Sythesis, Characterization and Catalysis of [ η~5,η~1-C_5H_4-CHPh-PhO]TiCl_2

Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｃｏｎｓｔｒａｉｎｅｄ ｇｅｏｍｅｔｒｙｇｒｏｕｐ 4ｍｅｔａｌｌｏｃｅｎｅｃａｔａｌｙｓｔｓｈａｖｅｒｅｃｅｉｖｅｄｃｏｎｓｉｄ ｅｒａｂｌｅａｔｔｅｎｔｉｏｎｄｕｅｔｏｔｈｅｉｒｉｍｐｏｒｔａｎｃｅｉｎｃｏｍｍｅｒｃｉａｌａｐｐｌｉｃａｔｉｏｎ[1] .Ｔｈｅｓｔｒｕｃｔｕｒａｌｆｅａｔｕｒｅｏｆｔｈｉｓｔｙｐｅｏｆｍｅｔａｌｌｏｃｅｎｅｓｉｓｔｈａｔｏｎｅｏｆｔｈｅｔｗｏｃｙｃｌｏｐｅｎｔａｄｉｅｎｙｌｇｒｏｕｐｓｉｎａｎｓａ ｍｅｔａｌｌｏｃｅｎｅｃｏｍｐｌｅｘｅｓｉｓ…     

Systematic Studies on Corelation Between Hydrophobic Constant P and Solute Physico-chemical Parameters

ＳｙｓｔｅｍａｔｉｃＳｔｕｄｉｅｓｏｎＣｏｒｅｌａｔｉｏｎＢｅｔｗｅｅｎＨｙｄｒｏｐｈｏｂｉｃＣｏｎｓｔａｎｔＰａｎｄＳｏｌｕｔｅＰｈｙｓｉｃｏ┐ｃｈｅｍｉｃａｌＰａｒａｍｅｔｅｒｓ＊ＢＡＩＪｉａｎ－ｅ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，Ｌ...     

Studies on Acylthiosemicarbazides and Related Heterocycle（XXIII）──Synthesis and Bactericidal Activity of 5－（5－（3－pyridyl）－2H－tetrazole－2－ylmethyl）－2－arylamino－1，3，4－oxadia－zoles

ＳｔｕｄｉｅｓｏｎＡｃｙｌｔｈｉｏｓｅｍｉｃａｒｂａｚｉｄｅｓａｎｄＲｅｌａｔｅｄＨｅｔｅｒｏｃｙｃｌｅ（ＸＸＩＩＩ）──ＳｙｎｔｈｅｓｉｓａｎｄＢａｃｔｅｒｉｃｉｄａｌＡｃｔｉｖｉｔｙＯｆ５－（５－（３－ｐｙｒｉｄｙｌ）－２Ｈ－ｔｅｔｒａｚｏｌｅ－...     

Studies on Synthesis of a Cycloheptapeptide and Effects of Different Metal Ions on the Cyclization

ＩｎｔｒｏｄｕｃｔｉｏｎＣｙｃｌｉｃｐｅｐｔｉｄｅｓ ,ｗｈｉｃｈａｒｅｃｏｎｓｔｒａｉｎｅｄｃｏｎｆｏｒｍａ ｔｉｏｎａｌｌｙａｎｄｍｏｒｅｒｅｓｉｓｔａｎｔｔｏｐｒｏｔｅａｓｅｄｉｇｅｓｔｉｏｎｓｔｈａｎｔｈｅｉｒｌｉｎｅａｒｐｒｅｃｕｒｓｏｒｓ ,ｈａｖｅｂｅｅｎｏｆｇｒｅａｔｉｎｔｅｒｅｓｔａｓｓｙｎｔｈｅｔｉｃｔａｒｇｅｔｓｂｏｔｈａｓｐｏｔｅｎｔｉａｌｄｒｕｇｌｅａｄｓａｎｄａｓｍｏｄｅｌｓｆｏｒｃｏｎ ｆｏｒｍａｔｉｏｎａｌａｎａｌｙｓｉｓ .1 4 Ｃｕｒｒｅｎｔｍｅｔｈｏｄｓｆｏｒｓｙｎｔ…     

