Novel pyrrolo[1,2-a][3.1.6]benzothiadiazocine ring synthesis. Unusual Truce-Smiles type rearrangement of 1-{[1-(2-nitrophenyl)-1H-pyrrol-2-yl]sulfonyl(or sulfinyl)}acetone

Reaction of 1-{[1-(2-nitrophenyl)-1H-pyrrol-2-yl]sulfonyl}acetone with sodium hydroxide with or without zinc gave 1-(2-nitrophenyl)(1H-pyrrol-2-ylsulfonyl)methane by a Truce-Smiles type of transformation and 1-(2-nitrophenyl)-2-methylsulfonylpyrrole by deacetylation. Similar treatment of 1-{[1-(2-nitrophenyl)-1H-pyrrol-2-yl]sulfinyl}acetone gave only 1-(2-nitro-phenyl)(1H-pyrrol-2-ylsulfinyl)methane. 1-{[1-(2-Nitrophenyl)-1H-pyrrol-2-yl]sulfanyl}acetone, 2-{[1-(2-nitrophenyl)-1H-pyrrol-2-yl]sulfanyl}-1-phenyl-ethan-1-one or 2-{[1-(2-nitrophenyl)-1H-pyrrol-2-yl]sulfanyl}acetonitrile were reductively cyclised with sodium borohydride and 5% palladium-on-carbon into 6-methyl(or phenyl)-5,6-dihydro-7H-pyrrolo[1,2-a][3.1.6]benzothiadiazocin-7-ol or 6-amino-5H-pyrrolo[1,2-a][3.1.6]benzothiadiazocine-7-oxide, respectively.     

Preparation of Isoquinolin-(2(1H)-yl)but-2-enedioate Derivatives

One-pot, three-component reactions of isoquinoline, dimethyl/diethyl acetylenedicarboxylate, and indole, carbazole, pyrazole, or imidazole gave dimethyl/diethyl 2-(1-(1H-indol-1-yl)isoquinolin-2(1H)-yl)but-2-enedioate, dimethyl/diethyl 2-(1-(9H-carbazol-9-yl)isoquinolin-2(1H)-yl)but-2-enedioate, dimethyl 2-(1-(1H-pyrazol-1-yl)isoquinolin-2(1H)-yl)but-2-enedioate, or dimethyl 2-(1-(1H-imidazol-1-yl)isoquinolin-2(1H)-yl)but-2-enedioate respectively in good to excellent yields.     

蝶形主体分子的设计、合成及其包结性能的研究

设计、合成了两种蝶形主体分子：2，5－二（三苯甲基）对苯二酚1，2，5－二（二苯甲基）对苯二酚2.1和2可与许多有机小分子形成配位包合物。用IR表征了主体分子1和2 的包结物， 用¹H NMR测定了主客体分子的摩尔比：1•DMF (1：2)，1•DMSO (1:2)，1 •吡啶 （1：2），1•环戊酮 （2：3）和2•DMF 1：2），2•DMSO （1：2），2 •THF （1：1），2•苯甲醛（1：2），2•苯乙酮 （1：2），2•2，5－己二酮 （1：1），2 •N－甲基－2－吡咯烷酮 （1：3）。单晶X-射线衍射分析了包结物2·苯甲醛的晶体结构，在分子间氢键的相互作用下晶体得以稳定。     

