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1.
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
2.
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
3.
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
4.
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
5.
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
6.
The production of I(2P) in the photolysis of CH2I2 has been studied optoacoustically at excitation wavelengths between 365.5 and 247.5 nm. Bands found at 32200 and 47000 cm?1 correlate with I(2P) whilst those at 34700 and 40100 cm?1, which correlate with I(2P), give final 2P/2P ratios of 1.75 and 1.1, respectively, after curve crossing. 相似文献
7.
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
8.
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
9.
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
10.
A practical synthesis of [Ph3CH2F]BF4? is reported two routes, fluorination of [Ph3CH2OH]BF4? with DAST or hydrolysis of the phosphoranium salt, [Ph3FPh3]Br?. 相似文献
11.
LDA-induced cyclization of yields , the -isomer of which undergoes dehydration using Ph2S[OC(CF3)2Ph]2 to give the pyrethroid amide . 相似文献
12.
The vinylbromides and are allowed to react ith AgBF4 and AgPF6 in the presence of various olefins in CH2Cl2 as the solvent. Except for the reaction of cyclopentene with all other olefins used, react with vinyl cation to form the cycloaddition products , and in high yields. 相似文献
13.
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
14.
Flash vacuum pyrolysis of -methylbenzyl chloride-,-2 gives benzocyclobutene-,-2. This finding indicates that the reaction involves net δ-elimination of hydrochloric acid. 相似文献
15.
Micellar -C16H33(CH3)2CH2(CH3)2, 2CF3SO3? rapidly methylates bound thiophenoxide ions. 相似文献
16.
H. Krause K. Sille H.-D. Hausen J. Weidlein 《Journal of organometallic chemistry》1982,235(3):253-264
Reactions of urotropine (C6H12N4) with trimethylmetal derivatives of Al, Ga, In und Tl in various () molar ratios lead to stable and monomeric , or adducts in good yields, but no addition product could be isolated. The vibrational spectra (IR and Raman) of all compounds are recorded and partly assigned. Some characteristic frequencies of the C6N4-skeletons clearly show the symmetry changes in the series of the → → adducts (C3ν → C2ν → C3ν). The X-ray structure determinations of C6H12N4·.GaMe3 (MeCH3) and C6H12N4·.2GaMe3, are in good agreement with the vibrational spectra. Both compounds crystallize in monoclinic space groups (P21 and C2/c). The GaN distances are around 214 pm, and the values for the C6N4-skeletons are not significantly different from those for free urotropine. 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.
Wojciech Dmowski 《Journal of fluorine chemistry》1982,21(2):201-219
1-Phenylpentafluoropropene and its para-substituted analogs are susceptible to nucleophilic attack at both vinylic carbon atoms C-1 and C-2. They react with ethanolio sodium ethoxide to give predominantly substitution products, 1-ethoxy-1-phenyltetrafluoropropenes and 2-ethoxy-1-phenyltetrafluoropropenes , with only little formation of adducts, . 2-ethoxy-1H-1-phenylpentafluoropropanes . Alkenes , where the para-substituent X H,Cl,and CF3 give additionally 1,2-diethoxy-1-phenyltrifluoropropenes and, where X = CF3 also 2,2-diethoxy-1H-1-phenyltetrafluoropropane . Overall regioselectivity of nucleophilic attack of the ethoxide ion on alkenes exhibits the Hammett type correlation with Óp values of substituents X: CH3O and CH3 groups favour the attack on the vinylic carbon C-1, while CF3 and Cl substituents direct the attack on the C-2 carbon of alkenes . The E and Z isomers of 1-ethoxy and 1,2-diethoxy substituted alkenes and were formed in comparable amounts, while the E isomers of 2-ethoxy substituted alkenes were always formed with a 93 – 97 % selectivity. 相似文献
19.
The crystal structure of Ca6Eu2Na2(PO4)6F2 has been determined by single crystal X-ray diffraction. The unit cell constants are and the space group is . The structure was refined by normal full matrix least squares techniques. The final value of the refinement indicator is R = 0.065, based on 419 reflections.The structure of Ca6Eu2Na2(PO4)6F2 contains disordered cations in both the triangle and column positions. The occupation of the six triangle sites is and and of the four column sites , and . 相似文献
20.
Previous (1) work on ternary chalcopyrite solid solution formation has shown that the difference in end point axial ratios () is an important factor in determining the extent of mutual solubility. It was concluded that when complete solid solubility will not occur. In this work it is shown that complete solid solution formation in the systems AgAlS2AgInS2 (), AgGaS2AgInS2 () and AgAlSe2AgInSe2 () does occur. This shows that the value of as an upper limit for solid solution formation can be approached closely. 相似文献