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1.
Sodium dialkyldithiocarbamates readily attacked -propene to give S-(1,1,2,3,3,3-hexafluoropropyl)-N,N-dialkyldithiocarbamates, CF3CHFCF2SC(S)-NR2, and and -S-(1,2,3,3,3-pentafluoropropenyl)-N,N-dialkyldithiocarbamates, CF3CFCFSC(S)NR2. The pyrolysis of the former compound quantitatively gave the dialkylthiocarbamoyl fluorine, R2NC(S)F, while the latter compound and sodium tetraphenylborate formed the corresponding 1,3-dithiolan-2-ylium tetraphenylborate. -2-Methyl-2-pentene also reacted with sodium dialkyldithiocarbamate to give (CF3)2CHC[SC(S)NR2]CFCF3. The mechanism of this reaction is supposed to involve a 1,4-RSF-elimination. 相似文献
2.
-N-Isopropylacetimidoyl chloride, CF3CClNCF(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)CNCF(CF3)2, and the 1,5-tetrazole, CF3CF(CF3)2. Hexafluoropropylideniminolithium produces as a minor product the conjugated diimine, (CF3)2CNC(CF3)NCF(CF3)2, from nucleophilic attack at the imidoyl chlorine and as a major product the triimine, (CF3)2CNC(CF3)NC(CF3)2NC(CF3)2, from further attack at the isopropyl fluorine. A thio-amide, CF3C(S)NHCH(CF3)2, and a Δ3-1,2,4-dithiazoline, (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
3.
A.R. László Bursics Martin Murray F. Gordon A. Stone 《Journal of organometallic chemistry》1976,111(1):31-42
Bis(cyclopentadienyl)mercury readily undergoes Diels—Alder reactions with RCCR (R = CO2Me or CF3), CF3CFCFCF3, CF3CFCF2, (CF3)2CC(CN)2, C2(CN)4 and PhO to give stable adducts characterised by1H, 19F and 13C NMR, spectroscopy. Similar reactions of CF3CCCF3 and CF3CFCFCF3 with the cyclopentadiene derivatives Me3MC5H5 and (Me3M)2C5H4 (M = Si, Sn) are also described. 相似文献
4.
The fluoride ion induced isomerisation of 1-perfluoroalkenes RFCFCF2 (RF=C4F9, (I) -C5F11 (II), -C6F13 (III), -C7F15(IV) has been studied in the polar solvents DMF and VMSO. The reaction gives a mixture which changes to the thermodynamically stable isomer. 19F n.m.r. spectroscopy allows characterisation of products and shows that all alkenes formed are -derivatives. The products formed are explained on the basis of a cyclic intermediate involving participation of the metal cation. 相似文献
5.
Some fluoroalcohols have been prepared by free-radical addition of methanol, ethanol and isopropanol to fluoroolefins as C3F6, CFHCFCF3, (CF3)2CFCFCFCF3, H(CF2)4CFCF2, The general reaction is (1) RfCFCF2 + RR′CHOH = RfCFHCF2CRR′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
6.
It was found that the reaction of mesomeric fluorocarbanions of the CF3XCOY type with benzoic anhydride leads to the loss of benzoyl fluoride and the formation of mesomeric carbanions of the FCOXCOY type. In a similar reaction with perfluorocarboxylic acid anhydrides, besides a CF3→COF transformation, further change of COF into CORF is observed, leading to the formation of salts containing mesomeric anions of the RFCOXCOY type, which, upon acidification, give 1,1- -bis(perfluoroacyl)-2,2,2-trifluoroethanes CF3CH(CORF)2 , tris- (perfluoroacyl)methanes (RFCO)3CH and bis(trifluoroacetyl)- acetic ester (CF3CO)2CHCOOMe. It has been shown that perfluoroalkyl groups in β-diketones and β,β′-triketones may hinder enolization despite their electron-attracting effect. 相似文献
7.
The two perfluoro-azadienes CF2N.CRCF2 (R = CF3 or CF2Cl) show temperature dependent 19F n.m.r. spectra, with non-equivalent fluorine nuclei of the CF2N portion at low temperatures, which coalesce due to inversion at the nitrogen at higher temperatures (ΔG3 = 60 kJ mol?1). N.m.r. parameters have been obtained. One of the five-bond FF coupling constants is much larger (. 24 Hz) than the remainder (0·5–5·5 Hz), possibly due to ‘through-space’ coupling of fluorines in the -skew conformation. 相似文献
8.
Ronald Eric Banks 《Journal of fluorine chemistry》1982,21(1):46
Mechanistic and synthetic highlights of out studies during the past twenty years on azides derived from fluorocarbon systems {alkenes ( CF3CFCFN3), aza-alkenes and -cycloalkenes [(CF3)N3], arenes ( C6F5N3), and heteroarenes( 4-N3.C5F4N)} will be discussed with emphasis on recent results bearing on the synthesis of novel seven-membered -heterocycles. 相似文献
9.
