Acylwanderungen am 3(5)-Amino-pyrazol

Acyl Migrations on 3(5)-Amino-pyrazole 3(5)-Amino-pyrazole 1 form 3 isomeric monoacylation products, 4 diacylation products and 3 triacylation products by reaction with electrophiles like cyanates, isocyanates or carboxylic and chlorides, respectively. Acyl migrations are observed depending on the reaction temperature and the structure of the acyl residue. The structures of the acyl derivatives of 3(5)-amino-pyrazole were characterized by nmr-spectroscopy.     

Studies on the base-catalyzed Solvolysis of Propane-2-sulphonic Acid p-Cresylester

Products of the reaction of propane-2-sulphonic acid p-cresylester with sodium butoxide in butanol are the sodium salt of propan-2-sulphonic acid, di-n-butyl ether, p-cresyl-n-butyl ether and p-cresol. The reaction proceeds via propane-2-sulphonic acid n-butylester which is formed from the starting compound by an elimination-addition (sulphene) mechanism. The elimination step is an E1-cB reaction.     

Acylierung von Heterocyclen mit Kohlensäurederivaten. I. Kinetik und Mechanismus der Reaktion von 2-Aminobenzimidazolen mit Arylcyanaten

Acylation of Heterocycles with Carbonic Acid Derivatives. I. Kinetics and Mechanism of the Reaction of 2-Aminobenzimidazoles with Aryl Cyanates The second order rate constants for the reaction of 2-amino-benzimidazoles (2-ABI) with aryl cyanates forming 2-amino-benzimidazole aryl ester imide 3 have been determined in dependence on substituent effects by u. v. measurements. The results are interpreted by a six-membered cyclic transition state in which the electrophilic attack of the cyanate on the endocyclic N atom is catalyzed by an H bridge interaction of the exocyclic amino group of 2-ABI with the OCN group.     

Über die Reaktionen von Benzimidazol-2-carbonsäurehydrazid mit Elektrophilen

About the Reactions of Benzimidazole-2-carbohydrazide with Electrophilic Compounds Benzimidazole-2-carbohydrazide ( 1 ) reacts with aldehydes and ketones to form N-alkylidene-benzimidazole-2-carbohydrazides( 2a–j ). With carbon disulfide, diphenyl carbonate and cyanates, ring closure takes place to afford 1,2,4-triazines and 1,3,4-oxadiazoles. Attempts to synthezise 2-isocyanato-benzimidazole failed. ¹H-n.m.r. and ¹³C-n.m.r. spectroscopic data of the compounds are given.     

Environmental Control of Triplet Emission in Donor–Bridge–Acceptor Organometallics

Carbene‐metal‐amides (CMAs) are a promising family of donor–bridge–acceptor molecular charge‐transfer (CT) emitters for organic light‐emitting diodes. A universal approach is demonstrated to tune the energy of their CT emission. A blueshift of up to 210 meV is achievable in solid state via dilution in a polar host matrix. The origin of this shift has two components: constraint of thermally‐activated triplet diffusion, and electrostatic interactions between guest and polar host. This allows the emission of mid‐green CMA archetypes to be tuned to sky blue without chemical modifications. Monte‐Carlo simulations based on a Marcus‐type transfer integral successfully reproduce the concentration‐ and temperature‐dependent triplet diffusion process, revealing a substantial shift in the ensemble density of states in polar hosts. In gold‐bridged CMAs, this shift does not lead to a significant change in luminescence lifetime, thermal activation energy, reorganization energy, or intersystem crossing rate. These discoveries offer new insight into coupling between the singlet and triplet manifolds in CMA materials, revealing a dominant interaction between states of CT character. The same approach is employed using materials which have been chemically modified to alter the energy of their CT state directly, shifting the emission of sky‐blue chromophores into the practical blue range.     

Synthesis and reactivity of 4-chloro-3,3,4-trifluoro-methoxycarbonyl cyclobutene (CTMC)

An improved synthesis of CTMC is described. This cyclobutene is thermally stable towards electrocyclic ring opening. Its reactivity is explored and a number of radical adducts are described. A more complicated picture is observed with various nucleophiles. The strong dienophilic character of CTMC is illustrated by numerous examples. CTMC reacts well as a dipolarophile with diphenylnitrone, diphenylnitrilimine and diazoalkanes. The high reactivity of this cyclobutene is due to its inherent polarity and strain.     

A Novel Coenzyme A Analogue in the Anaerobic,Sulfate-Reducing,Marine Bacterium Desulfobacula toluolica Tol2T

Coenzyme A (CoA) thioesters are formed during anabolic and catabolic reactions in every organism. Degradation pathways of growth-supporting substrates in bacteria can be predicted by differential proteogenomic studies. Direct detection of proposed metabolites such as CoA thioesters by high-performance liquid chromatography coupled with high-resolution mass spectrometry can confirm the reaction sequence and demonstrate the activity of these degradation pathways. In the metabolomes of the anaerobic sulfate-reducing bacterium Desulfobacula toluolica Tol2^T grown with different substrates various CoA thioesters, derived from amino acid, fatty acid or alcohol metabolism, have been detected. Additionally, the cell extracts of this bacterium revealed a number of CoA analogues with molecular masses increased by 1 dalton. By comparing the chromatographic and mass spectrometric properties of synthetic reference standards with those of compounds detected in cell extracts of D. toluolica Tol2^T and by performing co-injection experiments, these analogues were identified as inosino-CoAs. These CoA thioesters contain inosine instead of adenosine as the nucleoside. To the best of our knowledge, this finding represents the first detection of naturally occurring inosino-CoA analogues.     

Deducing the Fatigue Crack Growth Rates of Natural Flaws in Silicon Nitride Ceramics: Role of R‐Curves

Fatigue failure is a concern when high‐strength, high‐toughness silicon nitride ceramics are used in mechanical components and the growth of natural flaws will determine the usable upper bound strength. In this study a fracture resistance curve (R‐curve) model is incorporated into an established method for deducing natural flaw growth rates from a combination of strength and fatigue life data for smooth specimens. Experimental data for a commercial silicon nitride, SL200, were examined. When compared with results deduced using a constant fracture toughness model, the new method gives more physically realistic growth rate results. Specifically, by incorporating the R‐curve the deduced fatigue threshold is equal to the reported intrinsic toughness for crack propagation of 2.2 MPa√m, whereas the constant fracture toughness model gives a physically unrealistic threshold value. Furthermore, much better agreement is achieved with the growth rates measured using macroscopic compact‐tension specimens. Overall, it is concluded that the R‐curve effect should not be ignored when deducing the fatigue crack growth rates of natural flaws in high‐toughness silicon nitride ceramics.