Pyryliumverbindungen. 38. Zur Ringtransformation von 2,4,6-Triaryl-thiopyryliumsalzen mit Essigsäureanhydrid zu Arylbenzenen und Thiobenzophenonen

Pyrylium Compounds. 38. About the Ring Transformation of 2,4,6-Triarylthiopyrylium Salts by Acetic Acid Anhydride to Arylbenzenes and Thiobenzophenones 2,4,6-Triarylthiopyrylium salts 5 react in the presence of an appropriate condensing agent (sodium acetate, carbonate, methoxide, tert-butoxide or potassium acetate) with acetic acid anhydride to yield arylbenzenes 3 and thiobenzophenones 6 . This ring transformation represents the first example of the conversion of the moiety into the thiocarbonyl group Under the same conditions 3,5-dimethyl-2,4,6-triphenylthiopyrylium perchlorate ( 13 ) forms via [1,5]-sigmatropic rearrangement the thiobenzophenone 15 . The structure of the new compounds 6 was proved by spectroscopic methods as well as by degradation reactions. Thus, hydrogen peroxide converts 6a to the known benzophenone 4 . Alkaline saponification gives the 2-hydroxy-benzophenone 8 , whereas heating with hydrochloric acid causes a selective cleavage of the acetoxy group to the 2-hydroxy-thiobenzophenone 7 .     

Tetrazolverbindungen. 1. 1-Aryl-5-(2-dialkylamino-vinyl)-1H-tetrazole aus 3-Chlor-propen-iminiumsalzen

Tetrazole Compounds. 1. 1-Aryl-5-(2-dialkylamino-vinyl)-1H-tetrazoles from 3-Chloropropeniminium Salts 3-Chloropropeniminium salts 1 react with excess sodium azide in refluxing alcohols to give mainly 1-aryl-5-(2-dialkylamino-vinyl)-1H-tetrazoles 3 ; in minor quantities isomeric 5-aryl-1-(2-dialkylamino-vinyl)-1H-tetrazoles 4 are formed. The reaction involves splitting off N₂ and C → N migration of the aryl and dialkylaminovinyl group, respectively. A cross-over experiment indicated that the rearrangement step proceeds intramolecularly. — The i.r., u.v., and n.m.r. spectroscopic data of the novel 1H-tetrazoles 3 as well as the u.v. spectra of some new starting products 1k—v are reported.     

Pyryliumverbindungen. XVIII, 2-Alkoxy-2H-pyrane aus tetra- und pentasubstituierten Pyryliumsalzen

Pyrylium Compounds. XVIII. 2-Alkoxy-2H-pyrans from Tetra- and Pentasubstituted Pyrylium Salts Alkali alkoxides add regioselectively to 2,3,4,6-tetrasubstituted pyrylium salts 7 (R' H), affording high yields of colourless crystalline 2-alkoxy-2H-pyrans 9 . The latte are also formed simply on refluxing 7 in the corresponding alcohol with triethylamine as proton acceptor. 3,5-Dialkylsubstituted 2,4,6-triarylpyrylium salts react analogously. The 2H-pyran structure of the adducts obtained follows from their n.m.r., i.r., u.v. and mass spectra as well as from their reaction with tetracyanoethylene to cycloadducts of type 10 . Acids regenerate from 9 the original pyrylium cations, whereas reaction of 9 with nitromethane or ethyl cyanoacetate provides benzene derivatives. -- The novel starting pyrylium salts 7b--o are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives     

Pyryliumverbindungen. 37. Arylbenzene aus 2,4,6-Triaryl-pyryliumsalzen und Carbonsäureanhydriden

