Parallel synthesis of novel heteroaromatic acromelic acid analogues from kainic acid

A range of new C-4 heteroaromatic acromelic acid analogues has been synthesized in a parallel fashion from (-)-alpha-kainic acid 1. Protection of the amine and carboxylate groups of 1 followed by ozonolysis gave methyl ketone 8. A silyl enol ether 9, generated regiospecifically from the methyl ketone 8 using "kinetic" conditions, was brominated in situ with phenyltrimethylammonium perbromide to give the key alpha-bromo ketone 10. Parallel cyclization reactions of bromo ketone 10 with thioamides and thioureas were then performed. The aromatic heterocyclic derivatives 11a-d and 19 produced were deprotected to give the new kainoid amino acids 6a-d and 25 in excellent yield. Compounds 6a and 6c show strong binding to the kainate receptor. Reaction of 10 with alternative condensing agents was also briefly investigated.     

Orientational ordering of 4-substituted phenylcyclohexanes studied by carbon-13 two-dimensional N.M.R.

Abstract

An N.M.R. method combining the techniques of separated local field spectroscopy (SLF) and variable angle spinning (VAS) is valuable in the investigtion of nematic liquid crystals. Rapid sample spinning causes the nematic director to align along the spinning axis, resulting in narrow peaks in the C-13 N.M.R. spectrum. SLF is a two-dimensional N.M.R. method which produces a first order splitting pattern for each carbon signal from which C–H dipolar coupling constants can be determined. The order parameters for all segments of the liquid crystal molecule can then be calculated. Results for three 4′-cyanophenylcyclohexanes are considered here. These compounds are trans-substituted at the 4 position of cyclohexane ring with n-pentane (PCH5), 1-pentene (3d ₁CP) and 3-pentene (1d ₃CP), respectively.     

Synthesis of Novel Unsymmetrical and Symmetrical Diacetylenic Ketones

A convenient and efficient method for the preparation of unsymmetrical and symmetrical diacetylenic ketones bearing a carboxylate group.     

Synthesis of a (thienylethenyl)benzimidazole platinum acetylide complex

A new platinum acetylide complex based on 6-dialkylaminobenzimidazol-2-yl-vinyl-2-thiophene-5-ylethyne was synthesized in seven steps and 2% overall yield.     

Heterogeneous reactions of sulfur dioxide with carbonaceous particles

The rate of adsorption of SO₂ on a prototype carbonaceous surface was measured at low pressure in a flow reactor. The measured rate indicates a maximum atmospheric loss of SO₂ by heterogeneous reaction of 1%/h for a particle density of 100 μg/m³. The capacity of carbon particles to adsorb SO₂ is limited at ～1 mg SO₂ g^?1 C. NO₂ has no effect on the rate of SO₂ adsorption or the saturation behavior.     

Approaches to the regiospecific synthesis of Anthracycline antibiotics

Synthetic approaches to anthracycline antibiotics were studied through the use of Claisen rearrangements on 1-methallyloxy-5-methoxyantraquinone (9) which required reducing conditions to proceed through a hydroquinone intermediate in situ. 1-(2′-Methylene-4′-pentenoxy)-5-methoxyanthraquinone (13) underwent a similar reductive rearrangement but also produced a spiro compound 16 as a result of an ene reaction between the phenol and side chain double bond. 1-Hydroxy-2-methally-5-methoxyanthraquinone (11) could not be oxidized to quinizarin 17. 1-Hydroxy-2-methally-5,9,10-trimethoxyanthracene (21) was oxidatively coupled to the dimer at C-2. Dimer 23 reacted with diazomethane to form a 1,3-dipolar adduct 24.     

The stereochemistry of cyclisation of n-t-butyldihydrocinnamamide to a β-lactam

Using a stereospecifically labelled precursor, the peroxide catalysed cyclisation of N-$\text{t}$-butyldihydrocinnamamide to the corresponding β-lactam was shown to proceed with complete loss of stereochemistry at the benzylic carbon atom.