Acylation of 2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro-[naphthalene-1,3′-pyrrol]-4-one with 5-arylfuran-2,3-diones

Russian Journal of Organic Chemistry -     

Synthesis and Crystal Structure of 3′-Ethyl 5′-Methyl 1-Benzyl-4′-methyl-2-oxo-3′,4′-dihydrospiro-[indoline-3,2′-pyrrole]-3′,5′-dicarboxylate

The crystal structure of the title compound(C24H24N2O5, Mr = 420.45) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 8.991(1), b = 11.166(1), c = 11.169(1) , α = 91.413(2), β = 105.887(2), γ = 90.992(2)°, V = 1077.8(2) 3, Z = 2, Dc = 1.296 g/cm3, F(000) = 444, μ(MoKα) = 0.091 mm-1, the final R = 0.0466 and wR = 0.1507 for 4185 observed reflections(I 2σ(I)). The single-crystal X-ray diffraction data indicated intermolecular C(17)–H(17)O(4), C(5)–H(5)… O(4) hydrogen bonds and C–H…π interaction in the structure.     

Rosenmund-Braun Reaction Products 4′,5′-Dicyanobenzo-15-crown-5 and 4′,5′-Dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 Hydrates: Spectroscopic Properties and Crystal Structure

The products of 4′,5′-dibromobenzo-15-crown-5 (I) cyanation by the Rosenmund-Braun reaction are studied by the ¹H NMR and IR spectroscopy methods. X-ray diffraction analysis of two isolated products, i.e., di(4′,5′-dicyanobenzo-15-crown-5) 1.6 hydrate {(CN)₂B15C5}₂ · 1.6H₂O (IIa) and 4′,5′-dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 dihydrate (CN)_3.85Br_0.15(B15C5)₂ · 2H₂O (III) is performed. Crystals IIa are monoclinic, a = 15.882(2) Å, b = 11.412(2) Å, c = 18.484(3) Å, β = 100.717(3)°, V = 3291.7(9) ų, Z = 4, space group P2₁/c, R = 0.0746 for 4775 reflections with I > 2σ(I). Crystals III are monoclinic, a = 15.956(3) Å, b = 11.425(2) Å, c = 18.865(4) Å, β = 99.32(3)°, V = 3394(1) ų, Z = 4, space group _P2₁/_{c, R} = 0.0692 for 2070 reflections with I > 2σ(I). Compounds IIa and III have similar structures with two crystallographically independent molecules in each (A and B in IIa; C and D in III). Four of the five O atoms of a macrocycle in molecules A and C form hydrogen bonds with the water molecules. The latter molecules lie above and below the cycle plane at a distance of ～2 Å from this plane. The A and C molecules have identical conformations (TTG TTG TTG TTG TTC) that differ from those of molecules B (TTG TGG STT SSG TTC) and D (TTC TSG STT SSG TTC).     

Synthesis and Crystal Structure of 4-Phenyl-5-(1′- t-butyl-5′-methyl-4′-pyrazolyl)-1,2,4-triazol-3-thione

The crystal structure of 4-phenyl-5-(1′-t-butyl-5′-methyl-4′-pyrazolyl)-1,2,4-triazol- 3-thione 5 (C16H19N5S, Mr = 313.42) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 6.680(2), b = 27.44(1), c = 9.388(4)(A。), β = 106.738(6)°, V = 1648(1)(A。)3, Z = 4, Dc = 1.263 g/cm3, μ= 0.200 mm-1, F(000) = 664, R = 0.0608 and wR = 0.1176. The results confirmed that 5 can be assigned to the thione tautomeric form.     

Thermal analysis of 5′-deoxy-5′-iodo-2′,3′-O-isopropylidene-5-fluorouridine

The melting temperature, melting enthalpy, and specific heat capacities (C _p) of 5′-deoxy-5′-iodo-2′,3′-O-isopropylidene-5-fluorouridine (DIOIPF) were measured using DSC-60 Differential Scanning Calorimetry. The melting temperature and melting enthalpy were obtained to be 453.80 K and 33.22 J g^?1, respectively. The relationship between the specific heat capacity and temperature was obtained to be C _p/J g^?1 K^?1 = 2.0261 – 0.0096T + 2 × 10^?5 T ² at the temperature range from 320.15 to 430.15 K. The thermal decomposition process was studied by the TG–DTA analyzer. The results showed that the thermal decomposition temperature of DIOIPF was above 487.84 K, and the decomposition process can be divided into three stages: the first stage is the decomposition of impurities, the mass loss in the second stage may be the sublimation of iodine and thermal decomposition process of the side-group C₄H₂O₂N₂F, and the third stage may be the thermal decomposition process of both the groups –CH₃ and –CH₂OCH₂–. The obtained thermodynamic basic data are helpful for exploiting new synthetic method, engineering design, and commercial process of DIOIPF.     

