Photorearrangement of 2-cyanobicyclo[2.2.1]hept-2-ene. Observation of 1,2- and 1,3-sigmatropic shifts

1982 ◽  
Vol 60 (13) ◽  
pp. 1657-1663 ◽  
Author(s):  
Ikbal A. Akhtar ◽  
John J. McCullough ◽  
Susan Vaitekunas ◽  
Romolo Faggiani ◽  
Colin J. L. Lock
Keyword(s):  
Single Crystals ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Major Product ◽  
Molecular Structures ◽  
Lithium Aluminum ◽  
Mercury Vapour ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Mercury Vapour Lamp

Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene, 4) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene 5 and 7-cyanotricyclo[4.1.0.03.7]heptane 6 in the ratio 20:1. These products were separated by preparative vpc. The structure of the major product 5 was determined by single crystal X-ray analysis. Reduction of 5 with lithium aluminum hydride gave the corresponding primary amine, which was converted to the p-bromobenzenesulfonamide 9, mp 150–151 °C, which gave single crystals from ethanol–water. The crystal and molecular structures are described. The minor product 6 was hydrogenated to give 7-cyanobicyclo[2.2. 1]heptane. Formation of 5 and 6 may involve concerted σ2s + π2s and σ2a + π2a processes respectively, which are photochemically allowed.

Synthesis of β-amino-α-ferrocenyl alcohols

2005 ◽  
Vol 2005 (11) ◽  
pp. 712-715 ◽  
Author(s):  
Hai-Ying Zhao ◽  
Zhan-Xi Bian ◽  
Bao-Guo Li
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Chain Structure ◽  
Lithium Aluminum ◽  
Polymeric Chain ◽  
X Ray ◽  
H Nmr ◽  
Hydrogen Bonding Interactions ◽  
Trimethylsilyl Ethers ◽  
New Compounds

β-Amino-α-ferrocenyl alcohols [FcC(OH)(R)CH2NH2] (R = Me, Et, nPr, iPr, Ph, p-MeOC6H4, o-ClC6H4, m-ClC6H4, p-ClC6H4, Fc; Fc = C5H4FeC5H5) were prepared by the reduction of cyanohydrin trimethylsilyl ethers of acylferrocenes with lithium aluminum hydride. All new compounds were characterised by elemental analysis, IR and 1H NMR spectroscopies. The X-ray crystal structure of β-amino-α,α-diferrocenylethanol shows that it has a polymeric chain structure with hydrogen bonding interactions between the OH proton and the N of NH2.

Reduction of Some Alkylisoxazoles with Lithium Aluminum Hydride

1975 ◽  
Vol 53 (20) ◽  
pp. 3011-3013 ◽  
Author(s):  
A. L. Khurana ◽  
A. M. Unrau
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Major Product ◽  
Major Constituent ◽  
Lithium Aluminum ◽  
Hydride Reduction

Lithium aluminum hydride reduction of alkyl substituted isoxazoles gave a variety of products. The major constituent was identified (i.r., n.m.r., m.s.) as hydroxyethylaziridine. Specifically, reduction of 3,4,5-trimethylisoxazole gave as the major product 2,3-dimethyl-3-β-hydroxyethylaziridine. Two of the more prominent minor products were identified as 2,3-dimethyl-3-ethylaziridine and 4-amino-3-methyl-2-pentanol. The corresponding products were identified when 3,5-dimethylisoxazole was reduced with LAH.

Development of a hybrid metal-oxides (Li2O-Al2O3-Al3Fe-Al3Fe5O12) reinforced polycaprolactone composite

MRS Advances ◽  
2019 ◽  
Vol 4 (63) ◽  
pp. 3485-3493
Author(s):  
N.N. Zurita-Méndez ◽  
J. Beltran-González ◽  
G. Carbajal-De la Torre ◽  
M.A. Espinosa-Medina
Keyword(s):  
Lithium Aluminum Hydride ◽  
Polymer Network ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
X Ray Diffraction ◽  
X Ray ◽  
Potential Applications ◽  
Nanometric Particles ◽  
Irregular Topography

