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1.
The new fluorinated peroxides HOC(CF3)2OOH, HOC(CF32OOC(CF3) 2OH, and (CH3) 3COOC(CF3) 2OH have been prepared by the insertion of hexafluoroacetone into the OH bonds of hydrogen peroxide and t-butyl hydroperoxide. In addition, the alkali metal salts (HOC(CF3) 2OOM (M=Li or Na) and (CH3) 3COOC(CF3) 2ONa have been prepared by neutralization of the corresponding protonic compound with the appropriate metal hydride.The new compounds are safer (i.e., less flammable and less explosive) than analogous or similar hydrocarbon peroxides, though they are somewhat less thermally stable than the parent hydroperoxides.  相似文献   

2.
Trifluorovinylsulfur pentafluoride (SF5CFCF2) and carbonyl fluoride will add, in the presence of cesium fluoride and acetonitrile, to form SF5CF(CF3)C(O)F. This new acid fluoride serves as a source for preparing derivatives containing the SF5CF(CF3) - grouping. The following new compounds have been prepared and characterized: SF5CF(CF3)X where X = C(O)F, C(O)CH3, C(O)OH, C(O)NH2, CN. The dimer, (SF5CFCF2)2, has also been prepared. Infrared, mass, and nmr spectra are presented in order to support their proposed structure.  相似文献   

3.
The reaction of (CF3)3COOH with perfluoroacyl fluorides in the pressure of NaF results in the formation of new peroxy esters of the type, (CF3)3COOC(O)Rf. Addition of the hydroperoxide to CF3NCF2 yields the unstable amine (CF3)3COOCF2N(H)CF3. These reactions of (CF3)3COOH are compared with analogous reactions of CF3OOH and SF5OOH.  相似文献   

4.
HPLC along with FT-IR technique was used to study the formation of organic peroxides in the Cl2-ethane-air photoreaction system. Ethyl hydroperoxide (CH3CH21OOH, EHP) and peroxyacetic acid ( CH3C(O)OOH, PAA) were conformed to be the peroxide product in the reaction system. In addition, methyl hydroperoxide (CH3OOH, hydroxymethyl hydroperoxide (HOCH2OOH, HMHP) and two unidentified organic peroxides were detected for the first time. EHP and were the dominant peroxide products. The identification of HMHP showed that Criegee biradical CH2OO may be formed as an intermediate in the oxidation of ethane. Simulation results showed that photooxidation of ethane may make substantial contribution to source of organic peroxides in the atmosphere.  相似文献   

5.
The formation of organic peroxides in the Cl-atom-initiated photooxidation of CH4 in O2-N2 mixtures at 101 325 Pa and 298 K was studied with HPLC and FT-IR methods. Four peroxidic products were detected, which were H2O2, hydroxymethyl hydroperoxide (HOCH2OOH; HMHP), methyl peroxide (CH300H; MHP) and dimethyl peroxide (CH300CH3). A chromatogram peak at retention time of 8.08 min was assigned tentatively to peroxyformic acid (HC(O)OOH). The identification of HMHP in the reaction system showed that one of the reaction paths for the self-reaction of CH300. led to producing Criegee intermediate CH2OO. The formation mechanism of organic peroxide in the photooxidation of CH4 is more complicated than it was assumed before. Photooxidation of CH4 is probably an important source of organic peroxides in the troposphere. Project supported by the State Scientific and Technological Commission of China (Grant No. E96-05)  相似文献   

6.
Reactions of potassium perfluoro-t-butoxide with acyl fluorides lead to the corresponding perfluoro-t-butyl esters in high yield. The compounds [(CF3)3CO]2CO, (CF3)3COC(O)F, CF3C(O)OC(CF3)3, CH3C(O)OC(CF3)3 and CF3OOC(O)OC(CF3)3 have been thus obtained and some physical and chemical properties of each are reported.  相似文献   

