o-Phenylenediamine as a New Catalyst in the Highly Regioselective Conversion of Epoxides to Halohydrins with Elemental Halogens – A Reinvestigation

Summary. In contrast to a previous report, o-phenylenediamine is not a catalyst in the ring opening reaction of epoxides by means of bromine or iodine. The o-phenylenediamine is just a reactant which reacts with iodine to give phenazine-2,3-diamine and hydrogen iodide, or with bromine to give a mixture of brominated and polymerized products as well as hydrogen bromide. The hydrogen halogenides are in fact the real epoxide ring opening reactants.     

o-Phenylenediamine as a New Catalyst in the Highly Regioselective Conversion of Epoxides to Halohydrins with Elemental Halogens

The regioselective ring opening of epoxides using elemental iodine and bromine in the presence of o-phenylenediamine as a new catalyst affords vicinal iodo alcohols and bromo alcohols in high yields. The major advantages of this method are versatility, high regioselectivity, a cheap and commercially available catalyst, mild and neutral reaction conditions, and short reaction times. Fourier transform Raman spectroscopy was used to study the reaction of iodine with o-phenylenediamine. The results indicate that the complex [(Diamine)I]⁺·I₅^– is formed, and we suggest that the major nucleophile is the pentaiodide ion. This bulky nucleophile has a fundamental role in the high regioselectivity observed attacking the less sterically hindered epoxide carbon.     

Molecular structure of <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">o</Emphasis>-and <Emphasis Type="Italic">p</Emphasis>-hydroxybenzyl)cytisine

The molecular structures of N-(o-and p-hydroxybenzyl)cytisine were investigated by NMR spectroscopy, x-ray structure analysis, and molecular modeling. It was found that NMR resonances of the OH and aromatic protons in N-(o-hydroxybenzyl)cytisine were doubled because of the presence of two conformers in solution. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 165–168, March–April, 2008.     

Preparation of a Polymer via Condensation of <Emphasis Type="Italic">o</Emphasis>-Phenylenediamine with <Emphasis Type="Italic">p</Emphasis>-Xylylene Dibromide and Its Properties

Condensation of para-dibromoxylene and ortho-phenylenediamine in glass ampule at 150°С in an alkaline aqueous solution has yielded polymer with completely substituted N–H hydrogen atoms, capable of formation of polymeric cation-radicals. Complexes of this polymer and N,N,N',N'-tetrabenzyl-o-phenylenediamine with Co(II), Ni(II), Cu(II), and Ag(I) have been obtained, and their structure has been studied.     

Synthesis of 1,2-Diamino-1-phenylpropane Diastereoisomers from <Emphasis Type="Italic">u</Emphasis>-<Emphasis Type="Italic">N</Emphasis>-Trifluoroacetyl-2-amino-1-phenylpropan-1-ol

Summary. A new simple procedure for the synthesis of diastereomeric 1,2-diamino-1-phenylpropanes starting from u-N-trifluoroacetyl-2-amino-1-phenylpropan-1-ol (N-trifluoroacetylnorephedrine) is described. The trifluoroacetyl protecting group was particularly suitable for the protection of the amino group in order to reduce side reactions.     

Synthesis of derivatives of <Emphasis Type="Italic">o</Emphasis>-aminoacetophenone and <Emphasis Type="Italic">o</Emphasis>-aminobenzyl alcohol

Oxidation of 2′-hydroxy-8-methylspiro[4H-benz-1,3-oxazin-2-one-6,1′-cyclopentane] or N-mesyl-2-(cyclopent-1-en-1-yl)-6-methylaniline provided the corresponding ketones. The rearrangement of these ketones oximes under treatment with thionyl chloride gave rise to nitriles of 5-(2-amino-3-methylphenyl)-5-oxopentanoic or 5-(2-methanesulfamido-3-methylphenyl)-5-hydroxypentanoic acids. By heating 5-(2-acetylamido-3-methylphenyl)-5-oxopentanoic acid with LiH in THF3-(2,8-dimethylquinol-4-on-3-yl)propanoic acid was obtained.     

New tin(<Emphasis Type="SmallCaps">iv</Emphasis>) <Emphasis Type="Italic">o</Emphasis>-iminosemiquinone complexes

New tin(iv) mono- and bis-o-iminosemiquinone complexes were obtained by the exchange reaction of radical anion lithium salt of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-imino-benzoquinone with tin(iv) organochlorides. The compounds synthesized were characterized by EPR spectroscopy and X-ray diffraction analysis. Substituents on the tin atom were found to affect stability of paramagnetic metal derivatives formed.     

Synthesis of <Emphasis Type="Italic">o</Emphasis>(<Emphasis Type="Italic">m</Emphasis>)-carborane-containing azomethines

A method of preparative synthesis of o(m)-carborane-containing azomethines via the condensation of o(m)-carboranyl-C-methylene-4-formylbenzoates with aliphatic, cycloaliphatic, and aromatic amines was developed.     

