4H-Chromenone Glycosides from Eranthis hyemalis (L.) SALISBURY

Investigation of the tubers of Eranthis hyemalis (Ranunculaceae) afforded six chromenone glycosides. Their structures have been elucidated mainly by spectroscopic (FAB-MS, 2D-NMR techniques) and chemical methods (acidic and enzymatic hydrolysis) as 9-{[(β-D -glucopyranosyl)oxy]methyl}-8,11-dihydro-5-hydroxy-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one ( 1 ), 9-{[(β-D -gentiobiosyl)oxy]methyl}-8,11-dihydro-5-hydroxy-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one( 2 ), 9-{[(β-D -glucopyranosvl)oxy]melhyl}-8,11-dihydro-5-hydroxy-2-(hydroxy-methyl)-4H-pyrano[2,3-g][1]benzoxepin-4-one( 3 ), 8-{(2E)-4-[(β-D -glucopyranosyl)oxy]-3-methylbut-2-enyl}-5,7-dihydroxy-2-methyl-4H-1-benzopyran-4-one ( 4 ), 8-{(2E)-4-[(β-D -glucopyranosyi)oxy]-3-methylbut-2-enyl}-5,7-dihydroxy-2-(hydroxymethyl)-4H-1-benzopyran-4-one ( 5 ), and 7-{[(β-D -glucopyranosy1)oxy]methyl}-2,3-dihydro-2-(l-hydroxy-1-methylethyl)-4-methoxy-5H-furo[3,2-g][1]benzopyran-5-one ( 6 ). Compound 2 exhibited negative inotropic activity.     

Synthesis of 1-[3-methyl-2(3H)-benzazolon-5- or 6-yl]-4-{4-[cis-2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl-methyl)-1,3-dioxolan-4-yl]methyleneoxyphenyl}piperazines

Reactions of 3-methyl-6-[4-(4-hydroxyphenyl)-1-piperazinyl]-2(3H)-benzoxazolone, 3-methyl-6-[4-(4-hydroxy-phenyl)-1-piperazinyl]-2(3H)-benzothiazolone and 1,3-dimethyl-5-[4-(4-hydroxyphenyl)-1-piperazinyl]-2(3H)-benzimidazolone with cis-{[2-(2,4-dichlorophenyl) -2-(1H-imidazol-1-ylmethyl)]-1,3-dioxolan-4-yl}methyl meth-anesulfonate in the presence of sodium hydride furnish the title compounds.     

Synthesis of novel 6-(substituted amino)-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinones via azo coupling

Abstract  

6-(Substituted amino)-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinones were prepared from β-aryl glutaconic acid, which, on fusion with aniline, results in 4-(4-ethoxyphenyl)-1-phenylpyridine-2,6(1H,5H)-dione. This, on further treatment with phosphorus oxychloride gave 6-chloro-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinone, and further treatment with secondary amines yielded 6-(substituted amino)-4-(4-ethoxyphenyl)-1-phenyl-2(1H)-pyridinones. These were subjected to azo coupling with different aryldiazonium chlorides furnishing two isomers, which were separated by column chromatography. All compounds were characterized by elemental analysis, and use of IR and NMR spectral data, and were evaluated for antimicrobial activity.     

Preparation and Structure of (E)-1-(3′-Hydroxy-2-Furanyl)-3-(3″-Hydroxy-4″-Methoxyphenyl)-2-Propen-1-One

Abstract

A facile procedure is presented for the synthesis of (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2- propen-1-one (6). Galactosylisomaltol (1) was condensed with isovanillin (2) under strong alkaline conditions at 25 [ddot]C to form (E)-1-(3′-O-β-D-galactopyranosyloxy-2′-furanyl)-3-(3″- hydroxy-4″-methoxyphenyl)-2-propen-1-one (4). (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2-propen-1-one (6) was obtained by acid hydrolysis of 4 in a 53.9% yield. This hetero-cyclic 2-propen-1-one was characterized on the basis of spectral data (IR and ¹H NMR), physicochemical properties, and conversion to a mono-O-acetyl derivative.     

