Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XV. Phosphorylation of Allyl Halides with Elemental Phosphorus

Elemental phosphorus (red or white) reacts with allyl chloride and allyl bromide in a two-phase system aqueous KOH-organic solvent to form tertiary symmetrical and mixed phosphine oxides among which tris(prop-2-enyl)-, bis(prop-2-enyl)[(E)-prop-1-enyl]-, bis(prop-2-enyl)[(Z)-prop-1-enyl]-, (prop-2-enyl)[(E)-prop-1-enyl][(Z)-prop-1-enyl]-, bis[(E)-prop-1-enyl](prop-2-enyl)-, bis[(Z)-prop-1-enyl](prop-2-enyl)-, tris-[(E)-prop-1-enyl]-, and bis[(E)-prop-1-enyl][(Z)-prop-1-enyl]phosphine oxides were identified. The conditions (room temperature, 60% aqueous KOH-dioxane) allowing preparation from white phosphorus and allyl bromide of tris(prop-2-enyl)- and bis(prop-2-enyl)[(E)-prop-1-enyl]phosphine oxides as major products in the total yield of up to 96% were found.     

Synthesis of new functionally substituted hetarylcarbamates from methyl {4-[(2<Emphasis Type="Italic">E</Emphasis>)-3-(4-methoxyphenyl)-prop-2-enoyl]phenyl}carbamate

Three-component condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}- carbamate with ninhydrin and L-proline in methanol–water (10: 1) afforded methyl {4-[1,3-dioxo-1′- (4-methoxyphenyl)-1,1′,2′,3,5′,6′,7′,7a′-octahydrospiro[indene-2,3′-pyrrolizin]-2′-ylcarbonyl]phenyl}carbamate. Heating of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}carbamate with isatin and benzylamine in methanol gave methyl {4-[4′-(4-methoxyphenyl)-2-oxo-5′-phenyl-1,2-dihydrospiro[indole-3,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate. The condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2- enoyl]phenyl}carbamate with sarcosine and 11H-indeno[1,2-b]quinoxalin-11-one generated in situ from ninhydrin and o-phenylenediamine in boiling ethanol led to the formation of methyl {4-[4′-(4-methoxyphenyl)-1′-methyl-11,11a-dihydro-5aH-spiro[benzo[b]phenazine-6,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate.     

An unusual reaction of propargylamines with CH2I2 and Et3Al

N-{2-[(1-R-Cyclopropyl)methyl]prop-2-enyl}-N,N-dimethylamines were prepared in 80-90% yields by the reaction (5 h, 23-25 C) of propargylamines R-C=C-CH₂NMe₂ (where R = alkyl, Ph) with a system of reactants CH2I2-Et₃Al taken in the molar ratio [propargylamine]: [Et₃Al]: [CH₂I₂] = 1: 6: 6. In the case of phenyl-substituted propargyl- amine, N-({1-[(1-phenylcyclopropyl)methyl]cyclopropyl}methyl)-N,N-dimethylamine is selectively formed in 76% yield upon the elongation of the reaction time to 4 days.     

Cyclization of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(prop-2-yn-1-yl)methanesulfonamides to <Emphasis Type="Italic">N</Emphasis>-(hydroxymethyl)-1,2,3-triazoles

Three-component heterocyclizations of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide, trifluoro-N-pheny-N-(prop-2-yn-1-yl)methanesulfonamide, and trifluoro-N,N-di(prop-2-yn-1-yl)methanesulfonamide with formaldehyde and sodium azide afforded N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-, N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-N-phenyl-, and N,N-bis{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}trifluoromethanesulfonamides as the major products together with minor 1-(hydroxymethyl)-1H-1,2,3-triazole isomers.     