A New Method for the Synthesis of Ketone Diperoxide

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｔｈｅｒｍａｌａｎｄｐｈｏｔｏｃｈｅｍｉｃａｌｄｅｃｏｍｐｏｓｉｔｉｏｎｏｆｔｈｅｄｉｐｅｒｏｘｉｄｅｏｆｔｈｅｃｙｃｌｉｃｋｅｔｏｎｅｓｈａｓｂｅｅｎｆｏｕｎｄｔｏｐｒｏｖｉｄｅｔｈｅｇｅｎｅｒａｌａｎｄｆａｃｉｌｅｓｙｎｔｈｅｓｅｓｏｆｍａｃｒｏｃｙｃｌｉｃｃｏｍｐｏｕｎｄｓ［１，２］．Ｔｈｅｕｓｅｏｆｄｉｐｅｒｏｘｉｄｅｓａｓｉｎｉｔｉａｔｏｒｓｉｎｐｏｌｙｍｅｒｉｚａｔｉｏｎｈａｓａｌｓｏｂｅｅｎｓｔｕｄｉｅｄ［３］．Ｆｏｒｔｈｅｓｅｒｅａｓｏｎｓ，ａｂｅｔ…     

Studies on Systems of Lithium and Potassium Halides from Salt Lake and Bittern Resources（V）──The Quaternary Reciprocal System Li￣＋■Br￣－，I￣－－H＿2O and Boundary Ternary System NH＿4Br－NH＿4I－H＿2O at 25℃

ＳｔｕｄｉｅｓｏｎＳｙｓｔｅｍｓｏｆＬｉｔｈｉｕｍａｎｄＰｏｔａｓｓｉｕｍＨａｌｉｄｅｓｆｒｏｍＳａｌｔＬａｋｅａｎｄＢｉｔｔｅｒｎＲｅｓｏｕｒｃｅｓ（Ｖ）──ＴｈｅＱｕａｔｅｒｎａｒｙＲｅｃｉｐｒｏｃａｌＳｙｓｔｅｍＬｉ￣＋，Ｂｒ￣－，Ｉ（－）－Ｈ...     

Structures of Cytochrome b_5 Mutated at the Charged Surface-Residues and Their Interactions with Cytochrome c

ＩｎｔｒｏｄｕｃｔｉｏｎＭｉｃｒｏｓｏｍａｌｃｙｔｏｃｈｒｏｍｅｂ5(Ｃｙｔｂ5)ｉｓａｍｅｍｂｅｒｏｆｃｙｔｏｃｈｒｏｍｅｂ5ｆａｍｉｌｙ ,ａｎｄｉｔｓｅｒｖｅｓａｓａｎｅｌｅｃｔｒｏｎｃａｒｒｉｅｒｉｎａｓｅｒｉｅｓｏｆｅｌｅｃｔｒｏｎ ｔｒａｎｓｆｅｒｐｒｏｃｅｓｓｅｓｉｎｂｉｏｌｏｇｉｃａｌｓｙｓ ｔｅｍｓ .1 3 Ｃｙｔｂ5ｉｓａｍｅｍｂｒａｎｅｐｒｏｔｅｉｎｗｉｔｈＭｒ～ 16ｋＤａ ,ｃｏｎｓｉｓｔｉｎｇｏｆｔｗｏｄｏｍａｉｎｓ ,ｏｎｅｈｙｄｒｏｐｈｏｂｉｃｄｏｍａｉｎｗｈｉｃｈａｎｃｈｏｒｓｔｈ…     

Studies on Organophosphorus Compounds 97．Cu_2Ocatalyzed Reaction of Isocyanoacetate with 1－Oxoalkylphosphonate．A Novel Stereoselective Synthesis of β－Phosphoryl α，β－Dehydroamino Acid Derivatives

ＳｔｕｄｉｅｓｏｎＯｒｇａｎｏｐｈｏｓｐｈｏｒｕｓＣｏｍｐｏｕｎｄｓ９７．Ｃｕ_２ＯｃａｔａｌｙｚｅｄＲｅａｃｔｉｏｎｏｆＩｓｏｃｙａｎｏａｃｅｔａｔｅｗｉｔｈ１－Ｏｘｏａｌｋｙｌｐｈｏｓｐｈｏｎａｔｅ．ＡＮｏｖｅｌＳｔｅｒｅｏｓｅｌｅｃｔｉｖｅＳｙ...     

