Allene 396 Subject

Sote 1. In the final stage of the distillation the remaining liquid is subjected to a relatively higli temperature. This causes dimerization of the greater part of the yne-allene RCeC-CH=C=CH2, which is formed as a by product. 

In the 1980 s three monographs were published that cover parts of the present book, namely Quinone Diazides, by Ershov, Nikiforov, and de Jonge (1981), Aromatic Diazo Compounds, by Saunders and Allen (1985), and Williams Nitrosa-tion (1988). The book of Saunders and Allen which is actually the third edition of Saunders original book (1936, 1949), focuses on synthesis and preparative methods. The other two books emphasize rather the mechanistic and physical organic aspects of their subjects. 

Reviews on the subjects of this section were written by Hamilton and Morgan (1944), Nesmeyanov (1963, 1972), Reutov and Ptitsyna (1972), and by Saunders and Allen (1985, Secs. 14.11-14.27). 

Peroxidation of lipids is another factor which must be considered in the safety evaluation of liposome administration. Smith and coworkers (1983) demonstrated that lipid peroxides can play an important role in liver toxicity. Allen et al. (1984) showed that liposomes protected by an antioxidant caused less MPS impairment than liposomes subjected to mild oxidizing conditions. From the study of Kunimoto et al. (1981) it can be concluded that the level of peroxidation in freshly prepared liposome preparations and those on storage strongly depends both on the phospholipid fatty acid composition and on the head group of the phospholipid. Addition of appropriate antioxidants to liposomes composed of lipids which are liable to peroxidation and designed for use in human studies is therefore necessary. 

More recently copper phosphate cements have been suggested for use as controlled-release agents for supplying trace amounts of copper to cattle and sheep over an extended period (Allen et al., 1984 Mansion et al., 1985 Prosser et al., 1986). The cements were prepared with a Cu/P ratio of 1 1 to ensure that the matrix was an add phosphate and so subject to dissolution in aqueous solutions. They released copper at a constant rate for 90 days. 

Blyth, C. S., Allen, E. M., and Lovingood, B. W., Effects of amphetamine (dexedrine) and caffeine on subjects exposed to heat and exercise stress, Research Quarterly, 31, 553, 1960. 

For small projects, and for simple choices between alternative processing schemes and equipment, the decisions can usually be made by comparing the capital and operating costs. More sophisticated evaluation techniques and economic criteria are needed when decisions have to be made between large, complex projects, particularly when the projects differ widely in scope, time scale and type of product. Some of the more commonly used techniques of economic evaluation and the criteria used to judge economic performance are outlined in this section. For a full discussion of the subject one of the many specialist texts that have been published should be consulted Brennan (1998), Chauvel et al. (2003) and Vale-Riestra (1983). The booklet published by the Institution of Chemical Engineers, Allen (1991), is particularly recommended to students. 

Cohen, I. Bernard. Ethan Allen Hitchcock, soldier, humanitarian, scholar, discoverer of the "true subject" of the Hermetic Art. Worcester (MA) American Antiquarian Society, 1952. 30-136 p. 

The allene host 20 exhibits high inclusion selectivity in competition experiments using mixtures of solvents 26). In fact, preliminary results indicate that it can be used for the separation of constitutional isomers, of homologues, and of aliphatic from alicyclic or aromatic compounds (Table 3). Other derivatives of the allene, e.g. 21, are also functional as host molecules, and are currently being subjected to further investigations 22). 

If the alkenes and acetylenes that are subjected to the reaction mediated by 1 have a leaving group at an appropriate position, as already described in Eq. 9.16, the resulting titanacycles undergo an elimination (path A) as shown in Eq. 9.58 [36], As the resulting vinyltitaniums can be trapped by electrophiles such as aldehydes, this reaction can be viewed as an alternative to stoichiometric metallo-ene reactions via allylic lithium, magnesium, or zinc complexes (path B). Preparations of optically active N-heterocycles [103], which enabled the synthesis of (—)-a-kainic acid (Eq. 9.59) [104,105], of cross-conjugated trienes useful for the diene-transmissive Diels—Alder reaction [106], and of exocyclic bis(allene)s and cyclobutene derivatives [107] have all been reported based on this method. 

Photo-addition of allene to the enone (90) yield adduct (91) in 75 % yield, which was subjected to ketalization in 77% yield. Epoxidation of (92) with perbenzoic acid followed by chromatography on alumina afforded two expoxides (93) and (94). Both (93) and (94) could be converted separately through (95) and (96) respectively which was the common intermediate leading to isoishwarane (98) and ishwarane following a deketalization-retroaldol-aldol process to furnish the keto-alcohol (97) (99) 30>. 

This system was described in one report and has been synthesized by a copper-assisted cycloisomerization of alkynyl imines. The authors proposed the following mechanism at first, 372 could undergo a base-induced propargyl-allenyl isomerization to form 373 next, coordination of copper to the terminal double bond of the allene (intermediate 374) would make it subjected to intramolecular nucleophilic attack to produce a zwitterion 375. The latter would isomerize into the more stable zwitterionic intermediate 376, which would be transformed to the thiazole 377 (Scheme 55) <2001JA2074>. 

