Sodium and its derivs

Sodium Sulfide. See in this Vol under Sodium and Its Derivatives ... 

Comprehensive reviews are available which describe the organic reactions of sodium and its derivatives (2, 3, 5, 9, 10, 15, 18, 22, 27, 28, 30). The most recent of these (27) gives a fairly complete survey of the organic reactions of sodium and its derivatives, with well over 600 references to the literature, but its treatment of these reactions is necessarily superficial, in view of its wide scope. The purpose of the present paper is to supplement these reviews by providing a more intensive discussion of a limited phase of organosodium chemistry. This discussion is therefore limited to the reactions of organic compounds with sodium metal. The reactions of such sodium derivatives as sodamide, sodium hydride, sodium alkoxides, and organosodium compounds are omitted. 

Surface heterogeneity may be inferred from emission studies such as those studies by de Schrijver and co-workers on P and on R adsorbed on clay minerals [197,198]. In the case of adsorbed pyrene and its derivatives, there is considerable evidence for surface mobility (on clays, metal oxides, sulfides), as from the work of Thomas [199], de Mayo and co-workers [200], Singer [201] and Stahlberg et al. [202]. There has also been evidence for ground-state bimolecular association of adsorbed pyrene [66,203]. The sensitivity of pyrene to the polarity of its environment allows its use as a probe of surface polarity [204,205]. Pyrene or ofter emitters may be used as probes to study the structure of an adsorbate film, as in the case of Triton X-100 on silica [206], sodium dodecyl sulfate at the alumina surface [207] and hexadecyltrimethylammonium chloride adsorbed onto silver electrodes from water and dimethylformamide [208]. In all cases progressive structural changes were concluded to occur with increasing surfactant adsorption. 

Calcium Phosphates. The alkaline-earth phosphates are generally much less soluble than those of the alkaH metals. Calcium phosphates include the most abundant natural form of phosphoms, ie, apatites, Ca2Q(P0 3X2, where X = OH, F, Cl, etc. Apatite ores are the predominant basic raw material for the production of phosphoms and its derivatives. Calcium phosphates are the main component of bones and teeth. After sodium phosphates, the calcium salts are the next largest volume technical- and food-grade phosphates. Many commercial appHcations of the calcium phosphates depend on thek low solubiHties. 

Chemical degradation studies carried out on streptovaricias A and C, which are the primary components of the cmde complex, yielded substances shown ia Figure 1. Streptovaricia A (4), consumes two moles of sodium periodate to yield variciaal A [21913-68-8] (1), 0 2 200, which accounts for the ahphatic portion of the molecule, and prestreptovarone [58074-37-6] (2), C2C)H2C)N02, which accounts for the aromatic chromophore of the streptovaricias (Fig. 2). Streptovaricia G (9) is the only other streptovaricia that yields prestreptovaroae upoa treatmeat with sodium periodate. Treatmeat of streptovaricias A (4), B (5), C (6), E (8), and G (9) with sodium periodate and osmium tetroxide yields streptovarone [36108-44-8] (3), C24H23NO2, which is also produced by the reaction of prestreptovarone with sodium periodate and osmium tetroxide (4,65). A number of aliphatic products were isolated from the oxidation of streptovaricia C and its derivatives (66). 

Free thiocyanic acid [463-56-9] HSCN, can be isolated from its salts, but is not an article of commerce because of its instabiHty, although dilute solutions can be stored briefly. Commercial derivatives of thiocyanic acid are principally ammonium, sodium, and potassium thiocyanates, as weU as several organic thiocyanates. The chemistry and biochemistry of thiocyanic acid and its derivatives have been reviewed extensively (372—374). 

The diazotization of amino derivatives of six-membered heteroaromatic ring systems, particularly that of aminopyridines and aminopyridine oxides, was studied in detail by Kalatzis and coworkers. Diazotization of 3-aminopyridine and its derivatives is similar to that of aromatic amines because of the formation of rather stable diazonium ions. 2- and 4-aminopyridines were considered to resist diazotization or to form mainly the corresponding hydroxy compounds. However, Kalatzis (1967 a) showed that true diazotization of these compounds proceeds in a similar way to that of the aromatic amines in 0,5-4.0 m hydrochloric, sulfuric, or perchloric acid, by mixing the solutions with aqueous sodium nitrite at 0 °C. However, the rapidly formed diazonium ion is hydrolyzed very easily within a few minutes (hydroxy-de-diazonia-tion). The diazonium ion must be used immediately after formation, e. g., for a diazo coupling reaction, or must be stabilized as the diazoate by prompt neutralization (after 45 s) to pH 10-11 with sodium hydroxide-borax buffer. All isomeric aminopyridine-1-oxides can be diazotized in the usual way (Kalatzis and Mastrokalos, 1977). The diazotization of 5-aminopyrimidines results in a complex ring opening and conversion into other heterocyclic systems (see Nemeryuk et al., 1985). 