<Emphasis Type="Italic">N</Emphasis>-aryl-<Emphasis Type="Italic">o</Emphasis>-iminobenzoquinones as novel regulators of radical polymerization

The effect of a number of quinoid compounds on methyl methacrylate polymerization initiated by azo-bis(isobutyronitrile) has been studied. It has been revealed that N-aryl-o-iminobenzoquinones, in contrast to o-benzoquinones, can provide radical polymerization of methyl methacrylate in controllable mode. The efficiency of the compounds as chain growth regulators has been found to depend on their composition and reaction conditions. It has been established that 4,6-di-tert-butyl-N-(2,6-diethylphenyl)-o-iminobenzoquinone and 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone under radical initiation conditions provide the synthesis of poly(methyl methacrylate) with wide-range molecular weight, retaining polydispersity indices about ~1.4–1.8 up to deep conversions.     

Conformational Polymorphism in Racemic 2,4-Di-<Emphasis Type="Italic">o</Emphasis>-Benzoyl-6-<Emphasis Type="Italic">o</Emphasis>-Tosyl <Emphasis Type="Italic">myo</Emphasis>-Inositol 1,3,5-Orthoacetate

The title compound, C₂₉H₂₆O₁₀S, yields two conformational polymorphs concomitantly from dichloromethane-methanol mixture; the major polymorph grows as plates (Form I, monoclinic, P2₁/n) and the minor polymorph grows as needles (Form II, triclinic, P-1). The two forms differ mainly in orientation of the tosyl group. In Form I, sulfonyl oxygen of the tosyl group makes intermolecular C −H…O interactions, whereas the same group in Form II is involved in an intramolecular short dipolar S=O…C=O (sulfonyl-carbonyl) contact. The molecular organization and the influence of various weak non-covalent interactions that stabilize these conformers in the crystal lattices are discussed.     

An Improved Stereocontrolled Route to <Emphasis Type="Italic">cis</Emphasis>-Erythrinanes by Combined Intramolecular <Emphasis Type="Italic">Strecker</Emphasis> and <Emphasis Type="Italic">Bruylants</Emphasis> Reaction

Summary. Condensation of (2-iodophenyl)ethylamines with cyclohexanoylacetaldehyde provided the corresponding aldimines which were reduced yielding secondary phenethylcyclohexanoylethylamines. These in turn were appropriate intermediates to prepare several erythrinanes by a sequential intramolecular Strecker and intramolecular Bruylants reaction. In contrast, the C-ring homologue schelhammeranes were not available on this route.Part of PhD thesis, LMU München, D     

Copolymer of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diallyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylammonium chloride with maleic acid as drug carrier

A copolymer of N,N-diallyl-N,N-dimethylammonium chloride with maleic acid of constant composition was prepared under the conditions of radical initiation. The possibility of the functionalization of the copolymer with drugs containing amino groups by polymer-analogous transformations was examined. Conditions were found for preparing conjugates of the copolymer with isoniazid. The structures and the quantitative compositions of the conjugates were determined by ¹³С NMR spectroscopy, and the possibility of preparing conjugates with controlled drug content was demonstrated.     

<Emphasis Type="Italic">Z</Emphasis>-and <Emphasis Type="Italic">E</Emphasis>-conformers of <Emphasis Type="Italic">N</Emphasis>-chloroacetylcytisine

N-Chloroacetylcytisine was synthesized by acylation of (–)-cytisine. Stable Z- and E-conformers with respect to rotational isomerism around the N-12–CO bond were found in PMR spectra at room temperature. The point at which PMR resonances of the Z- and E-conformers coalesced upon heating was measured. The transition barrier between the conformers was estimated.     

Photolysis of <Emphasis Type="Italic">o</Emphasis>-iodo- and <Emphasis Type="Italic">o</Emphasis>-bromophenols in aqueous solution of sodium sulfite and organic solvents

The photochemical reaction of o-iodo- and o-bromophenol in an aqueous sodium sulfite solution proceeds via both nonchain and chain mechanisms. The formation of the intermediate product, aromatic radical anion, was observed. The quantum yield of the photochemical reaction of o-iodophenol increases, when the electron donor diphenylamine is irradiated. In the photolysis of o-halophenols in organic solvents, free iodine is evolved in addition to aromatic products. The products of the photolysis of o-iodophenol in ethanol and carbon tetrachloride were identified by gas chromatography-mass spectrometry. These are phenol in the case of ethanol and a mixture of o-chlorophenol and hydroxychloro-substituted biphenyls in the case of carbon tetrachloride. The quantum yields were determined for all photochemical reactions studied.     

