New conversion of Friendlander reaction of 3-amino-1H-benzo[f]chromene-2-carbonitriles with cyclohexanone

Two different skeletons of heterocyclic compounds, quinoline and quinazolinone analogs could be obtained by a novel one-pot synthesis from substituted 3-amino- 1H-benzo[f]chromene-2-carbonitrile derivatives and cyclohexanone in DMF in the catalyst of anhydrous Zinc chloride under reflux. A plausible mechanism was proposed. 2007 Jia Rong Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Synthesis of 11H-Indeno[1,2-b]quinolines via the Friedlnder Reaction

The quinoline nucleus occurs in several natural compounds (cincona alkaloids) andpharmacologically active substances displaying a broad range of biological activity1.The biological activity of quinoline compounds has been found to possess antiasthmatic,an…     

Reformatsky Reaction of Methyl α-Bromoisobutyrate with 2-Oxo-2H-benzo[f]chromene-3-carboxylic Acid Esters and N-Benzylamide

Reformatsky reagent derived from methyl -bromoisobutyrate reacts with methyl and ethyl 2-oxo-2H-benzo[f]chromene-3-carboxylates and N-benzyl-2-oxo-2H-benzo[f]chromene-3-carboxamide to afford the corresponding derivatives of 4-(1-methyl-1-methoxycarbonylethyl)-2-oxo-3,4-dihydro-2H-benzo[f]chromene-3-carboxylic acid as a single stereoisomer.     

X-ray Diffraction Investigation of Ethyl 2-（2-Amino-3-ethoxycarbonyl-4H-benzo[f]chromene-4-yl） Cyanoacetate

The title compound,ethyl 2-(2-amino-3-ethoxycarbonyl-4H-benzo[f]chromene-4-yl) cyanoacetate 4,has been synthesized and its crystal structure was characterized by X-ray single-crystal diffraction.The crystal belongs to monoclinic,space group P21/n with a=12.9408(18),b=11.1870(13),c=13.8975(19),β=109.261(2)°,Z=4,C21H20N2O5,Mr=380.39,V=1899.3(4)3,Dc=1.330 g/cm3,μ=0.096 mm-1,F(000)=800,S=1.027,R=0.0535 and wR=0.1012 for 1365 observed reflections(I 2σ(I)).X-ray analysis reveals N-H…π interactions,π…π interactions and hydrogen bonds in the title molecule.     

Correction to: Complementary pairing of o-quinone methides with 3-(N,N-diethylamino)acrolein – synthesis of 1H-benzo[f]chromene-2-carbaldehydes

In the online version electronic supplementary material was mistakenly included.

     

Synthesis of 3-chloro-6,6-diphenyl-6,11-dihydropyrido[1’,2’:1,2]imidazo- [4,5- b ]quinoline based on reaction of 2-chloromethyl-4,4-diphenyl- 4h-3,1-benzoxazine with 2-amino-5-chloropyridine

Chemistry of Heterocyclic Compounds -     

Sequential Tether-Directed Synthesis of New [3 : 2 : 1] Hexakis-Adducts of C60 with a Mixed Octahedral Addition Pattern

A new concept for the regioselective synthesis of [3 : 2 : 1] hexakis-adducts of fullerene C₆₀ was developed. Based on sequential tether-directed remote functionalizations, chiral [3 : 2] pentakis-adducts with an incomplete octahedral addition pattern were synthesized via stepwise cyclopropanation of C₆₀ with suitable macrocyclic tri- and bifunctional cyclomalonate tethers. The four resulting stereoisomers were isolated using chiral HPLC. The corresponding pairs of enantiomers show mirror image behavior in their CD-spectra. The pentakis-adducts served as suitable building blocks for the spatially controlled synthesis of mixed hexakis-adducts. Implementation of functional group-bearing monomalonates afforded octahedral [3 : 2 : 1] hexakis-adducts suitable for the construction of larger molecular and supramolecular fullerene architectures in excellent yield.     

[3 + 3] Cyclocondensation of 1-alkyl-3,4-dihydroisoquinolines with β-keto esters. New annelation reaction in a series of cyclic Schiff’s bases

A new annelation reaction in a series of cyclic Schiffs bases is described with examples of [3 + 3] cyclocondensation of 1-alkyl-3,4-dihydroquinolines and acetoacetic esters.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1492–1500, October, 2004.     