Synthese und Struktur hochfunktionalisierter 2, 3‐Dihydro‐1H‐1, 3, 2‐diazaborole

Synthesis and Structure of Highly Functionalized 2, 3‐Dihydro‐1H‐1, 3, 2‐diazaboroles A series of differently substituted 2, 3‐dihydro‐1H‐1, 3, 2‐diazaboroles has been prepared by various methods. 1, 3‐Di‐tert‐butyl‐2‐trimethylsilylmethyl‐1H‐1, 3, 2‐diazaborole ( 7 ), 2‐isobutyl‐1, 3‐bis(1‐cyclohexylethyl)‐1H‐1, 3, 2‐diazaborole ( 8 ), 1, 3‐bis‐(1‐cyclohexylethyl)‐2‐trimethylsilylmethyl‐1H‐1, 3, 2‐diazaborole ( 9 ) 1, 3‐bis(1‐methyl‐1‐phenyl‐propyl)‐2‐trimethylsilylmethyl‐1H‐1, 3, 2diazaborole ( 10 ) and 2‐bromo‐1, 3‐bis(1‐methyl‐1‐phenyl‐propyl)‐1H‐1, 3, 2‐diazaborole ( 11 ) were formed by reaction of the corresponding 1, 4‐diazabutadienes with the boranes Me₃SiCH₂BBr₂, iBuBBr₂ and BBr₃ followed by reduction of the resulting borolium salts [R¹ = tBu, Me(cHex)CH, [Me(Et)Ph]C; R² = Me₃SiCH₂, iBu, Br] with sodium amalgam. Treatment of 11 and 12 with silver cyanide afforded the 2‐cyano‐1, 3, 2‐diazaboroles 13 and 14 . An alternative route to compound 8 is based on the alkylation of 2‐bromo‐1, 3, 2‐diazaborole 12 with isobutyllithium. Equimolar amounts of 13 and isobutyllithium give rise to the formation of 15 . The new compounds were characterized by ¹H‐, ¹³C‐, ¹¹B‐NMR, IR and mass spectra. The molecular structures of 7 and meso ‐10 were confirmed by x‐ray structural analysis.     

Substituted imidazole complexes of platinum(IV) halides

Platinum(IV) halides formed complexes of the type PtL₂X₄ [L=1-vinyl imidazole (1,-VIm), 1-methylimidazole (1-MeIm), 1,2-dimethylimidazole (1,2-Me₂Im), 1-vinyl-2-methylimidazole (1-V-2-MeIm), 2-methylimidazole (2-MeIm), 2-ethylimidazole (2-EtIm), 2-isopropylimidazole (2-i-PrIm), and 4-methylimidazole (4-MeIm); X=Cl, Br] in neutral aqueous solution. The 1-n-butylimidazole (1-n-BuIm) ligand yielded only (LH)₂PtX₆ compound in the same medium. The compounds were characterised by elemental analyses, IR, UV-VIS and ¹HNMR spectra.     

The relationship between transannular secondary bonding strength and conformation in diphenyldithiophosphinate stibocanes X(CH2CH2S)2SbS2PPh2 (X = O,S)

The two stibocanes 1-oxa-4,6-dithia-5-stibocane diphenyldithiophosphinate O(CH₂CH₂S)₂SbS₂PPh₂ 1 and 1,3,6-trithia-2-stibocane diphenyldithiophosphinate S(CH₂CH₂S)₂ · SbS₂PPh₂ 2 were prepared from the corresponding chloro oxa- and thia-stibocanes 3 and 6 , and the ammonium salt of diphenyldithiophosphinic acid in CH₂Cl₂. 1 and 2 were characterized by IR, EI-MS and multinuclear NMR (¹H, ¹³C, ³¹P{¹H}). The crystalline state of 1 features two Sb1 ? S1 intermolecular interactions [3.987(2) Å] that results in a dimer. Alongside 1 displays both an endocyclic, transannular Sb1 ? O1 interaction [2.555(6) Å] and an exocyclic Sb1 ? S4 secondary interaction [3.327(2) Å]. The coordination geometry at the antimony could be described as AX₄YE ψ-trigonal bipyramid geometry with A = Sb, X = S1, S2, S3,O1; Y = S4; S1, S2 and the lone pair lays on the equatorial plane with O1 and S4 in axial positions. The Sb1 ? S4 secondary bonding is face capping one of the planes form by the lone pair, S2 and S3 of the trigonal bipyramid. 2 also displays both an endocyclic, transannular Sb1 ? S2 interaction [2.949(3) Å] and an exocyclic Sb1 ? S5 secondary interaction [3.216(3) Å]. The antimony becomes five-coordinate, giving the AX₄YE ψ-trigonal bipyramid geometry with S1, S3 and the lone pair laying on the equatorial plane with S2 and S4 in axial positions. The Sb1 ? S5 also here is face capping the plane form by the lone pair, S3 and S4 of the trigonal bipyramid. The conformation of the eight membered ring in 2 is boat-chair. In 1 the main conformation is chair-planar. Die Konformation des Achtringes in 2 ist Wanne-Sessel. In 1 ist die Konformation des Achtringes Sessel-planar.     

