By modification of the known Bitter conditions for making N-substituted amides by addition of acrylonitrile to olefinic compounds, it is possible to apply this reaction to new monoenic fatty acids. Procedures are presented for the addition of acrylonitrile to oleic acid (2a), methyl m-5-eicosenoate (3), erucic (4), and brassidinic (5) acids, and the addition of acetonitrile to brassidinic acid. Yields of 54 to 80-84% of the respective monoacrylamides (10-12) and acetoamide (8) were obtained in crystalline form from the monoenic fatty acids by applying the proper ratio of reactants and by the mode of addition. Evidence is adduced, showing that it is possible to determine the addition sites in the Bitter products by mass spectrometry, and also that mass spectral analysis of Bitter products from olefinic compounds could be of general utility for the assignment of double bond position in the carbon chain.The formation of acylamino fatty acids of structure CHS [CH2]zCH(NHCOR) [ by interaction of nitriles and monoenic acids in the presence of strong acids (designated the Ritter reaction) is well documented.1-6Earlier investigators in the fatty acid field have noted that the CVmonoenic acids, oleic (2a)2b and petroselinic (l),2c lend themselves to smooth Ritter reaction with a variety of saturated and unsaturated aliphatic nitriles, dinitriles,8 and hydrogen cyanide, but in no case was the position of the addition determined.With the exception of 1 -> 6 and 2 -> 7 conversions, reactions of acrylonitrile with some other monoenic fatty acids do not appear to have been studied. Our interest in such a study emerged from a research project aimed at exploring the ability of Ritter-type products (6-7, 10-12) from acrylonitrile to undergo the Diels-Alder reaction.7We have presented here the application of the Ritter reaction to a variety of pure homologs of long-chain unsaturated acids in the Ci8 to C22 range (see Scheme I) and results of a mass spectral study of the Ritter products 7-12. Results of the Ritter Reaction.-The procedures and results of the Ritter reaction between acrylonitrile and a series of monoenic fatty acids described here relate to the following substrates: oleic (2a), m-5-eicosenoic (3), cfs-13-docosenoic (erucic 4), and íraras-13-docosenoic (brassidinic, 5) acids. We also included in this study the reaction between acetonitrile and 2b, and the catalytic reduction of methyl acrylamidostearate (9) into methyl propionamidostearate (10).The experimental part describes the series of experiments which give the optimum yields of once-recrystallized material obtained from a series of reactions in which variations in the ratio of reactants and in the mode of addition were studied. Other features were determined after three or more recrystallizations from acetone.(1) Deceased.(2) (a) L. I. ICrimen and D.
The photochemistry of the title compound in the solid and in solution at low temperatures has been investigated. The solid €,€-isomer gives the €,Z-isomer plus a dimer F ; one crystal form of the €,€-isomer is reversed photochromic. The solid Z,Z-isomer also gives the dimer F, whereas the EZ-isomer appears to give the €.€-isomer as the primary photoproduct. In methylcyclohexane-isohexane at -1 85" the 'El-isomer is isomerised to €,Z; the latter is reversibly isomerised into Z,Z but also gives two dimers, one of them F. At -1 00" the same isomerisation processes occur, with in addition reversible conversion of the €,Z-isomer into the 1,8a-dihydrophenylnaphthalene. At these low temperatures the isomerisation of the €,€-to the Z,Z-isomer proceeds via the €,Z-form. The isomerisation processes do not proceed through the dihydrophenylnaphthalenes or cyclobutenes.IN a previous paper we treated qualitatively the photochemistry of bis-$-methoxybenzylidenesuccinic anhydride : we described its three geometrical isomers and the conditions for their interconversion. Heller and his co-workers have since reported 2-4 on the thermal and photochemical reactions of a variety of other fulgides and fulgimides. They give structural assignments to the geometric isomers of these materials and of the corresponding fulgenic acids; Elbe and Kobrich also discuss the assignments for the latter. The structure assignments are based mainly on n.m.r. spectroscopy, although evidence based on the chemical shift of the vinyl proton signal is sometimes arnbigu0us.l However, combination of the n.m.r. results with a crystal structure analysis gives confidence in the general correctness of the picture. In keeping with the other authors2-5 we adopt the E,Z nomenclature for isomers A-C: E and 2 are respectively equivalent to trans and cis as used previously.
Die Darstellung der 2-Pyrrolidondcrivate 6a, b uber die P-Formyldicarbonsaure-diester 4a, b wird beschrieben -ausgehend von l a bLw. 1 b und 2a bzw. 2b; mehrtagiges Stehenlassen von 4a oder 4b fuhrt in Ethanol in Gegenwart von Ammoniumcarbonat zu 5a sowie zu 6a, b, wobei 5b nicht isoliert worden ist. 6 a kann in die lsomeren 7 und 8 getrennt werden. 5a entsteht auch bei der Reaktion von 4a mit Ethanol in Gegenwart von p-Toluolsulfonsaure, welches sich nach 3tagigem Srehenlassen bei Raumtemperatur in Ethanol in Anwesenheit von Ammoniumcarbonat nicht verandert. Synthesis of Substituted 2-PyrrolidonesThe preparation of the 2-pyrrolidone derivatives 6a, b ilia P-formyldicarboxylates 4a, bstarting from l a , b and 2a, b -is described; reaction of 4a and 4b in ethanol in the presence of ammonium carbonate gave 5a and 6a, b, respectively. 6 a was separated by chromatography into the isomers 7 and 8. 5a is also obtained by reaction of 4a in ethanol in the presence ofp-toluenesulfonic acid; 5a in ethanol in the presence of ammonium carbonate at room temperature remained unchangcd after 3 days. in Ethanol bei Raumtemperatur im Laufe von 3 Tagen mit Ammoniumcarbonat reagieren, so entstehen in relativ guten Ausbeuten Mischungen der Acetale 5a und der 2-Pyrrolidonderivate 6a, b; die Acetale 5a konnten destillativ aus der Reaktionsmischung entfernt werden; der aus 6a bzw. 6b bestehende, jedoch noch verunreinigte Ruckstand wurde saulenchromatographisch gereinigt und im Falle von 6a in die beiden Isomeren 7 und 8 getrennt.Unterschiede sind in den IR-Spektren (CHC13) zu sehen. Die Carbonylbanden der cyclischen C = 0 -NH-Gruppierungen und der beiden Estergruppen sind jeweils als 'C
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