Simple total synthesis of sarkomycin

A simple total synthesis of sarkomycin starting from methyl 2-oxo-5- vinylcyclopentane-1-carboxylate is described.     

Spirodionic acid, a novel metabolite from Streptomyces sp., part 1: structure elucidation and Diels-Alder-type biosynthesis

Spirodionic acid (1), a novel microbial metabolite with a spiro[4.5]decene skeleton, the 6-ethyl-2H-pyrone 5, dihydrosarkomycin (6), and other metabolites were isolated from the strain Streptomyces sp. Tü 6077. Structural elucidation was accomplished by NMR spectroscopic and mass-spectrometric studies, and the biosyntheses of compounds 1, 5, and 6 were investigated by feeding experiments with (13)C-labeled precursors. All results indicate a biogenetic sequence with metabolite 5 and sarkomycin (7) as precursors in the formation of spirocyclus 1 through an intermolecular Diels-Alder-type reaction.     

Sarkomycin and its analogs

Summary Racemic sarkomycin was synthesized. It was obtained in the form of its semicarbazone.     

α-Phosphoryl Cyclopentanones as Possible Intermediates in the Total Synthesis of Sarkomycin

Abstract

In an effort to synthesize sarkomycin 1 trans-2-diphenylphosphinoyl-3-tris (methylthio) methyl-cyclopentanone 7 and trans-2-diphenylphosphinoyl-3-carbo-methoxy-cyclopentanone 8 were prepared. The Horner-Wittig reaction of the latter with formaldehyde failed. (±)-Sarkonycin 1 was prepared by a sequence of reactions starting from diethyl 2-oxopropanephosphonate. The key steps in this synthesis involve the intramolecular carbenoid cyclization of 1-diazo-2-oxopropanephosphonate 10 and the Horner-Wittig reaction of 2-diethoxyphosphoryl-3-carboxy-cyclopentanone 12 with formaldehyde.     

A new and unusually flexible route to cyclopentanoids synthesis of sarkomycin and prostaglandins

Combination of the dianion of dialky 3-hexenedioate and β-bromopropionate leads directly to a 2,3-disubstituted cyclopentanone, which can be transformed to a variety of primary prostaglandins and sarkomycin.     

The efficient consecutive β-carboxylation and α-alkylation of cyclic α,β-enones; a new route to sarkomycin

Sequential one-pot introduction of a carboxy group equivalent and an alkyl group at the respective β- and α-positions of cyclic enones has been achieved through a 1,4-addition reaction of [methoxy(phenylthio)(trimethylsilyl)methyl] lithium followed by direct trapping of the resulting enolate with alkyl halides. The present method proved to be applicable to a simple synthesis of sarkomycin.     

Perfluoro and polyfluorosulfonic acids: XVI. Difluoromethanesulfonic acids as a precursor of CF2: In the synthesis of difluoromethyl poly- and perfluoroalkanesulfonates

Difluoromethanesulfonic acid (1) readily reacts with P₂O₅ at room temperature to give difluoromethyl difluoromethanesulfonate (2) and SO₂ in stead of the expected acid anhydride. If perfluorosulfonic acid (3) perfluorocarboxylic acid (5) or KI was added to this reaction mixture, difluoromethyl perfluorosulfonate (4), difluoromethyl perfluorocarboxylate (6) and HCF₂I (7) was formed respectively in addition to 2. A similar result was obtained using POCl₃ or SOCl₂ instead of P₂O₅ as dehydrating agent. The mechanisms of the formation of difluorocarbene were discussed.     

Thermotropic mesophases of ionic amphiphiles

In part I of this article the thermotropic mesophases of anhydrous ionic amphiphiles were discussed. In this part the thermotropic mesophases of ionic amphiphiles in aqueous media, as determined by thermal analysis, microscopic studies, X-ray diffraction and other techniques are reviewed. The fatty acids saturated or unsaturated that are found in the above molecules are: Lauric acid (C₁₂H₂₄O₂); myristic acid (C₁₄H₂₈O₂); palmitic acid (C₁₆H₃₂O₂); stearic acid (C₁₈H₃₆O₂); arachic acid (C₂₀H₄₀O₂); behenic acid (C₂₂H₄₄O₂); oleic acid (C₁₈H₃₄O₂).     

