Molecular rearrangement organic

Murray, A. W. Molecular rearrangements. Organic Reaction Mechanisms 2001,473-603. 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

J.M. Lalancette et al., Reduction of Functional Groups with Sulfurated Borohydrides, Synthesis 1972, 526. J. Malek u. M. Cerny, Reduction of Organic Compounds by Alkoxyaluminohydrides, Synthesis 1972, 217. S.-C. Chen, Molecular Rearrangements in Lithium Aluminium Hydride Reduction, Synthesis 1974, 691. 

Photochemistry as topic is covered in several introductory textbooks 101 -107) yhe annuai literature is surveyed in a specialist periodical report108). Two series of monographs have to do with selected chapters from organic photochemistry 109) or photochemistry in general110). A series on molecular rearrangements also covers photochemical reactions U1). 

Beynon, J.H. Lester, G.R. Williams, A.E. Specific Molecular Rearrangements in the Mass Spectra of Organic Compounds. J. Phys. Chem. 1959, 63, 1861-1869. 

SHORTER, J. Correlation Analysis in Organic Chemistry (OUP, 1973). STEVENS, T. s. and WATTS, N. E. Selected Molecular Rearrangements (Van Nostrand Reinhold, 1973). 

J. Kovar, M. Hudlicky, and I. Ernest, Preparative Reactions in Organic Chemistry. VIII. Molecular Rearrangements, NCSAV, Prague, 1965, p. 989. 

Molecular rearrangements of diynes coordinated to triosmium carbonyl clusters have been reported.179 Triosmium clusters can act as templates for the rearrangement of l,4-dipyridylbuta-l,3-diyne, leading to the formation of fused-ring organic products, in a manner similar to that previously reported for other 1,3-diyne compounds. 

Organic molecules adsorbed at the surface of Si02 are excited by light absorption and are enabled to undergo molecular rearrangement 64 ... 

Buscemi, S., Vivona, N. and Caronna, T. (1996) Photoinduced molecular rearrangements. The photochemistry of some 1,2,4-oxadiazoles in the presence of nitrogen nucleophiles. Formation of 1,2,4-triazoles, indazoles, and benzimidazoles. Journal of Organic Chemistry, 61 (24), 8397-8401. 

Molecular rearrangements involving carbocations as reactive intermediates are very common in organic chemistry. The first-formed carbocation, which is less stable, can rearrange by 1,2-shift of either H or alkyl group to more stable carbocation. 

Hydride, either binary or complex, reductions of organic functional groups are expensive routes to C—H bonds, consequently such reactions are used only for specialty chemical and expensive product (pharmacueticals, etc.) synthesis. Reactions as described in 1.6.4 and 1.6.5 are used. Commonly used reactions involve NaH, KH, bo-ranes, alanes, silanes and occasionally stannanes. Detailed discussions of hydride reductions can be found in standard treatises on organic chemistry - - . Molecular rearrangement ... 

Tennant, G. Molecular rearrangements [in organic chemistry]. Annu. Rep. Prog. Chem., Sect. B, Org. Chem. 1972, 68, 241-272. 

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