Silica Gel Catalyzed Conversion of Dialkyl 2-(2-Hydroxy-1-naphthyl)-3-(1,1,1-triphenyl-λ 5 -phosphanylidene) Succinates to Alkyl 3-Oxo-3 H -benzo[ f ]chromene-1-carboxylates in Solvent-free Conditions

Protonation of the highly reactive 1:1 intermediates produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates by 2-hydroxynaphthalene leads to vinyltriphenylphosphonium salts, which undergo aromatic electrophilic substitution reaction with conjugate base to produce dialkyl 2-(1-hydroxy-2-naphthyl)-3-(1,1,1-triphenyl- u 5 -phosphanylidene) succinates. Silica gel was found to catalyze conversion of dialkyl 2-(1-hydroxy-2-naphthyl)-3-(1,1,1-triphenyl- u 5 -phosphanylidene) succinates to alkyl 3-oxo-3H-benzo[f]chromene-1-carboxylates in solvent-free conditions at 60°;C in fairly good yields.     

A new convenient four-component synthesis of 6-amino-2H, 4H-pyrano[2,3-c]pyrazole-5-carbonitriles and one-pot synthesis of 6 ′-amino-5-cyano-1,2-dihydrospiro-[(3H)-indole-3,4 ′-(4 ′H)-pyrano[2,3-c]pyrazol]-2-ones

A new convenient method for the synthesis of 6-amino-2H,4H-pyrano[2,3-c]pyrazole-5-carbonitriles, namely, four-component condensation of carbonyl compounds (aromatic aldehydes, heterocyclic ketones), malononitrile, β-keto esters, and hydrazine hydrate in ethanol in the presence of triethylamine as a catalyst, which occurs selectively, is developed. One-pot two-step modification of this method is proposed for the synthesis of spiro[(3 H)-indole-3,4 ′-(4′H)-pyrano[2,3-c]pyrazol]-2-ones.     

Reaction of 1-substituted 3,5-diamino-1,2,4-triazoles with β-keto esters: synthesis and new rearrangement of mesoionic 3-amino-2H-[1,2,4]triazolo-[4,3-a]pyrimidin-5-ones

Reaction of 3,5-diamino-1-R-1,2,4-triazoles (R=Ph, Bn) with β-keto esters results in the reversible formation of N-(5-amino-1-R-1,2,4-triazol-3-yl)-substituted enaminoesters (8). Subsequent transformations depended on the reaction conditions. Compounds 8 undergo intermolecular reactions of condensation and amidation in the absence of solvent. However, in the presence of acetic acid they form 3-amino-5-oxo-2-R-2,5-dihydro-[1,2,4]triazolo[4,3-a]pyrimidin-4-ium-8-ides (10) followed by rearrangement to 3-amino-1-R-[1,2,4]triazolo[4,3-a]pyrimidin-5-ones (11). The transformation of 10 into 11 represents a new type of rearrangement in the azolopyrimidine series. Heating of enaminoesters 8 in ethanol with sodium ethoxide present, proved to be a suitable method for the preparation of the mesoionic compounds 10.     

3H-Pyrroles as a platform for the catalyst-free construction of dihydropyrrolo[2,1-b]oxazoles: [4 + 2]-cycloaddition vs [2 + 3]-annulation with 1-cyano-3-hydroxyalkynes

Non-aromatic pyrrole isomers, 3,3-dialkyl-2-aryl-3H-pyrroles, were reacted with 1-cyano-3-hydroxyalkynes under mild, catalyst-free conditions (20–60?°C) to regio- and stereoselectively afford (Z)-2-(dihydropyrrolo[2,1-b]oxazolylidene)acetonitriles in 62–82% yield, thus evidencing the preference for [2?+?3]-annulation over the [4?+?2]-Diels-Alder alternative. The reaction involves initial nucleophilic addition of the pyrrole moiety at the triple bond followed by tandem ring closure of an anionic intermediate.     

Formation of 3a′,8′-dimethyl-3a′,5′-dihydro-1′H,3′H-dispiro-[cyclohexane-1,3′-furo[3,4-f][2]benzofuran-5′,1″-cyclohexane]-1′,7′(4′H)-dione in the reaction of 3-acetyl-4-methyl-1-oxaspiro[4.5]dec-3-en-2-one with potassium hydroxide

3a′,8′-Dimethyl-3a′,5′-dihydro-1′H,3′H-dispiro[cyclohexane-1,3′-furo[3,4-f][2]benzofuran-5′,1″-cyclohexane]-1′,7′(4′H)-dione was synthesized by reaction of 3-acetyl-4-methyl-1-oxaspiro[4.5]dec-3-en-2-one with potassium hydroxide in water.     