Chiroptical properties and conformation of some 2-alkyl substituted dicarboxylic acids

CD spectra in EPA (a mixture of ethanol, isopentane and diethyl ether) at 25° and -185° were measured for the following acids and their methyl esters: (R)-2-methyl-, (R)-2-ethyl-, (R)-2-n-propyl-, (R)-2-n-butyl-, (R)-2-n-hexyl-, (R)-2-isobutyl-, (S)-2-isopropyl- and (S)-2-cyclohexylsuccinic acids, (R)-2-methylglutaric acid, (R)-2-methylsuberic acid, (R,R)-2,3-dimethyl-succinic acid and (+)-trans-Caronic acid (3,3-dimethyl-1,2-cyclopropane-dicarboxylic acid). The CD data are explained in terms of the conformation around the C₁C₂, C₂C₃ and C₃C₄ bonds.     

Hydrogen‐bonded complexes of 2‐pyridone with centrosymmetric and non‐centrosymmetric dicarboxylic acids

2‐Pyridone (2‐oxo­pyrimidine) forms hydrogen‐bonded com­plexes with di­carboxyl­ic acids, the molar ratio of 2‐pyridone/di­carboxyl­ic acid being 2:1 for the complexes with oxalic acid (ethanedioic acid), 2C₅H₅NO·C₂H₂O₄, (I), and trans‐β‐hydro­muconic acid (trans‐hex‐3‐enedioic acid), 2C₅H₅NO·C₆H₈O₄, (II), and 1:1 for the complexes with trans‐glutaconic acid (trans‐pent‐2‐enedioic acid), C₅H₅NO·C₅H₆O₄, (III), and l ‐­tartaric acid (l ‐2,3‐di­hydroxy­butane­dioic acid), C₅H₅NO·C₄H₆O₆·H₂O, (IV). Common features in the hydrogen‐bonding patterns were found for the centrosymmetric and non‐centrosymmetric acids, respectively. The 2‐pyridone mol­ecule takes the lactam form in these crystals.     

PREPARATION AND PROPERTIES OF PYRIDINE DICARBOXYLIC ACID COMPLEXES OF THE LANTHANIDES

Abstract

The preparation and spectroscopic properties of eleven hydrated lanthanide (III) dipicolinate and quinolinate complexes are reported for the first time. The complexes are of three general types: M(dipi)(dipiH)(H₂O)₄, M(dipiH)₃(H₂O) and M(quin)(quinH)(H₂O)₃ [where M =lanthanide (III); dipiH₂ =pyridine-2,6-dicarboxylic acid (dipicolinic acid); quinH₂ =pyridine-2, 3-dicarboxylic acid (quinolinic acid)], and evidence is presented which indicates that they may be six-coordinate.     

Hydrogen‐bonded structures of the 1:1 and 1:2 compounds of chloranilic acid with pyrrolidin‐2‐one and piperidin‐2‐one

In the four compounds of chloranilic acid (2,5‐dichloro‐3,6‐dihydroxycyclohexa‐2,5‐diene‐1,4‐dione) with pyrrolidin‐2‐one and piperidin‐2‐one, namely, chloranilic acid–pyrrolidin‐2‐one (1/1), C₆H₂Cl₂O₄·C₄H₇NO, (I), chloranilic acid–pyrrolidin‐2‐one (1/2), C₆H₂Cl₂O₄·2C₄H₇NO, (II), chloranilic acid–piperidin‐2‐one (1/1), C₆H₂Cl₂O₄·C₅H₉NO, (III), and chloranilic acid–piperidin‐2‐one (1/2), C₆H₂Cl₂O₄·2C₅H₉NO, (IV), the shortest interactions between the two components are O—H...O hydrogen bonds, which act as the primary intermolecular interaction in the crystal structures. In (II), (III) and (IV), the chloranilic acid molecules lie about inversion centres. For (III), this necessitates the presence of two independent acid molecules. In (I), there are two formula units in the asymmetric unit. The O...O distances are 2.4728 (11) and 2.4978 (11) Å in (I), 2.5845 (11) Å in (II), 2.6223 (11) and 2.5909 (10) Å in (III), and 2.4484 (10) Å in (IV). In the hydrogen bond of (IV), the H atom is disordered over two positions with site occupancies of 0.44 (3) and 0.56 (3). This indicates that proton transfer between the acid and base has partly taken place to form ion pairs. In (I) and (II), N—H...O hydrogen bonds, the secondary intermolecular interactions, connect the pyrrolidin‐2‐one molecules into a dimer, while in (III) and (IV) these hydrogen bonds link the acid and base to afford three‐ and two‐dimensional hydrogen‐bonded networks, respectively.     

