Synthesis and structure of N-alkyl(aryl)aminocarbonyl-1,4-benzoquinone imines

New N-alkyl(aryl)aminocarbonyl-1,4-benzoquinone imines were synthesized by reaction of isocyanates with the corresponding substituted 4-aminophenols, and their structure was determined on the basis of ¹H and ¹³C NMR spectra and X-ray diffraction data.     

Synthesis of aryl(γ-pyridyl)methanes and their conversion to substituted benzo[g]isoquinolines

New substituted pyridine bases of the aryl(-pyridyl)methane type were obtained from 1,2,5-trimethyl-4-piperidone by successive transformations. The new substituted pyridine bases were catalytically dehydrocyclized to di(tri)methylbenzo[g]isoquinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1077–1084, August, 1976.     

Synthesis of 1-[(1,2-dithiol-3-ylidene)methyl]pyrrolo[1,2-a]pyrazines and 2-[(1,2-dithiol-3-ylidene)methyl]pyridines from 1,2-dithiole-3-thiones

Benzo- and pyridoannulated 1,2-dithiole-3-thiones react with compounds containing an activated methyl group such as 1-methyl-3,4-dihydropyrrolo[1,2-a]pyrazine and 2-methylpyridines to furnish substituted 1,2-dithiol-3-ylidenes.     

Cascade radical reactions via alpha-(arylsulfanyl)imidoyl radicals: competitive [4 + 2] and [4 + 1] radical annulations of alkynyl isothiocyanates with aryl radicals

Aryl radicals react with 2-(2-phenylethynyl)phenyl isothiocyanate through a novel radical cascade reaction entailing formation of alpha-(arylsulfanyl)imidoyl radicals and affording a new class of compounds, i.e. thiochromeno[2,3-b]indoles. These derivatives are formed as mixtures of substituted analogues arising from competitive [4 + 2] and [4 + 1] radical annulations. The isomer ratio is strongly dependent on the aryl substituent and is correlated to its capability to delocalize spin density. The presence of a methylsulfanyl group in the ortho-position of the initial aryl radical results in complete regioselectivity and better yields, as the consequence of both strong spin-delocalization effect, which promotes exclusive [4 + 1] annulation, and good radical leaving-group ability, which facilitates aromatization of the final cyclohexadienyl radical. Theoretical calculations support the hypothesis of competitive, independent [4 + 2] and [4 + 1] annulation pathways. They also suggest that rearrangement onto the sulfur atom of the [4 + 1] intermediate does not occur via a sulfuranyl radical but rather through either a transition state or a sulfur-centered (thioamidyl) radical; the latter is possibly the preferred route in the presence of an o-methylsulfanyl moiety that can act as a leaving group in the final ipso-cyclization process.     

Synthesis of N-alkyl(acyl)-1,2,3,4-tetrahydro-4-methylspiro [quinoline-2-cyclohexanes] and their conversions

The alkylation and acylation of 1,2,3,4-tetrahydro-4-methylspiro[quinoline-2-cyclohexane] and its bromo (methyl) derivatives substituted in the benzene ring, as well as 1,2,3,4-tetrahydro-4-methylspiro[benzo(h)quinoline-2-cyclohexane], were studied. It was established that the N-allyl derivatives ofspiro[tetrahydroquinolinecyclohexanes] are converted to their 8-allyl-substituted analogs by the action of sulfuric acid, boron trifluoride etherate, and aluminum chloride. It was shown that the N-acyl-substituted spiro[tetrahydroquinolinecyclohexanes] are recyclized to spiro[indan-1-cyclohexanes] in phosphoric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 789–796, June, 1993.     

Preparative Synthesis of 4,4'-Bis[5-alkyl(aryl)benzoxazol-2-yl]biphenyls

An attempt was made to prepare 4,4'-bis[5-alkyl(aryl)benzoxazol-2-yl]biphenyls by reaction of dimethyl 4,4'-biphenyldicarboxylate with substituted o-aminophenols in a high-boiling solvent in the presence of boric acid.     

Some methyl substituted benzo[b]naphtho[2,3-d]thiophenes

Seven benzo[b]naphtho[2,3-d]thiophenes have been prepared with methyl groups substituted in the 6,7, and 8-positions. These compounds are structurally related to the sulfur analogs of cholanthrene and methylcholanthrene.     

