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1.
The syntheses of four novel 1,1-difluoro-2-alkoxymethanimines, RONCF2, are reported. The oxime ethers are prepared in excellent yield by dehydrofluorination of the amines, RON(H)CF3 (RCF3, (CF3)2CF, CH3, (CH3)3C) with KF. These oxime ethers are thermally stable at 24°C and are characterized by IR, NMR, and physical properties. The two perfluoro compounds undergo dimerization to give CF3N(OR)CFNOR in the presence of CsF at room temperature.  相似文献   

2.
The following substances could be prepared by Grignard reactions or by conversions with trichlorosilane: C6F5CH2CHCH2, C6F5(CH2)3SiCl3, CF3(CF2)9CH2CHCH2, CF3(CF2)7(CH2)2SiCl3, CF3(CF2)11(CH2)3CHCH2 und CF3(CF2)11(CH2)5SiCl3.They were characterized by spectroscopical and microanalytical methods.  相似文献   

3.
The nitroxide CF3N(?)CMe2CMeCH2 abstracts the aldehydic hydrogen from benzaldehyde, yielding the benzoyl compound PhCO2N(CF3)CMe2CMeCH2 (82%), the benzylic hydrogen from cumene, yielding PhCMe2ON(CF3)CMe2CMeCH2 (80%), and the methylene group hydrogen from fluorene, oxidises benzoin to benzil, and hydroquinol to quinone, attacks the Si'&'2.sbnd;H bond of trimethylsilane, and adds to tetrafluoroethylene to give the compound R1N(CF3)OCF2CF2ON(CF3)R1 (R1 = CMe2CMeCH2, 97%), and to hexafluoropropene to give the 2:1-adduct.In a similar manner, the nitroxide CF3N(?)CMe2CHMe2 adds to tetrafluoroethylene to give the compound R2N(CF3)OCF2CF2ON(CF3)R2 (R2 = CMe2CHMe2, 75%) and to hexafluoropropene to give a similar adduct (71%), and abstracts a benzylic hydrogen from toluene.  相似文献   

4.
New CF2X-analogues of 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene (1) (X=H, Cl) were synthesised by the condensation of polyfluoroketones with malononitrile followed by dehydration using thionyl chloride (or phosphorus pentoxide). The heterocyclisation reactions of new CF2X-analogues of 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene with amidines, 5-aminopyrazoles and 3-methyl-2-pyrazolin-5-ones were systematically investigated.  相似文献   

5.
A series of new polyfluorinated dienes 3, containing the novel -CFCHCHCF-, pattern has been synthesized (50–70% yields) by reacting perfluoroalkyl iodides with perfluoroalkyl-ethylenes in the presence of copper. The monoalkenes RfCFCHCH2CF2R′f and the saturated compounds RfCF2CH2CH2CF2R′f were obtained by varying the experimental conditions. The 1H and 19F NMR spectra are analysed and the reaction mechanism is discussed.  相似文献   

6.
Allenes (CF3)2CCC(COOMe)2 and (CF3)2CCC(COOEt) Ph were prepared by Cs-catalyzed condensation of octafluoroisobutene with dimethyl malonate and ethyl phenylacetate respectively. A stable salt
is formed from (CF3)2CCC(COOMe)2 and CsF. Similar salts were prepared through the condensation of octafluoroisobutene with ethyl cyanoacetate and malononitrile. Allenes (CF3)2CCOMe2 and (CF3)2CCCHPh were synthesized by dehydrofluorination of olefines (CF3)2CHCFCRR′ under the action of octafluoroisobutene and CsF mixture; the latter allene has been isolated only as a cycloadduct with octafluoroisobutene.  相似文献   

7.
Methods for the regioselective synthesis of Mannich bases starting from unsymmetrical ketones are described. The Mannich base on the more substituted carbon is obtained by reaction with (CH3)2N+CH2,CF3CO2- in CF3CO2H and its isomer on the less substituted carbon with (iPr)2N+CH2,ClO4- in CH3CN. In the first case, the orientation corresponds to a non-selective attack of the immonium salt on a mixture of enols in which the more-substituted isomer is predominant. In the second ease, use of a bulky immonium salt induces a selectivity favoring the less-substituted enol.  相似文献   