Monomer-isomerization polymerization. XIX. Monomer-isomerization copolymerizations of methylbutenes and 2-butene with Ziegler-Natta catalyst

The copolymerization of 3-methyl-1-butene (3M1B), 2-methyl-2-butene (2M2B), or 2-methyl-1-butene (2M1B) with trans-2-butene (2B) was attempted in the presence of a Ziegler-Natta catalyst. It was found the 3M1B underwent monomer-isomerization copolymerization with 2B to give a copolymer consisting of both 3M1B and 1-butene (1B) units, with an infrared (IR) spectrum in good agreement with that obtained from the copolymerization of 3M1B with 1B under similar conditions. When the apparent copolymerization parameters obtained by a TiCl₃–(C₂H₅)₃Al catalyst were compared, the apparent reactivity of 3M1B observed in the 3M1B-2B system was much higher than that in the 3M1B-1B system. However, 2M2B and 2M1B did not undergo monomer-isomerization copolymerization with 2B, and only the homopolymer of 1B was obtained under similar conditions.     

Synthetic and spectroscopic study of 5-amino-2-acyl-1,2,4-thiadiazolin-3-ones

5-Amino-2-acyl-1,2,4-thiadiazolin-3-ones 2–1 can be synthesized from 5-amino-2H-1,2,4-thiadiazolin-3-one ( 1–1 ) via a selective acylation with an acid anhydride in pyridine. The ¹H nmr spectral characteristics of 5-amino-2-acyl-1,2,4-thiadiazolin-3-ones 2–1 is in particular, compared with 5-amino-2H-1,2,4-thiadiazolin-3-one ( 1–1 ) and 5-amino-2-alkyl-1,2,4-thiadiazolin-3-ones 1–2, 1–3 . The 5-amino group of 2–1 appeared as two peaks in its ¹H nmr spectrum, which merged to a single peak at a higher temperature, while those of compound 1–1, 1–2 and 1–3 appear only as a single peak. The restricted rotation of the C(5)-N(5) (at amino) bond of 5-amino-2-acetyl-1,2,4-thiadiazolin-3-one (2a-1) is about 14.5 Kcal/mol.     

Redistribution studies and preparation of chlorobromodisilanes

Distribution reactions between Si₂Cl₆ and Si₂Br₆ yield all mixed chlorobromodisilanes of the form Si₂Cl_xBr_6-x. Further redistributions prevent the separation of the mixed compounds by vacuum distillation. A direct preparation of 1, 1, 1-tribromo-2, 2, 2-trichlorodisilanes via 1, 1, 1-triphenyl-2, 2, 2-trichlorodisilane by means of HBr/AlBr₃ yields a pure compound.     

A polarographic study of the complexes formed in alkaline solution by the cadmium(II) ion with ethylenediamine,N-(2-hydroxyethyl)ethylenediamine,and N,N′-bis(2-hydroxyethyl)ethylenediamine

A multiple regression analysis of polarographic data has been used to determine the formulas and formation constants of complexes formed in alkaline solution by reaction of cadmium(II) ion and hydroxide ion with ethylenediamine (en), N-(2-hydroxyethyl)-ethylenediamine (hn) and N,N′-bis(2-hydroxyethyl)ethylenediamine (2hn). The complexes formed are designated by the general formula Cd(A)_p(OH)_p^2?q and the formation constants are given as log β_pq. The complexes found and their formation constants are: for en, 1 : 2 (10.3), 1 : 3 (12.3), and 1 : 2 : 1 (12.2); for hn, 1 : 2 (9.5), 1 : 2 : 1 (12.2), and 1 : 2 : 2 (12.6); and for 2hn, 1 : 2 (8.9), 1 : 1 : 2 (11.1), 1 : 2 : 1 (11.2), and 1 : 2 : 2 (12.6). It is concluded that in each case for which the hydroxide ion is reacted, a proton is removed from an alcoholic hydroxyl group which is coordinated to form a five-membered chelate ring linking a nitrogen atom and oxygen atom to the cadmium(II) ion.     