Photoinduced Electron Transfer between N,N,N′,N′-Tetra-(p-methylphenyl)-4,4-diamino-1,1′-diphenyl Ether (TPDAE) and Fullerenes (C_(60)/C_(70)) by Laser Flash Photolysis

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｐｈｏｔｏｉｎｄｕｃｅｄｅｌｅｃｔｒｏｎｔｒａｎｓｆｅｒ (ＰＥＴ)ｉｓｏｎｅｏｆｔｈｅｍｏｓｔｉｎｔｅｒｅｓｔｉｎｇｆｅａｔｕｒｅｓｏｆｄｏｎｏｒ ａｃｃｅｐｔｏｒｓｙｓｔｅｍｓｆｏｒｔｈｅｄｅｓｉｇｎａｎｄｔｈｅｃｏｎｓｔｒｕｃｔｉｏｎｏｆａｒｔｉｆｉｃｉａｌｍｏｌｅｃｕｌａｒｄｅｖｉｃｅｓｆｏｒｅｎｅｒｇｙｃｏｎｖｅｒｓｉｏｎａｎｄｉｎｆｏｒｍａｔｉｏｎｐｒｏｃｅｓｓｉｎｇｗｈｉｃｈｈａｖｅａｎｕｍｂｅｒｏｆｐｏｔｅｎｔｉａｌｌｙｉｎｔｒｉｇｕｉｎｇａｐｐｌｉｃａｔ…     

Synthesis, Structure and Magnetic Properties of Two New Homotrinuclear Bis(oxamato) Copper(II) Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＭｏｌｅｃｕｌａｒｍａｇｎｅｔｉｓｍｏｆｐｏｌｙｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓｉｓｏｆｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｆｏｒｄｅｓｉｇｎｉｎｇｎｅｗｍａｇｎｅｔｉｃｍａｔｅｒｉａｌｓａｎｄｆｏｒｉｎｖｅｓｔｉｇａｔｉｎｇｔｈｅｒｅｌａｔｉｏｎｓｈｉｐｂｅｔｗｅｅｎｔｈｅｓｔｒｕｃｔｕｒｅａｎｄｔｈｅｒｏｌｅｏｆｔｈｅｐｏｌｙｍｅｔａｌｌｉｃａｃｔｉｖｅｓｉｔｅｓｉｎｂｉｏｌｏｇｉｃａｌｓｙｓｔｅｍｓ.1 4 Ｊｏｕｒｎａｕｘｅｔａｌ .5ｈａｖｅｒｅｃｅｎｔｌｙｐｒｏｐ…     

Investigation of Some Functionalization Reactions of 4‐Benzoyl‐5‐phenyl‐1‐(4‐methoxyphenyl)‐1H‐pyrazole‐3‐carbonyl Chloride and Their Antimicrobial Activity

The 1H‐pyrazole‐3‐carboxylic acid 1 was converted via reactions of its acid chloride 3 with various asymmetrical disubstituted urea and alcohol derivatives into the corresponding novel 4‐benzoyl‐N‐(N′,N′‐dialkylcarbamyl)‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxamide 4a , b and alkyl 4‐benzoyl‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxylate 7a‐c , respectively, in good yields (57%‐78%). Friedel‐Crafts reactions of 3 with aromatic compouns for 15 min.‐2 h led to the formation of the 4‐3‐diaroyl‐1‐(4‐hydroxyphenyl)‐5‐phenyl‐1H‐pyrazoles 9a‐c , 4‐benzoyl‐1‐(4‐methoxyphenyl)‐3‐aroyl‐5‐phenyl‐1H‐pyrazoles 10a , b and than from the acylation reactions of 9a‐c were obtained the 3,4‐diaroyl‐1‐(4‐acyloxyphenyl)‐5‐phenyl‐1H‐pyrazoles 13a‐d . The structures of all new synthesized compounds were established by NMR experiments such as ¹H, and ¹³C, as well as 2D COSY and IR spectroscopic data, and elemental analyses. All the compounds were evaluated for their antimicrobial activities (agar diffusion method) against eight bacteria and two yeasts.     

Synthesis of Some Novel 3,6‐Bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole Derivatives

The cyclization of 1‐amino‐2‐mercapto‐5‐[1‐(4‐ethoxyphenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐1,3,4‐triazole which was synthesized from p‐ethoxyaniline with various triazole acid in absolute phosphorus oxychloride yields 3,6‐bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole derivatives 9a?j , and their structures are established by MS, IR, CHN and ¹H NMR spectral data.     