Synthese funktioneller Carbonsäure-Silylester

Synthesis of Functional Carboxylic Acid Silylester Di-tert-butylsilandiol reacts with organic acid chlorides to chlorosilanoles R₂Si(OH)Cl 1 (R = t-Bu). The phosphoric acid silylester 2 is obtained from 1 and POCl₃. Lithiated halogenosilanoles react with carboxylic acid chlorides to give silylesters ( 3 – 7 ). Lithium (trimethyl-acetoxy)silanolate 8 is obtained in the reaction of the lithiated diol with the chloride of trimethylacetic acid. The analogous reaction with benzoyl chloride lead to the formation of the bis(benzoic acid) silylester 9 . The condensation product 10 is obtained in the reaktion of the lithiated aminosilanol (t-Bu)₂Si(NH₂)OLi with trimethylacetic acid chlorid and condensation of the formed ester with aminosilanol.     

Formation and tribological properties of composite Langmuir–Blodgett films of stearic acid with molybdenum disulfide and amorphous carbon

The morphology and tribological properties of Langmuir–Blodgett mono- and bilayers of stearic acid with particles of molybdenum disulfide (MoS₂) and amorphous carbon (С), prepared on silicon and steel substrates by horizontal deposition (stearic acid–MoS₂ and stearic acid–С monolayers) and by the “roll” technique (stearic acid–MoS₂/stearic acid–С bilayers), were studied. Incorporation of C and MoS₂ particles into the structure of a stearic acid film enhances its wear resistance by a factor of 2.8 and 5.5, respectively. The presence of MoS₂ and С particles and of their aggregates of size from ~220 nm to 16.3 μm in stearic acid layers was confirmed by atomic force microscopy.     

The Crystal Structure of Mer-Trans (NH3-NH2)-Potassium Trinitroglycinatoamminecobaltate(III) Monohydrate

Some new oxozirconium(IV) complexes: ZrO(An)₂, ZrO(Gly)₂, ZrO(HSal)₂, ZrO(HPth)₂, ZrO(Pic)₂(HPic)₂, and ZrO(Quin)₂(H Quin)₂ have been isolated from the reactions of ZrO(CH₃COO)₂CH₃COOH with anthranilic acid (HAn), glycine (HGly), salicylic acid (H₂Sal), phthalic acid (H₂Pth), picolinic acid (HPic), and 8-quinolinol (HQuin) respectively. Their important infrared bands and wherever possible molar conductance and molecular weight have been reported.     

Synthon preference in a hydrated β‐resorcylic acid structure and its cocrystal with thymine

Multicomponent crystals or cocrystals play a significant role in crystal engineering, the main objective of which is to understand the role of intermolecular interactions and to utilize such understanding in the design of novel crystal structures. Molecules possessing carboxylic acid and amide functional groups are good candidates for forming cocrystals. β‐Resorcylic acid monohydrate, C₇H₆O₄·H₂O, (I), crystallizes in the triclinic space group P with one β‐resorcylic acid molecule and one water molecule in the asymmetric unit. The cocrystal thymine–β‐resorcylic acid–water (1/1/1), C₅H₆N₂O₂·C₇H₆O₄·H₂O, (II), crystallizes in the orthorhombic space group Pca2₁, with one molecule each of thymine, β‐resorcylic acid and water in the asymmetric unit. All available donor and acceptor atoms in (I) and (II) are utilized for hydrogen bonding. The acid and amide functional groups are well known for the formation of self‐complementary acid–acid and amide–amide homosynthons. In (I), an acid–acid homosynthon is observed, while in (II), an amide–acid heterosynthon is present. In (I), the β‐resorcylic acid molecule exhibits the expected intramolecular S(6) motif between the hydroxy and carbonyl O atoms, and an intermolecular R₂²(8) dimer motif between the carboxylic acid groups; only the former motif is observed in (II). The water solvent molecule in (I) propagates the discrete dimers into two‐dimensional hydrogen‐bonded sheets. In (II), thymine and β‐resorcylic acid molecules do not form self‐complementary amide–amide and acid–acid homosynthons; instead, a thymine–β‐resorcylic acid heterosynthon is observed. With the help of the water molecule, this heterosynthon is aggregated into a three‐dimensional hydrogen‐bonded network. The absence of thymine base pairing in (II) might be linked to the availability of additional functional groups and the preference of the donor and acceptor hydrogen‐bond combinations.     