The formation of alkyne and alkynyl complexes by reaction of 1-alkynes with trans-[M(N2)2(PH2PCH2CH2PPh2)2] (M  Mo OR W) and with [Mo(Ph2PCH2PPh2)3]: X-ray structure of trans-[Mo(CCPh)2(PH2PCH2CH2PPh2)2]

Reaction of RCCH (R  Ph, CO₂Meor CO₂Et) with trans-[M(N₂)₂(dppe)₂] (M  Mo or W; dppe  Ph₂PCH₂CH₂PPh₂) or [Mo(dppm)₃] (dppm  Ph₂PCH₂PPh₂) gives the alkyne complexes [M(RCCH)₂(diphos)₂] (diphos  dppe, M  Mo, R = Ph; dihpos  dppm, M  Mo, R  Ph or CO₂Me) and the alkynyl complexes trans-[M(cCR)₂(dppe)₂], [MH₂(CCR)₂ (dppe)₂] (M  Mo or W. R  Ph, CO₂Me or CO₂Et) and cis-[WH(CCCO₂Me)(dppe)₂]: the X-ray structure of trans-[Mo(CCPh)₂(dppe)₂] is reported.     

[3+2] Cycloaddition reactions of 1-substituted 3,3,3-trifluoropropenes with diazo compounds and nitrilimines – synthesis of pyrazolines and pyrazoles

Chemistry of Heterocyclic Compounds - 1,3-Dipolar cycloaddition reactions of 3,3,3-trifluoropropene derivatives containing a sulfonyl, sulfamide, or sulfoximine substituent in position 1 with...     

Reactions of N-(2-chloroacetyl)-α-amino acids with 3-cyanopyridine-2(1H)-thiones. New promising route to 3,4-dihydropyrido[3",2":4,5]thieno[3,2-e][1,4]diazepine-2(1H),5-diones

The reactions of N-(2-chloroacetyl)--amino acids with 3-cyanopyridine-2(1H)-thiones afforded N-(3-aminothieno[2,3-b]pyridin-2-ylcarbonyl)--amino acids. Heating of the latter smoothly produced 3,4-dihydropyrido[3",2":4,5]thieno[3,2-e][1,4]diazepine-2(1H),5-diones in high yields.     

Synthesis and Crystal Structure of 1-（4-Chlorophenyl）-2-cyano-3-amino-3a-hydroxy-3a,3b ,6, 7-te trah y drobenzo[ 4,5]indene

1 INTRODUCTION dimerization of α,β-unsaturated ketones[10]. Herein we discuss the crystal structure of the title compound In the early seventies three groups of investiga- synthesized by the reaction of 2-cyano-3-(4-chloro- tors[1~3] have established that low-valent titanium phenyl)-3-(1-tetralon-2-yl) induced by TiCl4/Zn system. can abstract oxygen from ketones or aldehydes, lead- When 2-cyano-3-(4-chlorophenyl)-3-(1-tetra- lon-2-yl) ing to the formation of olefins. A variety of other…     

Synthesis and structure of hydrazones obtained by the reaction of 2-[6-methyl-2,4-dioxo-1-(thietan-3-yl)-1,2,3,4-tetrahydropyrimidin-3-yl]acetic acide hydrazide with β-dicarbonyl compounds

Reaction of 2-[6-methyl-2,4-dioxo-1-(thietan-3-yl)-1,2,3,4-tetrahydropyrimidin-3-yl]acetic acid hydrazide with β-dicarbonyl compounds proceeds regioselectively; the structure of the formed hydrazones is governed by the structure of the β-dicarbonyl reaction component. The reaction with acetyl- and propionylacetone afforded 3-[2-(5-alkyl-3-methyl-1H-pyrazol-1-yl)-2-oxoethyl]-6-methyl-1-(thietan-3-yl)pyrimidin-2,4(1H,3H)-diones, with aroylacetones, 5-hydroxypyrazoline derivatives which are present in DMSO solutions in E′ conformation with respect to the amide bond. The condensation products with acetoacetic acid derivatives have a linear structure and consist of mixtures of E,Z- and E′,Z′-isomers owing to the geometric and conformational isomerism.