Synthesis of [125I]‐, [2H]‐, and [3H]‐Labeled 3‐Iodothyronamine (T1AM)

3‐Iodothyronamine (T₁AM) is a novel metabolite of thyroid hormone. In HEK‐293 cells expressing an orphan G‐protein coupled receptor, the trace amine receptor, T₁AM, potently increased cAMP accumulation. In mice, T₁AM rapidly induced hypothermia and bradycardia within minutes of administration. These results suggest the existence of a new signaling pathway, the stimulation of which leads to rapid physiological and behavioral consequences. Isotope‐labeled T₁AM derivatives would be useful to study the biology and pharmacology of T₁AM. Herein we describe efficient syntheses of [¹²⁵I]‐, [²H]‐, and [³H]‐T₁AM.     

Alkylation of 3-tert-Butylpyrimido[4′,5′:3,4]pyrazolo[5,1-c]-[1,2,4]triazine-4,10(1H,9H)-diones and -dithiones

Russian Journal of Organic Chemistry - The condensation of 7-amino-1-benzyl-3-tert-butyl-4-oxo-1,4-dihydropyrazolo[5,1-c][1,2,4]triazine-8-carbonitrile with formic acid afforded...     

Vibrational spectra and structure of cesium salts of icosahedral monocarba-closo-dodecarborate anion, [CB11H12]–, and its nido-derivative, [CB100H13]–

The Raman and IR spectra of the cesium salts of monocarbon carboranes, [closo-CB₁₁H₁₂]^– and [nido-CB₁₀H₁₃]^–, are reported and the assignment of the normal modes is given. Quantum-chemical calculations of the geometry of undistorted closo-anions B₁₂H₁₂ ^2– and CB₁₁H₁₂ ^– were carried out and normal coordinate analysis for the latter was performed. Structural parameters and spectral characteristics of isoelectronic closo-polyhedra [B₁₂H₁₂]^2–, [CB₁₁H₁₂]^–, and p-C₂B₁₀H₁₂ and those of the closo- and nido-structures were compared.     

Hydrothermal Synthesis,Structural Investigation and Characterization of an Organic-inorganic Hybrid, [Co（BIIM）3]2H[BW12040]·7H2O

An organic-inorganic hybrid based on a-Keggin-typed [BWI2040]5- anionic cluster, [Co（BIIM）3]2H[BWx2040]＇7H20 （BIIM = 2,2＂-biimidazole）, was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490（10）, b = 33.270（3）, c = 18.9660（16） A, β = 105.9950（10）°, V= 7490.5（11） A3, C36HsoBCo2N24047W12, Mr = 3905.80, Dc = 3.45 l g/cm3, μ（MoKa） = 18.886 rnm-1, F（000） = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections （1 〉 2tr（/））. The compound consists of two isolated [Co（BIIM）3]2＋ cations and one [BW12040]5 anion, in which each Co2＋ ion is coordinated by six N atoms from three BIIM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N-H...O（polyoxometalate and wate） hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W--Oterminal···πimidazole ring interactions which cooperate with the classical N-H···O hydrogen bonds to stabilize the structural packing.     

化合物[H3DETA]3[H2DETA]2[Pr(SiW11O39)2]·2H2O的水热合成及晶体结构

通过水热合成制得了硅钨杂多酸镨化合物[H3DETA]3[H2DETA]2[Pr(S iW11O39)2].2H2O[DETA:二乙烯三胺].晶体结构解析表明:该化合物属于三斜晶系,P1-空间群,a=1.200 0(2)nm,b=2.026 1(4)nm,c=2.239 2(5)nm,α=111.60(3)°,β=92.92(3)°,γ=103.56(3)°;V=4.863 8(17)nm3,Z=2,ρ=4.152 g/cm3,μ=26.519 mm-1,F(000)=5 374.化合物中Pr3+键合两个[S iW11O39]8-构成一个[Pr(S iW11O39)2]13-多阴离子,Pr3+与两个[S iW11O39]8-阴离子的八个氧原子配位构成一个畸变的四方反棱柱.此外,多阴离子[Pr(S iW11O39)2]13-和有机分子还通过氢键形成一个大的空腔.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

Heterocyclizations of Di- and Tricarbonyl Indole Derivatives. Synthesis of β-Carbolines, 3H-[1,2,5]Triazepino-[5,4-a]indol-4(5H)-one,and 5,10-Dihydro[1,2]diazepino-[4,5-b]indol-4(3H)-one

Russian Journal of Organic Chemistry - A synthetic approach to β-carbolines has been proposed on the basis of heterocyclization of ethyl 2-(2-benzoyl-1H-indol-3-yl)acetate with...     