Synthesis of 1′-substituted 4′,4′-dimethyl-6′-methoxy-4′H-spiro[cyclohexane-1,3′-isoquinolines]

The reaction of 1-(4-methoxyphenyl)-1-(1-methylcyclohexyl)ethanol with nitriles in concentrated sulfuric acid afforded 1′-substituted 6′-methoxy-4′,4′-dimethyl-4′H-spiro[cyclohexane-1,3′-isoquinolines] as a result of consecutive Wagner-Meerwein rearrangement and Ritter reaction.     

Synthesis of 5′-deoxy-5′-[18F]fluoro-adenosine by Radiofluorination of 5′-deoxy-5′-haloadenosine Derivatives

5-Deoxy-5-[¹⁸F]fluoro-adenosine was synthesised by nucleophilic radiofluorination reactions of 5-deoxy-5-haloadenosines. The homogeneous isotope exchange in 5-deoxy-5-fluoro-adenosine was also investigated. The conversion of these reactions was found to be rather low and depends on the strength of the halogen-carbon bond: 0.248% for chloride-, 0.488% for bromide- and 1.070% for iodide-derivative; there was no reaction observed in the case of fluoro-compound.     

Synthesis of 2′-5′,3′-5′ linked triadenylates

2′-5′,3′-5′ Linked triadenylates have been synthesized by direct bisadenylylation of adenosine 2′ and 3′ hydroxyls with an adenosine 5′-phosphorochloridite followed by oxidation.     

Synthesis and spatial structure of methyl substituted 2-phenylpiperidine-4-spiro-5′-imidazolidine-2′,4′-diones

Piperidine-4-spiro-5-irnidazolidine-2, 4-diones have been synthesized from the appropriate methyl substituted 2 phenyl-4-hydroxypiperidines and 4-cyano-4-aminopiperidines by the Bucherer—Bergs and Strecker methods. The stereocheinical composition and spatial structure of the compounds synthesized have been established from¹H and¹³C NMR data.Moscow State Academy of Fine Chemical Technology, Moscow 117571. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 798–801, June, 1994. Original article submitted May 11, 1994.     

5′-鸟嘌呤核苷三磷酸(5′-GTP)和5′-尿嘧啶核苷三磷酸(5′-UTP)二钠盐的制备

前言核苷三磷酸是含有两个高能磷酸键的高能化合物。除了参与核糖核酸合成外,在生物体内的生命活动中起着重要的作用。ATP 主要用于供给合成细胞的物质所需要的能量,也是被称为“第二信使”的环化AMP(3′5′-cyclicAMP)的前体。而后者已知与多种生化过程有关。CTP 参与重要磷脂类的合成。GTP 在蛋白质合成中是必不可少的。UTP 是肝脏中重要解毒剂尿二磷葡萄糖醛酸(UDPG)的前体,与肝糖元、酸性粘多糖的合成密切相关。根据已知的生理功能有些兄弟研究单位作了一些临床应用试验,还值得进一步探讨。     

Preparation of (4′S) and (4′R)-Spiro(oxirane-2-4′-5α-cholestan-3′β-ol), Potent Inhibitors of 4-Methyl Sterol Oxidase

(4′R)- and (4′S)-Spiro(oxirane-2,4′-5α-cholestan-3′β-ol) (1) and (2) were made from (4′R)- and (4′S)-spiro(oxirane-2,4′-5α-cholestan-3-one) (8) and (9). Alkaline hydrogen peroxide oxidation of 4-methylene-5α-cholestan-3-one (7) gave compounds (8) and (9) as a readily separable (1:1) mixture. Reduction of (9) to (2) provided access to a compound which could not be made by other methods.     

