (py) or 4-methyl-pyridine (4-mepy). Ph2SnCl2, Me2SnCl2, Bu2SnCl2 and Bu2Sn(NCS)2 form simultaneously and adducts with py or 4-mepy and adducts with 2,2′-bipyridine or 1,10-phenanthroline (phen); the enthalpies of formation of the phen adducts are similar to those of adducts with 4-mepy. With BuSnCl3 and PhSnCl3 it was not possible to obtain data for each step in addition of pyridine or 4-mepy. Adduct stabilities increase with increasing chloride substitution and in the order Bu < Me < Ph; adducts of Bu2Sn(NCS)2 are more stable than those of Bu2SnCl2.Tributylphosphine does not react with Ph3SnCl but gives adducts with the other tin compounds; only PhSnCl3 adds a second molecule of this base. The adducts are more stable than those with heterocyclic bases. Tributylamine brings about disproportionation of the compounds R2SnX2 to R4Sn and SnX4NBu3. 相似文献
13.
William R. Cullen Mangayarkarasy Williams Frederick W.B. Einstein Anthony C. Willis 《Journal of organometallic chemistry》1978,155(2):259-270
The β-chlorovinylphosphines R2PF2)3 (R = C6H5, C6H11) react with Fe(CO)5 yielding compounds of stoichiometry . The crystal structure of one of these (R = C6H11) has been determined from X-ray diffraction data and refined by least-squares to = 0.037 (2313 reflections with > 2.3σ). Crystals are triclinic, space group , = 10.253(5), = 15.590(7), = 9.390(4)Å, α = 99.88(3), β = 103.21(2), γ = 92.02(2)°, = 2. The fluorinated π-allyl group is σ-bonded to one Fe atom and π-bonded to the other. 相似文献
14.
Giovanni Fronza Claudio Fuganti Piero Grasselli Giuseppe Pedrocchi-Fantoni Carlo Zirotti 《Tetrahedron letters》1982,23(40):4143-4146
The synthesis of the 2,6-dideoxy sugars -digitoxose (14), 2-deoxy--fucose (15) and -mycarose (16) from the C4 and C5 chiral synthons (1), (2) and (3), through the intermediacy of the C7 adducts (4), (8) and (12), obtained by addition of diallylzinc onto (1), (2) and (3), is reported. 相似文献
15.
16.
Acid catalyzed cyclization of ()-HCO-(CH2)-4-CH=C(Me)-CH(SPh)SiMe3 affords -2-substituted cyclohexanol, while () compound affords the isomer. Those cyclized products are transformed to the corresponding α-methyl γ-lactones. 相似文献
17.
Adenosine cyclic 3′,5′-phosphoramidate was synthesized by reacting adenosine cyclic 3′,5′-phosphate with POCl3, in trimethyl phosphate for 1 h at O°C, followed by in situ treatment of the reaction mixture with a suspension of (NH4)2CO3 in anhydrous DMF or pyridine or DMF/pyridine mixture for 30 min at 25° C. Diastereoisomers (P)- and (P)- the relative quantities of which depended on the solvent of (NH4)2CO3 treatment, were separated by reversed phase partition chromatography. Hydrolysis of (RP)- and (SP)- proceeded with predominant (90% in 0.1 N HCl, 100% in 0.1 N NaOH) -P-O-C bond breaking. 相似文献
18.
The chlorinative ene-type reaction of isoprenoids ( → ) has been performed by electrolysis in CH2Cl2-H2O-NaCl system. The reaction provides useful allylic chlorides for terpene synthesis in high yields and is affected strikingly by the nature of halide ions and solvents. dl-Theaspirane was prepared from α-dihydroionol the electrolysis. 相似文献
19.
Saturated and benzylic organomagnesium compounds are shown to readily undergo addition reactions with the conjugated enynes HCHCH2R′, with R′ = alkyl, OH, OC4H9, NHC25, N(C2H5)2, by refluxing for several hours in benzene or toluene.This reaction leads to both υ-acetylenic compounds (1,2-addition) and β-allenic compounds (1,4-addition). 相似文献
20.
Haruhisa Shirahama Kiyoharu Hayano Yoshiro Kanemoto Shunjiro Misumi Toshikazu Ohtsuka Nobuhiro Hashiba Akio Furusaki Shizuaki Murata Ryoji Noyori Takeshi Matsumoto 《Tetrahedron letters》1980,21(50):4835-4838
Two cyclohumulanoids, dl-bicyclohumulenone () and dl-africanol ( were synthesized through newly developed conformationally selective transannular cyclization of humulene 9,10-epoxide (). The epoxide was converted to a bicyclohumulenediol diacetate in 70% yield by treatment with BF3·OEt2-Ac2O, while treatment of with trimethylsilyl trifluoromethansulfonate gave an africen-10-ol (a and b) in 80% yield. The two intermediates and furnished the natural products and in 30 and 8 % yield from respectively. 相似文献