吡啶基咪唑[4,5-f]1,10-菲咯啉合成、表征及与瓜环作用的光谱学考察

设计合成了2个吡啶基菲咯啉衍生物2-(3-吡啶基)咪唑[4,5-f]1,10-菲咯啉(G1)和2-(4-吡啶基)咪唑[4,5-f]1,10-菲咯啉(G2),通过元素分析、质谱和核磁共振氢谱对其结构进行了表征。 利用紫外吸收光谱和荧光光谱法考察了所合成化合物与六元瓜环Q[6]、七元瓜环Q[7]的相互作用,以及体系pH值对主-客体相互作用的影响。 在酸性条件下,Q[6]、Q[7]与Gl以及Q[6]与G2均发生包合形成1∶1的包合物,并有荧光增敏作用;Q[7]与G2作用形成1∶2包合物,且对G2有荧光猝灭作用;Q[6]、Q[7]与G1的包合常数分别为3.00×104和1.86×104 L/mol;Q[6]、Q[7]与G2的包合常数分别为1.64×104和1.01×103 L/mol。 随着体系酸性减弱,瓜环与客体作用减弱,在中性条件下,瓜环未与客体发生包合作用。     

Sulfur-rich heterocycles from 2-metalated benzo[b]thiophene and benzo[b]furan: synthesis and structure

The reaction of 2-lithiated benzo[b]thiophene with 8 equiv of elemental sulfur was found to give pentathiepino[6,7-b]benzo[d]thiophene. In contrast, treatment of 2-lithiated benzo[b]furan with sulfur under similar conditions produced the interesting ring system bis(benzo[4,5]furo)[2,3-e:3',2'-g][1,2,3,4]tetrathiocine. Both of these new cyclic polysulfides were studied by X-ray crystallography. Two polymorphic forms of pentathiepino[6,7-b]benzo[d]thiophene were found, displaying similar conformations but different packing schemes, which was also evident from powder diffraction data.     

Synthesis of two new heterocyclic ring systems: Benzo[3,4] cyclohepta[1,2-d]-pyrimidines and benzo[3,4]cyclohepta[2,1-d] pyrimidines

Three 2,4-diamino-l(), 11-dihydro-9H-benzo[3,4]cyclohepta[ 1,2-d]pyrimidines (6a-6c) representing the first examples of a new ring system were synthesized from 2-benzosuberones and cyanoguanidine. Similarly, 2,4-diamino-6,7-dihydro-5H-benzo[3,4]cyelohepta[2,1-d]pyrimidine ( 24 ) was prepared from 1-benzosuberone. The ultraviolet spectral properties of these compounds were examined with reference to those of the analogs in which the central ring is five- and six-mernbered.     

