Carbon, acids chloride

Major constituents (greater than 5 mg/L) Minor constituents (O.Ol-lO.Omg/L) Selected trace constituents (less than 0.1 mg/L) Bicarbonate, calcium, carbonic acid, chloride, magnesium, silicon, sodium, sulfate Boron, carbonate, fluoride, iron, nitrate, potassium, strontium Aluminum, arsenic, barium, bromide, cadmium, chromium, cobalt, copper, gold, iodide, lead, Uthium, manganese, molybdenum, nickel, phosphate, radium, selenium, silver, tin, titanium, uranium, vanadium, zinc, zirconium... 

Condensations followed by silyl migrations are achieved easily with carbon acid chlorides, imid chlorides (7, 26-28), and adequate derivatives of carbonic acid such as phosgene [Eq. (5a)] and isocyanide dichlorides [Eq. (5b)] (29-31). After the primary condensation to the... 

Possibility [2] Use (CH3CH2CH2)2CuLi and a two-carbon acid chloride. 

Phosgene, a doubly noxious carbonic acid chloride (Cl-CO-Cl), could react with two proteins, I reasoned, and the novel cross-linked or double protein could elicit an immune response in the limg and consequent accumulation of fluid. So I proceeded, with Sam s encouragement, to syntliesize phosgene from the carbon eleven ( C02) produced by Martin Kamen in the 27.5 inch (70 cm) cyclotron near the Rat House, where I and Sam and Bill Libby had our laboratories. Mine, of course, amounted to less than eight feet [2.4 m] of bench in my office, which I had inherited from Henry Taube. Reduction of carbon dioxide over hot zinc powder was easy and quick. Then, addition of chlorine yielded the phosgene, all in about twenty minutes. We administered this to a poor rat and began to determine if the radioactivity was protein-bound as I expected. 

Phosgene, which, as stated on p. 57, may be considered as carbonic acid chloride, is very reactive, like all acid chlorides. It reacts easily with bases for instance, with sodium hydroxide it forms sodium chloride and sodium carbonate. 

Phosgene and tertiary carboxylic acid amides form very labile adducts (17 equation 6 not yet isolated or used for preparative purposes as such), which decompose with loss of CO2 very rapidly to give amide chlorides (see Section 2.7.2.2.1.i). Decomposition with evolution of CO2 is a common fate of primary adducts of carbonic acid chloride derivatives. Primary adducts from DMF and chloroformic acid esters (18), for example, decompose immediately to give alkoxymethyleneiminium chlorides, which react to give alkyl chlorides and DMF (equation 7). Adducts (19) from secondary and tertiary carboxamides... 

In the last reaction step the racemic trans-cyclopropyl-carbonic acid chloride is reacted with (i )-(+)-p-chlorophenethylamine in the presence of a base to the two main products, contaminated with small amounts originating from the (S)-amine (Scheme 20.3). 

The immobilization of biologically active compounds - enzymes, antibiotics, vitamins - was performed on several modified natural polymers - 4-aminobenzoylcellulose, cellulose carbonate, acid chloride of CMC and BIOZAN R. 

Figure 14.46 shows another successful Friedei-Crafts acylation, but this reaction contains a bonus. The reaction of the four-carbon acid chloride with benzene yields the unrearranged ketone. This result implies that acyl complexes are not prone to rearrangement (Fig. 14.46). 

The additional four carbon atoms required to synthesize 1-phenyl-1-butanol and 1-phenylbutane can be provided by a Friedel—Crafts reaction of benzene and a four-carbon acid chloride. This product, 1-phenyl-l-butanone, has a carbonyl group that can be reduced to provide products (a) and (b). Reduction of 1-phenyl-l-butanone with a metal hydride such as NaBH4 gives 1-phenyl-1-butanol. Reduction of 1-phenyl-l-butanone using either Clemmensen or Wolff—Kishner conditions gives 1-phenylbutane. 

By passing a mixture of carbon monoxide and hydrogen chloride into the aromatic hydrocarbon in the presence of a mixture of cuprous chloride and aluminium chloride which acts as a catalyst (Gattermann - Koch reaction). The mixture of gases probably reacts as the equivalent of the unisolated acid chloride of formic acid (formyl chloride) ... 

