Orthophosphoric acid has been found to accomplish the previously unsuccessful oyclization of azomethines of 3-formylcarbazoles and aminoacetal to substituted pyrido[4,3-b]carbazoles according to a scheme proposed by Cranwell and Sexton. By this method, there have been prepared 6,ll-dimethyl-(ellipticine), 5,6,11trimethyl-, 5,9,11-trimethyl-, 9-methoxy-5,ll-dimethyl-(9-methoxyellipticine), 9-methoxy-5,6,11-trimethyl-, 9-bromo-6,ll-dimethyl-, and 9-nitro-5,ll-dimethyl-6H-pyrido[4,3-blcarbazole.
Ethyl sodiomalonate
with fluorene-9-spiro-2'-oxiran gave two carboxybutyro-lactones,
(2a) and (3a). Fluorene-9-spiro-4'-(2'-methylenebutyrolactone) (3c) and
2-methylene-4,4-diphenylbutyrolactone (6c) have been prepared by the action of diethylamine and formaldehyde on their respective
2-oarboxybutyrolaotones. The reaction of trimethylsulphonium
iodide with 4,4'-diethoxybenzophenone gave 2,2-bis(4'-ethoxypheny1)vinyl
alcohol (6a) and not the oxiran.
The Mannich
reaction of a dialkylamine and formaldehyde with 2-carboxy-
butyrolactones leads directly to isolable
2-methylenebutyrolactones. It is suggested that this happens through a
concerted decarboxylation-elimination mechanism. 2-Methylene-3- and -4-phenylbutyrolactones
and their cysteine addition products, and
3-methylene-2-oxo-cis-2,3,3a,4,5,9b-hexhydronaphtho[1,2-b]furan
and its di-methylamine addition product have been
prepared. 3-Oxo-2,3,4,4a,6,6-hexahydro-naphtho[l,2-c]pyridazine has also been
synthesized.
Various 1,1-dialkylhydrazines
are alkylated by propiolic acid or 2- or 3-halopropenoic acids to give
(E)-3-(1,1-dialkylhydrazin-1- io)propenoates. ��� 3-Bromopropionic acid reacts with
N-aminomorpholine to give 1-amino-1-(2-carboxyethyl)-morpholinium bromide (11),
with N- aminopiperidine to give
bis(1-aminopiperidinium) 2-oxo-1-aza-5- azoniaspiro[4,5]decane
tribromide (10), with 1,1-diethylhydrazine to give 1,1-diethyl-3-oxopyrazolidinium
bromide (9) while with 1,1- dimethylhydrazine the 1 :
1 adduct of 3-(1,1-dimethylhydrazin-1- io)propionate
(5a) and 1-(2-carboxyethyl)-1,1-dimethylhydrazinium bromide (8a) is obtained.
The reaction of 1,1-dimethylhydrazine with methyl propiolate, methyl propenoate
and itaconic acid gives (1,1- dimethylpyrazol-1-ium)-3-olate (4),
(1,1-dimethyl-2-pyrazolin-1-ium)-3- olate (1a) and
(1,1-dimethyl-3-oxopyrazolidin-1-io-4-yl)acetate (7) respectively. 1,1-Dimethylhydrazine
reacts with ethyl 3-bromopropionate to give both 1-(2-ethoxycarbonylethyl)-1,1-dimethylhydrazinium
bromide (8b) and (1,1-dimethyl-2-pyrazolin-1-ium)-3-olate (1a) while its
reaction with bromoacetic acid gives the 1 : 1 adduct of (1,1- dimethylhydrazin-1-io)acetate
(5b) and 1-carboxymethyl-1,1- dimethylhydrazinium
bromide (8c).
The enol acetate of cholest-4-en-3-one reacts with acetic anhydride-boron trifluoride to give 6/3-acetylcholest-4-en-3-one. The structure of this product follows from its physical properties, and from reactions leading to 6-acetylcholest-4-ene, 6-acetylcholesta-3,5-diene, and 6-ethylidenecholest-4-en-3-one.THE enol acetate (I) of cholest-ken-3-one reacts rapidly (3 minutes at 20') with acetic anhydride-boron trifluoride l a to give 6/3-acetylcholest-4-en-3-one (IIa) . Longer reaction times result in further complex changes, as shown by infrared spectroscopy. The formation of 6-acetyl-A*-3-ketones in this way was reported recently by Mazur and his co-workers, though details of this work are not available.lh 6 p-Acetylcholest-4-en-3-one was characterised by its ultraviolet (Amax. 247 mp) and infrared spectra. It is strongly laevorotatory. Zderic and Limon assigned the structure 6S-acetylprogesterone to a product with similar properties (Amax. 246 mp; [E], -199") obtained by hydration of 6p-ethynylprogesterone. The structure and stereochemistry of (a) Young, Frostick, Sanderson, and Hauser, J. methanolic hydrochloric acid, to give 6-acetylcholesta-3,5-diene (IV) . The ultraviolet absorption of this dienone (lmax. 221 and 281 mp) may be compared with that of the Karplus,
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