Formation of intramolecular rings in ferramonocarbollide complexes

Addition of PPh 2Cl and Tl[PF 6] to CH 2Cl 2 solutions of [N(PPh 3) 2][6,6,6-(CO) 3- closo-6,1-FeCB 8H 9] ( 1) affords the isomeric B-substituted species [6,6,6-(CO) 3- n-(PHPh 2)- closo-6,1-FeCB 8H 8] [ n = 7 ( 2a) or 10 ( 2b)]. Deprotonation (NaH) of the phosphine ligand in 2a, with subsequent addition of [IrCl(CO)(PPh 3) 2] and Tl[PF 6], yields the neutral, zwitterionic complex [6,6,6-(CO) 3-4,7-mu-{Ir(H)(CO)(PPh 3) 2PPh 2}- closo-6,1-FeCB 8H 7] ( 3), which contains a B-P-Ir- B ring. Alternatively, deprotonation using NEt 3, followed by addition of HC[triple bond]CCH 2Br, affords [6,6,6-(CO) 3-7-(PPh 2CCMe)- closo-6,1-FeCB 8H 8] ( 4). Addition of [Co 2(CO) 8] to CH 2Cl 2 solutions of the latter gives [6,6,6-(CO) 3-7-(PPh 2-{(mu-eta (2):eta (2)-CCMe)Co 2(CO) 6})- closo-6,1-FeCB 8H 8] ( 5), which contains a {C 2Co 2} tetrahedron. In the absence of added substrates, deprotonation of the PHPh 2 group in compounds 2, followed by reaction of the resulting anions with CH 2Cl 2 solvent, affords [6,6,6-(CO) 3- n-(PPh 2CH 2Cl)- closo-6,1-FeCB 8H 8] [ n = 7 ( 6a) or 10 ( 6b)] plus [6,6-(CO) 2-6,7-mu-{PPh 2CH 2PPh 2}- closo-6,1-FeCB 8H 8] ( 7, formed from 2a), of which the latter species possesses an intramolecular B-P-C-P- Fe ring. Addition of Me 3NO to CH 2Cl 2 solutions of 2a causes loss of an Fe-bound CO ligand and formation of [6,6-(CO) 2-6,7-mu-{NMe 2CH 2PPh 2}- closo-6,1-FeCB 8H 8] ( 8), which incorporates a B-P-C-N- Fe ring. A similar reaction in the presence of ligands L yields [6,6-(CO) 2-6-L-7-(PPh 2CH 2Cl)- closo-6,1-FeCB 8H 8] [L = PEt 3 ( 9) or CNBu (t) ( 10)], in addition to 8.     

Benzindoles

The behavior of tetrahydro[4,5]- and tetrahydro[6,7]benzinodoles in the Vilsmeier reaction was investigated. It was established that the steric hindrance created by the cyclohexane ring condensed in the 4 and 5 positions has a substantial effect on the character of the reaction of tetrahydrobenzindoles with various N,N-disubstituted amines. A case of N-acylation in the investigated reactions is described. 3-Formyl-4,5,6,7-tetrahydro[4,5]- and 6,7,8,9-tetrahydro[6,7]-benzindoles were converted to the corresponding tryptamines.See [1] for communication 16.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 360–365, March, 1979.     

Synthesis of some novel tetracyclic imidazole derivatives

Representatives have been made of three new heterocyclic systems (IIH) containing an imidazole ring. Synthetic routes are described for compounds of type II where X = CH₂ (8H-dibenzo[3,4: 6,7]cyclohept[1,2-d] imidazoles), and X = CH₂CH₂ (8,9-dihydrodibenzo[3,4:7,8]cyclooct[1,2-d] imidazoles) and X = S (dibenzo[2,3:6,7] thiepin] 4,5-d] imidazoles). In addition, improved syntheses are presented for some previously known compounds employed as intermediates in this work.     

Mannich-type reactions of an isobasic isoquinoline

Base catalyzed reaction of 1-cyanomethylene-6,7-dimethoxy-1,2,3,4-tetrahyroisoquinoline (I) with 2 moles of formaldehyde gave rise to the 1,3-oxazino[4,3-a ]isoquinoline ring system (III). Reaction of I with a primary amine and 2 moles of formaldehyde gave pyrimido[ 6,1-a ]-isoquinoline (VI).     

A versatile synthesis of diverse 3,4-fused cinnolines via the base-catalysed condensation of 2-amino-2'-nitrobiaryls

Benzo[c]cinnolines, thieno[3,2-c]cinnolines, pyrido[3,2-c]cinnolines and the previously undescribed quinoxalino[6,7-c]cinnoline ring system are conveniently prepared by a short synthetic route comprised of Suzuki coupling, base-catalysed cyclisation and deoxygenation. The use of tandem borylation-Suzuki coupling further extends the scope of this process to include highly substituted benzo[c]cinnolines.     