7.
Vicinal perfluorodi-t-butoxycycloalkanes and isomers have been prepared in 50 to 70% yields through photochemical reactions of (CF3)3COOC(CF3)3 with perfluorocycloolefins (c-C5F8 and c-C6F10) under a 200-watt Hg lamp at ?20°C. The two isomers of vic-C5F8[OC(CF3)3]2 in 1:4 ratio have been fractionated and identified as cis- and trans-isomers respectively. The three isomers for vic-C6F10[OC(CF3)3]2 in 1:4:2 ratio have been fractionated and tentatively identified as equatorial-equatorial, axialequatorial and axial-axial respectively.New 2,2′ -perfluorodimethoxycycloalkyls have been prepared in 60 to 80% yields through photolysis of CF3OOCF3 with perfluorocycloolefins under a 2500-watt Hg-Xe lamp at ?20°C. The attempted separations of the rotational isomers have been unsuccessful. The need of a strong ultra-violet source for primary perfluorodialkyl peroxide is discussed and the mechanism and the radical chain sequences are presented.Another new synthesis of bis(perfluoro-t-butyl) peroxide [D(CF3)3CO-OC(CF3)3 ?34.5 kcal] from (CF3)3COF using difluoroamino radicals as the fluoroxy fluorine atoms acceptor is described.  相似文献   

8.
A new general synthesis of trifluoromethyl amines of the type, CF3N(X)H, is reported. The amines are prepared in excellent yield by the hydrolysis CF3N(X)C(O)F in the presence of NaF. The N-acyl fluorides are now available in considerable variety from the reaction of nucleophiles with the oxaziridine CF3NCF2O. Six new amines have been prepared and characterized [(X=CF3O, (CF3)2CFO, CH3O, C2H5O, (CH3)2CHO and (CH3)3CO)] and improved syntheses of CF3NHF and CF3NHOC(O)CH3 are reported. The new compounds are thermally stable at 22° and are characterized by IR, NMR and physical properties.  相似文献   

9.
The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O2CMe)(CO)2LF]2, where LF is the perfluoroalkyl substituted tertiary phosphine, P(C6H4-4-CH2CH2(CF2)7CF3)3, or P(CH2CH2(CF2)5CF3)3, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O2CMe)(CO)2P(C6H4-4-CH2CH2(CF2)7CF3)3]2 (1) or [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2 (2). The X-ray crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2 was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing.  相似文献   

10.
By pyrolyzing di-t-butyl peroxide over the temperature range of 405–450 K in the presence of hexafluoroacetone the kinetics of the addition reaction (1), CH3 + (CF3)2CO→; (CF3)2C(?)CH3, have been studied. Detailed analyses have shown that the principal product of the adduct radical, (CF3)2C(?)CH3, is CF3COCH3 from reaction (2), (CF3)2C(?)CH3 → CF3COCH3 + CF3. The rate constant of the addition reaction was determined to be k1(dm3/mol·s) = (1.1 ± 4.0) + 109 exp(-(3680 ± 480)/T) over the temperature range 405–450 K, based on the value k3 = 2.2 × 1010 dm3/mol·s for reaction (3), 2CH3 → C2H6. The results are discussed in relation to existing data for radical additions to carbonyl groups.  相似文献   

11.
Oligomeric peroxides formed in the synthesis of triacetone triperoxide (TATP) have been analyzed by mass spectrometry utilizing both electrospray ionization (ESI) and chemical ionization (CI) to form sodiated adducts (by ESI) and ammonium adducts (by CI and ESI). Tandem mass spectrometry and deuterium isotopic labeling experiments have been used to elucidate the collision‐induced dissociation (CID) mechanisms for the adducts. The CID mechanisms differ for the sodium and ammonium adducts and vary with the size of the oligoperoxide. The sodium adducts of the oligoperoxides, H[OOC(CH3)2]nOOH, do not cyclize under CID, whereas the ammonium adducts of the smaller oligoperoides (n < 6) do form the cyclic peroxides under CID. Larger oligoperoxide adducts with both sodium and ammonium undergo dissociation through cleavage of the backbone under CID to form acyl‐ and hydroperoxy‐terminated oligomers of the general form CH3C(O)[OOC(CH3)2]xOOH, where x is an integer less than the original oligoperoxide degree of oligomerization. The oligoperoxide distribution is shown to vary batch‐to‐batch in the synthesis of TATP and the post‐blast distribution differs slightly from the distribution in the uninitiated material. The oligoperoxides are shown to be decomposed under gentle heating. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

