Studies on organophosphorus compounds—XXXVI: Simple new routes to phosphorins from 2-hydroxy-, 2-mercapto-, and 2-aminobenzoic acids and their derivatives

2-Hydroxybenzoic acid heated with 2,4 - bis(4 - methoxyphenyl) - 1,3,2,4 - dithiadiphosphetane - 2,4 -disulfide, 1, gave 2 - (p - methoxyphenyl) - 4$\text{H}$ - 1,3,2 - benzoxathiaphosphorin - 4 - one 2 - sulfide, 3, and its thio-analogue, 4, while its ethyl or phenyl esters gave 4 as the sole product. 2 - Mercaptobenzoic acid and its ethyl ester when heated with 1 produced 3$\text{H}$ - 1,2 - benzodithiole - 3 - one, 8, 3$\text{H}$ -1,2 - benzodithiole - 3 - thione, 9, and 2- (p - methoxyphenyl) - 4$\text{H}$ - 1,3,2 - benzodithia - phosphorin - 4 - one 2 - sulfide, 10. The reaction of 2 -aminobenzoic acid with 1 gave 1,2 - dihydro - 2 - (p - methoxyphenyl) - 4$\text{H}$ - 3,1,2 - benzoxaphosphorin - 4 - one 2 - sulfide, 12. Reactions of 1 with methyl 2 - aminobenzoate and 2 - aminobenzamides are described. Mechanistic considerations for the formation of the heterocyclic phosphorus compounds are presented.     

Approche de la synthese d'anthracyclines oligosaccharidiques. Hemisynthese de la 4'-o-(2-desoxy l-fucosyl) daunorubicine

The preparation of the disaccharide 4 - O - (3,4 - di - O - acetyl - 2,6 - dideoxy - α - l - lyxo - hexopyranosyl) - 2, 3,6 - trideoxy - 3 - trifluoroacetamido - l - lyxo - hexopyranose, 11c, the N,N' - dimethyl derivative of which occurs naturally in numerous anthracyclines, is described. Glycosidation with daunomycinone followed by removal of the protecting groups led to 4' - O - (2 - deoxy - l - fucosyl) daunorubicine.     

Synthesis of (±)-ascochlorin, (±)-ascofuranone and LL-Z1272

Three antibiotics with a common structural feature as prenylated phenols were synthesized: (±)-ascochlorin (5 - chloro-2,4 - dihydroxy - 6 - methyl - 3 - [(2E',4/E') - 5' - (1′,2′,6′ - trimethyl - 3′-oxocyclohexyl) - 3' - methyl - 2',4' - p benzaldehyde), (±)-ascofuranone (5 - chloro - 2,4 - dihydroxy - 6 - methyl - 3 - [(2'E,6'E) - 7' - (3′,3′ - dimethyl - 4′ - oxo - 2′ - oxacyclopentyl) - 3',7 -dimethyl - 2',6' - heptadienyl] benzaldehyde) and LL-Z1272α (5 - chloro - 2,4 - dihydroxy - 6 - methyl -3 - [(2'E,6'E) - 3',7',11' - trimethyl - 2',6', 10' - dodecatrienyl] benzaldehyde)     

The synthesis of 3,6-diamino-2,3,4,6-tetradeoxy-dl-threo-hexopyranose derivatives,substrates for the synthesis of negamycin

Three synthetic routes to derivatives of 3,6 - diamino - 2,3,4,6 - tetradeoxy - DL - threo - hexopyranose were investigated. Addition of sodium azide in acetic acid to 6 - phthalimido - 5,6 - dihydro - 2 - pyrone gave 4-azido compound (7) of the erythro configuration. From methyl 2,4 - dideoxy - β -dl- erythro - hexopyranoside threo 4 - phthalimido - 6 - phthalimidomethyl - tetrahydro - 2 - pyrone (17) was obtained in three steps in low overall yield. Addition of sodium azide in acetic acid to butyl 6 - oxo - 2 - hydroxy - hex - 4 - enoate followed by methylation, amonolysis of the ester group, and reduction gave methyl 3,6 - diacetamido - 2,3,4,6 - tetradeoxy - α - DL - threo - hexopyranoside (26).     