8.
F-N-Isopropylacetimidoyl chloride, CF3CClNCF(CF3)2, has been used as a precursor for a variety of heterocyclic and acyclic compounds. Reaction with azide ion yields a mixture of the imidoyl azide, CF3(N3)CNCF(CF3)2, and the 1,5-tetrazole, CF3CNNNCF(CF3)2. Hexafluoropropylideniminolithium produces as a minor product the conjugated diimine, (CF3)2CNC(CF3)NCF(CF3)2, from nucleophilic attack at the imidoyl chlorine and as a major product the triimine, (CF3)2CNC(CF3)NC(CF3)2NC(CF3)2, from further attack at the isopropyl fluorine. A thio-amide, CF3C(S)NHCH(CF3)2, and a Δ3-1,2,4-dithiazoline, SSC(CF3)NC(CF3)2, are produced upon reaction of hyrogen sulfide with the imidoyl chloride. Pathways are proposed for each of the reactions.  相似文献   

9.
Interaction of NaCo(dmg)2py with (R)2CC(OSO2CF3)CCH in methanol provides a simple route to novel, stable cumulenyl complexes (R)2CCCCHCo(dmg)2py, where R = CH3 or C6H5. In the case of R = H the stable ene-yne complex H2CC(CCH)Co(dmg)2py was isolated. The formation and properties of these complexes are discussed.  相似文献   

10.
Novel η1-vinyl complexes of the type Cp(CO)(L)FeC(OMe)C(R)R′ (R = R′ = H, Me; R = H, R′ = Me; L = Me3P, Ph3P) are obtainied via methylation of the acyl complexes Cp(CO)(L)FeC(O)R (R = Me, Et, i-Pr) with MeOSO2F and subsequent deprotonation of the resulting carbene complexes [Cp(CO)(L)FeC(OMe)R]SO3F with the phosphorus ylide Me3PCH2. The same procedure can be applied for the synthesis of the pentamethylcyclopentadienyl derivative C5Me5(CO)(Me3P)FeC(OMe)CH2, while treatment of the hydroxy or siloxy carbene complexes [Cp(CO)(L)FeC(OR)Me]X (R = H, Me3Si; X = SO3CF3) with Me3CH2 results in the transfer of the oxygen bound electrophile to the ylidic carbon. Some remarkable spectroscopic properties of the new complexes are reported.  相似文献   

11.
Some fluoroalcohols have been prepared by free-radical addition of methanol, ethanol and isopropanol to fluoroolefins as C3F6, CFHCFCF3, (CF3)2CFCFCFCF3, H(CF2)4CFCF2, The general reaction is (1) RfCFCF2 + RR′CHOH = RfCFHCF2CRR′OH where Rf is a fluoroalkyl group, R and R′ are H or CH3. NMR data of these alcohols are reported. 2,2,3,4,4,4-hexafluorobutanol (HFB) shows the best solvent ability among the compounds of this class. Its properties and solvent power have been evaluated and compared to the ones of trifluoroethanol (TFE) and hexafluoroisopropanol (HFIP). Some toxicological data related to HFB, TFE and HFIP are also reported.Owing to their strong tendency to form hydrogen bonds, fluoroalcohols are excellent solvents for polymeric materials which possess receptive sites for hydrogen bonding formation. The bonding power of the OH has been investigated by IR and NMR Spectroscopy on amide-group containing substrates. The properties and the correlations observed have pointed out that HFB may be usefully used as solvent for some aliphatic polyamides as Nylon 6.The polymer-solvent system Nylon 6-HFB has been studied and the constants of Mark-Houwink equation determined.  相似文献   

12.
Triphenyltelluronium /gb-diketonates, RC(O)CHC(O)R1 (where R = CH3, Ph or CF3 and R1 = CH3, Ph, CF3 or 2-thienyl) have been prepared. Spectral data(IR, 1H and 13C NMR, mass spectroscopy) are presented and discussed in conjunction with molecular weight and conductivity data. It is concluded that weak coordination of the β-diketonate to the tellurium atom is a common structural feature of the compounds.  相似文献   

13.
The reaction of 1,1′-bis(pentafluorophenyl)ferrocene with fluorous alkoxides having the general formula NaOCH2(CF2)nCF3 (n = 0, 2, 5, 7, and 8) afforded a series of ferrocenes of general formula {η5-4-[CF3(CF2)nCH2O]C6F4C5H4}2Fe (1). The reaction of 1,1′-bis(4-tetrafluoropyridyl)ferrocene with the same fluorous alkoxides afforded a series of ferrocenes of general formula (η5-4-{2,6-[CF3(CF2)nCH2O]2C5F2N}C5H4)2Fe (2). Perfluoro(methylcyclohexane)/toluene partition coefficients increase with the number (2 or 4) and length (n) of the fluorous substituent. Complexes 1a and 2a (both n = 0) were structurally characterized.  相似文献   

