Reactions with carbon compounds

The reaction of an equimolar mixture of nitrogen trifluoride and carbon monoxide at 520°C in a nickel tube produces COF2 (90 to 95% yield), CF4, NO, and NO2 [1]  

The reaction has also been initiated at room temperature by irradiation with two CO2 lasers. The main products identified are COF2, CF4, N2, and O2. A 100% conversion of CO can be reached [2, 3]. 

Reaction with carbon dioxide occurs at 825°C also yielding COF2 (80% yield), CF4, NO, and 

A stoichiometric mixture of both gases can not be ignited when exposed to an electric discharge [4]. 

Phosgene and nitrogen trifluoride (1 1 ratio) react at 400°C in a nickel tube to quantitatively produce COFg according to 

---

A quite different type of reaction, which may also occur in food, is the reduction of azo dyes to colorless hydrazo compounds. Like in the reaction with carbon compounds, the reactive species is S032 and not HS03 (Wedzicha and Rumbelow, 1981). 

Occurrence ndPreparation. Carbonyl sulfide is formed by many high temperature reactions of carbon compounds with donors of oxygen and sulfur. A principal route is the foUowiag reaction (30) ... 

Reactions with Organic Compounds. The addition of biomine to unsatuiated carbon compounds occurs readily. 

Allylboron compounds have proven to be an exceedingly useful class of allylmetal reagents for the stereoselective synthesis of homoallylic alcohols via reactions with carbonyl compounds, especially aldehydes1. The reactions of allylboron compounds and aldehydes proceed by way of cyclic transition states with predictable transmission of olefinic stereochemistry to anti (from L-alkene precursors) or syn (from Z-alkene precursors) relationships about the newly formed carbon-carbon bond. This stereochemical feature, classified as simple diastereoselection, is general for Type I allylorganometallicslb. 

Due to the reversibility of this nitroaldol reaction, the easy epimerization at the nitro-sub-stituted carbon, and the often low yields in reactions with nitro compounds other than ni-tromethane, few stereoselective additions have been reported. Highly stereoselective reactions are known for the synthesis of cyclic systems (see Section 1.3.5.6.6.). 

Stereoselective reactions of this type known at present only deal with four- or five-membered cyclic iV-acyliminium ions. The reactions with carbon nucleophiles usually lead to rra/u-substi-tuted compounds with very high stereoselectivity due to steric control by the substituent already present in the ring. 

It is well established that sulfur compounds even in low parts per million concentrations in fuel gas are detrimental to MCFCs. The principal sulfur compound that has an adverse effect on cell performance is H2S. A nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Chemisorption on Ni surfaces occurs, which can block active electrochemical sites. The tolerance of MCFCs to sulfur compounds is strongly dependent on temperature, pressure, gas composition, cell components, and system operation (i.e., recycle, venting, and gas cleanup). Nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Moreover, oxidation of H2S in a combustion reaction, when recycling system is used, causes subsequent reaction with carbonate ions in the electrolyte [1]. Some researchers have tried to overcome this problem with additional device such as sulfur removal reactor. If the anode itself has a high tolerance to sulfur, the additional device is not required, hence, cutting the capital cost for MCFC plant. To enhance the anode performance on sulfur tolerance, ceria coating on anode is proposed. The main reason is that ceria can react with H2S [2,3] to protect Ni anode. 

Sodium is, like all other alkali metals, a very strong reducing agent (more reactive than lithium), which has extremely violent reactions with numerous compounds. It causes a large number of accidents. Sodium peroxide is a very reactive oxidant, which has violent interactions with reducing agents. Carbonates, and especially sodium hydroxide, are bases which react with acids (the reaction is aggravated by the formation of carbon dioxide). 

This silylene formation from 27 under mild conditions permits the synthesis of a variety of interesting carbo- and heterocycles, most of which are new types of compounds. The results are summarized in Schemes 5 and 6. The reactions with benzene and naphthalene represent the first examples of [2+1] cycloadditions of a silylene with aromatic C=C double bonds.59 623 The reactions with carbon disulfide and isocyanide (Scheme 6) are also of great interest because of their unusual reaction patterns.62b... 

The formato complex 0sH(K2-02CH)(C0)(P Pr3)2 has also been prepared by treatment of the hydride-chloro compound OsHCl(CO)(P Pr3)2 with NaOMe in benzene-methanol under carbon dioxide atmosphere. Under the same conditions, the reaction with carbon disulfide affords OsH(K2-S2COMe)(CO)(P Pr3)2.67... 

Carbon Dioxide Fixation Using Reactions with Other Compounds... 

Compound 145 on lithiation <1999SM(102)987> and subsequent reaction with carbon dioxide afforded compound 146. Sandmeyer reaction of 2-bromodi thieno[3,2-A2, 3 -with copper(l)cyanide in hot iV-methyl pyrrolidine (NMP) gave the corresponding nitrile 148 which was then converted to the tetrazole 149 with a mixture of sodium azide and ammonium chloride in NMP in low overall yield (Scheme 14) <2001JMC1625>. 

The iron slurries show exceptional reactivity toward oxidative addition reactions with carbon halogen bonds. In fact, the reaction with C.FcI is so exothermic that the slurry has to be cooled to 0 °C before the addition of C F L The reaction of iron with C F Br is also quite exothermic, hence, even for this addition, the iron slurry is cooled to about 0 ° C. The organoiron compound formed in the above reactions, solvated Fe(C.F )2, reacts with CO at room temperature and ambient pressure to yiela Fe(C,F3)2(CO)2(DMEL. 

Carbon atoms, energetic, reactions with organic compounds, 3,201... 

Compound 874, as a representative of derivatives with an electron-withdrawing substituent at C-[1 of the vinyl group, is easily prepared by elimination of one benzotriazole from 2,2-/fo(benzotriazol-l-yl)ethyl methyl ketone 873. The stereoselective elimination catalyzed by NaOH gives exclusively the (E) isomer of derivative 874. Addition of nucleophiles to the double bond of vinyl ketone 874 followed by elimination of benzotriazole leads to a,P unsaturated ketones 875. Amines used as nucleophiles do not need any catalysis, but reactions with carbon and sulfur nucleophiles require addition of a base. The total effect is nucleophilic substitution of the benzotriazolyl group at the i-carbon of orji-iinsaturatcd ketone (Scheme 142) <1996SC3773>. 

The reaction of compound 376 with hydrazine gives product 377 that has been transformed into similar triazoles 378, after reaction with carbon disulfide in the presence of alcoholic potassium hydroxide, benzoic acid in the presence of phosphoms oxychloride, or 3-[bis-(methylthiomethylene)]pentan-2,4-dione and l,l-dicyano-2,2-dimethylthioethylene, in refluxing -butanol (Scheme 40) (Table 55) <2000FES641>. 

The same starting compound 270 was also subjected to ring closure by using other reagents <2003PS1143> reaction of 270 with acetic anhydride afforded the methyl-substituted 272, whereas reaction with carbon disulfide yielded the 3-mercapto derivative 273. 

Norman Burkhardt, "Arthur Lapworth and Others Structure, Properties, and Mechanism of Reactions of Carbon Compounds Some Developments 1898 to 1939, with Particular Reference to Arthur Lapworth and his Work," typescript, 150 pp., with addenda, written 19731978, bound and deposited at Royal Society of London, 1980 8889. 

---