To the cold acid chloride add 175 ml. of pure carbon disulphide, cool in ice, add 30 g, of powdered anhydrous aluminium chloride in one lot, and immediately attach a reflux condenser. When the evolution of hydrogen chloride ceases (about 5 minutes), slowly warm the mixture to the boiling point on a water bath. Reflux for 10 minutes with frequent shaking the reaction is then complete. Cool the reaction mixture to 0°, and decompose the aluminium complex by the cautious addition, with shaking, of 100 g. of crushed ice. Then add 25 ml. of concentrated hydrochloric acid, transfer to a 2 htre round-bottomed flask and steam distil, preferably in the apparatus, depicted in Fig. II, 41, 3 since the a-tetralone is only moderately volatile in steam. The carbon disulphide passes over first, then there is a definite break in the distillation, after whieh the a-tetralone distils completely in about 2 htres of distillate. 

The success of the last reaction depends upon the inertness of the ester carbonyl groups towards the organocadmium compound with its aid and the use of various ester acid chlorides, a carbon chain can be built up to any reasonable length whilst retaining a reactive functional group (the ester group) at one end of the chain. Experimental details are given for l-chloro-2-hexanone and propiophenone. The complete reaction (formation of ketones or keto-esters) can be carried out in one flask without isolation of intermediates, so that the preparation is really equivalent to one step. 

Triiodobenzoyl chloride. Reflux 5 g. of 3 4 5-triiodo-benzoic acid, m.p. 289-290°, gently with 10 ml. of redistilled thionyl chloride for 2 hours. Distil off the excess of thionyl chloride on a water bath, and recrystallise the residue from carbon tetrachloride - light petroleum with the use of a little decolourising charcoal. The yield of the acid chloride (bright yellow needles, m.p. 138°) is 3-8 g. it keeps well in a stoppered bottle. 

The most general methods for the syntheses of 1,2-difunctional molecules are based on the oxidation of carbon-carbon multiple bonds (p. 117) and the opening of oxiranes by hetero atoms (p. 123fl.). There exist, however, also a few useful reactions in which an a - and a d -synthon or two r -synthons are combined. The classical polar reaction is the addition of cyanide anion to carbonyl groups, which leads to a-hydroxynitriles (cyanohydrins). It is used, for example, in Strecker s synthesis of amino acids and in the homologization of monosaccharides. The ff-hydroxy group of a nitrile can be easily substituted by various nucleophiles, the nitrile can be solvolyzed or reduced. Therefore a large variety of terminal difunctional molecules with one additional carbon atom can be made. Equally versatile are a-methylsulfinyl ketones (H.G. Hauthal, 1971 T. Durst, 1979 O. DeLucchi, 1991), which are available from acid chlorides or esters and the dimsyl anion. Carbanions of these compounds can also be used for the synthesis of 1,4-dicarbonyl compounds (p. 65f.). 

Acyl halides are intermediates of the carbonylations of alkenes and organic-halides. Decarbonylation of acyl halides as a reversible process of the carbo-nylation is possible with Pd catalyst. The decarbonylation of aliphatic acid chlorides proceeds with Pd(0) catalyst, such as Pd on carbon or PdC, at around 200 °C[109,753]. The product is a mixture of isomeric internal alkenes. For example, when decanoyl chloride is heated with PdCF at 200 C in a distillation flask, rapid evolution of CO and HCl stops after I h, during which time a mixture of nonene isomers was distilled off in a high yield. The decarbonylation of phenylpropionyl chloride (883) affords styrene (53%). In addition, l,5-diphenyl-l-penten-3-one (884) is obtained as a byproduct (10%). formed by the insertion of styrene into the acyl chloride. Formation of the latter supports the formation of acylpalladium species as an intermediate of the decarbonylation. Decarbonylation of the benzoyl chloride 885 can be carried out in good yields at 360 with Pd on carbon as a catalyst, yielding the aryl chloride 886[754]. 