Ruthenium/TFA-catalyzed coupling of activated secondary propargylic alcohols with cyclic 1,3-diones: furan versus pyran ring formation

A catalytic system consisting of the 16-electron allyl-ruthenium(II) complex [Ru(eta(3)-2-C3H4Me)(CO)(dppf)][SbF6] (dppf = 1,1'-bis(diphenylphosphino)ferrocene) and trifluoroacetic acid (TFA) has been used to promote the coupling between secondary propargylic alcohols and cyclic 1,3-diketones. The nature of the resulting products was found to be dependent on the ring size of the dicarbonyl compound employed. Thus, whereas 6,7-dihydro-5H-benzofuran-4-ones have been selectively obtained starting from 1,3-cyclohexanediones, via furan-ring formation, the use of 1,3-cyclopentanedione leads instead to 6,7-dihydro-4H-cyclopenta[b]pyran-5-ones via a pyran-ring formation process.     

The reactivity of defects at the sidewalls of single-walled carbon nanotubes: the Stone-Wales defect

The reactivity of 5/7/7/5 (Stone-Wales, SW) defects is compared to that of the pristine sidewalls of (5,5) and (10,0) carbon nanotubes (CNTs) using density functional theory (PBE). Infinite tube models (periodic boundary conditions) are used to investigate the reaction energy for CH(2) addition to the ten [5,6], [5,7], [6,7], and [7,7] C-C junctions resulting from SW rotations of the two unique bonds in (5,5) and (10,0) CNTs. In all cases, at least one of the junctions associated with the SW defects is more highly reactive than the pristine tubes. The orientation of these junctions with respect to the tube axis mainly determines the exothermicity. The [7,7] junctions are not the most reactive sites in SW defects of (5,5) and (10,0) CNTs.     

Simultaneous Formation of 8H-Isoquino[2,1-b][2,7]naphthyridin-8-ones and 13H-Pyrido[4′,3′:3,4]pyrrolo[2,1-b][3]benzazepin-13-ones,a Novel Potential Alkaloidal System

Condensation of 3,4-dihydro-6,7-dimethoxyisoquinoline ( 4 ) with 4-methylnicotinoyl chloride ( 12 ) in refluxing pyridine gives 5,6,13,13a-tetrahydro-2,3-dimethoxy-8H-isoquino[2,1-b][2,7] naphthyridin-8-one ( 11 ), along with some of its 13,13a-didehydro derivative 7 . A similar reaction of 4 with 4-(chloromethyl)nicotinoyl chloride ( 14 ) affords, in addition to 7 , the isomeric product 10,11-dihydro-7,8-dimethoxy-13H-pyrido[4′,3′:3,4]pyrrolo[2,1- b][3]benzazepin-13-one ( 3 ). Analogous pairs of products are obtained from 3,4-dihydro-6,7-(methylenedioxy)- and 3,4-dihydro-6,7,8-trimethoxy-isoquinolines ( 15 and 18 , resp.). The structure of 3 was established by extensive NMR data and confirmed by single-crystal X-ray studies. Structure 7 has the ring system of the Alangium alkaloids like alangimarinc ( 1 ), while the isomeric ring system 3 is predicted to be present in nature on biogenetic reasoning.     

Polycyclic N‐Heterocyclic Compounds. Part 81: Synthesis and Evaluation of Pentacyclic 1,2,4,5‐Tetrahydro[1]benzothieno[2′,3′:6,7]thiepino[4,5‐e]imidazo[1,2‐c]pyrimidine and Related Compounds as Potential Antiplatelet Aggregators

