Abstract Irradiation of (E)-3-(p-methoxyphenyl)-3-pentenyl, (E)-4-(p-methoxyphenyl)-4-hexenyl, and (E)-5-(p-methoxyphenyl)-5-heptenyl 9-phenanthrenecarboxylates (B-2E, B-3E, and B-4E, respectively) in benzene gave intramolecular [2+2] cycloadducts, cyclobutane derivatives (CB-2, CB-3, and CB-4, respectively) possessing the same conformation as an intermolecular [2+2] cycloadduct (CB-0) between methyl 9-phenanthrenecarboxylate (9-MCP) and trans-anethole (t-AN), and oxetane derivatives (OX-2, OX-3, and OX-4, respectively) arising from intramolecular cycloaddition between the carbonyl group and the olefinic double bond. However, (E)-4-(p-methoxyphenyl)-3-butenyl and (E)-5-(p-methoxyphenyl)-4-pentenyl 9-phenanthrenecarboxylates (A-2E and A-3E, respectively) afforded only products derived from oxetane precursors.

AbstractWie im getrennten Modellverbindungspaar (I)+(II), das sich photochemisch zum Cyclobutan (III) cyclisiert (keine Ausb.‐Angabe), geht auch der Ester (IV) eine Kopf‐Kopf‐Photocyclisierung zum Cyclobutan (V) ein; daneben entsteht das [2 + 2] Cycloaddukt (VI), das langsam durch MeCHO‐Eliminierung in (VII) übergeht [5 1% Ausb., bezogen auf (IV)].

AbstractDie 7‐Cyanheptafulvene (I) ergeben mit Ammoniak und primären Aminen die 2‐Iminoindolderivate (II) und/oder die 3‐Aminoisochinoline (III).

Abstract The reaction of tropone with aniline, p-toluidine, p-anisidine, and p-chloroaniline in the presence of copper(II) acetate gave 2-arylaminotropones and 2-arylamino-N-aryltroponeimines. However, when o-toluidine and o-anisidine were used, only the corresponding 2-arylaminotropones were obtained. The reaction of tropolone with methylamine, ethylamine, and isopropylamine afforded 3-aminotropolone derivatives, while the reaction with dimethylamine, pyrrolidine, and morpholine gave 3- and 5-aminotropolone derivatives, the latter being minor products.

The reaction of 8,8-dicyanoheptafulvene (1a) with ammonia and several kinds of amines in the presence of copper(II) acetate afforded 1,2-dihydro-2-iminocyclohepta[b]pyrrole derivatives (2) and/or 3-aminoisoquinoline derivatives (3). The reaction of 8-cyano-8-methoxycarbonylheptafulvene (1b) and amines has also been described.

The a u t o x i d a t i o n o f dibenzalacetone oxime i n t h e oresence of several kinds o f t r a n s i t i o n metal s a l t s gave 4-hydroxy-5-phenyl-3-styryl-4,5-dihydroisoxazole, accompanied w i t h c i n n a m o n i t r i l e and benzaldehyde.S i m i l a r treatment o f benzalacetophenone oxime, benzalacetone oxime and t h e i r p -s u b s t i t u t e d d e r i v a t i v e s a l s o a f f o r d e d 4-hydroxy-4,5-dihydroisoxazole d e r i v a t i v e s .Recently nalladium(I1)-induced c y c l i z a t i o n o f unsaturated ketoximes under an atmosphere o f argon t o g i v e isoxazoles o r p y r i d i n e s has been r e p ~r t e d .' , ~ I n t h i s paper we wish t o r e p o r t t h e oxidative c y c l i z a t i o n of d g -u n s a t u r a t e d ketoximes t o 4-hydroxy-4,5-dihydroisoxazoles under t h e c a t a l y t i c e f f e c t o f c o p p e r ( I I ) , c o b a l t ( I I ) , and manganese(I1) s a l t s .When a s o l u t i o n o f dibenzalacetone oxime (2, 3 mnol) and c o b a l t ( I 1 ) acetate (0.3 mmol) i n methanol (20 m l ) was s t i r r e d under an atmosphere of oxygen a t 30 ? 0.5'C, r a p i d uotake o f oxygen took place.Separation of t h e r e a c t i o n m i x t u r e gave 4-hydroxy-5-phenyl-3-styryl-4,5-dihydroisoxazole (Za), mp 194-195°C; 1 ) & $ , ~ 3235 cm-1; hkgH 293 nm ( l o g e 4.97).0-acetate, mo 128-130°C; v::: 1740 cm-1;$E1$13 5.68 (Cq-H, d, J=2 Hz), 6.34 (Cg-H, d, 5-2 Hz).Heating of 2 w i t h s u l f u r i c a c i d -a c e t i c a c i d gave 5-phenyl-3-

AbstractDie Carbonsäureamide (I) lassen sich in siedendem Tetrahydrofuran mit NaBH4, das durch Äthandithiol oder Phenylmercaptan aktiviert ist, in 86 ‐ 100%iger Ausbeute zu den primären Aminen (II) reduzieren (Äthylmercaptan ist unwirksam).

The polymer support having a phenacylalkyl side chain for the solid-phase peptide synthesis was found to give a better hydrazinolysis yield than the ordinary polymer support.

Sodium borohydride under the presence of thiols reduced nitro compounds to amine, hydroxylamine, azo, and azoxy compounds.

The reaction of tropolone and phosphorus oxychloride gave 2-chlorotropone. Similarly, 5-cyano-, 5-nitro, and 5-chlorotropolones afforded the corresponding 2-chlorotropone derivatives in moderate yields. 3-Cyanotropolone gave 2-chloro-7-cyanotropone, while 3-phenyltropolone afforded only 2-chloro-3-phenylbenzaldehyde. When 3-bromotropolone and 5-bromotropolone were treated similarly, 2, 7-dichloro- and 2, 5-dichlorotropones were obtained respectively, with a facile halogen exchange. The further treatment of 2, 5-dichlorotropone with phosphorus oxychloride afforded 2, 5-dichloro- and 3,4-dichlorobenzaldehydes. The reaction of 5-p-tolylazo-, 5-phenylazo-, and 5-p-nitrophenylazotropolones with phosphorus oxychloride gave the corresponding 5-arylazo-2-chlorotropones, which, on further treatment with an excess of the reagent, gave 2-aryl-4, 5-dichloroindazoles.

Abstract The reaction of tropone and potassium hydroxide in the presence of potassium ferricyanide gave tropolone, salicylaldehyde, and p-hydroxybenzaldehyde, while in the presence of the copper ammine complex it afforded 2-aminotropone and salicylonitrile. Similarly, when tropone was reacted with aqueous ammonia, methylamine, or dimethylamine, 2-aminotropone and its N-methyl derivatives were formed. The reaction of 2-phenyltropone with ammonia and methylamine, and the reaction of 2-α-naphthyltropone and 4-bromo-2-phenyltropone with methylamine in the presence of copper salt, also afforded 2-aminotropone derivatives and/or salicylaldehyde derivatives.