O‐2′,3′‐Ketal‐Nucleolipids of the Cytostatic 5‐Fluorouridine: Synthesis,Lipophilicity, and Acidic Stability

The synthesis of a series of cyclic and acyclic O‐2′,3′‐ketal derivatives of the cancerostatic 5‐fluorouridine ( 2a ) is described. The novel compounds were characterized by ¹H‐ and ¹³C‐NMR, and UV spectroscopy, as well as by elemental analyses. The lipophilicity values (log P, retention times in RP‐18 HPLC) of the cyclic ketals were determined and related to the ring tensions as well as the acid stability of the spiro‐linked ketal rings.     

Synthesis of (5′S)‐5′‐C‐Alkyl‐2′‐deoxynucleosides

We describe the synthesis of (5′S)‐5′‐C‐butylthymidine ( 5a ), of the (5′S)‐5′‐C‐butyl‐ and the (5′S)‐5′‐C‐isopentyl derivatives 16a and 16b of 2′‐deoxy‐5‐methylcytidine, as well as of the corresponding cyanoethyl phosphoramidites 9a , b and 14a , b , respectively. Starting from thymidin‐5′‐al 1 , the alkyl chain at C(5′) is introduced via Wittig chemistry to selectively yield the (Z)‐olefin derivatives 3a and 3b (Scheme 2). The secondary OH function at C(5′) is then introduced by epoxidation followed by regioselective reduction of the epoxy derivatives 4a and 4b with diisobutylaluminium hydride. In the latter step, a kinetic resolution of the diastereoisomer mixture 4a and 4b occurs, yielding the alkylated nucleoside 2a and 2b , respectively, with (5′S)‐configuration in high diastereoisomer purity (de=94%). The corresponding 2′‐deoxy‐5‐methylcytidine derivatives are obtained from the protected 5′‐alkylated thymidine derivatives 7a and 7b via known base interconversion processes in excellent yields (Scheme 3). Application of the same strategy to the purine nucleoside 2′‐deoxyadenine to obtain 5′‐C‐butyl‐2′‐deoxyadenosine 25 proved to be difficult due to the sensitivity of the purine base to hydride‐based reducing agents (Scheme 4).     

A Novel,One‐Pot Four‐Component Route to 2′‐Thioxo‐2′,3′‐dihydrospiro[indole‐3,6′‐[1,3]thiazin]‐2‐one Derivatives

An efficient route to 2′,3′‐dihydro‐2′‐thioxospiro[indole‐3,6′‐[1,3]thiazin]‐2(1H)‐one derivatives is described. It involves the reaction of isatine, 1‐phenyl‐2‐(1,1,1‐triphenyl‐λ⁵‐phosphanylidene)ethan‐1‐one, and different amines in the presence of CS₂ in dry MeOH at reflux (Scheme 1). The alkyl carbamodithioate, which results from the addition of the amine to CS₂, is added to the α,β‐unsaturated ketone, resulting from the reaction between 1‐phenyl‐2‐(1,1,1‐triphenyl‐λ⁵‐phosphanylidene)ethan‐1‐one and isatine, to produce the 3′‐alkyl‐2′,3′‐dihydro‐4′‐phenyl‐2′‐thioxospiro[indole‐3,6′‐[1,3]thiazin]‐2(1H)‐one derivatives in excellent yields (Scheme 2). Their structures were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses.     

Heterocyclic Systems Containing Bridged Nitrogen Atom: Synthesis and Antibacterial Activity of 3‐(2‐Phenylquinolin‐4‐yl)/3‐(1‐p‐Chlorophenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazine Derivatives

The condensation of 4‐amino‐5‐mercapto‐3‐(2‐phenylquinolin‐4‐yl)/3‐(1‐p‐chlorophenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazoles 1a‐b with chloroacetaldehyde 2a‐b , ω‐bromo‐ω‐(1H‐1,2,4‐triazol‐1‐yl)acetophenone 3a‐b , chloranil 4a‐b , 2‐bromocyclohexanone 5a‐b , 2,4′‐dibromoacetophenone 6a‐b and 2‐bromo‐6′‐methoxy‐2′‐acetonaphthone 7a‐b are described. The structures of the compounds synthesized were confirmed by elemental analyses, IR, 1H NMR and mass spectra. The antibacterial activities were also evaluated.     