Synthesis and microbial screening of 8-(benzyloxy)-5-(2-[1,3-diphenyl-1H-pyrazol-4-yl]thiazol-4-yl)quinolin-2(1H)-one derivatives

The present investigation describe the synthesis of 8-(benzyloxy)-5-(2-[1,3-diphenyl-1H-pyrazol-4-yl]thiazol-4-yl)quinolin-2(1H)-one derivatives. Quinolin-8-ol was transformed by five step synthetic procedures into 8-Benzyloxy-5-(2-bromo-acetyl)-1H-quinolin-2-one. Subsequently, 8-Benzyloxy-5-(2-bromo-acetyl)-1H-quinolin-2-one condensed with 1,3-Diphenyl-1H-pyrazole-4-carbothioic acid amide in the presence of acetonitrile to afford 8-(benzyloxy)-5-(2-[1,3-diphenyl-1H-pyrazol-4-yl]thiazol-4-yl)quinolin-2(1H)-one derivatives. Synthesized compounds were screened for their antimicrobial activity against gram-positive and gram-negative bacteria. Most of the synthesized compounds are found to be active against tested bacterial strains and fungal strain.     

Synthesis of 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide

The reaction of methyl 2-bromo-6-(trifluoromethyl)-3-pyridinecarboxylate ( 1 ) with methanesulfonamide gave methyl 2-[(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridine-carboxylate ( 2 ). Alkylation of compound 2 with methyl iodide followed by cyclization of the resulting methyl 2-[methyl(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridinecarboxylate ( 3 ) yielded 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 4 ). The reaction of compound 4 with α,2,4-trichlorotoluene, methyl bromopropionate, methyl iodide, 3-trifluoromethylphenyl isocyanate, phenyl isocyanate and 2,4-dichloro-5-(2-propynyloxy)phenyl isothiocyanate gave, respectively, 4-[(2,4-dichlorophenyl)methoxy]-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazine 2,2-dioxide ( 5 ), methyl 2-[[1-methyl-2,2-dioxido-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4-yl]oxy]propanoate ( 6 ), 1,3,3-trimethyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 7 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-[3-(trifluoromethyl)phenyl]-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 8 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-phenyl-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 9 ) and N-[2,4-dichloro-5-(2-propynyloxy)phenyl]-4-hydroxy-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2] thiazine-3-carboxamide 2,2-dioxide ( 10 ).     

Reduction of 4-arylidene-1,3-(2H,4H)isoquinolinediones

Catalytic hydrogenation of some 4-arylidene-1,3-(2H,4H)isoquinolinediones (1) afforded the corresponding 4-arylmethyl-1,3-(2H,4H)isoquinolinediones (2) , but reduction of 1 by sodium borohydride gave 4-arylmethyl-1(2H)isoquinolones (isocarbostyrils, 3). Compounds of type 1 studied had aryl substituents phenyl, 3,4-dimethoxyphenyl, 3,4-methyleneoxyphenyl and 2-furyl. In one example of sodium borohydride reduction of an N-methylisoquinolinedione derivative (1) the heterocylic ring was opened, and 2-(1-hydroxymethyl-2-phenylethenyl)-N-methylbenzamide (4) was obtained from 4-benzylidene-2-methyl-1,3-(2H,4H)isoquinolinedione.     

Chiral exo-Alkylidenecyclopentanes from (1S,4R)-7,7-Dimethyl-1-vinylbicyclo[2.2.1]heptan-2-one

(1S,4R)-7,7-Dimethyl-1-vinylbicyclo[2.2.1]heptan-2-one oxime in the system (CF₃CO)₂O-CF₃COOH and (1S,4R)-1-(1,2-dibromoethyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-one in the system MeONa-MeOH undergo fragmentation to give exo-alkylidenecyclopentane derivatives, (4R)-4-cyanomethyl-5,5-dimethyl-1-[(1E)-trifluoroacetoxyethylidene]cyclopentane and isomeric (4R)-4-carboxymethyl-1-[(1ZE)-2-methoxyethylidene]-5,5-dimethylcyclopentanes, respectively. The trifluoroacetate derivative undergoes unusual rearrangement, yielding an equilibrium mixture of two isomers with endo- and exocyclic double bond.     

Synthesis of four new vic-dioximes and their nickel(II), cobalt(II), copper(II) and cadmium(II) complexes

Four unsymmetrical vic-dioximes: [L¹H₂] N-(4-butylphenyl)amino-amphi-glyoxime, [L²H₂] N-(4-butylphenyl)amino-anti-glyoxime, [L³H₂] N-(4-phenylazophenyl)amino-amphi-glyoxime and [L⁴H₂] N-(4-phenylazophenyl)amino-anti-glyoxime have been prepared from amphi-chloroglyoxime, anti-chloroglyoxime, 4-butylaniline and 4-(phenylazo)aniline respectively. The complexes of these vic-dioximes with Ni^II, Co^II, Cu^II and Cd^II ions have been investigated. All are insoluble in common solvents. Their i.r. spectra and elemental analyses are given, together with mass and ¹H-n.m.r. spectra of the ligands.     