Pyrylium Compounds. 37. Arylbenzenes from 2,4,6-Triarylpyrylium Salts and Carboxylic Acid Anhydrides Refluxing 2,4,6-triarylpyrylium salts 1 with excess carboxylic acid anhydrides (RCH₂CO)₂O ( 2a : R = H, 2b : R = Me) in the presence of condensing agents like sodium or potassium acetate, sodium carbonate or methoxide, triethylamine or pyridine results in 1,3,5-triarylbenzenes 3 (R = H, Me). Under similar conditions, phenylacetic acid anhydride ( 2c ), generated in situ from sodium phenylacetate and excess 2a or 2b , yields 1,2,3,5-tetraarylbenzenes 3 (R = Ph). Thus, the reaction 1 + 2 → 3 represents a new and simple method for replacing the pyrylium heteroatom =O^⊕– by the =CR– moiety (R = H, Me, Ph). The structure of the arylbenzenes 3 was proved by spectroscopic methods, by comparison with literature data or by independent synthesis. As by-products 2-acyloxy-benzophenones 10 are formed. Reaction of 3,5-dimethyl-2,4,6-triphenyl-pyrylium perchlorate ( 11 ) with acetic acid anhydride/sodium acetate (or sodium phenylacetate) takes another course leading to 2-acetoxy-3,5-dimethyl-4,6-diphenyl-benzophenone ( 15 ), whereas treatment of 11 with propionic acid anhydride/sodium acetate follows the reaction scheme 1 + 2 → 3 giving 1,3,5-trimethyl-2,4,6-triphenylbenzene ( 16 ). The mechanisms of the different pyrylium ring transformations are discussed.     

Pyryliumverbindungen. 31 [1]. Reaktion 3-alkylsubstituierter 2,4,6-Triaryl-pyryliumsalze mit 1,3-Diketonaten: Ein Weg zur Darstellung 3-acylsubstituierter Benzophenone

Pyrylium Compounds. 31. Reaction of 3-Alkyl-2,4,6-triarylpyrylium Salts with 1,3-Diketonates: A Method for the Preparation of 3-Acylsubstituted Benzophenones Reaction of 3-alkyl-2,4,6-triarylpyrylium salts with 1,3-diketones in the presence of one equivalent of triethylamine or potassium tert-butoxide does not lead — as originally suspected — to the primary adducts of 2H-pyran structure 6 , but to the open-chain valence isomers 7 . Treatment of the latter with one equivalent of tert-butoxide in tert-butyl alcohol gives the same 3-alkyl-2,4,6-triarylacetophenones 9 which are obtained directly from 5 , 1,3-diketones and two equivalents of potassium tert-butoxide. However, on treating 7 with aqueous ethanolic sodium hydroxide 3-acylsubstituted benzophenones 10 are formed in good yields. The reaction sequence 5→7→10 can also be performed through a one-pot-procedure. — The i.r., u.v., n.m.r. and mass spectroscopic data of the novel products 7, 9 , and 10 are reported.     

Synthese von substituierten 5-Amino-1,2,4-triazolen

Synthesis of Substituted 5-Amino-1,2,4-triazoles N-Nitro-amidino-dithiocarbimidic acid dimethylester 1 reacts with monosubstituted hydrazines under formation of the substituted 5-amino-1, 2, 4-triazoles. Disubstituted hydrazines give under the same conditions N-nitro-amidino-S-methyl-isothiosemicarbazides. The reaction of some more hydrazine derivatives with 1 yields the adequate substituted 1, 2, 4-triazoles.     

Overview of R&D at TLK for process and analytical issues on tritium management in breeder blankets of ITER and DEMO

Safe, reliable, and efficient tritium management in the breeder blanket will have to face unprecedented technological challenges. Beside the efficiency for tritium recovery from the breeder blanket (Tritium Extraction (TES) and Coolant Purification Systems (CPS)), the accuracy for tritium tracking between the inner and the outer fuel cycle must also be demonstrated. This paper focuses on the recent R&D carried out at the Tritium Laboratory Karlsruhe to tackle these issues. For ITER, the recently consolidated TES and CPS designs comprise adsorption columns and getter beds operated in semi-continuous mode. Different approaches for the tritium accountancy stage (TAS) have been evaluated. Balancing static (batch-wise gas collection at the TBM outlets and the tritium plant) or dynamic (in/on-line) approaches with respect to the expected analytical performances and integration issues, the first conceptual design of the TAS for EU TBMs is presented. For DEMO, the overall strategy for tritium recovery and tracking has been revisited. The necessity for on-line real-time tritium accountancy and improved process efficiency suggest the use of continuous processes such as permeator and catalytic membrane reactor. The main benefits combining the PERMCAT process with advanced membranes is discussed with respect to process improvements and facilitated accountancy using spectroscopic methods.