N-Nitrosamine inhibitors Ascorbic acid and its derivatives, andDC-tocopherol have been widely studied as inhibitors of the N-nitrosation reactions in bacon (33,48-51). The effect of sodium ascorbate on NPYR formation is variable, complete inhibition is not achieved, and although results indicate lower levels of NPYR in ascorbate-containing bacon, there are examples of increases (52). Recently, it has been concluded (29) that the essential but probably not the only requirement for a potential anti-N-nitrosamine agent in bacon are its (a) ability to trap NO radicals, (b) lipophilicity, (c) non-steam volatility and (d) heat stability up to 174 C (maximum frying temperature). These appear important requirements since the precursors of NPYR have been associated with bacon adipose tissue (15). Consequently, ascorbyl paImitate has been found to be more effective than sodium ascorbate in reducing N-nitrosamine formation (33), while long chain acetals of ascorbic acid, when used at the 500 and lOOO mg/kg levels have been reported to be capable of reducing the formation of N-nitrosamines in the cooked-out fat by 92 and 97%, respectively (49). 

Selenienylalkynylcarbinols were prepared by the addition of Grignard reagents or the sodium salts of acetylenes to 2-formylselenophene and its derivatives. The alcohols were oxidized and the resulting ketones treated with hydrazine and hydroxylamine to give the diheteroaryls 81 and 82.94... 

Electroreductive one-electron initiation of cyclization was described for the series of E,E-, 1-dibenzoyl-l,6-heptadiene and its derivatives (Roh et al. 2002, Felton and Bauld 2004). In this case, the catalytic effect was also observed (the actual consumption of electricity was substantially less than theoretical). The same bis(enones) can also be cyclized on the action of the sodium salt of chrysene anion-radical in THF, but with no catalytic effect. Optimum yields were obtained only when 70-120 mol% of the initiator was used, relative to a substrate (Yang et al. 2004). The authors suggest that tight ion pairing of the sodium cation with the product anion-radical in THF (which is a somewhat nonpolar solvent) slows down the intermolecular electron transfer to the bis(enone) molecules. Such an electron transfer would be required for chain propagation. 

Quinoline homologs and derivatives, including those with double bonds in the side chains, were reduced selectively by catalytic hydrogenation over platinum oxide (side chain double bonds), and to dihydro- and tetrahydro-quinolines by sodium in butanol, by zinc and formic acid, and by triethylam-monium formate [319, 472]. Catalytic hydrogenation of quinoline and its derivatives has been thoroughly reviewed [439]. 

IsoquinoUne was converted to 1,2,3,4-tetrahydroisoquinoline in 89% yield by reduction with sodium in liquid ammonia and ethanol [473], and to a mixture of 70-80% cis- and 10% trans-decahydroisoquinoline by catalytic hydrogenation over platinum oxide in acetic and sulfuric acid [474]. Without sulfuric acid the hydrogenation stopped at the tetrahydro stage. Catalytic hydrogenation of isoquinoline and its derivatives is the topic of a review in Advances in Catalysis [439]. 

The first synthesis of the parent compound of the benzo[4,5]thieno[2,3-f]pyrrole ring system 387 <2003T1477> and its derivatives was accomplished using the same synthetic sequence (Scheme 42). Starting with 2-methyl-benzo[ ]thiophene-3-carbaldehyde 388, an intermediate 389 was obtained. Treatment of bromo compound 389 with sodium azide in ethanol led to the stable triazoline 390. 1,3-Dipolar cycloreversion of 390 was induced by a catalytic amount of />-TsOH to give the parent 2//-benzo[4,5]thieno[2,3-c]pyrrole 387. Alternatively, direct treatment of bromo compound 389 with excess ammonia furnished 387 in one step. Compound 387 was treated with di-/-butyl dicarbonate and 4-dimethylaminopyridine (DMAP) to give iV-BOC derivative 391. Reaction of 389 with... 

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