Green Aspect for Multicomponent Synthesis of Spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles]

An efficient, four-component reaction of isatin, 1,3-indanedione, ethyl acetoacetate, and ammonium acetate in ethanol/water (9:1) system furnished spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles] at room temperature. Merits of the method are mild reaction conditions, simple workup procedure, and ambient temperature. The synthesized compounds exhibit excellent fluorescence properties.     

Palladium-catalyzed synthesis of pyrimido[5’,4’:3,4]pyrrolo[1,2-f]phenanthridine-12,14(11H,13H)-diones and related compounds

Representatives of the new heterocyclic system, pyrimido[5’,4’:3,4]pyrrolo[1,2-f]phenanthridine, were obtained via the intramolecular C–H-arylation of 6-aryl-5-(2-bromophenyl) pyrrolo[3,4-d]pyrimidine-2,4-diones catalyzed by palladium complexes with N-heterocyclic carbene ligands (Pd/NHC).

     

Efficient and facile synthesis of 5-arylindeno[2′,1′:5,6]pyrido[2,3-d] pyrimidine-2,4(3H)-dione and 7-arylbenzo[h]pyrimido[4,5-b]quinoline-8,10(5H,9H)-dione under mild conditions

An efficient and facile method for the synthesis of 5-arylindeno[2′,1′:5,6]pyrido[2,3-d] pyrimidine-2,4(3H)-dione and 7-arylbenzo[h]pyrimido[4,5-b]quinoline-8,10(5H,9H)-dione derivatives from the reactions of 2-arylidene-2,3-dihydroinden-1-one (or 2-arylidene-3,4- dihydronaphthalen-1(2H)-one) and 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione under mild conditions was described. This is a simple, efficient, and very rapid synthetic method, which is believed to provide a useful process for the synthesis of these fused heterocyclic compounds. The products were confirmed by infrared, ¹H NMR, ¹³C NMR, and high-resolution mass spectrometry.     

Pyridine-2(1H)-thione in Heterocyclic Synthesis: Synthesis of Some New Nicotinic Acid Ester,Thieno[2, 3-b]pyridine,Pyrido[3′, 2′: 4, 5]thieno [3, 2-d]pyrimidine,and Thiazolylpyrazolo[3, 4-b]pyridine Derivatives

Nicotinic acid esters 3a–c were prepared by the reaction of pyridine-2(1H)-thione derivative 1 with α-halo-reagents 2a–c. Compounds 3a–c underwent cyclization to the corresponding thieno[2, 3-b]pyridines 4a–c via boiling in ethanol/piperidine solution. Compounds 4a–c condensed with dimethylformamide-dimethylacetal (DMF-DMA) to afford 3-{[(N,N-dimethylamino)methylene]amino}thieno[2, 3-b]- pyridine derivatives 6a–c. Moreover, compounds 4a–c and 6a–c reacted with different reagents and afforded the pyrido[3′,2′:4, 5]thieno[3, 2-d]pyrimidine derivatives 10a–d, 11a–c, 12a,b, 14a,b, 17, and 19. In addition, pyrazolo[3, 4-b]pyridine derivative 20 (formed via the reaction of 1 with hydrazine hydrate) reacted with ethylisothiocyanate yielded the thiourea derivative 21. Compound 21 reacted with α-halocarbonyl compounds to give the 3-[(3H-thiazol-2-ylidene)amino]-1H-pyrazolo[3, 4-b]pyridine derivatives 23a–c, 25, and 27a,b.     

A Large-Scale Synthesis of Spiro [Cyclopropane-1,9′- [9H] Fluorene] and Derivatives

Our studies of the conjugative properties of cyclopropanes required the synthesis of large quantities of spiro [cyclopropane-1,9′- [9H] fluorene] (1) and its derivatives.¹ The method of Corey² is suited for the preparation of modest (1–5 g) amounts of 1 in one step. This procedure has failed to produce the desired cyclopropane when applied to substituted fluorenones.³     

New Approach to Synthesis of Tetrahydroisoquino[2,l-c] [1,3]-benzodiazepine

A concise and efficient synthesis of the new compounds tetrahydroisoquino [2,1-c] [1,3] benzodiazepine 5 and 7 is reported.     