A closely related chemical, 2-hexanone, which is an /r-hcxanc metabolite, has also caused peripheral neuropathy in workers (Allen et al. 1975). This chemical is the subject of another publication in this series, Toxicological Profile for 2-Hexanone (ATSDR 1991). 

Most of the forementioned studies which examined the influence of various dietary fiber on the bioavailability of calcium by human subjects have depended upon the comparative measurements of calcium content of diets and calcium contents of stools and urine. As reviewed by Allen (3), calcium balance studies have distinct limitations relative to accuracy and precision. However, their ease of application and cost, laboratory equipment requirements, and real (or perceived) safety in comparison to available radioactive or stable isotope methods continue to make their use popular. In calcium balance studies, calcium absorption is assumed to be the difference between calcium excretion in the feces and calcium intake. Usually this is expressed as a percent of the calcium intake. This method assumes that all fecal calcium loss is unabsorbed dietary calcium which is, of course, untrue since appreciable amounts of calcium from the body are lost via the intestinal route through the biliary tract. Hence, calcium absorption by this method may underestimate absorption of dietary calcium but is useful for comparative purposes. It has been estimated that bile salts may contribute about 100 g calcium/day to the intestinal calcium contents. Bile salt calcium has been found to be more efficiently absorbed through the intestinal mucosa than is dietary calcium (20) but less so by other investigators (21). 

Novel alkenylphosphonium salts were subjected to the Wittig reaction (Scheme 12). Allylic deprotonation took place for phosphonium salts possessing such protons, and the olefination proceeded after double bond migration. In cases where such protons were absent, allene formation was observed. 

Allene is a versatile functionality because it is useful as either a nucleophile or an electrophile and also as a substrate for cycloaddition reactions. This multi-reactivity makes an allene an excellent candidate for a synthetic manipulations. In addition to these abilities, the orthogonality of 1,3-substitution on the cumulated double bonds of allenes enables the molecule to exist in two enantiomeric configurations and reactions using either antipode can result in the transfer of chirality to the respective products. Therefore, the development of synthetic methodology for chiral allenes is one of the most valuable subjects for the synthetic organic chemist. This chapter serves as an introduction to recent progress in the enantioselective syntheses of allenes. Several of the earlier examples are presented in excellent previous reviews [ ] ... 

The conformationally locked [46] bisallene 127 was first prepared by subjecting the allene dimer 126 to the DMS allene synthesis (Scheme 5.17) [47]. 

Reaction with a first aldehyde transforms 176 into the vinylphosphonium chloride 177, which for practical reasons is subjected to an anion-exchange process, leading to the phosphonium salt 178. From this, phenyllithium treatment liberates the allenic phosphorane 179, an intermediate that has previously been used to prepare allenes from aldehydes [69], in the present case providing the products 180. The same protocol has also been applied to o-alkynylbenzaldehydes to yield allenes of interest as model compounds for the study of Schmittel and Myers-type cyclization reactions [70]. 

Coupling of excess (Z)-l,2-dichloroethene (217) with propargyl alcohol first led to the enyne 218, which, when subjected to a second Pd-catalyzed coupling step with trimethylsilylacetylene, provided the mixed diacetylene 219. With all carbon atoms assembled, the allene function was generated by first producing the (unprotected) hydrazine derivative 220, which on treatment with either diethyl azodicarboxylate (DEAD) or 4-methyl-l,2,4-triazoline-3,5-dione (MTAD) under anaerobic conditions at 0 °C yielded the hydrocarbon 27. According to mechanistic studies, the latter process leads first to a mixture of ( )- and (Z)-diazenes. Sigmatropic elimination of... 

Apart from the treatment in general articles on allenes, this subject has been specifically reviewed by Johnson [1] in 1989 and Balci and Taskesenligil [2] in 2000. 

An early synthesis of allenylzinc reagents employed a two-step procedure in which monosubstituted allenes were subjected to lithiation in THF with tBuLi at -90 °C and the resulting allenyllithium intermediates were treated with ZnCl2. The allenylzinc reagents thus generated react in situ with aldehydes to afford mainly anti homopropargyl alcohols (Table 9.46) [98],... 

When propargylamine 183 was subjected to a homologative allenylation (Crabbe reaction) at 100 °C, the resulting allene underwent a spontaneous Diels-Alder reaction to give the adduct 184. This intramolecular cycloaddition-oxidation sequence provided a simple route to indole alkaloids such as hippadine and ds-trikentrin B [148]. 

The Ru-catalyzed cyclocarbonylation of a-allenic sulfonamides proceeds in the presence of Et3N under a CO atmosphere (20 atm) to yield ,/funsaturated lactams (Scheme 16.32) [36], In order to gain an insight into the reaction mechanism, a deuterium-substituted a-allenic sulfonamide was subjected to the carbonylation. The deuterium was found to be totally transferred to the methyl group. Based on this observation, a mechanism has been proposed which involves a ruthenacycle derived from addition of the Ru-H to the terminal double bond of allene (Scheme 16.33). 

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