Some reactions of 2-(4-substitutedphenyl)-2-(N-methyl-N-4-substitutedbenzamido) acetic acids

In situ generated 2,4-diaryl substituted münchnones from 2-(4-substitutedphenyl)-2-(N-methyl-N-4-substitutedbenzamido)acetic acids react with acetic anhydride in the presence of 2-nitromethylene thiazolidine, which is most likely acting as a base, and unexpectedly undergo a Dakin–West type reaction and a concurrent autoxidation reaction leading to the formation of (E)-1-(N,4-dimethylbenzamido)-1-(4-fluorophenyl)prop-1-en-2-yl acetate, 4-substitutedphenyl-N-methyl-N-(4-substitutedbenzoyl) benzamides and p-substituted benzoic acids. In addition, a novel and efficient access to N-acyl urea derivatives is described by the reaction between 2-(4-substitutedphenyl)-2-(N-methyl-N-4-substitutedbenzamido)acetic acids and cyclohexyl, isopropyl carbodiimides in the presence of a base. The structures of all new products were identified on the basis of NMR and IR spectra, along with X-ray diffraction data and HRMS measurements.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Thermische (E), (Z)-Isomerisierungen bei substituierten Propenylbenzolen

Thermal (E), (Z)-Isomerizations of Substituted Propenylbenzenes The thermal isomerizations of (E)- and (Z)-3,5-dimethyl-2-(1′-propenyl)phenol ((E)- and (Z)- 3 ), (E)- and (Z)-N-methyl-2-(1′-propenyl)anilin ((E)- and (Z)- 4 ), (E)- and (Z)-3,5-dimethyl-2-(1′-propenyl)anilin ((E)- and (Z)- 5 , (E)- and (Z)-2-(1′-propenyl)mesitylene ((E)- and (Z- 6 ), (E)- and (Z)-2-(1′-propenyl)mesitylene ((E)- and (Z)- 7 ), (E)- and (Z)-2-(1′-propenyl)toluene ((E)- and (Z)- 8 ), (E)- and (Z)-4-(1′-propenyl)toulene ((E)- and (Z)- 9 ) as well as of (E)- and (Z)-2-(2′-butenyl)-mesitylene ((E)- and (Z)- 10 ) in decane solution were studied (Scheme 2). Whereas the isomerization of the 2-propenylphenols (E)- and (Z)- 3 occurs already between 130 and 150° (cf. Table 1), the isomerization of the 2-propenylanilins 4 and 5 takes place only at temperatures between 220 and 250° (cf. Tables 2 and 3). The activation values and the experiments using N-deuterated 4 (cf. Scheme 4) show that 2-propenylphenols and -anilins isomerize via sigmatropic [1,5]-hydrogen-shifts. For the isomerization of the methyl-substituted propenylbenzenes temperatures > 360° are required (cf. Tables 4 and 5). The activation values of the isomerization of (E)- and (Z)- 6 and (E)- and (Z)- 9 are in accord with those of other (E), (Z)-isomerizations which occur via vibrationally excited singlet biradicals (cf. Table 7). Nevertheless, thermal isomerization of 2′-d-(Z)- 8 (cf. Scheme 6) demonstrates that during the reaction deuterium is partially transfered into the ortho-methyl group, i.e. 1,5-hydrogen-shifts must have participated in isomerization of (E)- and (Z)- 8 (cf. Scheme 8). Under the equilibrium conditions 2,4,6-trimethylindan ( 17 ) is formed slowly at 368° from (E)- and (Z)- 6 , very probably via a radical 1,4-hydrogen-shift (cf. Scheme 9). In a similar way 2-ethyl-4,6-dimethylindan ( 19 ; cf. Table 6) arises from (E)- and (Z)- 7 . Thermolysis of (E)- and (Z)- 10 in decane solution at 367° results in almost no (E),(Z)-isomerization. At prolonged heating 19 and 2,5,7-trimethyl-1,2,3,4-tetrahydronaphthalene ( 20 ) are formed; these two products arise very likely from an intermolecular radical process (cf. Scheme 10).     

The Isotopomeric (Z)- and (E)-2,3-Dimethyl(1,1,1,4,4,4-2H6)but-2-enes: Mechanistic Probes for Stereospecific Epoxidation

By unambiguous methods, (Z)- and (E)-2, 3-dimethyl(1, 1, 1, 4, 4, 4-²H₆)but-2-enes ( 3 ) were synthesized and transformed to the epoxides 4 with 3-chloroperbenzoic acids. Both the isotopomeric olefins and the epoxides are detected separately by ¹H-NMR at 400 MHz. Epoxidation of (Z)- 3 with [Rh^ICl(PPh₃)₃]/cumene hydroperoxide resulted in a 1: 1 mixture of (Z)- and (E)- 4 , while reaction of (Z)- 3 with [Fe^III(tpp)]Cl/PhIO gave only (Z)- 4 (tpp = tetraphenylporphyrin).     