Dehydrative ring closure reactions were carried out on fused 4‐(2‐hydroxyethylamino) (or 2‐hydroxyethoxy or 2‐hydroxyethylthio)pyrimidines ( 2a , 2b , 2c ) to give fused 2,3‐dihydroimidazo[1,2‐c] (or 2,3‐dihydrooxazolo[3,2‐c] or 2,3‐dihydrothiazolo[3,2‐c])pyrimidines. This reaction produced the pentacyclic 1,2,4,5‐tetrahydro[1]benzothieno[2′,3′:6,7]thiepino[4,5‐e]imidazo[1,2‐c]pyrimidine ( 3a ) and 1,2,4,5‐tetrahydro[1]benzothieno[2′,3′:6,7]thiepino[4,5‐e]thiazolo[3,2‐c]pyrimidinium chloride ( 3c ) from the 2‐hydroxyethylamino‐derivative and 2‐hydroxyethylthio‐derivative, respectively. In contrast, 2‐hydroxyethoxy‐derivative ( 2b ) gave the rearrangement product, 3‐(2‐chloroethyl)‐5,6‐dihydro[1]benzothieno[3′,2′:2,3]thiepino[4,5‐d]pyrimidin‐4(3H)‐one ( 4 ). Effects of the synthesized compounds on collagen‐induced platelet aggregation were also evaluated.     

Synthesis of Heterocyclic Compounds from 2-Phenyl-l,2,3-Triazole-4-Formylhydrize

Many compounds containing the 1,3,4-oxadiazole and/or1,2,3(or 4)-triazole and thiadiazole ring system are reported to possess antibacterial^[1], antiinflammatory^[2], anticonrulsant^[3],CNS stimulant^[4] and pesticidal^[5] activities and excellent anthelmintic properties^[6,7]. In view of this and the results of the combined different nuclei system in a molecular always enhancing the therapeutic activities,the present work deals with the synthesis of the combined different pharmacologically active nuclei system mentioned above in a molecular through some new method.     

Benzindoles. 24. Reduction of nitro-2,3-dimethyl[4,5]- and nitro-2,3-dimethyl[6,7]benzindoles

The reduction of nitro-2,3-dimethyl[4,5]- and -[6,7]benzindoles was studied; Benzindoles were obtained with an amino group in the benzene ring. Individual isomers can be separated as the acyl derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1481–1484, November, 1986.     

Unusual reactions of 5,5-dimethyl-2-(indenyl-2)-3-pyrazolidinone with acetylenedicarboxylates

[reaction: see text] Reaction of 5,5-dimethyl-3-pyrazolidinone (1) with 2-indanone (2) gave 5,5-dimethyl-2-(1H-indenyl-2)-3-pyrazolidinone (3) instead of the expected azomethine imine 4. Although reaction of 2-substituted 3-pyrazolidinones with acetylenedicarboxylates usually gives ring expansion products, such as 1,2-diazepines, treatment of 3 with dialkyl acetylenedicarboxylates (5, R = Me; 6 R = Et) resulted in the formation of rel-(7aR,12aS)-6,7-bis(alkoxycarbonyl)-3,4-dihydro-4,4-dimethyl-7aH-indano[1,2-b]pyrrolo[1,2-a]pyrimidin-2-ones (7, R = Me; 9, R = Et) as major products and 3,4-bis(alkoxycarbonyl)-7,7-dimethyl-2-(indenyl-2)-6,7-dihydro-2H,6H-1,2-diazepin-5-ones (8, R = Me: 10, R = Et) as minor products.     

Synthesis of thiopyrano[4″,3″:4′,5′]pyrido[3′,2′:4,5]furo[3,2-d]pyrimidines

<正>Reactions of the 6-hydroxy-thiopyrano[3,4-c]pyridine-5-carbonitrile derivative 1 withα-halo-carbonyl compounds gave the ortho-substituted intermediates 2a-c which were converted into furo[2,3-b]thiopyrano[4,3-d]pyridines 3a-c by fusion of a furan moiety under basic conditions.Further cyclization of 3a-c led to a fusion of a pyrimidine ring,yielding the tetracyclic products 6,7 and 8.In addition,condensation of 6 with various aromatic aldehydes afforded the corresponding imines 9a,b.Mannich reaction of 7 gave products 10a,b.     