吡啶盐/咪唑盐调控钴萘基二膦酸配位聚合物的结构和性质

通过引入质子化的1,3-二(4-吡啶基)丙烷(1,3-dppH₂²⁺)和双(咪唑-1-甲基)苯(1,4-bixH₂²⁺)作为阳离子模板,采用水热反应,得到3种基于1,4-萘二膦酸(1,4-ndpaH₄)配体的钴萘二膦酸配位聚合物：(1,3-dppH₂)₂[Co₄(1,4-ndpa)(1,4-ndpaH)₂(1,4-ndpaH₂)]·6H₂O (1)、(1,4-bixH₂)_0.5[Co(1,4-ndpaH)](2)和(1,4-bixH₂)_0.5[Co₂(1,4-ndpaH)(1,4-ndpaH₂)(H₂O)₂](3)。对配合物1～3分别进行了元素分析、红外光谱、单晶X射线衍射、...     

Bis(2‐cycloazylindolyl)titanium Complexes: Synthesis,Characterization, and the Catalytic Behaviors towards Hydroamination and Ring‐opening Polymerization of ϵ‐Caprolactone

The ligands 2‐pyrazol‐1‐yl‐1H‐indole (HL1) and 2‐ 1 , 2 , 4 ‐triazol‐1‐yl‐1H‐indole (HL2) individually reacted with Ti(NMe₂)₄ in tetrahydrofuran to form the corresponding complexes Ti(L1)₂(NMe₂)₂ ( 1 ) and Ti(L2)₂(NMe₂)₂ ( 2 ), respectively. The titanium complexes were fully characterized by NMR measurement and elemental analysis as well as the single‐crystal X‐ray diffraction of 1 and 2 . Both 1 and 2 exhibit high activities towards intermolecular hydroamination of terminal alkynes with high selectivity, and they also efficiently promote the ring‐opening polymerization of ?‐caprolactone.     

Monomer-isomerization polymerization. XVI. Monomer-isomerization polymerization of methylpentenes with Ziegler-Natta catalyst

The polymerizations of 4-methyl-1-pentene(4M1P), 4-methyl-2-pentene (4M2P), 2-methyl-2-pentene (2M2P), and 2-methyl-1-pentene (2M1P) with Ziegler-Natta catalyst have been investigated. Both 4M1P and 4M2P were found to polymerize with TiCl₃–(C₂H₅)Al catalyst to give high molecular weight poly(4M1P), while 2M2P and 2M1P did not give polymers with 4M1P units. However, when the polymerizations of 2M1P and 2M2P were carried out with ternary catalyst systems, TiCl₃–(C₂H₅)AlCl–(PPh₃)₂PdCl₂ and TiCl₃–(C₂H₅)AlCl–Ni(SCN)₂ polymers with 4M1P units were obtained in low yield. It was concluded that these four methylpentenes could polymerize with the monomer-isomerization polymerization mechanism to poly(4M1P). The results of the observed isomer distribution of methylpentenes recovered, and the rate of polymerization of four methylpentenes suggest that the isomerization from 2M1P to 4M1P with the above ternary catalyst systems might proceed via a direct one-step isomerization mechanism.     

Hydrothiolysis of carbofunctional α,β-unsaturated sulfides as an approach to the synthesis of 1,7-dithiocarbonyl compounds