O,O-dialkylphosphoroselenoic acids as functionalising reagents of monosaccharides—III: A novel synthesis of unsaturated sugars by eoxygenation of sugar epoxides with dialkylphosphoroselenoic acids

Sugar epoxides are transformed in almost quantitative yields, under mild reaction conditions, into their corresponding unsaturated monosaccharides by reaction with O,O-dialkylphosphoroselenoic acids salts. A mechanism involving the formation of a penta-coordinate phosphorus intermediate is proposed.The deoxygenation was performed with the following sugar epoxides: 5,6 - anhydro -1,2 - O - isopropylidene - α - D - glucofuranose (1), 5,6 - anhydro - 1,2 - O - cyclohexylidene - α - D - glucofuranose (2), methyl - 2,3 - anhydro - 4, 6 - O - benzylidene - α - D - allopyranoside (3), methyl - 2,3 - anhydro - 4,6 - O - benzylidene - α - D - mannopyranoside (4) and 3,4,6 - tri - O - acetyl - 1,2 - anhydro - α - D - glucopyranose (Brigl's anhydride) (5).     

Mikrochemische Studien

Ohne ZusammenfassungAbkürzungen AuCl Goldchlorid - AuBr Goldchlorid und Natriumbromid - AuJ Goldchlorid und Natriumjodid - PtCl Platinchlorid - PtBr Platinchlorid und Natriumbromid - PtJ Platinchlorid und Natriumjodid - KBiJ Kaliumwismutjodid - KCdJ Kaliumkadmiumjodid - JJK Jodjodkalium - J Alkoholische Jodlösung - HgCl Quecksilberchlorid - KFeCN Ferrocyankalium und Salzsäure - MgP Magnesiumacetat und Natriumphosphat - UAc Uranacetat - PMo Phosphormolybdänsäure - PWo Phosphorwolframsäure - SiWo Siliciumwolframsäure - Pi Pikrinsäure - Ge Gerbsäure - PdCl Palladiumchlorür - KHgJ Kaliumquecksilberjodid - Nd Niederschlag - L Länge - B Breite Am Schlusse dieser Arbeit statte ich meinem hochverehrten Lehrer, Herr Prof. Dr. Stephan R. v. Niementowski, meinen besten Dank ab für die zahlreichen, sehr geschätzten Weisungen und Ratschlge, die er mir zu erteilen die Güte hatte.     

Measurements of 27 elements in garden and lawn fertilizers using instrumental neutron activation analysis

Five locally available garden and lawn fertilizers were analyzed for elemental content using instrumental neutron activation analysis. The fertilizers were labeled as High Yield; Slow Release, 13-13-13; 16-8-4 and 28-4-4. The concentration ranges of the elements measured, in g/g, were: Ba<10-105; Br 0.55-272; Co 0.33-3.74; Cr 10.0-42.5; Cs0.09-1.02; Eu 0.05-0.42; Fe 1840-9830; Ga<1-4.6; Ge<0.1-1.23; Hf0.07-2.32; La 1.66-10.4; Na 57.6-3990; Nd<9; Ni<3-12.3; Rb 2.42-48.5; Sb 0.03-0.24; Sc 0.3-3.11; Se 2.68-10.2; Sm<0.4-2.13; Sr 21.7-214; Ta<0.01-0.052; Tb 0.05-0.28; Th 0.52-2.16; U 0.18-0.38; Zn 10.8-233 and Zr<1-8.95. Some of these elements are recognized as micronutritiens (e.g., Fe & Zn), and are necessary for plant growth. However, other elements may lead to undesirable environmental effects. The undiscriminating use of fertilizers, especially in home gardening, may result in the increase of toxic elements (Co, Cr, Se, Sb, Th, U etc.) in the underground water supply.     

Steroids from sponges

The sponges Stelleta clarella Tethya aurantia, Lissodendoryx noxiosa, Haliclona permollis and Haliclona sp. were examined for steroids. All sponges contained C₂₇-C₂₉, Δ⁵, mono and diunsaturated sterols. In addition, the sponge Tethya aurantia contained Z - 24 - propylidene - cholest - 5- en -3β-ol (19) and the 5α,8α-peroxides of cholesta - 5,7 - dien - 3β - ol, ergosterol, ergosta - 5,7,24(28) - trien - 3β - ol and 24ξ - ethyl - cholesta - 5,7 - dien - 3β - ol (29, 30, 31 and 32). The sponge Stelleta clarella also contained 24 - nor - cholesta - 4,22 - dien - 3 - one (21), cholesta - 4,22 - dien - 3 - one (22), 24ξ - methyl - cholesta - 4,22 - dien - 3 - one (24), ergosta - 4,24(28) - dien - 3 - one (25), (E) - stigmasta - 4,24(28) - dien - 3 - one (28), 5α - cholestanol (5), 5α - ergostanol (7) and 5α - poriferastanol (9) The possible biosynthetic significance of these hitherto undescribed peroxides and enones from marine sources is discussed. A synthesis of 19 is also described.     