There are several processes available for the manufacture of cryoHte. The choice is mainly dictated by the cost and quaUty of the available sources of soda, alumina, and fluoriae. Starting materials iaclude sodium aluminate from Bayer s alumina process hydrogen fluoride from kiln gases or aqueous hydrofluoric acid sodium fluoride ammonium bifluoride, fluorosiUcic acid, fluoroboric acid, sodium fluosiUcate, and aluminum fluorosiUcate aluminum oxide, aluminum sulfate, aluminum chloride, alumina hydrate and sodium hydroxide, sodium carbonate, sodium chloride, and sodium aluminate. 

Preparation of Arylcarboxylic Acids and Derivatives. The general Friedel-Crafts acylation principle can be successfully appHed to the preparation of aromatic carboxyUc acids. Carbonyl haUdes (phosgene, carbonyl chloride fluoride, or carbonyl fluoride) [353-50-4] are diacyl haUdes of carbonic acid. Phosgene [75-44-5] or oxalyl chloride [79-37-8] react with aromatic hydrocarbons to give aroyl chlorides that yield acids on hydrolysis (133) ... 

Carbon dioxide can be considered the acid anhydride of carbonic acid. Accordingly, it reacts with ben2ene, albeit ia low yield, to give ben2oic acid and ben2ophenone ia the presence of aluminum chloride. 

Acid Chloride Formation. Monoacid chlorides of maleic and fumaric acid are not known. Treatment of maleic anhydride or maleic acid with various reagents such as phosgene [75-44-5] (qv), phthaloyl chloride [88-95-9] phosphoms pentachloride [10026-13-8] or thionyl chloride [7719-09-7] gives 5,5-dichloro-2(5JT)furanone [133565-92-1] (4) (26). Similar conditions convert fumaric acid to fumaryl chloride [627-63-4] (5) (26,27). NoncycHc maleyl chloride [22542-53-6] (6) forms in 11% yield at 220°C in the reaction of one mole of maleic anhydride with six moles of carbon tetrachloride [56-23-5] over an activated carbon [7440-44-4] catalyst (28). 

Additional phosphonic acid is derived from by-product streams. In the manufacture of acid chlorides from carboxyUc acids and PCl, phosphonic acid or pyrophosphonic acid is produced, frequentiy with copious quantities of yellow polymeric LOOP. Such mixtures slowly evolve phosphine, particularly on heating, and formerly were a disposal problem. However, purification of this cmde mixture affords commercial phosphonic acid. By-product acid is also derived from the precipitate of calcium salts in the manufacture of phosphinic acid. As a consequence of the treatments of the salt with sulfuric acid, carbonate is Hberated as CO2 and phosphonic acid goes into solution. 

In general, if the desired carbon—phosphoms skeleton is available in an oxidi2ed form, reduction with lithium aluminum hydride is a powerful technique for the production of primary and secondary phosphines. The method is appHcable to halophosphines, phosphonic and phosphinic acids as well as thein esters, and acid chlorides. Tertiary and secondary phosphine oxides can be reduced to the phosphines. 

Ahyl alcohol undergoes reactions typical of saturated, aUphatic alcohols. Ahyl compounds derived from ahyl alcohol and used industriahy, are widely manufactured by these reactions. For example, reactions of ahyl alcohol with acid anhydrides, esters, and acid chlorides yield ahyl esters, such as diahyl phthalates and ahyl methacrylate reaction with chloroformate yields carbonates, such as diethylene glycol bis(ahyl carbonate) addition of ahyl alcohol to epoxy groups yields products used to produce ahyl glycidyl ether (33,34). 

The efficiency of the weathering of rocks in using carbonic acid produced in the carbon cycle is affected by various hydrologic, environmental, and cultural controls. The fact that the principal anion in fresh surface water worldwide almost always is bicarbonate attests to the overriding importance of this process. Exceptions are systems in which evaporite minerals are available for dissolution by groundwater or where human activities are major sources of sulfate or chloride inflow. 

Cellulose esters are commonly derived from natural cellulose by reaction with organic acids, anhydrides, or acid chlorides. Cellulose esters of almost any organic acid can be prepared, but because of practical limitations esters of acids containing more than four carbon atoms have not achieved commercial significance. 

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