Einfache Umwandlung von(–)-(R)-3-Hydroxybuttersäure in das (+)-(S)-Enantiomere und dessen Lacton(‒)-(S)-4-Methyloxetan-2-on

Simple Conversion of (R)-3-Hydroxybutanoic Acid to the (S)-Enantiomer and its Lactone (–)-(S)-4-Methylixetan-2-one Condensation of ( R )-3-hydroxybutanoic acid (1) with ethyl orthoacetate gives a 2-ethoxy-substituted (1,3)dioxanone 2 which is thermally labile: at ca. 100°, two competing processes commence, one leading to ethyl ( R )-3-acetoxybutanoate ( 3 ), the other one - with complete inversion of configuration - to the ( S )-4-methylixetan-2-one ( 4 ) and ethyl acetate. These can be readily separated by fractional distillation. Thus, enantiomerically pure ( S )-3-hydroxybutanoic acid (ent- 1 ) and l-2-alkyl-3-hydroxybutanoic-acid derivatives (such as 6 and 8 ) become available from the biopolymer PHB, the precursor to the acid 1 .     

Instructions to Authors (1994)

(1S,2R,6R,7R)-4-Phenyl-3,10-dioxa-5-azatricyclo[5.2.1.0^2,6]dec-4-en-9-one ((+)- 5 ) obtained in 6 steps from the Diels-Alder adduct of furan to 1-cyanovinyl (1S)-camphanate ((+)- 3 ) was reduced to the corresponding endo-alcohol (?)- 6 the treatment of which with HBr/AcOH provided (?)-(3aS,4S,6R,7S,7aR)-4β-bromo-3aβ,4,5,6,7,7aβ-hexahydro-2-phenyl-1,3-benzoxazole-6β,7α-diyl diacetate ((?)- 17 ). Elimination of HBr with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and acidic hydrolysis furnished (?)-(1R,2S,3R,4R)-4-aminocyclohex-5-ene-1,2,3-triol ( ? (?)-conduramine C₁;(?)- 1 ).     

Ring-Transformation von Imidazolidin–2,4-dionen ( = Hydantoinen) zu 4H-Imidazolen bei der Umsetzung mit 3-(Dimethylamino)-2,2-dimethyl-2H -azirin

Ring Transformation of Imidazolidine-2,4-diones ( = Hydantoins) to 4H-Imidazoles in the Reaction with 3-(Dimethylamino)-2,2-dimethyl-2H-azirines At ca. 70°, 3-(dimethylamino)-2,2-dimethyl-2H -azirine ( 1 ) and 5,5-disubstituted hydantoins 4 in MeCN or i-PrOH give 2-(1-aminoalkyl)-5-(dimethylamino)-4,4-dimethyl-4H -imidazoles 5 in good yield (Scheme 2). These products are decarboxylated 1:1 adducts of 1 and 4 . A reaction mechanism is suggested in analogy to the previously reported reactions of 1 and NH-acidic heterocycles containing the CO? NH? CO? NH moiety (Scheme 5). The formation of ureas 6 and 7 can be rationalized by trapping the intermediate isocyanate F by an amine. No reaction is observed between 1 and 1,5,5- or 3,5,5-trisubstituted hydantoins in refluxing MeCN or i-PrOH, but an N-isopropylation of 1,5,5-trimethylhydantoin ( 8b ) occurs in the presence of morpholine (Scheme 3). The reaction of the bis(azirine)dibromozink complex 11 and hydantoines 4 in refluxing MeCN yields zink complexes 12 of the corresponding 2-(1-aminoalkyl)-4H -imidazoles 5 (Scheme 4).     

Synthesis of the (2<Emphasis Type="Italic">S</Emphasis>,4<Emphasis Type="Italic">S</Emphasis>)-stereoisomers of 4-(indol-1-yl) and 4-arylamino derivatives of 5-oxoproline,proline, and 2-hydroxymethylpyrrolidine

Nucleophilic substitution of the halogen atom in dimethyl (S)-4-bromoglutamate followed by removal of the protecting groups and closure of a lactam ring afforded (2S,4S)-4-(indolin-1-yl)-5-oxoproline. The indoline fragment was oxidized into the indole fragment to give (2S,4S)-4-(indol-1-yl)-5-oxoproline; reduction of the carbonyl groups with BH3 yielded (2S,4S)-4-(indol-1-yl)prolines and (2S,4S)-2-hydroxymethyl-4-(indol-1-yl)pyrrolidines. Reduction of (2S,4S)-4-arylamino-5-oxoprolines with BH3 to the corresponding (2S,4S)-4-arylaminoprolines and (2S,4S)-4-arylamino-2-hydroxymethylpyrrolidines was studied.     