Allgemeiner Zugang zu Polyaminen mit Ethan-1,2-diamin-Einheiten: Synthese von nicht natürlich vorkommenden homologen und isomeren N1,4-Di(4-cumaroyl)sperminen

█tl="American"█The synthesis of the three N,N′-di(4-coumaroyl)tetramines, i.e., of (E,E)-N-{3-[(2-aminoethyl)amino]propyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1a ), (E,E)-N-{4-[(2-aminoethyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1b ), and (E,E)-N-{6-[(2-aminoethyl)amino]hexyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1c ), is described. It proceeds through stepwise construction of the symmetric polyamine backbone including protection and deprotection steps of the amino functions. Their behavior on TLC in comparison with that of 1,4-di(4-coumaroyl)spermine (=(E,E)-N-{4-[(3-aminopropyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(propane-1,3-diyl)bis[prop-2-enamide]; 2 ) is discussed.     

Preparation of glyceronucleoside phosphoramidite synthons and their use in the solid phase synthesis of acyclic oligonucleotides

The syntheses of N,N-diisopropylmethylphosphoramidites (3a,b) of 9-&{[2-dimethoxytrityl-hydroxy-1-(hydroxymethyl)ethoxy]-methyl}N₆-benzoyladenine, 2a, and 1-{[2-dimethoxytrityl-hydroxy-1-(hydroxymethyl)ethoxy]-methyl}thymine,2b, are described. Oligoacyclonucleotides, 2 - 8 units long, were synthesized using these synthons on either controlled pore glass or silica gel supports with average coupling yields up to 98%. The preparation of 1-{[2-dimethoxytrityl-hydroxy-1-(pentachlorophenylsuccinyl-hydroxymethyl)ethoxy]-methyl}thymine, 5, for the derivatization of long chain alkylamine controlled pore glass is also described.     

Methyl and Phenylmethyl 2-Acetyl-3-{[2-(dimethylamino)-1-(methoxycarbonyl)ethenyl]amino}prop-2-enoate in the Synthesis of heterocyclic systems: Preparation of 3-amino-4H-pyrido-[1,2-a]pyrimidin-4-ones

Methyl 2-acetyl-3-{[2-(dimethylamino)-1-(methoxycarbonyl)ethenyl]amino}prop-2-enoate ( 4 ) and phenyl-methyl 2-acetyl-3-{[2-(dimethylamino)-1(methoxycarbonyl)ethenyl]amino}prop-2-enoate ( 5 ) were prepared in three steps from the corresponding acetoacetic esters, and used as reagents for the preparation of N³-protected 3-amino-4H-pyrido[1,2-a]pyrimidin-4-ones 10 – 12 , 5H-thiazolo[3,2-a]pyrimidin-5-one 13 , 4H-pyrido[1,2-a]-pyridin-4-one 19 and 2H-1-benzopyran-2-ones 20 – 23 . Free 3-amino-4H-pyrido[1,2-a]pyrimidin-4-ones 24 – 26 were prepared from 10 – 12 by removal of the 2-(methoxycarbonyl)-3-oxobut-1-enyl or 3-oxo-2-[(phenyl-methoxy)carbonyl]but-1-envl as N-protecting group by various methods.     

The preparation and reactions of 1,3,4,5,6,7,8-heptafluoro-2-naphthyl prop-2-enyl ether: Formation of 1,3,4,5,6,7,8-heptafluoro-1-(prop-2-enyl)naphthalen-2-one and the photolysis and pyrolysis of this ketone [1].

1,3,4,5,6,7,8-Heptafluoro-2-naphthyl prop-2-enyl ether (8) was isomerised in boiling xylene to 1,3,4,5,6,7,8-heptafluoro- 1-(prop-2-enyl)naphthalen-2-one (9). Photolysis of (9) gave 2,5,7-trifluoro-3,4-(tetrafluorobenzo)tricyclo[3.3.1.O^2,7]non-3- en-6-one (11) (by a [2 + 2] addition) and 1,2,7-trifluoro-3,4- (tetrafluorobenzo) tricyclo [3.3.1.O^2,7]non-3-en-8-one (12) (via an initial [3,5] photochemically-allowed sigmatropic shift). Pyrolysis of (9) at 455° also gave (11), while at 490°, both (9) and (11) gave 1-fluorovinyl 4,5,6,7,8-pentafluoro-1-naphthyl ketone (19).     