Studies on complex compounds of thorium(IV) with pyridine and quinoline carboxylic acid. Part I

Summary Thorium acetylacetonate [Th(acac)₄] reacts with pyridine carboxylic acids in acetone giving eight coordinate thorum(IV) complexes of the compositions [Th(pic)₄] and [Th(picO)₄] (picH = picolinic acid, picOH = picolinic acidN-oxide). The complex [Th(dip)₂] · 3H₂O (dipH₂ = pyridine-2,6-dicarboxylic acid) is also reported. Thorium(IV) complexes of the types [Th(quin)₂] · 2H₂O and [Th(quind)₂(acac)₂] (quinH₂ = quinolinic acid or pyridine-2,3-dicarboxylic acid, quindH = quinaldinic acid) were prepared by the interaction of [Th(acac)₄] with the respective acids in acetone. The lower solubility and i.r. spectral studies of the complex [Th(quin)₂] · 2 H₂O suggest that it is polymeric.     

Organic Phosphorus Compounds 61. Esterification and chlorination of nitrilo-tri(methylene-phosphonic acid), N(CH2PO3H2)3, and hydroxyethylidenediphosphonic acid,H2O3PC(OH)(CH3)PO3H2, and the corresponding esters

Nitrilo-tri(methylenephosphonic acid) and hydroxyethylidenediphosphonic acid are esterified in high yield when treated with excess orthoformic acid ester under reflux. Because of the high temperature necessary to effect esterification a partial isomerization of hydroxyethylidenediphosphonate to the phosphate-phosphonate isomer V takes place. Chlorination of N(CH₂PO₃H₂)₃ or a mixture of the ester and the acid with PCl₅ yields tris(chloromethyl)amine, N(CH₂Cl)₃. Interaction of N(CH₂Cl)₃ and (EtO)₃P yields nitrilo-tri(methylenephosphonate), which on hydrolysis with HCl conc. produces N(CH₂PO₃H₂)₃. Chlorination of a mixture of hydroxyethylidene-diphosphonic acid and the corresponding ethyl ester IV which contained the phosphate-phosphonate isomer V gave the products VII to XI. Chlorination of the acid III with PCl₅ gave 4 products, i.e., VIII, IX, XI and Cl₂(O)POP(O)Cl₂. The ¹H- and ³¹P-NMR. spectra of the products are discussed.     

Fluorometry of hydrogen peroxide using oxidative decomposition of folic acid

Hydrogen peroxide (H₂O₂) is one of the most important reactive oxygen species. In the present study, a fluorometry method for detecting H₂O₂ utilizing folic acid was evaluated. Folic acid was decomposed by H₂O₂ in the presence of Cu(II) into pterine-6-carboxylic acid, leading to strong fluorescence enhancement. In the absence of the metal ion, superoxide and H₂O₂ could not decompose folic acid. Also, H₂O₂ plus sodium hypochlorite (a source of singlet oxygen) could not induce fluorescence enhancement. These results demonstrate that H₂O₂ can be selectively detected using folic acid plus Cu(II). The limit of detection (LOD; at S/N=3) for H₂O₂ is 0.5 μM. This method based on the fluorescence enhancement of folic acid was applied in order to determine small amounts of H₂O₂ generated through the autooxidation of semicarbazide (generation rate: ∼0.01 μM min⁻¹), a carcinogenic compound.      

Synthesis and characterisation of a new mixed [Si(IV), Al(III)] μ-oxo-isopropoxide and its acid complexes

Reaction of dimethyldiacetoxysilane with aluminium isopropoxide was carried out in 1 : 2 molar ratio in refluxing cyclohexane and a mixed [Si(IV), Al(III)] μ-oxo-isopropoxide of the composition Me₂SiO₂Al₂(OPrⁱ)₄ was isolated. This compound was characterised by elemental analysis and IR and NMR spectral studies. The tertiary butanol derivative, Me₂SiO₂Al₂(OBu^t)₄, was prepared by alcoholysis. Reactions of this mixed [Si(IV), Al(III)] μ-oxo-isopropoxide with monobasic bidentate carboxylic acids, such as trans-cinnamic acid (HCA) and dihydrocinnamic acid (HDCA) and with dibasic tridentate carboxylic acids such as salicylic acid (H₂SA) and benzilic acid (H₂BA) were also studied. Products of the type Me₂SiO₂Al₂(OPrⁱ)_4-n(L)_n [where HL = trans-cinnamic acid (HCA), dihydrocinnamic acid (HDCA) and n = 1,2,3 or 4] and Me₂SiO₂Al₂(OPrⁱ)_4-2n(L)_n [where H₂L = salicylic acid (H₂SA), benzilic acid (H₂BA) and n = 1 or 2] were isolated and characterised by elemental and spectral studies.