Synthesis of Novel <Emphasis Type="Italic">D</Emphasis>-<Emphasis Type="Italic">Seco</Emphasis>-Pregnenes

Summary. A new synthetic route was developed for the preparation of trans-3-hydroxy-16,17-seco-pregna-5,17(20)-dien-16-al, using Grob fragmentation as the key step. This seco-steroid contains a formyl group and an unsaturated side-chain in a sterically favourable position, and is therefore a promising starting material for the synthesis of novel condensed steroid heterocycles.Received March 22, 2003; accepted April 22, 2003 Published online September 25, 2003     

Synthesis of new hydrazones based on <Emphasis Type="Italic">o</Emphasis>- and <Emphasis Type="Italic">p</Emphasis>-hydroxybenzohydrazides

o- and p-Hydroxybenzohydrazides reacted with various unsaturated aromatic aldehydes to give the corresponding N′-(hydroxybenzoyl)hydrazones. Inhibitory activity of the obtained hydrazones against cathepsin E was evaluated.     

Thermochemical study on ternary complex of dysprosium <Emphasis Type="Italic">m</Emphasis>-nitrobenzoic acid with <Emphasis Type="Italic">o</Emphasis>-phenanthroline

A ternary binuclear complex of dysprosium chloride hexahydrate with m-nitrobenzoic acid and 1,10-phenanthroline, [Dy(m-NBA)₃phen]₂·4H₂O (m-NBA: m-nitrobenzoate; phen: 1,10-phenanthroline) was synthesized. The dissolution enthalpies of [2phen·H₂O(s)], [6m-HNBA(s)], [2DyCl₃·6H₂O(s)], and [Dy(m-NBA)₃phen]₂·4H₂O(s) in the calorimetric solvent (V_DMSO:V_MeOH = 3:2) were determined by the solution–reaction isoperibol calorimeter at 298.15 K to be \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [2phen·H₂O(s), 298.15 K] = 21.7367 ± 0.3150 kJ·mol⁻¹, \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [6m-HNBA(s), 298.15 K] = 15.3635 ± 0.2235 kJ·mol⁻¹, \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [2DyCl₃·6H₂O(s), 298.15 K] = −203.5331 ± 0.2200 kJ·mol⁻¹, and \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [[Dy(m-NBA)₃phen]₂·4H₂O(s), 298.15 K] = 53.5965 ± 0.2367 kJ·mol⁻¹, respectively. The enthalpy change of the reaction was determined to be \Updelta_\textr H_\textm^q = 3 6 9. 4 9 ±0. 5 6   \textkJ·\textmol ^{- 1} . \Updelta_{\text{r}} H_{\text{m}}^{\theta } = 3 6 9. 4 9 \pm 0. 5 6 \;{\text{kJ}}\cdot {\text{mol}}^{ - 1} . According to the above results and the relevant data in the literature, through Hess’ law, the standard molar enthalpy of formation of [Dy(m-NBA)₃phen]₂·4H₂O(s) was estimated to be \Updelta_\textf H_\textm^q \Updelta_{\text{f}} H_{\text{m}}^{\theta } [[Dy(m-NBA)₃phen]₂·4H₂O(s), 298.15 K] = −5525 ± 6 kJ·mol⁻¹.     

Synthesis of 6-methyl-8<Emphasis Type="Italic">H</Emphasis>-dibenzo[<Emphasis Type="Italic">a</Emphasis>,<Emphasis Type="Italic">g</Emphasis>]quinolizin-8-imines <Emphasis Type="Italic">via Reissert</Emphasis> compounds

Alkylation of Reissert compounds derived from 3-methylisoquinolines with several 2-cyanobenzylbromides followed by hydrolytic cleavage provided the corresponding 1-benzyl-3-methylisoquinolines. Treatment of the latter with methylmagnesiumiodide caused cyclization to the title compounds rather than formation of 2-acetylbenzylisoquinolines.     

Reaction of <Emphasis Type="Italic">o</Emphasis>-aminophenol and <Emphasis Type="Italic">o</Emphasis>-aminobenzyl alcohol with palladium(II) bis(isocyanide) complexes

Reactions of palladium(II) bis-isocyanide complexes cis-[PdCl₂(CNR)₂] (R = 2,6-Me₂C₆H₃, 2-Me-6-ClC₆H₃) with an equimolar amount of chelating N,O-binucleophiles, 2-aminophenol and (2-aminophenyl)-methanol, in acetonitrile at room temperature in 24 h selectively afforded the corresponding open-chain monocarbene complexes. The complexation involved one isocyanide ligand and amino group of the aromatic amine. Neither bis(carbene) complexes (in the reactions with 4 equiv of the nucleophile under harsh conditions) nor C,O-chelate structures were detected. The isolated complexes were characterized by elemental analyses, IR, NMR, and mass spectra, and X-ray diffraction data.     

Mono-<Emphasis Type="Italic">meso</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-butylporphyrin

Summary. Treatment of meso-tetra(tert-butyl)porphyrin with sulfuric acid/n-butanol affords a mixture of porphyrin and mono-tert-butylporphyrin in relatively high yield.