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.     

Preparation and antiviral properties of new acyclic, achiral nucleoside analogues: 1- or 9-[3-hydroxy-2-(hydroxymethyl)prop-1-enyl]nucleobases and 1- or 9-[2,3-dihydroxy-2-(hydroxymethyl)propyl]nucleobases

Acyclic, achiral nucleoside derivatives 1b-e of adenine, cytosine, 5-methylcytosine, and guanine, containing a 3-hydroxy-2-(hydroxymethyl)prop-1-enyl group on N-1 or N-9, have been prepared analogously to the previously described thymine derivative 1a. In contrast to the adenine and guanine derivatives, the cytosine derivative 9 was unstable, and was obtained in a low yield due to side reactions. These include cleavage of the propenyl group from the base, and the formation of a bicyclic compound. The thymine derivative, although stable under neutral conditions, likewise underwent a reversible cyclization reaction (Michael addition) in the presence of acids or bases. The 5-methylcytosine derivative was stable under neutral and basic conditions. Four other nucleoside derivatives 26a-d containing a 2,3-dihydroxy-2-(hydroxymethyl)propyl group on N-1 or N-9, three of which are new, have likewise been prepared. All compounds were evaluated as antiviral agents against HIV-1 and HSV-1 but were devoid of antiviral activity.     

5-{5-(bicyclo[2.2.1]hept-2-enyl)hydroxymethyl}-3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl<Emphasis Type="Italic">o</Emphasis>-benzoquinone and related polymers. Synthesis and some properties

A norbornene-containing ortho-quinone, 5-{5-(bicyclo[2.2.1]hept-2-enyl)hydroxymethyl)-3,6-ditert-butyl-o-benzoquinone, was synthesized by the nucleophilic addition of 5-(hydroxymethyl)bicyclo[2.2.1] hept-2-ene to 3,6-di-tert-butyl-o-benzoquinone. The structure of the compound was established by the X-ray analysis. The monomer obtained undergoes metathesis polymerization in the presence of Grubbs catalyst of the third generation with the formation of polynorbornene containing quinone fragments in the side chains.     

Reactions with Hydrazonoyl Halides 611: Synthesis of 2,3-Dihydro-1,3,4-Thiadiazoles

2-[1,2-Diaza-3-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))prop-2-enylidene]-3-phenyl-5-substituted 1,3,4-thiadiazolines and 2-{[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]cyanomethylene}-3-phenyl-5-substitu- ted 1,3,4-thiadiazolines were synthesized from hydrazonoyl halides and 4-{-2-aza-2-[(methylthiothioxomethyl)amino]vinyl}-2,3-dimethyl-1-phenyl-3-pyrazoin-5-one and 2-[4-(2,3-dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl)-1,3-thiazol-2-yl]ethane-nitrile, respectively. All synthesize compounds were elucidated by elemental analysis, spectra, and alternative synthesis routes, whenever possible.     

Preparation and properties of two new soluble carbazole-containing functional polyacetylenes

Two new functional polyacetylenes bearing carbazole group as pendant,poly {3-[（4-ethynylstyryl）-N-butyl]carba/ole}（P1） and poly{3-[4-（prop-2-ynyloxy）phenyl-N-butyl]carbazole}（P2）,were prepared using[Rh（nbd）Cl)₂-Et₃N as catalyst.The polymers were soluble in common organic solvents such as CHCl₃ and THK Their structures and properties were characterized and evaluated with FTIR,¹H NMR,UV,TGA,GPC,and CV,respectively.The results show that the polymers possess high thermal stability and well hole-injection property.     

