Cyanoethylation of Active Hydrogen Groups 23 and 120 g. of cyanoacetic acid, pyridine (150 g.) was added dropwise while stirring and cooling to 10-20°. The mixture was stirred for one-half hour at room temperature and then at 100-105°for four hours. The product was washed thoroughly with water and distilled in vacuum.The fraction boiling at 105-110°( 21 mm.) was collected as the product; yield 82 g., »16d 1.4824.Acrylonitrile (53 g.) was added dropwise to a stirred solution of 60.5 g. of cyclohexylidene-acetonitrile, 60 g. of tertiary butyl alcohol and 5 g. of "Triton B" while cooling to 28-37°. The mixture was stirred for two hours after the addition, then neutralized with dilute hydrochloric acid, taken up in an equal volume of ethylene dichloride and washed with water. The ethylene dichloride layer was evaporated to dryness in vacuum on a steam-bath and the residual oil (105 g.) distilled in vacuum.The fraction boiling at 210-235°( 1 mm.) solidified in the receiver to a crystalline mass; yield 43 g. After recrystallization from methanol the product, presumably XIV, formed colorless crystals, m. p. 81-82°. Anal.
Hydration and Rearrangement of Dicyclopentadiene 723 222 g. of bromine was added at -10°to a well-stirred mixture of 200 g. of the sodium enolate of ethyl formylacetate in 1500 cc. of absolute ethanol. Anhydrous hydrogen chloride was then passed into the mixture at -10°until 170 g. was absorbed. Stirring was continued for three hours at -10°and for twenty-four hours at room temperature. The mixture was then worked up as described under ethyl
Tetrahydro-ti.icyclopentadien.5 g Tricyclopentadien wurden in atherischer Losung bei Gegenwart von Platin mit Wasserstoff rednziert, i n 1 Stunde wurden dabei 1040ccm Wnsserstoff bei 20° und 723mm statt 1060 ccm anfgenommen. Nach dem Sbfiltrieren des Platins nnd dbdestillieren des Athers wird das Tetrahydro-tricyclopentatlien dnrch Umkrystallisieren aus Methylalkohol gereinigt und sclimilxt dann bei 43O. Eine Mischprobe mit Tricyclopentadien sclimilxt bei 33-36"; es zeigt ungefahr dieselbe rliisliclikeit wie das Tricyclopentadien. (Cl5H.I.I) Ber. C 89,03 H 10,97 Gef. ,) 89,35, 80,26 ,) 11,53, 11,13 Mol.-Gew. (in Benzol kryosk). 0,1094 g Subst. in 17,58 g Renzol, M = 192 0,2235 g ,. ,, 17,58 g ,, , d T = 0,32'io -If= 199 (in Campher) 0,0160 g Subst. in 0,1525 g Campher, C,H** Mo1.-Gew. Ber. 202. dT= 0,165O A = 20,6O M = 204 Das Produkt wird von konz. Salyetersanre nicht verandert, Rrom wird nicht anfgenommen; es ist unzersetzt destillierbar. Hochpolymere Verbindungen. 8. Mitteilung.') tiber die Polyiiierisation des Cyclopentadiens ; von B. 8taudinger nnd I . A. B~uson.~) L)as Cyclopentadien sollte als Butadienderivat bei der Polymerisation ein dem Kautschnk ahnliches, hochmolekulares Produkt liefern. Es gibt aber bekanntlich das Dimere, nnd es ist auffallend, daD diese Unterschiede in dem Verlauf der Polymerisation der verschiedenen Kohlenwasserstoffe mit konjn-I) 7. Mitteilung eiehe vorstehrnd. *) Vgl. Dissei.tation von H. A. B r u s o n , Ztlrich 1925.
The powerful cyanoethylating action of acrylonitrile in the presence of strong bases upon organic compounds possessing labile hydrogen atoms1 is strikingly evident with various types of ketones.Aromatic methyl ketones of the type R-CO-CHS as exemplified by acetophenone, ^-methylacetophenone, p-methoxyacetophenone, p-chloroacetophenone, p-bromoacetophenone, ^-acetyldiphenyl, and 2-acetylnaphthalene readily took up three molecular equivalents of acrylonitrile in the presence of strong alkali catalysts such as trimethylbenzylammonium hydroxide or potassium hydroxide to form crystalline in-cyanoethylation products (I).These are listed in Table I together with their physical and analytical data. Upon hydrolysis with aqueous sodium hydroxide or potassium hydroxide these tri-(cyanoethyl)-methyl aryl ketones yielded the corresponding aryl keto tricarboxylic acids R-CO-C(CH2CH2COOH)3. These are listed in Table II.Even acetomesitylene which because of steric hindrance reacts sluggishly, gave a small yield (30%) of the fn-cyanoethylation product (II). CH, CH,-/ N-CO-C(CH2CH2CN), \-|Z CH, (II)Propiophenone and desoxybenzoin which possess only two active hydrogen atoms contiguous to the carbonyl group, each took up two molecular equivalents of acrylonitrile to form y-benzoyl-7methylpimelonitrile (III) and 7-benzoyl-y-phenylpimelonitrile (IV), respectively. NCCH2CHí-C-CH2CH2CN C"H6-COZXCH, (HI) NCCH2CHr-C-CH2CH2CN C6Hí-CO/'xCeH, (IV)Upon hydrolysis with aqueous sodium hydrox-
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