Synthesis of some novel imidazolidine derivatives and their metal complexes with biological and antitumor activity

Halogenated imidazo(pyrazine,[1,4]diazocine and quinoxaline), 9,10‐anthraquinone‐ [6,7‐e], phenanthroline[5,6‐e] {imidazo[4,5‐b]pyrazine}, and naphtho[1,8‐ef]imidazo[4,5‐b][1,4] diazipen were obtained through interaction of imidazolidineiminothiones with the corresponding diamino compounds. Imidazo[4,5‐e] triazine and pyrrolo[2,3‐d]imidazole were prepared when the iminothiones were reacted with thiocarbohydrazide and with ethylphenyl acetate, separately. Some of the synthesized compounds exhibited better biological and antitumor activities. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:634–647, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20244     

Formation and Ring Contraction of Benzo[f][1,2]Thiazepine-1,1-Dioxides from and to Benzo[e][1,2]Thiazine-1,1-Dioxides

Alkoxide-promoted ring expansion of the novel ethyl 2-(6,7-dimethoxy-3-oxo-3,4-dihydrobenzo[e][1,2]thiazine-1,1-dioxide-2-yl)acetate 3a and analogous 4,4-diethyl derivative 3b and cyclization of methyl 2-[2-(phenylaminocarbonylmethyl sulfamoyl)-4,5-dimethoxyphenyl] acetate 9 to the corresponding new 3-carboxylates and 3-carboxanilide of 7,8-dimethoxy-4-hydroxy-2,5-dihydrobenzo[f][1,2]thiazepine-1,1-dioxide (5a,b and 10 respectively) is described. Compound 5a was deacylated upon treatment with sodium hydroxide followed by hydrochloric acid to give 7,8-dimethoxy-2,3-dihydrobenzo[f][1,2]thiazepine-1,1-dioxide-4 (5H)-one 8 and its N-ethyl derivative transferred to 6,7-dimethoxy-2-ethyl-3-oxo-3,4-dihydrobenzo[e][1,2]thiazine-1,1-dioxide 7 by the reaction with ethyl methyl ketone in the presence of pyrrolidine.     

Total synthesis of (-)- and ent-(+)-vindoline and related alkaloids

A concise 11-step total synthesis of (-)- and ent-(+)-vindoline (3) is detailed based on a unique tandem intramolecular [4 + 2]/[3 + 2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which three rings and four C-C bonds are formed central to the characteristic pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. As key elements of the scope and stereochemical features of the reaction were defined, a series of related natural products of increasing complexity were prepared by total synthesis including both enantiomers of minovine (4), 4-desacetoxy-6,7-dihydrovindorosine (5), 4-desacetoxyvindorosine (6), and vindorosine (7) as well as N-methylaspidospermidine (11). Subsequent extensions of the approach provided both enantiomers of 6,7-dihydrovindoline (8), 4-desacetoxyvindoline (9), and 4-desacetoxy-6,7-dihydrovindoline (10).     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

N-(-Chloro--hydroxy)propyl derivatives of 5-chloro-1-naphthylamine, 8-chloro-1-naphthylamine, and 5-cyano-1-naphthylamine were obtained. They were cyclized to 1,2,3,4-tetrahydro-3-hydroxy-7-chlorobenzo[f]quinoline (II), 1,2,3,4-tetrahydro-3-hydroxy-10-chlorobenzo-[fJquinoline (VII), and 1,2,3,4-tetrahydro-3-hydroxy-7-cyanobenzo[f]quinoline (X). Chlorination at the 6 position to form 1,2,3,4-tetrahydro-3-hydroxy-6,7-dichlorobenzo[f]quinoline occurs under the action of thionyl chloride on II at room temperature. The action of thionyl chloride on II, VII, and X at elevated temperatures leads not only to chlorination at the 6 position but also to aromatization of the tetrahydropyridine ring to form, respectively, 6,7-dichlorobenzo[f]quinoline (V), 6,10-dichlorobenzo[f]quinoline (VIII), and 6-chloro-7-cyanobenzo[f]quinoline (XIII).See [5] for Communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1522–1525, November, 1970.