Synthesis of Novel 3‐Acetyl‐2‐Aryl‐5‐(3‐Aryl‐1‐Phenyl‐Pyrazol‐4‐yl)‐2,3‐Dihydro‐1,3,4‐Oxadiazoles

A series of novel pyrazolyl‐substituted 1,3,4‐oxadiazole derivatives ( 4a‐4o ) were prepared by cyclization of the intermediate N′‐((3‐aryl‐l‐phenyl‐pyrazol‐4‐yl)methylene)arylhydrazide with acetic anhydride. The structures of the new compounds were confirmed by IR, ¹H NMR, MS and elemental analysis. Furthermore, preliminary bioassay of some of the title compounds indicated that they exhibited moderate inhibition against HIV‐1 PR.     

Functionalized 3,3′,5,5′‐Tetraaryl‐1,1′‐Biphenyls: Novel Platforms for Molecular Receptors

This paper describes the development of novel aromatic platforms for supramolecular construction. By the Suzuki cross‐coupling protocol, a variety of functionalized m‐terphenyl derivatives were prepared (Schemes 1–4). Macrolactamization of bis(ammonium salt) (S,S)‐ 6 with bis(acyl halide) 7 afforded the macrocyclic receptor (S,S)‐ 2 (Scheme 1), which was shown by ¹H‐NMR titration studies to form ‘nesting' complexes of moderate stability (K_a between 130 and 290 M ^?1, 300 K) with octyl glucosides 13 – 15 (Fig. 2) in the noncompetitive solvent CDCl₃. Suzuki cross‐coupling starting from 3,3′,5,5′‐tetrabromo‐1,1′‐biphenyl provided access to a novel series of extended aromatic platforms (Scheme 5) for cleft‐type (Fig. 1) and macrotricyclic receptors such as (S,S,S,S)‐ 1 . Although mass‐spectral evidence for the formation of (S,S,S,S)‐ 1 by macrolactamization between the two functionalized 3,3′,5,5′‐tetraaryl‐1,1′‐biphenyl derivatives (S,S)‐ 33 and 36 was obtained, the ¹H‐ and ¹³C‐NMR spectra of purified material remained rather inconclusive with respect to both purity and constitution. The versatile access to the novel, differentially functionalized 3,3′,5,5′‐tetrabromo‐1,1′‐biphenyl platforms should ensure their wide use in future supramolecular construction.     

Tandem Hydroformylation/Reductive Amination of 3‐Allyl‐2‐methylquinazolin‐4(3H)‐one

The 3‐allyl‐2‐methylquinazolin‐4(3H)‐one ( 1 ), a model functionalized terminal olefin, was submitted to hydroformylation and reductive amination under optimized reaction conditions. The catalytic carbonylation of 1 in the presence of Rh catalysts complexed with phosphorus ligands under different reaction conditions afforded a mixture of 2‐methyl‐4‐oxoquinazoline‐3(4H)‐butanal ( 2 ) and α,2‐dimethyl‐4‐oxoquinazoline‐3(4H)‐propanal ( 3 ) as products of ‘linear’ and ‘branched’ hydroformylation, respectively (Scheme 2). The hydroaminomethylation of quinazolinone 1 with arylhydrazine derivatives gave the expected mixture of [(arylhydrazinyl)alkyl]quinazolinones 5 and 6 , besides a small amount of 2 and 3 (Scheme 3). The tandem hydroformylation/reductive amination reaction of 1 with different amines gave the quinazolinone derivatives 7 – 10 . Compound 10 was used to prepare the chalcones 11a and 11b and pyrazoloquinazolinones 12a and 12b (Scheme 4).     

Synthesis of 2‐Aryl‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐2,5‐dihydro‐1H‐pyrrole‐3‐carboxylates by the Reaction between Hydrazones,Acetylenedicarboxylates, and 1‐Aryl‐N,N′‐bis(arylmethylidene)methanediamines

An efficient approach for the preparation of functionalized 2‐aryl‐2,5‐dihydro‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐1H‐pyrroles is described. The four‐component reaction between aldehydes, NH₂NH₂?H₂O, dialkyl acetylenedicarboxylates, and 1‐aryl‐N,N′‐bis(arylmethylidene)methanediamines proceeds in EtOH under reflux in good‐to‐excellent yields (Scheme 1). The structures of 4 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS, and, in the case of 4f , by X‐ray crystallography). A plausible mechanism for this type of reaction is proposed (Scheme 2).