9-Hydroxy [7]metacyclophane

A new pyrolytic access to a metacyclophane has been found by the flash vacuum thermolysis of spiro[5,7]trideca-l,4-dien-3-one ($\text{4}$) which gave 9-hydroxy[7]metacyclophane (7) , and 4-(6-heptenyl)phenol (8) . The mechanism of formation of 7 and 8 from the intermediate diradical ($\text{6}$) is discussed.     

Synthese von Derivaten des 2-Hydroxy-9-dimethylamino-9H-benzo[a]phenoxazoniumchlorids

Zusammenfassung Die Mitteilung befaßt sich mit der Darstellung von Muscarin-Derivaten mit aromatischen Aminen. Es wurden demnach Salze und Basen von 2-Hydroxy-5-arylamino-9-dimethylamino-9H-benzo[a]phenoxazonium (I) dargestellt. Die dargestellten Farbstoffe sollen als Indikatoren dienen.1. Mitt.:V. Stuka, Z. Stránský undE. Ruika, Collect. Czechoslov. Chem. Communic.28, 1399 (1963); 2. Mitt.:V. Stuka undZ. Stránský, Collect. Czechoslov. Chem. Communic. (im Druck).     

Synthese und Struktur von Vinamidinatodiiodalanen [1]

The diiodoalanes (C₅H₇R₂N₂)AlI₂ [ 6 ; R = Me ( a ), Ph ( c )] are obtained from the corresponding alanes (C₅H₇R₂N₂)AlH₂ ( 5 ) and [Me₃NH]I in good yields. (C₅H₇R₂N₂)AlI₂ [ 6 ; R = iso‐Pr ( b )] is alternatively prepared, as well as 6a , from the corresponding vinamidine lithium compound C₅H₇R₂NLi ( 8 ) and AlI₃. (C₅H₇Me₂N₂)AlBr₂ ( 9a ) is formed according to both methods. The X‐ray structures of 6a and 6b are reported.     

Synthese von [1]Benzothieno[2,3—c]pyrazol-Derivaten

Derivatives of [1]benzothieno[2.3-c]pyrazole, a new heterocyclic ring system, were synthesized by 1.3-dipolar cycloadditions: benzo[b]thiophene-1.1-dioxide and derivatives thereof reacted with diazomethane and diazoethane to yield substituted [1]benzothieno[2.3-c]pyrazolines. A similar reaction with ethyl diazoacetate gave the corresponding cyclopropa[b][1]benzothiophene-2.2-dioxide derivative.     

Synthese von Furo [2,3-b]chinolinen

A new route to furo[2,3-b]quinolines has been developed based on the use of N-arylaconamides as starting materials. These anilides when heated with polyphosphoric acid, readily underwent intramolecular cyclization to furnish the respective 1,2-dihydro-2-oxo-quinoline-3-acetic acids which were then transformed into the corresponding dihydrofuro[2,3-b]quinolines by literature procedures. Sequential treatment of the dihydro compound withNBS andDBU afforded the corresponding furo[2,3-b]quinoline. The NMR spectra of the furoquinolines are discussed.

---

---

Mitt.: siehe Lit.     

Synthese von [1]Benzothieno[2,3—d]isoxazol-Derivaten

Derivatives of [1]benzothieno[2.3—d]isoxazole, a new heterocyclic ring system, were synthesized by 1.3-dipolar cyclisations: benzo[b]thiophene-1.1-dioxide and its 3-methyl derivative reacted with nitrile oxides and nitrones to the corresponding substituted [1]benzothieno[2.3—d]isoxazolines and-isoxazolidines. Hydrogenolysis of the latter cleaved the isoxazolidine ring, yielding the corresponding 2-(-phenylamino-benzyl)-3-hydroxy-2.3-dihydro-benzo[b]thiophene-1.1-dioxides.

---

---

Mit 1 Abbildung

---

Herrn Prof. Dr.E. Hardegger zum 60. Geburtstag gewidmet.     

Synthese von pyridylphenyl-imidazo[2,1-b]thiazolen

The synthesis of the isomeric 6(5)-phenyl-5(6)-pyridyl-2,3-dihydroimidazo[2,1-b]thiazoles are described. Only the synthesis of 5-phenyl-6-(2-pyridyl)-2,3-dihydroimidazo[2,1-b]thiazole failed.     

