Fluorine chloroform

Vincenti M, Biazzi S, Ghiglione N, Valsania MC, Richardson SD (2005) Comparison of highly-fluorinated chloroformates as direct aqueous sample derivatizing agents for hydrophilic analytes and drinking-water disinfection by-products. J Am Soc Mass Spectrom 16(6) 803-813... 

Nitric oxide Aluminum, BaO, boron, carbon disulflde, chromium, many chlorinated hydrocarbons, fluorine, hydrocarbons, ozone, phosphine, phosphorus, hydrazine, acetic anhydride, ammonia, chloroform, Fe, K, Mg, Mn, Na, sulfur... 

A number of inhalation anesthetics have been introduced to clinical practice, some of which are Hsted in Table 1. AH agents introduced after 1950, except ethyl vinyl ether, contain fluorine. Agents such as ether, chloroform, trichloroethylene (Tdlene), cyclopropane, and fluoroxene (Fluoromar), which were once used, have been displaced by the newer fluorinated anesthetics. 

At 225—275°C, bromination of the vapor yields bromochloromethanes CCl Br, CCl2Br2, and CClBr. Chloroform reacts with aluminum bromide to form bromoform, CHBr. Chloroform cannot be direcdy fluorinated with elementary flourine fluoroform, CHF, is produced from chloroform by reaction with hydrogen fluoride in the presence of a metallic fluoride catalyst (8). It is also a coproduct of monochlorodifluoromethane from the HF—CHCl reaction over antimony chlorofluoride. Iodine gives a characteristic purple solution in chloroform but does not react even at the boiling point. Iodoform, CHI, may be produced from chloroform by reaction with ethyl iodide in the presence of aluminum chloride however, this is not the route normally used for its preparation. 

Xenon difluoride [4, 5, 7, 8,10] is a white crystalline material obtained through the combination of fluorine and xenon m the presence of light The reagent is commercially available and possesses a relatively long shelf-life when stored cold (freezer) Xenon difluoride is very effective for small-scale fluormation of alkenes and activated nucleophilic substrates. The reactions are usually conducted between 0 °C and room temperature in chloroform or methylene chloride solutions Hydrogen fluoride catalysis is sometimes helpful Xenon difluoride reacts in a manner that usually involves some complexation between the substrate and reagent followed by the formation of radical and radical cation intermediates... 

This method can be adapted for the synthesis of biologically active compounds the 2,2-difluoro derivative of the antibacterial pleuromutalin a tricyclic terpenoid, was prepared in 31% yield from 2-diazopleuromutahn and dilute fluorine in chloroform in the presence of potassium fluoride at 50 °C [96]... 

Mg ribbon and fine Mg shavings can be ignited at air temps of about 950°F (Ref 26). Oxides of Be, Cd, Hg, Mo and Zn can react explosively with Mg when heated (Ref 8). Mg reacts with incandescence when heated with the cyanides of Cd, Co, Cu,Pb, Ni or Zn or with Ca carbide (Ref 9). It is spontaneously flam-mable when exposed to moist chlorine (Ref 10), and on contact with chloroform, methyl chloride (or mixts of both), an expl occurs (Ref 4). Mg also reacts violently with chlorinated hydrocarbons, nitrogen tetroxide and A1 chloride (Ref 14). The reduction of heated cupric oxide by admixed Mg is accompanied by incandescence and an expin (Ref 7).Mg exposed to moist fluorine is spontaneously flammable (Ref 11). When a mixt of Mg and Ca carbonate is heated in a current of hydrogen, a violent ex pin occurs (Ref 12). When Mo trioxide is heated with molten Mg, a violent detonation occurs (Ref 1). Liq oxygen (LOX) gives a detonable mixt when... 

Some of the fluorinated hydrocarbons—e.g., trifluoromethane 44), 1,1-difluoroethane 45), and difluorodichloromethane 82)—are known to be chemically inactive and physiologically inert. Stepwise replacement of the chlorine atoms in chloroform by fluorine yields the dichlorofluoromethane and chlorodifluoromethane, neither of which is as toxic as the original substance (7). 

The violent or explosive reactions which carbon tetrachloride, chloroform, etc., exhibit on direct local contact with gaseous fluorine [1], can be moderated by suitable dilution, catalysis and diffused contact [2], Combustion of perfluorocy-clobutane-fluorine mixtures was detonative between 9.04 and 57.9 vol% of the halocarbon [3], Iodoform reacts very violently with fluorine owing to its high iodine content [4], Explosive properties of mixtures with 1,2-dichlorotetrafluoroethane have been studied [5],... 

Mixtures of the tetraoxide with dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethylene and tetrachloroethylene are explosive when subjected to shock of 25 g TNT equivalent or less [1], Mixtures with trichloroethylene react violently on heating to 150°C [2], Partially fluorinated chloroalkanes were more stable to shock. Theoretical aspects are discussed in the later reference [2,3], The effect of pressure on flammability limits has been studied [4],... 

In studying the reactivity of iV-fluoropyridinium fluoride 127 obtained from pyridine 126 by treatment with fluorine gas in chloroform at low temperature (Scheme 30), Kiselyov studied reactions with isocyanides in the presence of trimethylsilylazide <2005TL4851>. A mixture of products was obtained in which, besides tetrazolylpyr-idine 128 and a nicotinamide derivative 129 also tetrazolo[l,5-tf]pyridine 1 was obtained in very poor yield (5-10%). 