ABSTRACTThis paper addresses the chemical synthesis and characterization of a composite formed by Li2O-Al2O3-Al3Fe-Al3Fe5O12/PCL which were obtained by the process of reduction of ferric chloride (FeCl3) with lithium aluminum hydride (LiAlH4) in an open atmosphere. The goal of the development of this hybrid material was to perform a superparamagnetic material with several potential applications. The results of the characterizations by scanning electron microscopy (SEM) and vibrating sample magnetometer showed a Li2O-Al2O3-Al3Fe-Al3Fe5O12 “desert rose stone”-like morphology 3D hierarchical powders formation when particles were sintered at 850 °C. Homogeneous nanometric particles after calcination at 1100 °C were observed. X-ray diffraction analysis were performed to determine their composition. Subsequently, the superparamagnetic powders were added by dispersion in a polycaprolactone (PCL) matrix, and then, were evaluated by SEM for the observation of their morphologies. The composite material presented a polymer network with an opened structure, a well dispersion of the oxides particles into the interstices with irregular topography and reliefs.

STEROIDS: I. 12β-METHYL-12α-HYDROXYPROGESTERONE

1961 ◽  
Vol 39 (3) ◽  
pp. 548-554 ◽  
Author(s):  
George Just ◽  
R. Nagarajan
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Major Product ◽  
Lithium Aluminum ◽  
Hydride Reduction

Lithium aluminum hydride reduction of 3α,12α -diacetoxypregnan-20-one (Ia) gives as the major product pregnane-3α,12α,20β-triol (III), whereas the reduction of the corresponding dihydroxypregnanone I affords mainly the epimeric 3α,12α,20α-triol II. Triol III was transformed to 12β-methyl-12α-hydroxyprogesterone (VIII).

The Chemistry of Sulfur Curing. IV. Effects of Organic Accelerators on the Reaction of Cyclohexene with Sulfur

1968 ◽  
Vol 41 (5) ◽  
pp. 1339-1347 ◽  
Author(s):  
James R. Wolfe
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Major Product ◽  
Lithium Aluminum ◽  
Radical Mechanism ◽  
Secondary Products ◽  
Tetramethylthiuram Disulfide ◽  
Hydride Reduction ◽  
Free Radical Mechanism ◽  
Cis And Trans

Abstract Cyclohexene reacts with sulfur at 140° in the presence of zinc dimethyldithio-carbamate, tetramethylthiuram monosulfide, or tetramethylthiuram disulfide, to produce 2-cyclohexene-1-thiol as the major product after lithium aluminum hydride reduction of the polysulfide compounds. Secondary products are cis- and trans-1, 2-eyclohexanedithiol and cyclohexanethiol. Zinc dimethyldithiocarbamate is postulated to promote the reaction via an ionic mechanism as it causes more trans than cis-1, 2-cyclohexanedithiol to be formed. Tetramethylthiuram monosulfide and disulfide are postulated to promote the reaction via a free radical mechanism as they cause more cis- than trans-1, 2-cyclohexanedithiol to be formed.

scholarly journals Spirolucidine, a new Lycopodium alkaloid

1984 ◽  
Vol 62 (2) ◽  
pp. 298-302 ◽  
Author(s):  
William A. Ayer ◽  
Leslie F. Ball ◽  
Lois M. Browne ◽  
Motoo Tori ◽  
Louis T. J. Delbaere ◽  
...  
Keyword(s):  
Spectroscopic Data ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
X Ray ◽  
Hydride Reduction ◽  
Crystallographic Study ◽  
Lycopodium Alkaloid ◽  
Relative Stereochemistry ◽  
New Type

The structure of spirolucidine, a new type of Lycopodium alkaloid related to the lucidines, has been determined. Chemical and spectroscopic data, together with biogenetic considerations, led to the correct constitution of spirolucidine. An X-ray crystallographic study of tetrahydrodeoxyspirolucidine, the lithium aluminum hydride reduction product of spirolucidine, confirmed the constitution and established the relative stereochemistry of the alkaloid.

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