Bis(1-N,N-dimethylimmonio-3-phenylprop-2-en-3-yl) sulfide diperchlorate and (1-N,N-dimethyl-immonio-3-phenylprop-2-en-3-yl) (5,5-dimethyl-1-morpholiniocyclohex-2-en-3-yl) sulfide diperchlorate react with hydrogen sulfide giving rise to the corresponding 1,7-thioxoimmonio sulfides. Treating with the hydrogen sulfide (1-N,N-dimethylimmonio-3-phenylprop-2-en-3-yl) (1-oxo-2-phenyl-inden-3-yl) sulfide perchlorate led to preparation of (1-oxo-2-phenylinden-3-yl) (1-thioxo-3-phenylprop-2-en-3-yl) sulfide. The hydrothiolysis of (5,5-dimethyl-1-morpholiniocyclohex-2-en-3-yl) (1-N,N-dimethylimmonio-2-phenylinden-3-yl) sulfide diperchlorate and (5,5-dimethyl-1-morpholiniocyclohex-2-en-3-yl) (1-oxo-2-phenylinden-3-yl) sulfidea perchlorate resulted in products of the sulfide bond cleavage in the initial immonium salts.     

Water Reduction and Dihydrogen Addition in Aqueous Conditions With ansa-Phosphinoborane

Ortho-phenylene-bridged phosphinoborane (2,6-Cl₂Ph)₂B-C₆H₄-PCy₂ 1 was synthesized in three steps from commercially available starting materials. 1 reacts with H₂ or H₂O under mild conditions to form corresponding zwitterionic phosphonium borates 1-H₂ or 1-H₂O . NMR studies revealed both reactions to be remarkably reversible. Thus, when exposed to H₂, 1-H₂O partially converts to 1-H₂ even in the presence of multiple equivalents of water in the solution. The addition of parahydrogen to 1 leads to nuclear spin hyperpolarization both in dry and hydrous solvents, confirming the dissociation of 1-H₂O to free 1 . These observations were supported by computational studies indicating that the formation of 1-H₂ and 1-H₂O from 1 are thermodynamically favored. Unexpectedly, 1-H₂O can release molecular hydrogen to form phosphine oxide 1-O . Kinetic, mechanistic, and computational (DFT) studies were used to elucidate the unique “umpolung” water reduction mechanism.     

Photoinduzierte 1, 3-dipolare Cycloaddition von 3-Phenyl-2H-azirinen an Azodicarbonsäure-diäthylester. 32. Mitteilung über Photoreaktionen

Irradiation of 2, 2-dimethyl-3-phenyl- ( 1a ), 2, 3-diphenyl-2H-azirine ( 1b ) or the azirine-precursors 1-azido-1-phenyl-propene ( 2a ) and 1-azido-1-phenyl-ethylene ( 2b ), respectively, in benzene in the presence of azodicarboxylic acid diethylester, yields the corresponding 1, 2-carbethoxy-3-phenyl-Δ³-1, 2, 4-triazolines 4a–d (Scheme 1). Refluxing 4 ( a, c or d ) in 0, 2–0, 4M aqueous ethanolic potassium hydroxide leads to the formation of the 1-carbethoxy-3-phenyl-Δ²-1, 2, 4-triazolines 6 ( a, c or d ). Under the same conditions 4b is converted to 3, 5-diphenyl-1, 2, 4-triazole ( 7b , Scheme 2). In 10M aqueous potassium hydroxide solution heating of either 4 ( c or d ) or 6 ( c or d ) yields the 3-phenyl-1, 2, 4-triazoles 7 ( c or d ). Photolysis of 1-carbethoxy-5, 5-dimethyl-3-phenyl-Δ²-1, 2, 4-triazoline ( 6a ) in benzene in the presence of oxygen and trifluoroacetic acid methylester gives the 5-methoxy-2, 2-dimethyl-4-phenyl-5-trifluoromethyl-3-oxazoline ( 13 , Scheme 5). 5, 5-Dimethyl-3-phenyl-1, 2, 4-triazole seems to be the intermediate, which on losing nitrogen gives the benzonitrile-isopropylide ( 3a ).     