12.
We report on the solid‐state structures of bis(nonafluoro‐tert‐butyl) peroxide [(F3C)3CO]2 and bis(undecafluoro‐2‐methyl‐2‐butyl) peroxide [(C2F5)(F3C)2CO]2. These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid‐state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180°, as well as elongated O?O bonds because of the bulky perfluorinated alkyl groups. The perfluorinated alkyl peroxides are insensitive to both impact (>40 J) and friction (>360 N), and resistant towards mineral acids (HX; X=F, Cl, Br) and elemental halogens (X2). Ferrocene is oxidized by [(F3C)3CO]2 to [FeIIICp2][OC(CF3)3].  相似文献   

13.
Preparation and Spectroscopic Characterization of Perfluoro(isopropyl)-trifluoroacetylperoxide (CF3)2C(F)OOC(O)CF3 The reaction of perfluoroacetone (CF3)2CO with OF2 in a ratio 2 : 1 yields Perfluoro(isopropyl)-trifluoroacetylperoxide (CF3)2C(F)OOC(O)CF3. The reaction only occurs under CsF-catalysis. (CF3)2C(F)OOC(O)CF3 is characterized by vibrational, nmr and mass spectra. Using an excess of OF2 does not give any stable product.  相似文献   

14.
Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (RFO)2P(O)H in 42-89% yield, where RF=HCF2CH2, H(CF2)2CH2, H(CF2)4CH2, CF3CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH, CF3(CH3)2C, (CF3)2CH3C, CF3CH2CH2, C4F9CH2CH2 and C6F13CH2CH2. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (RFO)2P(O)Cl in 49-96% yield. The chloridate (CF3CH2O)2P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF3CH2O)2P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF3CH2O)2P(O)Br and iodidate (CF3CH2O)2P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts.  相似文献   

15.
Trifluoromethylated phosphines R2PCF3 (R = NEt2, Me, 1Pr) were methylated by CH4OSO2CF3, yielding the corresponding phosphonium salts [R2P(CF3)CH3] [F3CSO3]. Treatment with LiN(SiMe3)2 at −80°C furnished the phosphorus ylides R2P(CF3) = CH2 that could be trapped by use of hexafluoroacetone with formation of stable 1,2λ5σ5-oxaphosphetanes. The single-crystal X-ray structure determination of one of these oxaphosphetanes showed a distorted trigonal bipyramid at phosphorus with the P-CF3 group in an axial position. © 1996 John Wiley & Sons, Inc.  相似文献   

16.
The radical addition reactivity of tert-butyl α-trifluoromethylacrylate (CH2C(CF3)COOC(CH3)3) (BFMA) with cyclic ethers was investigated in order to compare to that of perfluoroisopropenyl ester. One to one addition compound of BFMA with tetrahydrofuran (THF) was produced in fairy high yields in the presence of 2,2′-azobisisobutyronitrile, benzoyl peroxide or di-tert-butyl peroxide to give 2-substituted THF derivative. Time-conversion investigation showed much higher reactivity of BFMA compared to that of 2-benzoxypentafluoropropene [CF2C(CF3)OCOC6H5]. Radical additions of BFMA with 1,4-dioxane, 1,3-dioxolane and tetrahydropyran were also examined to afford corresponding 1:1 addition products in fairly high yields by achieving carbon-carbon bond formation. It is then concluded that no interconversion of fluoroalkylcarbon radical and hydrocarbon radical may take place in the reaction system of BFMA which possesses two less fluorines in the vinyl group compared to 2-benzoxypentafluoropropene. The method may be a facile way to prepare trifluoromethyl-substituted organic compounds accompanied by the formation of carbon-carbon bonds by the aid of fluorine atoms.  相似文献   