Investigations on the question of multiple mechanisms in the cope rearrangement

The possible occurrence of the ionic Cope rearrangement, and other non-concerted mechanisms is discussed. The synthesis of 2 - (1 - ethyl - 1 - propenyl) -2- (3 - p - methoxyphenylallyl)malononitrile (1b) and its clean thermal 1,3 rearrangement to (1 - ethyl - 5 - p - methoxyphenyl - 2 - methyl - 4 - pentenylidene)malononitrile (4) are reported. This result contrasts with the rearrangement of 2 - (1,1 - dideuterioallyl) - 2 -(1 - ethyl - 1 - propenyl)malononitrile (1c) which isomerizes cleanly in a 3,3 rearrangement. Rearrangement of 2 - (1 - cyclohexenyl) - 2 - (3 - p - methoxyphenylallyl)malononitrile (11), however, leads sluggishly to [2 - (p - methoxy - α - vinylbenzyl)cyclohexylidene]malononitrile (19) (3,3 shift) and rearrangement of 2 - (1 - isopropyl - 2 - methyl - 1 - propenyl) - 2 -(3 - p - methoxyphenylallyl)malononitrile (12) leads, also slowly, to (1 - isopropyl - 5-p- methoxyphenyl - 2,2 - dimethyl - 4 - pentenylidene)malononitrile (14) (1,3 shift). Rearrangement of 1b in the presence of sodium borohydride allows interception of the proposed ionic intermediates and isolation of 2 - (1 - ethylpropylidene)malononitrile (5) and anethole (21c). Ion trapping experiments also gave positive results in the 3,3 rearrangement of 11. These results are discussed in terms of the ionic Cope rearrangement.     

The synthesis of peptides containing purine and pyrimidine derivatives of DL-alanine

The incorporation of the “base-bearing amino acids”, DL - β - (uracil - 1 - yl)alanine 1 (Uala), DL - β - (thymin - 1 - yl)alanine 2 (Tala), DL - β - (cytosin - 1 - yl)alanine 3 (Cala) and DL - β - (adenin - 9 - yl 4 (Aala) into peptides has been studied. The carboxyl group of each of these compounds was protected by the formation of the ethyl ester. The t - butoxycarbonyl (t-BOC) group was suitable for the protection of the α-amino group of 1 but not that of 2, 3 and 4 because of the formation of ring substituted compounds. Peptides containing the amino acids 1–4 and L-serine were synthesised, however, by the mixed anhydride method; uracil, thymine and adenine residues needed no protection, neither did the cytosine residue provided that it was not present in the intermediate which was treated with ethyl chloroformate to produce the mixed anhydride. In this case reaction with the cytosine residue occurred. By these procedures, four protected dipeptides, namely α - N - t - BOC - L - seryl derivatives of 1–4 and three protected tetrapeptides, namely α - N - t - BOC - L - seryl - DL - β - (thymin - 1 - yl)alanyl - L - ethyl ester (t - BOC - Ser - Tala - Ser - Tala - OEt), t - BOC - Ser - Aala - Ser - Aala - OEt and t - BOC - Ser - Uala - Ser - Uala - OEt were obtained. For the protection of the α-amino group of 2 or 3 the formyl group was found to be satisfactory.     

Addition reactions of nucleophiles to dibenzoylacetylene

Several enamine diones have been prepared through the nucleophilic addition of different amines to dibenzoylacetylene (DBA). Thus, the reaction of aniline, piperidine, o-aminophenol and N-phenylbenzylamine with DBA gave the corresponding 1:1 adducts namely, 1,4 - diphenyl - 2 - (N - phenylamino)but - 2 - ene -1,4 - dione (1), 1,4 - diphenyl - 2 - piperidinobut - 2 - ene - 1,4 - dione (2), 2 - (N - 2 - hydroxyphenylamino)1,4 - diphenylbut - 2 -ene - 1,4 - dione (3) and 1,4 - diphenyl - 2 - (N - phenylbenzylamino)but - 2 - ene - 1,4 - dione (4). UV absorption data reveal that the adducts 1 and 3, formed from aniline and o-aminophenol, respectively, are the E-isomers, arising through a trans-mode of addition whereas the adducts 2 and 4, formed from piperidine and N-phenyl-benzylamine are the Z-isomers, formed through a cis-mode of addition.The reaction of N-phenaeylaniline with DBA gave 2,3 - dibenzoyl - 1,4 - diphenylpyrrole (5), whereas the reaction of 1,8 - diaminonaphthalene with DBA gave a mixture of products consisting of 2 - benzoyl - 2 - phenacyl -2,3 - dihydroperimidine (11) and 2 - benzoylperimidine (12). The reaction of 2-aminopyridine with DBA gave a mixture of two 1:1-adducts, 2 - (2 - imino - 1(2H) - pyridyl) - 1,4 - diphenylbut - 2 - ene - 1,4 - dione (14) and 1,4 -diphenyl - 2 - (N - 2 - pyridylamino)but - 2 - ene - 1,4 - dione (15).     

Synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from salmonella strasbourg

The pentasaccharide α - Tyv - (1→3) - β - d - Man - (1→4) - α - l - Rha - (1→3) - d - Gal - (4←1) -α - d - Glc 1, the repeating unit of the O-specific polysaccharide chain of the lipopolysaccharide from S. Strasbourg, was obtained by glycosylation of benzyl - 2,6 - di - O - benzyl - 4 - O - (2,3,4 - tri - O - benzyl - 6 - O - benzoyl - α - d - glucopyranosyl) - β - d - galactopyranoside with 1,2 - methylorthoacetyl - 3 - O - acetyl - 4- O - [3 - O - (2,4 - di - O - acetyl - 3, 6 - dideoxy,- α - d - arabino - hexopyranosyl) - 2,4,6 - tri - O - acetyl - β - d - mannopyranosyl] - β - l - rhamnopyranose 3 followed by removal of protecting groups. The structure of the synthetic pentasaccharide was proved by methylation analysis and ¹³C NMR.     

Deoxycholic acid degradation by a pseudomonas sp: Phenolic and neutral products

The microbial degradation of deoxycholic acid by Pseudomonas sp. MR108 was studied, and four products were isolated. Evidence is presented that one is the phenol 3,12β - dihydroxy - 9,10 - secoandrosta -1,3,5(10) - trien - 9,17 - dione (11) and that the other three are the neutral compounds 3aαH - 4α - [3' - propionic acid] - 5α - hydroxy - 7aβ - methyl - hexahydro -1 - indanone - δ - lactone (12), 12β - hydroxyandrosta -1,4 - dien -3,17 - dione (10), and 12α - hydroxyandrosta - 1,4 - dien - 3,17 - dione (7).     

Diisophorone and related compounds—IV: 2,7-Epoxydiisophoranes: synthesis and reactions of 3,4-diketo-2,7-epoxydiisophoran-1-OL

Selenium dioxide oxidises 2,7 - epoxydiisophoran - 1 - ol - 3 - one to the corresponding yellow 3,4-diketone. This is reduced to diisophor - 2(7) - en - 1 - ol - 3 - one (“diisophorone”) by Zn in acetic acid or on catalytic hydrogenation, or to 2,7 - epoxydiisophorane - 1,3,4 - triol by LAH or NaBH₄. Alkaline H₂O₂ cleaves ring A of the 3,4-diketone, providing a degradation of the diisophorane- to the bicyclo[3.3.1]nonane-system. The resulting 3 - (2' - carboxy - 2',2' - dimethyl)ethyl -2, 3 - epoxy -1 - hydroxy - 5,7,7 - trimethylbicyclo(3.3.1]nonane - 2- carboxylic acid is convertible into its dimethyl ester by the action of diazomethane.     

1,2,4-triazines and condensed derivatives—XIV : Thermal and acid catalysed degradations of 3-alkylthio-6,7-dihydro-[1.2.4]Triazino[1.6-c]quinazolin-5-ium-1-olates

3 - Alkylthio - 6,7 - dihydro - [1.2.4]triazino - [1.6-c]quinazolin - 5 - ium - 1 - olates (3), prepared by condensation of 3 - alkylthio -6-(2- aminophenyl) - 1,2,4 - triazin - 5(2H) - ones (1) with aldehydes, ketones or their equivalents are transformed by thermolysis and/or acid treatment into 3 - alkylthio - [1.2.4]triazino[5.6-b]indoles (4) and/or 4-(5- alkylthio - s - triazol -3-yl)- quinolines (5). Alkylation and acylation reactions of the compounds 5 are discussed, as well as their NMR and UV spectra and those of their alkylation and acylation products.     