14.
The reaction of isocyanides, CNR, with hydroxy- and methoxy-alkyl complexes of platinum(II), PtOH(R)(Ph2 PCHCHPPh2)_and PtOCH3(R)(Ph2PCHCHPPh2) (R  CF3, CH2 CN) affords insertion products Pt(CONHR)(R)(Ph2PCHCHPPh2) and Pt[C(OCH3)NR] (R)(Ph2PCHCHPPh2) containing the carboxamido and imidoyl moiety, respectively.  相似文献   

15.
The order of reactivity and the selectivity of 1,1-dimethyl-1-silaethene (Me2SiCH2), generated from 1,1-dimethylsilacyclobutane at 611°, toward a variety of substrates was determined using standard competition experiments. The observed reactivity order was Ph2CO>ROH, ArOH ? m-ClPhNH2 CH3CN, which indicates that with these substrates and under the reaction conditions used, Me2SiCH2 is behaving like an electrophilic species. Within a given class of substrates, polar effects were found to be generally unimportant, while increased steric effects caused a decrease in rate (up to 50%).  相似文献   

16.
The three component reaction (Et2N) 3P/CF3Br/ RnSiCl4-n (n = 1,2,3; RCH3,Ph) gives CF3-substituted organyl(chloro)silanes for the first time. Their genesis will be elucidated.  相似文献   

17.
Bis(cyclopentadienyl)mercury readily undergoes Diels—Alder reactions with RCCR (R = CO2Me or CF3), CF3CFCFCF3, CF3CFCF2, (CF3)2CC(CN)2, C2(CN)4 and PhNCONNCO to give stable adducts characterised by1H, 19F and 13C NMR, spectroscopy. Similar reactions of CF3CCCF3 and CF3CFCFCF3 with the cyclopentadiene derivatives Me3MC5H5 and (Me3M)2C5H4 (M = Si, Sn) are also described.  相似文献   

18.
Electron impact fragmentation patterns were obtained for 1-dephenylphospha-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis[C3F7(OCF(CF3)CF2)xOCF(CF3]-2,4,6-triazine (x=1 and 2) and their pentafluorophenyl analogues. In each instance the ion R2PN2C+ (RC6H5 or C6F5) constituted the base peak. Based on the observed metastable peaks, fragmentation pathways leading to the formation of this and other significant ions are postulated and similarities to s-triazine and diphenyl phosphazene trimer breakdown patterns are discussed.  相似文献   

19.
3,3-Difluoroallyltrimethyltin has been prepared by the reaction of β-trimethylstannylethylidenetriphenylphosphorane with chlorodifluoromethane. This tin compound reacts with n-butyllithium in tetrahydrofuran at -95°C to generate gem-difluoroallyllithium. The latter, however, is not stable in solution at that temperature. If generated in situ in the presence of a triorganochlorosilane, products of the type R3SiCF2CHCH2 are obtained in good yield. Addition to the CO bond of 3-pentanone to give (C2H5)2C(OH)CF2CHCH2 was achieved by the method of alternate, incremental additions.  相似文献   

20.
An improved procedure for the preparation of phenyl(fluorodichloromethyl)mercury involving the reaction of phenylmercuric chloride with sodium methoxide and fluorodichloromethane in THF/methanol at ?40° is described. This procedure gives PhHgCCl2F in high yield and generally of about 85% purity. Reactions of the PhHgCCl2F thus prepared with olefins [cyclohexene, cyclooctene, allyltrimethylsilane, vinyltriethylsilane, Me2CCHCl, Me2CC(Br)Me, CH2C(Me)CH2Cl and norbornene] gave the expected cyclopropanes in high yield. This mercury reagent added CClF to the CN bond of PhNCCl2, giving 1-phenyl-2-fluoro-2,3,3-trichloroaziridine and to the CS bond of thiobenzophenone. The thiirane formed was, however, unstable to the reaction and work-up conditions and only its desulfurization product, Ph2CCClF, could be isolated. Fluorochlorocarbene transfer from this mercurial also could be induced by the action of sodium iodide in DME. Evidence is presented which shows that PhHgCCl2F is more reactive in CClF transfer than indicated in a previous report.  相似文献   

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