17.
Forty bis(fluoroalkyl) phosphoramidates (RFO)2P(O)R were prepared in 10-91% yield by treating phosphorochloridates (RFO)2P(O)Cl where RF was HCF2CH2, HCF2CF2CH2, HCF2CF2CF2CF2CH2, CF3CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH and (CH3)2CF3C with nucleophiles HR, where R was NH2, NHMe, NMe2, NHEt and NEt2 in diethyl ether at 0-5 °C. The bulky chloridate [(CH3)2CF3CO]2P(O)Cl reacted with ammonia, methylamine, dimethylamine and ethylamine, but not with diethylamine—even on heating in the presence of 4-dimethylaminopyridine—due to steric hindrance at phosphorus. Fluorinated phosphoramidates have lower basicity and nucleophilicity than their unfluorinated counterparts: (EtO)2P(O)NH2 is more easily hydrolysed by HCl than (CF3CH2O)2P(O)NH2 and whereas, (EtO)2P(O)NH2 is known to react with oxalyl chloride and thionyl chloride to give (EtO)2P(O)NCO and (EtO)2P(O)NSO respectively, (CF3CH2O)2P(O)NH2 reacted only with oxalyl chloride to give (CF3CH2O)2P(O)NCO in 10% yield. Two other new fluorinated species, (CF3CH2O)2P(O)NHOMe and (CF3CH2O)2P(O)N3, were prepared by nucleophilic substitution of bis(trifluoroethyl) phosphorochloridate with methoxyamine and azide ion.  相似文献   

18.
Photolysis of a solution of Cp*RuCp (1) in CF3CO2H generates salt [CpRu(C5Me4CH2)]-(O2CCF3)(2 • O2CCF3). The reaction of compound 1 with oleum at 20 °C through the intermediate dication [η5-(CH2C5Me4)Ru(μ:η55-C5H4C5H5)Ru(C5Me4CH2)-η6]2+ leads to the triply charged cation η7CH2)2C5Me3Ru(μη55-C5H4C5H4)Ru(C5Me4CH2)-η6]3+. Synthesis of pentamethylmetallocene derivatives CpMC5Me4X (M = Ru, Fe; X = CHO, CH2OH, CH2An) has been accomplished. The reactions of 1-hydroxymethyl-2,3,4,5-tetramethylruthenocene with acids CF3CO2H, HBF4, CF3CO2H/NaB[C6H3(CF3)2]4, and picric acid C6H2(NO2)3OH afforded salts 2•X (X = CF3CO2, BF4, B[C6H3(CF3)2]4), and (2,3,4,5-tetram ethylruthenocenyl)methyl picrate [CpRu(C5Me4CH2)-η6][(C6H2(NO2)3O] (2•C6H2(NO2)3O). Structure of the latter was characterized by single crystal X-ray diffraction.  相似文献   

19.
Twenty nine bis(fluoroalkyl) phosphates (RFO)2P(O)OR were prepared in 18-75% yield by treating phosphorochloridates (RFO)2P(O)Cl, where RF was HCF2CH2, HCF2CF2CH2, H(CF2)4CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH and (CH3)2CF3C with methanol, ethanol, propanol and isopropanol in diethyl ether in the presence of triethylamine. The bulky chloridate [(CH3)2CF3CO]2P(O)Cl reacted with methanol, ethanol and propanol, but not with isopropanol - even on heating in the presence of the catalyst 4-dimethylaminopyridine - due to steric hindrance at phosphorus. The relative reactivities of three of the chloridates decreased in the order [(CF3)2CHO]2P(O)Cl > [(FCH2)2CHO]2P(O)Cl > [(CH3)2CF3CO]2P(O)Cl. Also described is the synthesis of phosphates (CF3CH2O)2P(O)OCH2R, where R = CH2Br, CH2Cl, CH2F and CHF2, and diphosphates [H(CF2)nCH2O]2P(O)OCH2(CF2)2CH2OP(O)[OCH2(CF2)nH]2, where n = 1, 2 and 4.  相似文献   

20.
It has been found that treatment of SF5-alkyl halides, especially SF5(CH2)2Br, with silver salts such as CH3C(O)OAg, p-CH3C6H4SO3Ag, CF3SO3Ag and AgNO3 provides convenient pathways for preparing the following ester compounds: SF5CH2CH2R (R = CH3COO, TosO, CF3SO3, NO3), SF5(CH2)3OTos, and SF5(CF2)4(CH2)2OAc. Important derivatives prepared from these esters include SF5(CH2)2OH; SF5(CF2)4(CH2)2OH. Several alkenes SF5C(Br)CH2 and SF5CH2(COOCH3)CCHC(O)OCH3 are obtained using silver salts. The use of alkali metals salts with SF5(CH2)3Br is studied and yields SF5(CH2)3I; also, a pathway has been developed that extends for SF5(CH2)3− the chain by two-carbon atoms and also produces the first SF5-containing malonic acid.  相似文献   

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