Synthesis of novel tricyclic 2H,7H-furo[3′,4′:6,7]cyclohepta-[1,2-b]pyran system

The reaction of 8-hydroxy-1,3-dimethyl-4H-cyclohepta[c]furan-4-one with the ethoxymethylene derivatives of malononitrile or ethyl cyanoacetate in the presence of KOH gave noncyclic cyanovinyl derivatives as their potassium salts rather than the expected α-pyrone derivatives. They are smoothly cyclized to the target α-pyrones by refluxing with acid. The corresponding 3-benzamido-2H-pyran-2-ones can be obtained in a single vessel from the 2-aryl-4-ethoxymethylene-4H-1,3-oxazol-5-ones using the same scheme. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1632–1638, November, 2008.     

One Pot Synthesis of Some New Spiro[3H-Indol-3,5′(4′H)-[1,2,4] Oxadiazol]-2-Ones and Bis[Spiro[3H-Indol-3,5′(4′H)-[1,2,4] Oxadiazol]-2-Ones]

A facile preparation of the title compound by 1,3-dipolar cycloaddition reaction of benzonitrile oxides with isatin imines or isatin diimines, in excellent yield, are reported.     

Novel Synthesis of Pyrano[2,3-d]Thiazole,Thiazolo[3,2-a]Pyridine,and Pyrazolo [3′,4′:4,5] Thiazolo[3,2-a]Pyridine Derivatives

Cyclocondensation of 2-cyanomethyl-4-thiazolidinone (1) with tetracyanoethylene (2) furnished pyrano[2,3-d]thiazole derivative (4) . Benzo[e]pyrano[2,3-d]thiazole derivative (6) was obtained by cyclization of compound (1) with salicylaldehyde. In a similar manner, condensation of compound (1) with 2-hydroxy-1-naphthaldehyde in refluxing ethanol yielded naphtho[e]pyrano[2,3-d]thiazole derivative (7) . Interaction of compound (9) with benzylidenemalononitriles (10) (1 : 1 molar ratio) at reflux temperature in ethanol in the presence of piperidine afforded thiazolo[3,2-a]pyridines (12a-c) . Treatment of compound (12a) with hydrazines furnished pyrazolo[3′,4′:4,5] thiazolo[3,2-a]pyridines (14a,b) . The reaction of compound (1) with benzyli-denecyanoacetate (16) yielded 5-hydroxythiazolo[3,2-a]pyridine derivative (21) . Cyclization of bis(thiazolinone) (23) with benzylidenemalononitriles (10) produced bis(thiazolopyridine) derivatives (25a,b) .     

Synthesis, crystal structure, and thermal analysis of hexahydrogen dodecavanadate of composition [NH3 · H2O]6 · H6[Ca4V12O40] · 6H2O

Dihydrogen dodecavanadate of composition [NH₃ · H₂O]₆ · H₆[Ca₄V₁₂O₄₀] · 6H₂O was synthe-sized and studied by X-ray crystallography and TGA analyses. The crystals are cubic, space group I $\bar 4$ 3m;; unit cell parameters: a = 13.518(2) ?, V = 2470.4(3) ?³, ??_calc = 2.2334 g/cm³, Z = 2.     

Synthesis and structure of Mu-4, the new layered aluminophosphate [(C2H5)2NH2]4[Al8P10O40H2]·[H2O]2.5

The title compound (named Mu-4) is a new layered aluminophosphate with a unusual A1/P ratio for this kind of materials. Mu-4 was obtained from a quasi non-aqueous mixture involving mainly diethylformamide (DEF) as solvent, in addition to limited amounts of water. DEF is decomposed during the synthesis and the resulting protonated diethylamine is occluded in the as-synthesized material. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is triclinic, a=8.632(4) Å, b=9.267(7) Å, c= 17.461(10) Å, α=86.66(5)°, β=82.20(4)° and γ=89.28(5)°, space group P-1. The structure consists of anionic double sheets essentially built from double 4-ring (D4R) units. The inorganic layers are in strong interaction with water and the protonated amine which is located in the interlayer spacing. Another type of diethylamine protrudes into the 8-membered rings (8-MR) present in the layers. The characterization of this new aluminophosphate by ¹³C, ²⁷Al and ³¹P solid state NMR spectroscopy is also reported.     

Synthesis of Green Colored Photochromic 6′-Arylamino Spiro [2H]Naphth[1,2-b]oxazines

The published route to a series of 6′-arylamino substituted photochromic spirooxazines has been investigated with improvements made to perform the synthesis in satisfactory yield. The route has been exemplified with several novel derivatives prepared (including hydroxyl functionalised). Additionally, a one-pot procedure for the conversion of suitably functionalized 1,2-naphthoquinones into the photochromic compounds is reported.