Carbonates, reaction with acids

Plutonium reacts with hydrogen at high temperatures forming hydrides. With nitrogen, it forms nitrides, and with halogens, various plutonium hahdes form. Halide products also are obtained with halogen acids. Reactions with carbon monoxide yields plutonium carbides, whde with carbon dioxide, the products are both carbides and oxides. Such reactions occur only at high temperatures. 

Oxygen isotope ratios may be directly measured as CO2 when produced by acid reaction with carbonate or as CO when a compound is pyrolyzed. Water samples are commonly analyzed for 0/ 0 by equilibration with a headspace of CO2. 

In the commonly used Welland process, calcium cyanamide, made from calcium carbonate, is converted to cyanamide by reaction with carbon dioxide and water. Dicyandiamide is fused with ammonium nitrate to form guanidine nitrate. Dehydration with 96% sulfuric acid gives nitroguanidine which is precipitated by dilution. In the aqueous fusion process, calcium cyanamide is fused with ammonium nitrate ia the presence of some water. The calcium nitrate produced is removed by precipitation with ammonium carbonate or carbon dioxide. The filtrate contains the guanidine nitrate that is recovered by vacuum evaporation and converted to nitroguanidine. Both operations can be mn on a continuous basis (see Cyanamides). In the Marquerol and Loriette process, nitroguanidine is obtained directly ia about 90% yield from dicyandiamide by reaction with sulfuric acid to form guanidine sulfate followed by direct nitration with nitric acid (169—172). 

DiisononylPhthalate andDiisodeeylPhthalate. These primary plasticizers are produced by esterification of 0x0 alcohols of carbon chain length nine and ten. The 0x0 alcohols are produced through the carbonylation of alkenes (olefins). The carbonylation process (eq. 3) adds a carbon unit to an alkene chain by reaction with carbon monoxide and hydrogen with heat, pressure, and catalyst. In this way a Cg alkene is carbonylated to yield a alcohol a alkene is carbonylated to produce a C q alcohol. Due to the distribution of the C=C double bond ia the alkene and the varyiag effectiveness of certain catalysts, the position of the added carbon atom can vary and an isomer distribution is generally created ia such a reaction the nature of this distribution depends on the reaction conditions. Consequendy these alcohols are termed iso-alcohols and the subsequent phthalates iso-phthalates, an unfortunate designation ia view of possible confusion with esters of isophthaUc acid. 

A good technical grade of carbon tetrachloride contains not more than the following amounts of impurities 1 ppm acidity as HCl, 1 ppm carbon disulfide if manufactured by carbon disulfide chlorination, 20 ppm bromine, 200 ppm water, and 150 ppm chloroform. The residue should not exceed 10 ppm on total evaporation. The product should give no acid reaction with bromophenol blue, and the starch iodine test should indicate the absence of free chlorine. 

Hydrogen cyanide is a weak acid and can readily be displaced from a solution of sodium cyanide by weak mineral acids or by reaction with carbon dioxide, eg, from the atmosphere however, the latter takes places at a slow rate. 

The dimer acids [61788-89-4] 9- and 10-carboxystearic acids, and C-21 dicarboxylic acids are products resulting from three different reactions of C-18 unsaturated fatty acids. These reactions are, respectively, self-condensation, reaction with carbon monoxide followed by oxidation of the resulting 9- or 10-formylstearic acid (or, alternatively, by hydrocarboxylation of the unsaturated fatty acid), and Diels-Alder reaction with acryUc acid. The starting materials for these reactions have been almost exclusively tall oil fatty acids or, to a lesser degree, oleic acid, although other unsaturated fatty acid feedstocks can be used (see Carboxylic acids. Fatty acids from tall oil Tall oil). 

Ca.rhoxyla.tlon, This is the process of iatroduciag a carboxyUc acid group iato a phenol or naphthol by reaction with carbon dioxide under appropriate conditions of heat and pressure. Important examples are the carboxylation of phenol and 2-naphthol to give sahcyhc acid and 2-hydroxy-3-naphthoic acid, respectively. 

G. Reactions with Carbon Dioxide and Some Carbonic Acid Derivatives... 

Chloroacetic acid, reaction with salicyl-aldehyde, 46, 28 Chloroacetone, 46, 3 Chloroacetyl fluoride, 45, 6 o-Chloroacetyl isocyanate, 46,16 -Chloroaniline, reaction with carbon disulfide and aqueous ammonia,... 

Dialkyl sulphones may be converted to sulphonic acids by reaction with carbon tetrachloride and base at 80 °C209. This reaction proceeds by initial formation of a-chloro sulphones which are then converted to a thiiren intermediate which decomposes to give a sulphonic acid (equation 92). 

Type 66 nylon is a polyamide first commercialized by DuPont just prior to World War II. At that time, the needed hexamethylenediamine was made from adipic acid by reaction with ammonia to adiponitrile followed by reaction with hydrogen. The adipic acid then, like now, was made from cyclohexane. The cyclohexane, however, was derived from benzene obtained from coal. The ammonia was made from nitrogen in the air by reaction with hydrogen from water obtained in the water-gas shift reaction with carbon monoxide from the coal. So, in the 1950s, nylon was honestly advertised by DuPont as being based on coal, air, and water. 