Synthesis of 2,5-bis(piperidinomethyl)piperidine and 1,5-bis(aminomethyl)-3-azabicyclo[3.2.1]octanones

Schmidt reaction of mono- and bis-Mannich bases1 and2 c derived from cyclopentanone gave the corresponding basically substituted 2-piperidones3 and4, respectively. Reduction of the latter afforded5. DoubleMannich reaction of2 a–c with primary amines gave 3-azabicyclo[3.2.1]octanone derivatives6 a–e and7. The transamination of2 a was investigated.     

Novel synthesis of C-3-(hetero)aryl [1,2,3]triazolo[1,5-a]pyridines using the Stille reaction

Herein, we report a novel and high yielding approach for the preparation of the first C-3-organometallic substituted [1,2,3]triazolo[1,5-a]pyridine and its application to the Stille reaction using MAOS.     

Tricarbonylmanganese(I) derivatives of [Di(pyrazolyl)(2-pyridyl)methyl]aryl scorpionates

The cobalt(II) chloride catalyzed Peterson rearrangement reactions between sulfinyldi-(pyrazolyl) and aryl(pyridyl)methanone derivatives yield di(pyrazolyl)(pyridyl)hetero-scorpionate ligands. Reaction of these ligands with Mn(CO)₅Br in the presence of a silver salt produces the monometallic complexes {[κ³-PhC(pz)₂(2-py)]Mn(CO)₃}(O₃SCF₃) (1a), {[κ³-PhC(pz)₂(2-py)]Mn(CO)₃}(PF₆) (1b), {[κ³-PhC(^4-Mepz)₂(2-py)]Mn(CO)₃}(PF₆) (2), {[κ³-p-BrC₆H₄C(pz)₂(2-py)]Mn(CO)₃}(PF₆) (3), and the bimetallic complexes [(CO)₃Mn{m-C₆H₄[C(pz)₂(2-py)]₂}Mn(CO)₃](BF₄)₂ (5a) and {m-C₆H₄[C(pz)₂(2-py)Mn(CO)₃]₂}(PF₆)₂ (5b) (pz = pyrazolyl ring, py = pyridyl ring). These octahedral manganese complexes show interesting structural diversity, with the complexes being organized in the solid state into complex supramolecular structures by an array of non-covalent forces.     

[α-(2-氧代烷基)-α-(取代苯胺基)甲基苯基]-β-D-吡喃阿洛糖苷的合成及镇静活性研究

以豆腐果苷为原料, 通过Mannich反应与取代苯胺和脂肪酮共合成了七个豆腐果苷衍生物, 均未见文献报道. 其结构经¹H NMR, IR, MS和HRMS确认, 并进行了药理活性筛选. 结果表明, 部分化合物均具有良好的镇静活性. 其中, 化合物2a (200 mg/kg), 2b (200 or 100 mg/kg)和2e (200 mg/kg)与豆腐果苷相比较, 具有更强的疗效.     

N‐[Tris(hydroxymethyl)methyl]glycine (tricine)

The title compound, C₆H₁₃NO₅, adopts a zwitterionic form where the carboxylic acid H atom is transferred to the amino group. The methyl–glycine backbone is planar. The tris(hydroxy­methyl)­methyl group is rotated as a rigid group around the amino–methyl bond by 22 (1)° and the carboxylic acid plane is rotated by 19.76 (12)° from the plane of the main skeleton. Apart from their H atoms, the three hydroxy­methyl groups adopt a propeller‐like conformation around the amino–methyl bond, close to C₃ symmetry.     

One-step synthesis of substituted 4,7-bis[alkyl(aryl)imino]-3-oxa-6-thia-1-azaspiro[4.4]nona-1,8-dienes

Alkyl-(aryl) isocyanides react with benzoyl isothiocyanate in the presence of dialkyl acetylenedicarboxylates or dibenzoylacetylene in one-pot to afford highly substituted 4,7-bis[alkyl(aryl)imino]-2-phenyl-3-oxa-6-thia-1-azaspiro[4.4]nona-1,8-dienes, with double insertion of the isocyanide, in 38-45% yields (based on the isocyanide).     

Radical cascade transformations of tris(o-aryleneethynylenes) into substituted benzo[a]indeno[2,1-c]fluorenes

Oligomeric o-aryleneethynylenes with three triple bonds undergo cascade radical transformations in reaction with a Bu 3SnH/AIBN system. These cascades involve three consecutive cycle closures with the formation of substituted benzo[ a]indeno[2,1- c]fluorene or benzo[1,2]fluoreno[4,3- b]silole derivatives. The success of this sequence depends on regioselectivity of the initial attack of the Bu 3Sn radical at the central triple bond of the o-aryleneethynylene moiety. The cascade is propagated through the sequence of 5-exo-dig and 6-exo-dig cyclizations which is followed by either a radical attack at the terminal Ar substituent or radical transposition which involves H-abstraction from the terminal TMS group and 5-endo-trig cyclization. Overall, the transformation has potential to be developed into an approach to a new type of graphite ribbons.     

