The resolution of 3-methyl-5-bromoadamantanecarboxylic acid

Hamill, H.; McKervey, M. Anthony

doi:10.1039/c2969000864a

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“…The rotation of 1-cyano-3-bromo-5--methyladamantane was calculated by means of the theory of pair interactions 6 • 7 • The rotatory power may be lowered up to one hundreth of that of the corresponding model compound. Such a decrease causes difficulties in measurements of rotations at the D .line or in measurements of ORD and CD curves particularly when the substances are not optically pure 5 …”

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Absolute configuration of (S)-(+)-3-ethyl-5-methyladamantane-1-carboxylic acid and (S)-(+)-1-amino-3-ethyl-5-methyladamantane

Červinka¹,

Fábryová²,

Hájíček³

1974

Collect. Czech. Chem. Commun.

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The absolute configuration of (S)-( + )-3-ethyl-5-methyladamantane-1-carboxylic acid (Ia) and (S)-( + )-1-amino-3-ethyl-5-methyladamantane (!Ia) has been det~rmined by comparison of CD curves of the corresponding ( + )-N-methylthioamide I!d and salicylideneimino derivative lie with curves of the analogous derivatives of (S)-( + )-2-methylbutyric acid and (S)-( + )-2-aminobutane, resp. The absolute configuration has been proved by degradation of the (S)-( +)-acid !a to the amine Ila and comparison of CD curves of its salicylidene derivative lie.*** The molecule of adamantane represents a highly symmetric system ('ld symmetry).The appropriate substitution of this system may lead to compounds of two chirality types. Thus, by substitution at Cc 2 ) and Cc 6 ) carbon atoms a system is formed possessing the axial chirality; 2,6-dichloroadamantane-1,3,5,7-tetracarboxylic acid is the first substance of this type, prepared in the optically active form 1 . Appropriate SUbStitution at C(l)• C(3)• C(S)• and C(7) Carbon atoms Of the adamantane ring system results in substances of a central chirality, as shown for the first time by von Schleyer 2 • The first attempts in this respect to resolve the acids Ia, Ib, and Ic (Stepanov and Baklan 3 ) or to prepare the optically active acid Id (Malfer 4 ) were unsuccessful. Later on, the acid Id was resolved with the use of dehydroabietylamine (Me Kervey 5 ); the thus-obtained acid, though inactive at the D line, afforded by degradation the optically active 1-methyl-7-methylenebicyclo[3.3.1 Jnonan-3-one. When resolved with quinine 6 • 7 , the optical rotation of the acid Id at the D line was [a]~0 -0·36° (chloroform). In the recent time, ( + )-1-amino-3-ethyl-5-methyladamantane has been prepared 8 • In the present paper we wish to report determination of the absolute configuration Part XLVIII in the series Asymmetric Reactions; Part XLVII: This Journal38, 3299 (1973). Present address: Research Institute of Pharmacy and Biochemistry, Prague 9. All the adamantane derivatives prepared in the present work were inactive at the sodium D line but afforded monotonous positive ORD curves in the region of shorter wavelengths. On the basis of this effect, the absolute configuration is ascribed to these derivatives.

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confidence: 98%