Versuche zur Synthese von [2.2]- und [2.3]Cyclopentadienophanen

Synthetic Attempts towards [2.2]- and [2.3]Cyclopentadienophanes . The first [2.2]Cyclopentadienophane (=2,2,3,3,8,8,9,9-octamethyltricyclo[8.2.1.1^4,7]tetradecatetraene; 1b ) has been synthesized (Scheme 5) by reductive coupling of 6,6-dimethylfulvene 3 → 5 (50%) followed by base-induced twofold condensation of 1,2-di(cyclopentadienyl)-1,2-dimethylbutane 5 with acetone to give difulvene 15 (95%). Reductive coupling of 15 gives a complex mixture of tautomers of 16 , 17 , and 1b , which contains ca. 50% of the target molecule 1b . Other synthetic attempts towards [2.2]cyclopentadienophanes 1a and 1b and [2.3]cyclopentadienophane 18 are discussed.     

Furochinoline, 9. Mitt.: Synthese von Furo[2,3-b]chinolinen

The synthesis of a wide variety of furo[2,3-b]quinolines starting from substituted 3-vinyl-2-quinolones is described. The procedure involves acetoxycyclisation of the vinyl-quinolone by treating with iodine in the presence of silver acetate and dehydroacetoxylation of the resulting 3-acetoxy-2,3-dihydrofuro[2,3-b]quinoline with phosphoric or polyphosphoric acid. The NMR spectra of the furoquinolines are discussed.

---

---

8. Mitt.:P. Lakshminarayana, K. Kanakarajan undP. Shanmugam, Z. Naturforsch.30 b, 426 (1975).     

Synthese von 4H-Pyrano[2,3-d]pyrimidinen

Summary Good yields of substituted 5-(5R-2-furyl)-4H-pyrano[2,3-d]pyrimidines4 were obtained in the reaction of 2-ethoxymethyleneamino-3-cyano-4H-pyranes2 with ammonia. Compounds2 were prepared by the condensation of the starting 2-amino-5-acetyl-3-cyano-6-methyl-4H-pyranes1 with ethyl orthoformate. Spectral properties of the bicyclic system4 in relation to compounds3 are discussed.

     

Synthese von Thieno[2,3—f]chinolin-Derivaten

Catalytic hydrogenation of 2.3-dihydro-thieno[2.3?f]-quinoline-1.1-dioxide yielded 2.3.6.7.8.9-hexahydrothieno-[2.3?f]quinoline-1.1-dioxide, which was substituted via the corresponding chloroacyl compounds to several 6-aminoacyl-derivatives.Skraup's synthesis using 6-amino-2.3-dihydro-3-morpholino-benzo[b]thiophen-1.1-dioxide gave 2.3-dihydro-3-morpholino-thieno[2.3?f]quinoline.     

Synthese von 2,4-Diamino-thieno[2,3-d]pyrimidin-Derivaten

Synthesis of 2,4-Diamino-thieno[2,3-d]pyrimidines Condensation of 2-aminothiophene-3-carbonitrile ( 4 ) with guanidine or sequential addition of CS₂ and NH₃ to 4 provides 2,4-diaminothieno[2,3-d]pyrimidine ( 7 ). This compound yields, after sequential addition of sec-BuLi and either [3-(trifluoromethyl)benzene]sulfenyl chloride ( 8 ) or the corresponding disulfide 9 , followed by acidic work up, 2,4-diamino-6-{[3-(trifluoromethyl)phenyl]thio}thieno[2,3-d]pyrimidine ( 10 ). In another approach, 2-amino-5-{[3-(trifluoromethyl)phenyl]thio}thiophene-3-carbonitrile ( 11 ) obtained from 4 and 8 is transformed to 10 by condensation with guanidine. Corresponding to the second route, 2,4-diamino-6-[(naphth-2-yl)thio]thieno-[2,3-d]pyrimidine ( 16 ) is synthesized. Oxidation of 10 with m-chloroperbenzoic acid gives 2,4-diamino-6-{[3-(tri-fluoromethyl)phenyl]sulfinyl}thieno[2,3-d]pyrimidine ( 13 ).     

Synthese und Eigenschaften von Bis-[dialkylamino-methylarsino]-methanen

Synthesis and Properties of Bis-[dialkylamino-methyl-arsino]-methanes The reactions of methan-bis-[methyl-chlorarsine] H₂C[As(CH₃)Cl]₂ with secondary amines lead to the formation of bis-[dialkylamino-methylarsino]methanes H₂C[As(CH₃)NR₂]₂. The cleavage of the As? N bond with acid molecules HX (X?OH, OR, SR, NR₂, halogen) results in the formation of the compounds H₂C[As(CH₃)X]₂. The IR and ¹H-NMR spectra are discussed and presented.