Straightforward Preparation of (2E,4Z)-2,4-Heptadien-1-ol and (2E,4Z)-2,4-Heptadienal

Abstract

A concise synthesis of (2E,4Z)-2,4-heptadien-1-ol and (2E,4Z)-2,4-heptadienal is presented. Commercially available (Z)-2-penten-1-ol was converted to ethyl-(2E,4Z)-2,4-heptadienoate by reaction with activated MnO₂ and (carboethoxymethylene)triphenylphosphorane in the presence of benzoic acid as a catalyst. Ethyl-(2E,4Z)-2,4-heptadienoate was converted to (2E,4Z)-2,4-heptadien-1-ol with LiAlH₄. The alcohol was partially oxidized to (2E,4Z)-2,4-heptadienal with MnO₂. The title compounds are male-specific, antennally active volatile compounds from the Saltcedar leaf beetle, Diorhabda elongata Brulle (Coleoptera: Chrysomelidae) and have potential use in the biological control of the invasive weed saltcedar (Tamarix spp).     

Tetramethylcyclotetraarsoxane Bridged Copper(I) Halides with Porous Sheet and Framework Structures [CuX{cyclo-(MeAsO)4}] (X=Cl,Br, I) and [Cu3X3{cyclo-(MeAsO)4}2] (X=Cl,Br)

Open sheet and framework structures [CuX{cyclo-(MeAsO)₄}] (X=Cl, Br, I) 1 – 3 and [Cu₃X₃{cyclo-(MeAsO)₄}₂] (X=Cl, Br) 4 and 5 may be prepared by self-assembly from CuX and methylcycloarsoxane (MeAsO)_n in acetonitrile solution. 1 – 3 exhibit 4⁴ nets in which (CuX)₂ units are connected through μ-1 _KAs¹ : 2 _KAs³ coordinated (MeAsO)₄ ligands into large 28-membered rings. In contrast, adjacent [CuX] chains in 4 and 5 are connected into sheets by μ₄-K⁴ As coordinated (MeAsO)₄ building blocks, with μ-1 _KAs¹ : 2 _KAs³ bridging of these layers by independent (MeAsO)₄ cyclotetramers leading to the generation of a porous framework structure. 1 – 5 were characterised by X-ray structural analysis.     

Nucleoside und Nucleotide. Teil 15. Synthese von Desoxyribonucleosid-monophosphaten und -triphosphaten mit 2(1H)-Pyrimidinon, 2(1H)-Pyridinon und 4-Amino-2(1H)-pyridinon als Basen

Nucleosides and Nucleotide. Part 15. Synthesis of Deoxyribonucleoside Monophosphates and Triphosphates with 2(1H)-Pyrimidinone, 2(1H)-Pyridinone and 4-Amino-2(1H)-pyridinone as the Bases The phosphorylation of the modified nucleosides 1-(2′-deoxy-β-D -ribofuranosyl)-2(1 H)-pyrimidinone (M_d, 4 ), 4-amino-1-(2′-deoxy-β-D -ribofuranosyl)-2(1 H)-pyridinone (Z_d, 6 ) and the synthesis of 1–2′-deoxy-β-D -ribofuranosyl-2(1 H)-pyrimidinone-5′-O-triphosphate (pppM_d, 1 ), 1-(2′-deoxy-β-D ribofuranosyl)-2(1 H)-pyridinone-5′-O-triphosphate (pppII_d, 2 ), and 4-amino-1-(2′-deoxy-βD -ribofuranosyl)-2(1 H)-pyridinone-5′-O-triphosphate (pppZ_d, 3 ) are described. The nucleoside-5′-monophosphates pM_d (5) and pZ_d (7) were obtained by selective phosphorylation of M_d (4) and Z_d (6) , respectively, using phosphorylchloride in triethyl phosphate or in acetonitril. The reaction of pM_d (5) pII _d (8) or pZ_d (7) with morpholine in the presence of DCC led to the phosphoric amides 9, 10 and 11 , respectively, which were converted with tributylammonium pyrophosphate in dried dimethylsulfoxide to the nucleoside-5′triphosphates 1, 2 and 3 , respectively.