Über einige weitere Umsetzungen des Ω‐Nitroacetophenons Über aliphatische Nitroverbindungen XII

Abstract

191 Anilino-isonitrosoacetophenon. Entsteht analog aus Bromisonitrosoacetophenon und Anilin. Aus Toluol erhiilt man das Produkt in Form gelblicher Bliittchen. Leicht loslich in Alkohol, Ather, Chloroform, Benzol. Schwer loslich in Ligroin. Schmp. 147 O. Die Verbindung ist identisch mit der aus Chlorisonitrosoacetophenon zu erhaltenen21). Schmp. und Mischschmp. 147 0. Aminomethyl-phen yl-carbinol. 1,83 g Chlorisonitrosoacetophenon werden in 100 ccm abs. Ather gelost. Dann liilt man unter mechanischem Riihren 30 ccm LiA1H4-Losung (1 ccm = 36 mg LiAlH,, gelost in Ather) zutropfen. Hierbei tritt eine leichte Triibung in der Losung auf. Danach erhitzt man unter Ruhren 4 Stunden unter RuckfluS und zersetzt dann das Reaktionsgemisch mit 3 ccm Waaser. Nachdem man noch eine weitere Stunde geruhrt hat, filtriert man vom Niederschlag ab und extrahiert diesen 4 Stunden mit dem Filtrat im Soxhlet. Die Atherlosung wird mit Natriumsulfat getrocknet und dann der Aminoalkohol mit wasserfreier Oxalsiiure, gelost in abs. Ather, als Oxalat gefallt. Durch Umkristallisieren aus Alkohol-Wasser erhiilt man das Oxalat in gliinzenden Bliittchen oder Niidelchen. Schmp. 236O. Aiisbeute 51% d. Th.

Nitro-Mannich Reaction

“…Dornow et al later reported high-yielding nitro-Mannich reactions of nitroacetophenone and nitroacetone with a variety of methanolamines formed from secondary amines and formaldehyde (Scheme ). , They also demonstrated that nitroacetophenone and nitroacetone react with preformed aryl imines in the presence of acetic anhydride. By refluxing the reaction mixture elimination of the alkylacetamide occurred to form nitroalkenes 42 in low to good yields.…”

The Chemistry of Imines.

“…Some of the active hydrogen materials which have been added to N-benzylideneanilines are: acetoacetic esters and benzoylacetic esters (235), diethyl malonate (174, 235, 278), methyl ethyl ketone (the methyl group adds rather than the methylene) (174), 2methylbenzopyrrole (active hydrogen is in the 3-position) (203), benzopyrrole (adds in the 3-position) (202), antipyrine (204), -cyanoethyl acetate, ethylmalonamide, malonamide (161), methyl ketones with boron trifluoride etherate in equimolar amounts (methylene ketones do not react under these conditions) (248), Kojic acid (adds in the 6-position) ( 14), 2-methylquinoline methyl iodide (139), methyl nitrite, diethylamine favors the addition of ethyl and propyl nitrites (163), isopropyl nitrite fails to react (125), benzyl nitrite adds very easily in the presence of diethylamine (63), -nitroethyl acetate (65), 8-hydroxy quinoline (adds in the 7-position) (210), -phenylethyl acetate with an aluminum chloride catalyst (155), benzyl sodium sulfonate with phenyllithium (172), acetophenone with an amine hydrochloride catalyst (149), the sodium salt of phenylacetic acid in sodamide (253), the ethyl ester of phenylacetic acid (155), acetic anhydride (mono product) (4), a-and /3-naphthol (22), nitroacetonitrile (230), ethylnitroacetic acid (65, 66) and -nitroacetophenone (69). N-Benzylidene-o-carboxyaniline exists as an equilibrium of the imine and the cyclic addition product (249).…”

“…For example, it has been reported that acetylene adds to N-butylidene-tbutylamine in the presence of cuprous chloride at 45' in dioxane to give 3-t-butylaminohexyne-3 (177). (253), the ethyl ester of phenylacetic acid (155), acetic anhydride (mono product) (4), a-and @naphthol (22), nitroacetonitrile (230), ethylnitroacetic acid (65,66) and w-nitroacetophenone (69). N-Benzylidene-o-carboxyaniline exists as an equilibrium of the imine and the cyclic addition product (249).…”

α‐Substituted Chalcones: A Key Review

“…An old paper by Dornow and coworkers [126] described the synthesis of α‐nitrochalcone by reacting α‐NO 2 ‐acetophenone with a Schiff base that was pre‐prepared from benzaldehyde. The reaction was performed in diethyl ether in the presence of acetic anhydride (Ac 2 O) (reaction 1, Figure 30).…”