Neal O. Brace 《Journal of fluorine chemistry》1982,20(3):313-327
Free radical addition of an F-alkyl iodide (RFI) to an alkenol or ester, followed by appropriate reduction is an efficient method for preparing the corresponding F-alkyl-alkanols of the homologous series, RF(CH2)n?OH. When n = 2,4 or higher, the two steps take place smoothly. The 1,2,3-substituted systems RFCH2CHYCH2Z, however, are susceptible to surprising difficulties. Reduction of RFCH2CHICH2ON to RF(CH2)3OH by hydrogen and catalyst (strong base acid acceptor), can be done either in one step or RFCHCHCH2OH; however, dehydrohalogenation may also give the epoxide, and reduction in this case leads to the secondary alcohol, RFCH2CH(CH3)OH. By contrast, reduction of RFCH2CHICH2OAc by tributyltin hydride or with hydrogen over palladium (diethylamine acid acceptor) goes smoothly. Zinc and acid reduction of RFCH2CHICH2OAc gives elimination to RFCH2CHCH2; even RFCHCICH2OH gives RFCHCCH2 besides RFCHCHCH2OH. RFCHCICH2CH2OH, however, with zinc and acid is reduced cleanly to RFCHCHCH2CH2OH. 相似文献
10.
Pangbu Hong Kenkichi Sonogashira Nobue Hagihara 《Journal of organometallic chemistry》1981,219(3):363-369
Reactions of ketenes (R1R2CCO) with (η5-C5H5)Ni(PPh3)CCR (I) and (η5-C5H5)Fe(CO)(L)CCR (III, L = CO and PPh3) give σ-cyclobut-1-en-3-onyl complexes, {(η5-C5H5)Ni(PPh3)}R1R2 (VI) and (η5-C5H5)Fe(CO)(L)R1R2 (IX)}, (2 + 2) cycloaddition products, in good yields. The σ-cyclobutenonyl complexes also can be prepared by the reaction of I and III with acyl chlorides in the presence of triethylamine. 相似文献
11.
After a review of 1-perfluoroalkene RFCFCF2 synthesis, with RFC4F9, C5F11, C6F13, we have studied their fine structures by 19F N.M.R. This study has led us to first generalize the rules set for the chemical shifts and coupling constants of olefinic fluorine atoms of fluoropropene and their derivatives. Then, we have been able to determinate unambiguously the chemical shifts of the difluoromethylene groups of the perfluorinated chains. We have thus shown, by irradiation, that inversions may take place in the chemical shifts of the CF2 groups at the β and γ position of the double bond. 相似文献
12.
Different methods for the preparation of fluorinated iminium salts RR1CNR2R3+MF6? (R=R1=F ; R2=R3=CH3, C2H5 M=As, Sb 4a ? c R=H, R1=F; R2=R3=CH3 M=As, Sb 5a, b R=R1=CF3; R2=H, R3=CH3 M=Sb 12 R=R1=CF3; R2=R3=CH3 M=As 14) are reported, the spectroscopic properties (IR, NMR) of the cations of these salts are briefly discussed. By F?-addition to these salts, to 16, perfluoroalkyl-bis(alkyl)-amines ( (CF3)2CFN(CH3)2 15) can be prepared; from the methylation of CF3NCF2 bis(trifluoromethyl) methylamine (CF3)2NCH3 (11) was obtained. 相似文献
13.
The reactivity of perfluoroalkenylmagnesium bromides RFCFCFMgBr (RFC4F9, C6F13), obtained from the corresponding l-bromo-perfluoroalkenes, has been investigated.These Grignard reagents react with carbonyl compounds to give, with good yields, a series of new α-β unsaturated polyfluorinated alcohols RFCFCFC(OH)RR′ (1). The synthesis and spectrographic characteristics of these compounds are reported and discussed.Perfluoroalkenyl mercuric and tin derivatives are obtained from the reaction of the perfluorinated Grignard reagents with mercuric salts and organotin halides respectively : Spectroscopic identification and some chemical properties of these new perfluorinated organometallic compounds are given.The good reactivity of these unsaturated derivatives towards protic acids and electrophiles, leading to the cleavage of the perfluoroalkenyl group, is used to study the possibilities of transmetallation reactions.Somes examples of these reactions are reported. 相似文献
14.
