Electrochemically prepared surface-enhanced Raman scattering-active silver substrates with improved stabilities

New Hofmann type clathrates in the form of M(pp)₂Ni(CN)₄·2G (where pp = 1-phenylpiperazine, G = 1,4-dioxane and M = Ni, Co or Cd) have been prepared in powder form and their FT-IR and FT-Raman spectra are reported. The results suggest that the present compounds are similar in structure to the Hofmann type clathrates and their structures consist of conjugated polymeric layers of |M–Ni(CN)₄|_∞ with the pp bound to the metal (M) atom.     

Design and Synthesis of Two Aromatic Amines with Dendritic Structure

The design and synthesis of two aromatic amines with dendritic structures, i.e. 3,4,5‐tribenzyloxyaniline (3,4,5‐G₁‐NH₂) and 2,5‐dibenzyloxyaniline (2,5‐G₁‐NH₂), were conducted. A coupling reaction of three or two equivalents of benzyl bromide to one equivalent of methyl hydroxybenzoate generated methyl 3,4,5‐tribenzyloxybenzoate (3,4,5‐G₁‐COOCH₃), methyl 2,5‐dibenzyloxybenzoate (2,5‐G₁‐COOCH₃) and 2,6‐dibenzyloxybenzoate (2,6‐G₁‐COOCH₃) in high yields. All G₁‐COOCH₃ derivatives were studied by X‐ray analysis. The results show that these dendrons have sufficient volume to be used as the fine ligands for certain catalysts. The amide intermediates (benzamide, G₁‐CONH₂) were obtained by reaction between ammonia and G₁‐COOCH₃. Interestingly, 2,6‐dibenzyloxybenzamide (2,6‐G₁‐CONH₂) can not be prepared in the same condition, which may be due to the overlarge steric block. Sodium hypochlorite was an effective oxidant to generate methyl carbamates G₁‐ NHCO₂CH₃.     

SYNTHESIS AND REACTIONS OF SOME 2-THIENYL- AND 2-THENOYL-DERIVATIVES OF THIAZOLE AND THIADIAZOLINE AND THEIR SELENIUM ANALOGS

Abstract

2-(Thiocyanatoacetyl)thiophene 2 and its selenium analog 3 couple with diazotized anilines and yield 3-aryl-2-imino-5-(2-thenoyl)-2,3-dihydro-1,3,4-thiadiazoles 6 and 3-aryl-2-imino-5-(2-thenoyl)-2,3-dihydro-1,3,4-selenadiazoles 7 respectively. The reactions of both 6 and 7 with nitrous acid, acetic anhydride and benzoyl chloride are described. Azo coupling of 2-amino-4-(2-thienyl)thiazole 17 and its selenazole analog 18 with diazotized anilines yielded the arylazo derivatives 19 and 20 respectively. Reaction of the hydrazidoyl bromide 16 with potassium thiocyanate, potassium selenocyanate, thiourea and selenourea yields 6, 7, 19, and 20 respectively.     

Das elastische Jahrhundert. Synthesekautschuke

Synthetic rubbers help to solve severe problems in rubber‐technology arising from the sensitivity natural rubber shows towards UV‐radiation (e.g. sunlight), heat, and ozone: For this reason more than half of the rubber demand nowadays is satisfied by the chemical industry. However, synthetic rubbers are superior to its natural counterpart not only in regard to their ageing resistance and robustness towards several chemicals: They can easily be adapted to new challenges born by a more and more demanding technology – e.g. using improved concepts in the design of rubber molecule architectures, new catalysts or post‐polymerization altering of the elastomers. These challenges demand for a deep and clear understanding of rubber's chemistry and physics.     

Unusual Hofmann elimination at low temperature. Reaction of 3-hydroxymethylpyrrolidines withp-toluensulfonyl chloride

Summary Trans-2-aryl-3-hydroxymethyl-1-methylpyrrolidines suffer an unusual Hofmann elimination when treated withp-toluensulfonyl chloride in basic medium at room temperature.

---

Ungewöhnliche Hofmann-Eliminierung bei niederer Temperatur. Die Reaktion von 3-Hydroxymethylpyrrolidinen mitp-Toluolsulfonylchlorid (Kurze Mitt.)

Zusammenfassung Trans-3-hydroxymethylpyrrolidine erleiden in basischem Medium bei Behandlung mitp-Toluolsulfonylchlorid eine ungewöhnliche Hofmann-Eliminierung.

     

含蒽醌生色团的水溶性聚合物的制备及其光致电子转移

采用1-氨基蒽醌经酰氯化,合成含双键的单体,再与丙烯酰胺单体共聚,随后对共聚物进行了Hofmann反应,制得含伯胺侧基和蒽醌生色团的水溶性聚合物．利用傅立叶红外光谱、核磁共振氢谱及紫外,可见光等测试手段对所合成的聚合物的结构进行了表征,并探讨了含蒽醌生色团的水溶性聚合物的光致电子转移性能．     

Synthesis of piperidinones incorporating an amino acid moiety as potential SP antagonists

Substituted (±)-trans-1-benzyl-6-oxo-2-phenylpiperidine-3-carboxamides (type I) and the acylated derivatives of (±)-trans-5-amino-1-benzyl-6-phenylpiperidin-2-one (type II) were prepared by the reaction of (±)-trans-1-benzyl-6-oxo-2-phenylpiperidine-3-carboxylic acid and some common reagents to provide the products in satisfactory yields. Newly synthesized compounds share the same moiety with common SP antagonists and thus similar activities might be expected.     

3-硝基-2-氨基苯甲酸的合成

以邻苯二甲酸酐为起始原料,经硝化、脱水、酰胺化、霍夫曼重排4步反应合成了3-硝基-2-氨基苯甲酸,总收率19%,其结构经1H NMR, IR和元素分析表征.探讨了酰胺化和霍夫曼重排反应条件对产率的影响.结果表明, n(脲素) ∶ n(3-硝基邻苯二甲酸酐)=2.0 ∶ 1.0,于50 ℃～60 ℃反应5 h～6 h,酰胺化反应收率85%～91%.n(NaClO) ∶ n(3-硝基-2-甲酰胺基苯甲酸)=1.2 ∶ 1.0,于60 ℃反应3 h,重排反应收率94%.     

Novel annulated products from aminonaphthyridinones

2-(4-Methoxyphenyl)-1-oxo-1,2-dihydro-1,6-naphthyridine-4-carboxamide (4c) underwent Hofmann rearrangement with iodobenzene diacetate in methanol to give the corresponding 4-amino compound (6c). This, when reacted with 2,4-pentanedione and then hot phosphoryl chloride (attempted Combes synthesis) gave a new heterocyclic system, 6-(4-methoxyphenyl)-2-methylpyrido[3,2-c]pyrrolo[2,3-e]azocin-7(6H)-one (9c). This showed typical pyrrole-type reactivity at the 3-position. Alternatively, an attempt to convert the 4-NH₂ in 6c to 4-OH by diazotization gave, instead, a [1,2,3]triazolo[1,5-a]pyridine-3-carboxaldehyde (16c). The same series of reactions on a benzo analog, 2-methyl-1-oxo-1,2-dihydrobenzo[b][1,6]naphthyridine-4-carboxamide (4a), gave the same results.