Synthesis and Crystal Structure of Chiral Spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyrolactam-6-oxo-dirings[3.1.0]hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)}

A novel compound of chiral spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyro-lactam-6-oxo-dirings3.1.0hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)} was synthesized via tandem nucleophilic substitution reaction under mild conditions=and its structure was determined by IR =1H NMR=elemental analysis and X-ray diffraction.The crystal structure of this compound is of monoclinic system=space group P21 with a=9.7356(9)=b=12.2760(12)=c=14.9577(14)=β=101.0300(10)°=Mr=680.66=Z=2=V=1754.6(3)3=Dc=1.288 g/cm3=μ(MoKα)=1.216 mm-1=F(000)=716=the final R=0.0434 and wR=0.0996.     

Synthesis and Crystal Structure of Ethyl 5-Amino-1-[（5′-methyl-1′- t-butyl-4′-pyrazolyl）carbonyl]-3-methylthio-1H-pyrazole-4-carboxylate

1INTRODUCTIONPolarizedketenedithioacetalshavebeenex-tensivelyusedasbuildingblocksinorganicsyn-thesis,especiallyinthesynthesisofheterocycliccompounds[1～6].Pyrazoleanditsderivativesrepre-sentoneofthemostactiveclassesofcompoundspossessingwidespectraofbiologicalactivities.Overthepastfewyears,considerableevidenceshavebeenaccumulatedtodemonstratetheefficacyofpyrazolederivatives,suchasantibacterial[7],fun-gicidal[8],herbicidal[9],insecticidal[10]andotherbiologicalactivities[11,12].Uptonow,alarg…     

Die indikatoreigenschaften des vicinalen m-Xylenolphthaleins (3′ ,5′ ,3′' ,5′'-Tetramethylphenolphthalein)

Ohne ZusammenfassungMit 1 Abbildung     

2′-5′连接寡聚核苷酸——2′-5′A核的固相合成

本文用磷酸三酯法,在交联聚丙烯酰吗福啉载体上,以1,3,5-三甲苯磺酰氯(MS)加N-甲基咪唑(N-Mein)为缩合剂,合成了2′-5′相连的寡聚腺苷酸——2′-5′A核。每个保护的单体接到载体上的收率是令人满意的,分别是100％,64％和89％。在合成过程中,我们对合成一系列中间体和制备载体的方法进行了改进,使产物收率大大提高,分离操作得以简化。     

Synthesis of 4′-alkyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-ones

N-Boc-protected 8-azaspiro[bicyclo[3.2.1]octane-3,2′-oxirane] reacted with primary aliphatic amines through opening of the epoxide ring with formation of the corresponding amino alcohols which were converted into N-chloroacetyl derivatives. The latter underwent cyclization to N-Boc-protected 4′-alkyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-ones by the action of sodium hydride in DMF, and subsequent treatment with hydrogen chloride in ethyl acetate afforded 8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-one hydrochlorides.     

Synthesis of 3-(3′-Acetyl-5′-aroyl-1′,3′,4′-oxadiazolyl-2′)-chromones

A general method has been proposed for synthesizing 3-(3-acetyl-5-aroyl-1,3,4-oxadiazolyl-2)-chromones that has been based on conversion of 3-formylchromones to acylhydrazones and of theacylhydrazones into the heterocyclic chromones.     

Syntheses of 5′-O-glycosylnucleosides

A general synthetic approach to 2,3-unsaturated glycosides connecting with nucleosides involving Ferrier rearrangements of glycals is discussed. The new compounds were identified by NMR and MS (HRFAB⁺). The hydroxylation of the resulting 2,3-unsaturated glycosides was completed using OsO₄ to give 5′-O-glycosylnucleosides in good yield.     

Synthesis and Crystal Structure of 1-[(1′-Phenyl-5′-methyl-4′-pyrazolcarbonyl)- 3-methylthio-5-amino-1H-yl-1,2,4-triazole

1INTRODUCTIONTheCIDT(N-cyanoimido-S,S-dimethylthiocarbo-nate)hasbeenwidelyutilizedinorganicsynthesisduringthelasttwodecadesandhasbecomeveryusefulforconstructingfunctionalizedheterocyliccom-poundsbecauseoftheirversatility.MuchattentionhasrecentlybeenfocusedonthedevelopmentofCIDTaswellastheirsyntheticapplications[1～4].Meanwhile,manypyrazoleandtriazolederivativesarereportedtoshowvariousbiologicalactivities,suchasantifungal[5],herbicidal[6～8],insectcidal[9]andotheractivities[10～12].Thu…