Pentacoordinated aminosulphur (IV) trifluorides, R2NF3, (in this paper the lone pair in S(IV)-derivatives is always considered as a ligand) and aminosulphur(VI)-oxidetrifluorides, R2NS(O)F3, readily lose a fluoride ion to Lewis acids (AsF5, SbF5, BF3) to give sulphur-containing cationic species [R2NF2]+ and [R2NS(O)F2]+ with tetracoordinated sulphur. Tetracoordinated neutral dialkylaminosulphur(IV)-oxidefluorides, R2N(O)F, and amino-imino sulphur(IV)fluorides, R2N(=NRf)F, give three-coordinated sulphur cations [R2NO]+] or [R2NNRf]+.The three-coordinated sulphur(VI)cation [R2NS(O)NR]+ has also been formed. 相似文献
15.
1,2,3,4,7,7-Hexafluorobicyclo[2,2,1]hepta-2,5-diene gave 1,2,3,4-tetrafluorebenzene in at least 73% yield when heated to 450°C in a sealed tube; the CF2 bridge appeared, in part, as octafluorocyclobutane. Nucleophilic attack by sodium methoxide- methanol on the diene occurred exclusively at the CFCF bond, causing the formation of 1,2,4,7,7-pentafluoro-3-methoxybicyclo- [2,2,1]hepta-2,5-diene and a 1,4,5,6,7,7-hexafluoro-5-methoxybicyclo [2,2,1]hept-2-ene thought, on the basis of 19F nmr data, to be the 6--F,5--MeO isomer. Radical attack on 1,2,3,- 4,7,7-hexafluorobicyclo[2,2,1]hepta-2,5-diene by bistrifluoromethyl nitroxide took place at both olefinic sites, with a . 10:1 preference for the CFCF linkage; all three geometrical isomers of 5,6-bis(bistrifluoromethylamino-oxy)-1,4,5,6,7,7- hexafluorobicyclo[2,2,1]hept-2-ene were formed. 相似文献
16.
Several kinds of perfluoro-2,4-dialkyloxolanes (A), having such alkyl groups as RfR′fCF3 (2a); RfC2F5, R′fCF3 (3a); RfCF3, R′fC2F5 (4a); RfR′fC2F5 (5a); RfCF3, R′fnC3F7 (6a) on the 2 and 4 positions of the oxolane ring, respectively, were treated with AlCl3 in a heterogeneous reaction to give the corresponding perfluoro-2,5,5-trichloro-2,4-dialkyloxolanes (B). For purposes of comparison, the respective reactions of perfluoro-2-methyl-oxolane (la), perfluoro-2-n-butyloxolane (7a), and perfluoro-2, 5-dimethyloxolane (8a) with AlCl3 were also conducted. An increasingly higher reaction temperature was needed for the reaction of A with AlCl3 to give B as the carbon number of A increased. Cis- and trans-perfluoro-4-chloro-2,4-dimethyl-γ-butyrolactones (2c) were obtained from the hydrolytic reactions of cis- and trans-perfluoro-2,5,5-trichloro-2,4-dimethyloxolanes (2b), respectively, with fuming H2SO4. Physical properties and 19F nmr data are given for these new compounds. 相似文献
17.
A series of new polyfluorinated dienes 3, containing the novel -CFCHCHCF-, pattern has been synthesized (50–70% yields) by reacting perfluoroalkyl iodides with perfluoroalkyl-ethylenes in the presence of copper. The monoalkenes RfCFCHCH2CF2R′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
18.
Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O(CH3) and i-C3F7N(CH3 with symdimethylethylenediamine (1). In contrast, CF3C(O)NSF2 and (Rf)2SF2 (Rf = CF3, i-C3F7 form only acyclic compounds, CF3C(O)N(CH3)CH2CH2N(CH3)C(O)CF3 and RfSN(CH3)CH2CH2N(CH3)SRf with (1). With PF3, PF5 and OPF3, cyclic compounds F, F3, and -(O)F result. When the latter two compounds are reacted further with LiNC(CF3)2, N(CH3)CH2CH2N(CH3)PF2NC(CF3)2 and (O)NC(CF3)2) form. 相似文献
19.
Perfluorinated olefins of general formula CF3(CF2)pCFCF(CF2)mCF3 (3 ? m + p ? 25) are oxidized by potassium permanganate or ruthenium tetroxide. The linear high molecular weight perfluorinated carboxylic acids so obtained are characterized by 19F N.M.R. spectroscopy. 相似文献
20.
The structure of (Ph3SiN)2C has been determined by single crystal X-ray diffraction. The structure was solved by direct methods and refined to R = 0.071 for 593 independent diffractometer data. The crystals are rhombohedral, R with a = b = c 18.201(20) Å, α = β = γ = 48.82(2)°, and Z = 4. The three crystallographically independent molecules each have linear SiNCNSi chains lying along the crystallographic threefold axes; in two of the molecules the central carbon atom lies on a centre of symmetry. Principal mean bond lengths and angles are: Si, 1.696(25); SiC, 1.846(20); NC, 1.164(30); CC, 1.387(14) Å; CSi, 108.2(6); and CSiC, 110.8(6)°. 相似文献