Stable carbenes. Synthesis and properties of benzimidazol-2-ylidenes

A new stable crystalline carbene, 1,3-bis(1-adamantyl)benzimidazol-2-ylidene, was synthesized by decomposition of 1,3-bis(1-adamantyl)-2,3-dihydro-1H-benzimidazol-2-ylacetonitrile on heating under reduced pressure. Heteroaromatic 1,3-R₂-disubstituted benzimidazol-2-ylidenes, both stable (R = 1-Ad) and generated in situ (R = Me, Bzl), as well as 1,3,4,5-tetraphenylimidazol-2-ylidene (generated in situ), reacted with acetonitrile to give the corresponding insertion products, 1,3-disubstituted 2-cyanomethyl-2,3-dihidro-1H-(benz)-imidazoles. The geometric parameters of 1,3-bis(1-adamantyl)benzimidazol-2-ylidene, determined by X-ray analysis, suggest its lower aromaticity as compared to imidazol-2-ylidenes and 1,2,4-triazol-5-ylidenes. The structures of 2-cyanomethyl-2,3-dihydro-1H-benzimidazoles, 2-cyanomethyl-1,3,4,5-tetraphenyl-2,3-dihydro-1H-imidazole, and 1-(1-adamantyl)-5-cyanomethyl-3,4-diphenyl-4,5-dihydro-1H-1,2,4-triazole are characterized by partial conjugation in the heteroring; some compounds exhibit luminescence under UV irradiation. 1,3-Bis(1-adamantyl)benzimidazol-2-ylidene reacted with molecular sulfur in benzene to give 1,3-bis-(1-adamantyl)-2,3-dihydro-1H-benzimidazole-2-thione, but it failed to react with selenium under analogous conditions.     

Reactions of salicylaldehyde with some conjugated olefins

Some condensation reactions of salicylaldehyde with various conjugated olefins, 1a, 1b, 1c, 2a, 2b, 2c , and 3 , were studied. In the condensations with 1a, 1b , and 1c gave 2,2-dimethyl-2H-chromene derivatives via “3–2 cyclization”, while the condensations with 2a, 2b, 2c , and 3 gave 2-methyl-2H-chromen-2-yl)acetic acid derivatives via “3–4 cyclization”.     

一对手性Salen型席夫碱对映体的合成、结构与生物活性

采取分步反应法以1R,2R-环己二胺(或1S,2S-环己二胺)与2-羟基萘甲醛和水杨酸苯酯反应,合成了一对手性Salen型席夫碱对映体:1R-(2-羟基苯甲酰亚胺)-2R-(2-羟基萘甲亚胺)环己烷(1a)和1S-(2-羟基苯甲酰亚胺)-2S-(2-羟基萘甲亚胺)环己烷(1b),对其进行了单晶结构、圆二色光谱、元素分析、红外光谱表征及生物活性实验。单晶结构与圆二色光谱分析表明1a和1b互为对映体;生物活性实验显示1a具有一定的抑菌活性。     

Study on the synthesis of the lanthanide chelates of α′-(trifluoromethyl)polyfluoroalkyl β-diketones and their application as 1H NMR shift reagents

The synthesis of the lanthanide chelates of α′-(trifluoromethyl)polyfluoroalkyl β-diketones Ln {CF₃CF₂[CF₂OCF(CF₃)]_n COCHCOC(CH₃)₃}₃ [ 1 , n=1; Ln=Eu (1a) , Pr (1b) , Nd (1c) , Sm (1d) , Gd (1e) , Tb (1f) , Dy (1g) , Er (1h). 2 , n=2; Ln=Eu (2a) , Pr (2b) , Nd (2c) , Sm (2d) , Gd (2e) , Tb (2f) , Dy (2g) and Er (2h) ] was reported and the ¹H NMR shift properties were studied using alcohol, ketone, ether and amine as substrates. Compounds 1a, 1b, 2a and 2b induce shifts similar to that induced by Ln(fod)₃ (Ln=Eu, Pr). However compounds 1a and 2a are superior to Eu(fod)₃, because their ¹H signal shifts to higher field in the presence of substrate than that of Eu(fod)₃, does. For example, Δh for 1a and 2a is close to zero ppm in the presence of alcohol. A very satisfactory first order spectra can be obtained using 1a, 2a, 1b and 2b as ¹H NMR shift reagents. 1c, 1f, 1g, 2c, 2f and 2g produce upfield shifts, and 1h and 2h produce downfield shifts. 1c and 2c induce shifts smaller than that of 1b and 2b , whereas 1f, 1g, 1h, 2f, 2g and 2h induce very large shifts.