Poly(ether ketone)s 3, 4, 5, 6, and 7 were soluble in polar aprotic solvents such as DMAc and NMP and in chlorinated solvents such as chloroform. The improved solubility of these fluorinated poly(ether ketone)s can be explained by the presence of both the flexible hexafluoroisopropylidene groups and the bulky 1,4-naphthalene moieties, which inhibit polymer crystallization and facilitate the penetration of solvent molecules between the polymer chains. 

The solubility is generally improved by the introduction of fluorine atoms into aromatic condensation polymers. Poly(carbonate)s containing hexafluoroisopropylidene units are much more soluble than Bisphenol A poly(carbonate) (3). All of the hexafluoroisopropylidene-unit-containing poly(carbonate)s become soluble in acetone, ethyl acetate, chloroform, and dimethyl sulfoxide (DMSO) in addition to the solvents of Bisphenol A poly(carbonate) (3). Colorless, transparent, and flexible films are prepared from hexafluoroisopropylidene-unit-containing poly(carbonate)s by casting or pressing. 

Four poly(ether ketone)s obtained from 2,2-bis[4-(4-fluorobenzoyl)-phenyl]-1,1,1,3,3,3-hexafluoropropane (9) or 2,2-bis[4-(4-fluorobenzoyl)-phenyl]propane (10) with Bisphenol AF (1) or Bisphenol A (4) are all soluble in chloroform, benzene, THF, and aprotic polar solvents such as DMF, DMAc, and NMP.15 Poly(ether ketone) from 9 and 1, which has the highest fluorine content, dissolves easily in ethyl acetate. 

The incorporation of fluorine atoms improves the solubility of aromatic condensation polymers without causing them to lose their high thermal stability and modifies the processability. Hexafluoroisopropylidene-unit-containing poly-(azomethine)s and copoly(azomethine)s are readily soluble in highly polar solvents such as DMAc, HMPA, and NMP, and they also dissolve completely in dichloromethane, chloroform, and THF, whereas poly(azomethine)s derived from 21 and 22 and having no fluorine atom are insoluble in these solvents.20 Accordingly, the solubility of aromatic poly(azomethine)s is remarkably improved by substituting isopropylidene units with fluorine atoms. 

FIGURE 3. The NMR spectra of the two racemic diastereomers of lV-(4-methyl-2-pentyl)-a-methoxy-a-trifluoromethylphenylacetamide prepared from racemic a-methoxy-a-(trifluoromethyl)phenylacetic acid [MTPA, ( )-83] and racemic 4-methyl-2-pentylamine [( )-84] (A) 60-MHz proton spectrum in chloroform-4 with tetramethylsilane (TMS) as the internal standard (B) 94.1-MHz fluorine-19 spectrum in chloroform-4 with trifluoroacetic acid as the internal standard. Reprinted with permission from Reference 76. Copyright (1969) American Chemical Society... 

Hydrophobic, fluorinated hyperbranched grafts were synthesized from an ethyl chloroformate activated hyperbranched 3-PAA/Au graft using the fluorinated alkyl amine H2N(CH2)(CF2)6CF3. Reaction of an activated 3-PAA/Au film with H2N(CH2 ) (CF2 leCFs produced a fluorinated film that almost doubled in thickness. XPS analysis showed 46 atom-% F in the product fluoramidated graft which is 86% of the theoretical atomic concentration for a homogenous... 

The electrofluorination of acetophenone and benzophenone takes place in anhydrous HF and in the presence of solvents such as chloroform and acetonitrile [38]. The fluorination of the aromatic rings occurred to various extent. Further uses of anhydrous hydrogen fluoride as a liquid environment for electrofluorination processes have been reported, for example, by Matalin etal. [39]. In particular, systems with low conductivity in liquid hydrogen fluoride and nonselective processes have been studied and optimized. The fluorination of benzene and halobenzenes in the presence of Et4NF—(HF) in an undivided cell has been studied by Horio et al. [40] Cathodic dehalogenation is observed to accompany the anodic fluorination process. 

Fluorination of adenine derivatives using elemental fluorine (1% F2 in Fie delivered at a rate of 5-10 j.mol F2 min ) gave the C-8 fluoro analogues in moderate yields <1996JA10408>. Although chloroform was the optimum solvent, this was not suitable for less-soluble, unprotected compounds and ethanol was substituted, although a reduction in yield was observed (Scheme 13). 

For about one hundred years, and longer in some parts of the world, diethyl ether and chloroform had no rivals. This was despite major drawbacks, the main ones being the flammability and slow onset of diethyl ether, and the hepatotoxicity and cardiac arrhythmias induced by chloroform. New discoveries in organic fluorine chemistry at the end of World War II paved the way for the synthesis of modern fluorinated anaesthetic alkanes and ethers. 

Halothane was introduced into clinical practice in 1956. It was not the first fluorinated anaesthetic— fluoroxene (Fluoromar) holds that distinction—but it was the first to achieve widespread acceptability. Halothane is a fluorinated alkane 1-bromo, 1-chloro -2,2,2-trifluoroethane (Figure 3.2). It has a characteristic odour, similar to chloroform, and requires a stabiliser, thymol (0.01%), to prevent degradation by light. Halothane has a blood/gas partition coefficient of 2.4 able 3.2) but its lack of irritant qualities makes possible the use of relatively high inspired concentrations (2-4%). For that reason, inhalation induction is characteristically smooth and rapid. Compared to sevoflurane, and possibly isoflurane, recovery from halothane anaesthesia is delayed. 

Chlorination of methane, in which chlorine is substituted for one to all four of the hydrogens in methane, produces methyl chloride (CH3C1), methylene chloride (CH2C12), chloroform (CHC13), and carbon tetrachloride (CCf). The substitution of chlorines and fluorines in methane results in chlorofluorocarbons (see Dichlorodifluoromethane). 

---