Complexation and fluorescence behavior of 9,10-bis[bis(beta-hydroxyethyl)aminomethyl]anthracene

9,10-Bis[bis(beta-hydroxyethyl)aminomethyl]anthracene (1) showed weak emission, suggesting that photoinduced electron transfer (PET) from amine group to excited anthracene occur. The PET fluoroionophore (1) was found to display unique photophysical properties in the presence of the guest metal cations in H(2)OCH(3)OH (1:1, v/v). Complexation of 1 with guest metal cations increased the fluorescence intensity.     

Synthesis of maleopimaric and citraconopimaric acids N-[3-(pyrimidin-2-yl)aryl]amides

Acylation of 6-methyl-N-[4-(pyridin-3-yl)pyrimidin-2-yl]benzene-1,3-diamine, 4-methyl-N-[4-(pyridin-3-yl)pyrimidin-2-yl]benzene-1,3-diamine, and N-[4-(pyridin-3-yl)pyrimidin-2-yl]benzene-1,3-diamine with maleopimaric and citraconopimaric acid chlorides, with benzotriazolyl maleopimarate afforded N-[3-(pyrimidin-2-yl)aryl]amides of maleopimaric and citraconopimaric acids. By the reaction of substituted N-arylamides of maleopimaric acid with methanesulfonic acid biologically active methanesulfonates were obtained.     

4-Substituted aryl(methyl)ethynylfluorosilanes

Conclusions The reaction of 4-substituted aryl magnesium bromides with methyl(ethyl)difluorosilane, as well as the reaction of ethynyl magnesium bromide with 4-substituted phenyl(methyl)difluorosilanes, led to the synthesis of 4-substituted phenyl(methyl)-ethynylfluorosilanes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1115–1116, May, 1987.     

Design and synthesis of tris[bis(benzylammonium)aryl]phosphines with bulky meta-substituents

A novel 3,5,3′,5′,3″,5″-hexakis(dimethylamino)methyl substituted triphenylphosphine analogue has been prepared. The six amine functionalities of the corresponding phosphine oxide and sulfide were alkylated quantitatively with methyl iodide and benzyl bromide, as well as with G1 and G2 Fréchet dendrons to afford the respective hexa-ammonium triarylphosphine oxides and sulfides. The phosphine sulfide derivatives were deprotected with P(n-Bu)₃ to afford a series of hexa-ammonium triarylphosphines that range from small molecules to first and second generation dendrimers (MW up to 5451.44). Upon formation of the hexa-ammonium salt a clear shift in ³¹P NMR is observed, indicative for opening of the C-P-C angle of the triaryl phosphine. Calculations on the hexacationic phosphines show an increased barrier of rotation around the P-C(aryl) bond with increasing size of the N-substituents. The calculated structure of the G2-dendron alkylated hexa-ammonium triarylphosphine shows that this dendritic phosphine has a disc-like rather than a cone-like structure, with an estimated cone angle of approximately 180°     

Reaction of ene-bis(phosphinylallenes): [2+2] versus [4+2] cycloaddition

Reaction of ene-bis(phosphinylallenes), derived from ene-bis(propargyl alcohols) and chlorodiphenylphosphine, was investigated. Benzene-bridged bis(phosphinylallenes) exclusively gave intramolecular [2+2] cycloadducts in the presence of dimethyl fumarate in sharp contrast to the reaction of benzene-bridged bis(sulfinylallenes), which gave the corresponding [4+2] cycloadducts. On the other hand, substituted ethylene- or five-membered heterocycle-bridged bis(phosphinylallenes) provided [4+2] cycloadducts. Reaction of benzene-bridged diallene bearing both a sulfinyl group and a phosphinyl group on the two allenyl groups was also described.     

Synthesis and transformations of some (heteroaryl)acetylazides, (heteroaryl)methyl isocyanates and alkyl (heteroaryl)methyl carbamates

The synthesis of two complex acetyl azides 6 and 10 having an heteroaryl residue bound to the acetyl group through the ring nitrogen, and their further transformations into the corresponding carbamates 7a-b and 11a-b and isocyanates 16 and 14 are described. Hydrolysis of these products results in the elimination of the substituted methyl group from the heterocyclic residue and formation of 1-unsubstituled heterocycles. A similar transformation was also observed under mass measurement conditions.