Reactions of the 1-halo-7-(2-hydroxyethoxy)cycloheptenes and the 3-halo-4-(2-hydroxyethoxy)bicyclo[3.2.1]oct-2-enes with potassium t-butoxide

Reactions of 1 - bromo - 7 - (2 - hydroxyethoxy)cycloheptene 2 and its chloro analogue 3 with potassium t-butoxide in dimethyl sulphoxide or tetrahydrofuran gave cycloheptatriene and cis - 8,11 - dioxabicyclo[5.4.0]undec - 2 - ene 18 as the major products together with small amounts of the trans-isomer 17,8,11-dioxabicyclo[5.4.0]undec - 1(7) - ene 14, 8,11 - dioxabicyclo[5.4.0] - undec - 1 - ene 19, cyclohept - 2 - enone ethylene ketal 15, cyclohept - 3 - enone ethylene ketal 16, and 1- and 2 - t - butoxycyclohepta - 1,3 - diene 20. Similar reactions of 3 - bromo - and 3 - chloro - 4 - (2 - hydroxyethoxy)bicyclo[3.2.1]oct - 2 - ene 4 and 5 gave 4,7 - dioxatricyclo[7.2.1.0^3,8]dodeca - 2 - ene 26 as the major product together with small amounts of 3,6 - dioxatricyclo[7.2.1.0^2,7]dodeca - 2(7) - ene 27 and bicyclo[3.2.1]oct - 3 - ene - 2 - one ethylene ketal 28. Mechanisms for these transformations are discussed.     

Novel preparation of N′-arylthiocarbamoyl-N,N-dialkylamidines and their synthetic utilities

Treatment of 5-(arylimino)-4-(dialkylamino)-5H-1,2,3-dithiazoles (2) with NaOH in aqueous EtOH at room temperature gave N′-arylthiocarbamoyl-N,N-dialkylamidines (3) in good to excellent yields. The reaction of 3 with sulfur monochloride, thiophosgene, thionyl chloride, sulfuryl chloride, N-phenylimidoyl dichloride, and phthaloyl chloride in CH₂Cl₂ gave 2, 5-(arylimino)-4-(dialkylamino)-Δ³-thiazoline-2-thiones (5), 5-(arylimino)-4-(dialkylamino)-5H-2-oxo-1,2,3-dithiazoles (6), 5-(arylimino)-4-(dialkylamino)-5H-2,2-dioxo-1,2,3-dithiazoles (7), 5-(arylimino)-4-(dialkylamino)-2-(phenylimino)-Δ³-thiazolines (8), and 3-(arylimino)-4-(dialkylamino)-2,5-benzothiazocine-1,6-diones (10) as major products, respectively.     

Synthesis of Tri-And Tetrasaccharides Present in the Linkage Region of Heparin and Heparan Sulphate

Abstract

The methyl glycosides of the the tri-and tetrasaccharides present in the linkage region of heparin, methyl O-(β-D-galactopyranosyl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside and methyl O-(β-D-glucopyranosyluronic acid)-(l→3)-O-(β-D-galactopyranosyl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside sodium salt, were synthesized together with their phosphate containing analogues, methyl O-(β-D-galactopyranosyl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside 2-(disodium phosphate) and methyl O-(β-D-glucopyranosyluronic acid)-(l→3)-O-(β-D-galactopyrano-syl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside 2-(disodium phosphate) sodium salt, which are glycosides of the structure found in the linkage region of heparan sulphate.     

Stereospecific synthesis of new 2,3,4,5-piperidinetetracarboxylic acids and 2,3,5-piperidinetricarboxylic acids

Diels-Alder adducts of 1,2-dihydropyridine with maleic and acrylic acid derivatives were stereospecifically converted by way of RuO₄ oxidation into new r-2,c-3,c-4,c-5-piperidinetetracarboxylic acid, r-2,t-3,t-4,c-5-piperidinetetracarboxylic acid, r-2,c-3,c-5-piperidinetricarboxylic acid, and r-2,t-3,c-5-piperidinetricarboxylic acid.     

Iron(II) complexes of pyrazol-4,5-dione-5-oximes

The complexes Fe(po)₂·H₂O, Fe(Ppo)₂·H₂O and Fe(PPo)₂·2py, where poH = 3 - methyl - 4 - oxime - 1H - pyrazole - 4,5 - dione and PpoH = 3 - methyl - 4 - oxime - 1 - phenyl - 1$\text{H}$ - pyrazole - 4,5 - dione, have been prepared. The magnetic susceptibilities and Mössbauer spectra of the complexes have been investigated.