In vitro cytotoxicity activity on several cancer cell lines of acridone alkaloids and N-phenylethyl-benzamide derivatives from Swinglea glutinosa (Bl.) Merr

The methanol extract from the stems and fruits of Swinglea glutinosa (Rutaceae) afforded 11 known acridone alkaloids and three N-phenylethyl-benzamide derivatives, glycocitrine-IV, 1,3,5-trihydroxy-4-methoxy-10-methyl-2,8-bis(3-methylbut-2-enyl)acridin-9(10H)-one, 1,3,5- trihydroxy-2,8-bis(3-methylbut-2-enyl)-10-methyl-9-acridone, citbrasine, citrusinine-II, citrusinine-I, 5-dihydroxyacronycine, pyranofoline, 3,4-dihydro-3,5,8-trihydroxy-6-methoxy-2,2,7-trimethyl-2H-pyrano[2,3-a]acridin-12(7H)-one, 2,3-dihydro-4,9-dihydroxy-2-(2-hydroxy-propan-2-yl)-11-methoxy-10-methylfuro[3,2-b]acridin-5(10H)-one, bis-5-hydroxyacronycine, N-(2-{4-[(3,7-dimethylocta-2,6-dien-1-yl)oxy]phenyl}ethyl)benzamide, N-(2-{4-[(3,7-dimethyl-4-acethyl-octa-2,6-dien-1-yl)oxy]phenyl}ethyl)benzamide, and severine acetate. All compounds isolated were examined for their activity against three cancer cell lines: human lung carcinoma (COR-L23), human breast adenocarcinoma (MCF7), human melanoma (C32), and normal human fetal lung cell line, MRC-5. The acridones tested exhibited weak cytotoxicity but the amides showed moderate nonselective cytotoxic activity.     

Disulphides in the volatile oil of Ferula behboudiana Rech. f. & Esfand

A study on the volatile oil of Ferula behboudiana by gas chromatography and gas chromatography-mass spectrometry showed the presence of 27 compounds. Two disulphide derivatives, 1-sec-butyl-2-[(E)-3-(methylthio) prop-1-enyl] disulphane (1) and 1-sec-butyl-2-[(Z)-3-(methylthio)prop-1-enyl] disulphane (2) (59.4%), were isolated from the oil by thin layer chromatography and their structures were elucidated by spectroscopic techniques. Glubolol (12.5%), α-pinene (8.8%), α-bisabolol (6.1%) and β-pinene (3.9%) were the other major compounds.     

Photomagnetic properties of iron(II) spin crossover complexes of 2,6-dipyrazolylpyridine and 2,6-dipyrazolylpyrazine ligands

The photomagnetic properties of the following iron(II) complexes have been investigated: [Fe(L1)2][BF4]2, [Fe(L2)2][BF4]2, [Fe(L2)2][ClO4]2, [Fe(L3)2][BF4]2, [Fe(L3)2][ClO4]2 and [Fe(L4)2][ClO4]2 (L1 = 2,6-di{pyrazol-1-yl}pyridine; L2 = 2,6-di{pyrazol-1-yl}pyrazine; L3 = 2,6-di{pyrazol-1-yl}-4-{hydroxymethyl}pyridine; and L4 = 2,6-di{4-methylpyrazol-1-yl}pyridine). Compounds display a complete thermal spin transition centred between 200-300 K, and undergo the light-induced excited spin state trapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. The presence of sigmoidal kinetics in the HS --> LS relaxation process, and the observation of LITH hysteresis loops under constant irradiation, demonstrate the cooperative nature of the spin transitions undergone by these materials. All the compounds in this study follow a previously proposed linear relation between T(LIESST) and their thermal spin-transition temperatures T(1/2): T(LIESST) = T(0)- 0.3T(1/2). T(0) for these compounds is identical to that found previously for another family of iron(II) complexes of a related tridentate ligand, the first time such a comparison has been made. Crystallographic characterisation of the high- and low-spin forms, the light-induced high-spin state, and the low-spin complex [Fe(L4)2][BF4]2, are described.     