Dietz and Peover examined the electrochemical reduction of cis and trans stilbene (114) in DMF containing carbon dioxide, 9>. The first electron transfer to trans-114 affords a planar radical anion (115) which then undergoes rapid reaction with carbon dioxide to produce, ultimately, 2,3-diphenylsuc-cinic acid (116) in... 

Thiadiazinotriazolopyrimidines can be prepared in several ways from the hydrazine-substituted thiadiazino-pyrimidine 186. Reaction with carbon disulfide gives the thione 187 reaction with either anhydrides or orthoformates with sulfuric acid gives the substituted triazoles 188, and reaction with cyanogen iodide gives the aminotriazole 189 (Scheme 47) <2004HC0335>. 

As in Section 5.06.9.1, the assignments are sometimes arbitrary. Important routes to oxadiazoles, aminooxadiazoles, oxadiazolinones, and oxadiazolinethiones involving the reaction of hydrazides RCONHNH2 with carboxylic acids, acyl chlorides, alkyl esters, or trialkyl orthoesters are described in Section 5.06.9.2.1, reactions with carbon disulfide... 

In the case of sodium tris-(/>-nitrophenyl)-methide the carboxylation reaction with carbon dioxide to give the acid fails to take place, although less stable carbanions are readily carbonated.410... 

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>. 

Reaction with Carbon Bisulphide.—Ammonia and the primary amines of the aliphatic series combine with carbon bisulphide to form ammonium salts of dithiocarbamic acids, e.g. 

Deprotonation of a methylene group in 2d followed by reaction with carbon dioxide and acidic workup yielded a racemic mixture of (3,5-di-ter -butylpyrazol-l-yl)(3, 5 -dimethylp5rrazol-l-yl)acetic acid (Hbpa ) (3d) (Scheme 14). Reaction of 3d with base and anhydrous ZnCl2 5delded [Zn(bpa )Cl] that crystallized as a cross-linked dimer [(bpa )ZnCl]2 (16) (Scheme 15, Fig. 16). 

As reported by Steel et al. three structural isomers of bis(camphor-pyrazol-l-yl)methane (21a, 21b and 21c) are formed by coupling of camphorpyrazole 10 [i.e., (4S,7i )-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-l(2)H-indazole] with CH2CI2 (121). Isomer 21c can be separated from the other two structural isomers by crystallization or column chomatography. Deprotonation at the bridging carbon atom, subsequent reaction with carbon dioxide and acidic workup yields the enantiopure bis(camphorpyrazol-l-yl)acetic acid Hbpa (8) (Scheme 17, Fig. 19) (116). Due to missing substituents at the p5rrazolyl carbon C5 and a hence likely ortho metallation, isomers 21a and 21b are not suited for his reaction (72). 

The reductive ring opening of six-membered nitrogen-containing heterocycles was studied with A-phenyltetrahydroisoquinoline (391). Its lithiation with lithium and a catalytic amount of DTBB (4.5%) afforded the benzylic intermediate 392, which was allowed to react with electrophiles giving, after hydrolysis, functionalized amines 393 (Scheme 110) . It is noteworthy that in the reaction with carbon dioxide, instead of the corresponding lactam, amino acid 393 with X = CO2H was exclusively isolated. 

Carboxylic acids are obtained from Grignard reagents by reaction with carbon dioxide. Scheme 7.3 includes some specific examples of procedures described in Organic Syntheses. 

The reaction involves the transfer of an electron from the alkali metal to naphthalene. The radical nature of the anion-radical has been established from electron spin resonance spectroscopy and the carbanion nature by their reaction with carbon dioxide to form the carboxylic acid derivative. The equilibrium in Eq. 5-65 depends on the electron affinity of the hydrocarbon and the donor properties of the solvent. Biphenyl is less useful than naphthalene since its equilibrium is far less toward the anion-radical than for naphthalene. Anthracene is also less useful even though it easily forms the anion-radical. The anthracene anion-radical is too stable to initiate polymerization. Polar solvents are needed to stabilize the anion-radical, primarily via solvation of the cation. Sodium naphthalene is formed quantitatively in tetrahy-drofuran (THF), but dilution with hydrocarbons results in precipitation of sodium and regeneration of naphthalene. For the less electropositive alkaline-earth metals, an even more polar solent than THF [e.g., hexamethylphosphoramide (HMPA)] is needed. 

Barium hydroxide decomposes to barium oxide when heated to 800°C. Reaction with carbon dioxide gives barium carbonate. Its aqueous solution, being highly alkahne, undergoes neutrahzation reactions with acids. Thus, it forms barium sulfate and barium phosphate with sulfuric and phosphoric acids, respectively. Reaction with hydrogen sulfide produces barium sulfide. Precipitation of many insoluble, or less soluble barium salts, may result from double decomposition reaction when Ba(OH)2 aqueous solution is mixed with many solutions of other metal salts. 

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