The ph:.toc[lemical reduction of the (3-keto-rr-caproic and 0-keto-n-caprylic acids yielded the corresponding D-0-hyclrosyacids. This observatiori is contrasted to bioreductiori of 0-ketobutyric acid to L-P-hydrosybutyric acid. The Oasis for the assigrunent of the above configuratio~is is discussed. L-a-Hydrosyn-1-aleramide was reduced with lithiuni aluriiirii~~m h>-dride and the product was acetylated to yielcl ~-l-acetamido-2-acetosype1it'~i11e. The enantioniorphic form of the latter cor~~pound was ol~tained through the Curci~ls degradation of D-6-hydror).-71-caprohydrazide. The configuratior~s assigned to the P-hydroxy-ncaprylic acids are based on the Levene-hlarkcr Rule for the optical rotations of hornologous compounds. The 0-hydrasy-n-caproic and 0-hydroxy-n-caprylic acids derived from ustilagic acid were thus sho\v~i to belong to the L-series. The use of infrared spectroscopy in conliguratior~al correlatior~s is discussed and the infrared spectra of ~-f l -h~d r o r y b u t~r h 4 . d r a z i d e , L-0-hydrosy-7t-caprohydrazide, L-and ~~-P-h~dros~-r~-ca~r~lhydrazirles artd D-, L-, and ~~-1-acetamido-2-acetoxypentane are given.Friednlann (6) found that the pl~,.tochekical reduction of p-ketobutyric acid yielded a large preponderance of the dextrorotatory form of P-hydroxybutyric acid (rotation measured in water). We have confirmed the work of Friedmann and have extended the biorecluction of P-ketoacids, by rapidly fermenting baker's yeast (22, pp. 75-117), to the P-keto-n-caproic and P-keto-ncaprylic acids. The P-hydroxy-n-caproic and P-hg.clroxy-n-caprylic acids thus obtained possessed levorotatory methyl ester and hydrazide derivatives, the rotations nleasur-ed in chloroform and water, respectively. On the other hand, the methyl ester and hydrazide derivatives of the phytochemicallp produced P-hydroxybutyric acid were dextrorotatory ~~r l d e r the same conditions of measurement. The magnitudes of the rotations of the methyl esters were such that it appeared, on the basis of the Levene-Marker R~l l e (20) for the establishment of the configurational relationship of homologous compounds, that the biored~~ction yielded configurationally related 8-l~ydroxy-n-caproic and Phydroxy-n-caprylic acids but gave a fl-hyclrorybutyric acid of opposite relative configuration. This apparent inconsistency in the stereochemical course of the phy toreduction of these homologous co~npoiinds was definitely established by the correlation of the configuratiorls of the P-hydroxybutyric acids and the p-hydroxy-n-caproic acids on the following basis. Karrer and Iclarer (10) and Levene and Haller (15) independently correlated the configurations of the Phydroxybutyric acids with those of the lactic acids. T h e co~lfigurational relationships between the lactic acids and the a-hydrox~r-n-valeric acids were estab-1 il/ianzrscript
SommaireEn faisant r6agir la solution aqueuse des sels de diazonium monosubstitu6s avec des solutions d'acides cinnamiclues substitu6s selon les conditions publi6es par Nleerwein, il a 6t6 possible de sl,nth6tiser un certain nombre de d6riv6s du stilbdne avec un groupement substituant dans chacun des anneaux benz6niques.De cette fagon ont 6t6 synth6tis6s pour la premidre fois les con.rpos6s suivants: 4nr6thode ont aussi 6t6 pr6par6s les compos6s suivants dont la synthdse selon une autre nr6thoclc a d6ji 6t6 rapport6e: 2-chloro-4'-m6thoxystilbdne,2,2'-dim6thoxystilbdne,2,l'-dirn6thox-vstilbdne,4,4'-dinitrostilbdne, -1-nr€tlrll-l'-nitrostilbine,2-rnetlroxl-l'-nitro'tilbene.t +-nr6thoxy-4'-nitrostil-tJCne. fait I'essence de la r6action. Il en r6sulte que la solubilit6 trds variable des acides cinnamiques substitu6s dans ce solvant nous empeche d'op6rer dans des conditions de milieu absolument identiques. C'est sans doute pour cette t Manuscrit regu le 17 septembre 1917, Contribution du Ddpartement de Chi.mie de la Faculti d,es Sciences, Uniaersitt Lawl', Qu6.bec. Can. J. Res. Downloaded from www.nrcresearchpress.com by MICHIGAN STATE UNIVERSITY on 02/20/15 For personal use only. Can. J. Res. Downloaded from www.nrcresearchpress.com by MICHIGAN STATE UNIVERSITY on 02/20/15 For personal use only.
158. Schematic, theory, use, and results for a computerized pressure viscosimeter.
The Darapsky method has been successfully applied to the synthesis of aminoacids from substituted cyanoacetic esters, RCH (CN)COOC2H5. R=CH3CH (CH2)4CH3, CH3CH(CH2)5CH3, CH3(CH2)11, HOCH2CH2, o-ClC6H4CH2, p-CH3C6H4O(CH2)2, p-CH3C6H4O(CH2)3, p-C2H5C6H4O(CH2)2, p-C2H5C6H4O(CH2)3, p-ClC6H4O(CH2)2, p-ClC6H4O(CH2)3, p-BrC6H4O(CH2)3. The esters were prepared by condensation of cyanoacetic ester with suitable bromides. When treated with hydrazine hydrate, they gave rise to hydrazides, which were identified by their anisal derivatives. Azides were obtained by the action of nitrous acid on hydrazides at low temperature and were transformed by heating with alcohol into carbethoxyaminonitriles. Finally, the latter by hydrolysis yielded the following amino acids: dl-α-amino-β-methylcaprylic acid, dl-α-amino-β-methylpelargonic acid, dl-α-aminomyristic acid, dl-α-amino-γ-hydroxybutyric acid, dl-α-amino-γ-p-methylphenoxybutyric acid, dl-α-amino-δ-p-methylphenoxyvaleric acid, dl-α-amino-γ-p-ethylphenoxybutyric acid, dl-α-amino-δ-p-ethylphenoxyvaleric acid, dl-α-amino-γ-p-chlorophenoxybutyric acid, dl-α-amino-δ-p-chlorophenoxyvaleric acid, and dl-α-amino-δ-p-bromophenoxyvaleric acid.
The condensation of monosubstituted cyanoacetic esters with hydrazine gave rise to 4-R-3-amino-5-pyrazolones. The pyrazolones prepared were those in which R = o-chlorobenzyl, β-p-methylphenoxyethyl, γ-p-methylphenoxypropyl, β-p-ethylphenoxyethyl, β-p-chlorophenoxyethyl, γ-p-chlorophenoxypropyl, γ-p-bromophenoxypropyl, or n-dodecyl.The ultraviolet absorption spectra of these pyrazolones were determined in neutral, acid, and alkaline medium.
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