Novel Synthesis of Agaritine,a 4-Hydrazinobenzyl-Alcohol Derivative Occurring in Agaricaceae

The 4-hydrazinobenzyl alcohol ( 3 was prepared (58%)) by diiobutylaluminiumhydride reduction of methyl 4-hydrazinobenzoate ( 4 ), whereas LiA1H₄ or LiBh₄ reduction of 4 proceeded further to yield (via intermediate 3 ) (4-tolyl)hydrazine ( 5 ). The alcohol 3 was stable under O₂-free conditions and exhibited no tendency to eliminate H₂O, neither thermally nor with H⁺ catalysis. Oxidation of 3 with SeO₂ yielded 4-(hydroxymethyl)benzine-diazonium ion ( 8 ), identified by its azo coupling product 9 with 2-naphthol. Condensation of 3 with 1-benzyl 5-Hydrogen N-(benzyloxycarbonyl)-L-glutamate ( 10 ) in presence of dicyclohexylcarbodiimide afforded 81% of N²-(benzyloxycarbonyl)-L- glutamic acid 1-(benzyl-ester) 5-{2-[4-(hydroxymethyl)phenyl]hydrazide} ( 11 ) which upon controlled hydrogenolysis (quinoline-sulfur-poisoned Pd/C catalyst) gave 82% of L-Glutamic acid 5-{2-[4-(hydroxymethyl)phenyl] hydrazide} ( 1 ), i. e. agaritine, a metabolite of Agaricus bisporus. Without poisoning of the catalyst, hydrogenolysis of ( 11 ) yielded L-glutamic acid 5-[2-(4-tolyl)hydrazide] ( 12 ).     

二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基的合成

以1,4-环己二酮、丙二酸二乙酯及多元醇等为原料, 经过两次“一锅煮”法合成了六种二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基螺环树形化合物, 其中烷氧基为异戊氧基、三羟甲基甲氧基、2,2-二溴甲基-3-羟丙氧基、2,2-二羟甲基丙氧基、二羟甲基膦甲氧基和(N-羟甲基-N-二羟甲基氨基乙基)甲氧基. 利用IR, NMR, MS和元素分析对合成的化合物进行了结构认证, 对影响反应的因素进行了讨论.     

Reactions of [2-iodo-3-(perfluoroalkyl)propyl]glycidyl ethers with alcohols under basic conditions

On treatment with sodium alkoxides in the corresponding alcohols, [2-iodo-3-(perfluoroalkyl)propyl]glycidyl ethers are converted into 3-alkoxy-1-[3-(perfluoroalkyl)prop-2-enyloxy]-propan-2-ols in 56–78% yields, while its reaction with 2,2,2-trifluoroethanol and phenol under phase transfer conditions (NaOH, CH₂Cl₂-H₂O, Bu₄N⁺I⁻, 35–40 °C) gives 3-alkoxy1-[2-iodo-3-(perfluoroalkyl)propoxy]propan-2-ols (yields 45–72%).     

新型Bluco类β-内酰胺酶分子探针的合成

以2-氰基-6-羟基苯并噻唑为原料,与溴乙醛缩二乙醇缩合制得缩醛后再水解合成中间体6-(2-羰乙基)苯并[d]噻唑-2-甲腈(2);7-苯乙酰氨基-3-氯甲基头孢菌烷酸二苯甲酯依次经碘代和Wittig反应得(Z)-3-[3-(2-氰基苯并[d]噻唑-6-氧)丙-1-烯]-8-羰基-7-(2-苯乙酰氨基)-5-噻-1-氮[4.2.0]辛-2-烯-2-甲酸二苯甲酯(5);5经脱保护、缩合和氧化反应合成了3个新的Bluco类似物,其结构经1H NMR,13C NMR和HR-MS(ESI)表征。