Octal one

In this experiment, advantage is made of the fact that lithium-ammonia reduction usually proceeds to give trans-fused Decalins 4). Thus, hydrogenation of A -octal one-2 over palladium catalyst gives essentially cw-2-decalone as the product, whereas the lithium-ammonia reduction of the octalone gives the trans ring fusion. 

However, the 0,01-dimethyl octal one 129 and the tricyclic enone 132 behaved differently. Marshall and Andersen (45) obtained from 129 a mixture of isomers 130 and 131 (54% axial and 46% equatorial, when R=isopropyl and 82% axial and 17% equatorial when R=methyl) while Spencer and collaborators (46) isolated a =1 1 mixture of 133 and 134 from 132. By comparison with enones 127 which have an angular methyl group, the replacement of that group for a hydrogen atom in 129 and 132 must have eased the approach of the reagent on the top face to give products 131 and 134 with the equatorial alkyl group via a boat-like transition state. 

The above stereoelectronic arguments were proposed by Stork and Darling (61) to explain why the more stable isomer is not necessarily always obtained (62). For example, reduction of the octal one 221 with lithium-ammonia-ethanol followed by oxidation afforded the trans-2-decalone 222 even though the isomeric cis-2-decalone 223 is about 2 kcal/mol more stable than 222. Conformation 226 of the enolate dianion is the most favored sterically but it is electronically disfavored. Conformations 224 and 225 are both electronically favored but 225 is less favored sterically than 224. Therefore,... 

The stereochemistry of the 1,4-addition to A -octal-l-one and 1,1-di-methyl-A -octal-2-one has been investigated by House and Marshall, respectively. In summary, steric and stereoelectronic factors play a part in the mechanism of conjugate addition of Grignard compounds. With methylmagnesium iodide, the introduction of an axial methyl group into steroidal 5a-A -3-ketones (3) and 5 -A -3-ketones (6) is favored by stereo-electronic factors in the transition state. 

TABLE 3-1 Percent Cis Ring-fused Product Obtained on Hydrogenation of Octal-1 (9)-en-2-one (9), Testosterone and Cholestenone... 

It should be said that the phase plane of itself cannot be guaranteed to give the whole behavior, for, in computing phase planes, one cannot be sure that one has started in the regions of attraction of all the steady or periodic solutions present. In 1956, the theory that is needed for this to be done systematically was 20 years into the future, and the calculating engines were just beginning to become really powerful. Fortran had not been invented, and each cell had to be addressed by its number, in octal 7... 

Formation of an enamine radical cation 45 was proposed as the chain initiation step in the autooxidation of enamines and SchifFs bases of a,/ -unsaturated ketones to give unsaturated 1,4-diones37. Pyrrolidine enamine of 10-methyl-A1(9)-octal-2-one (44) reacts with oxygen at room temperature to produce, after acid hydrolysis, 10-methyl-A1 (9)-octalin-2,8-dione (47) in 20% yield. Addition of a catalytic amount of FeCl3, Cu(OAc)2 or CuCl2 causes a pronounced enhancement in the oxidation rate and increases the yield to 80-85% after 1 h. 

R) (-)-10-METHYL-1-OCTAL-2-ONE. 70. 35 (R)-(+)-2-Methyl-2-(3-oxobutyl)cyclohexanone (91306-30-8), 70, 36 METHYL 1a,4ap,8aa)-2-OXODECAHYDRO-1-NAPHTHOATE, 70. 256 Methyl 3-phenyl-5-carboxamidopyrrole-2-carboxylate. 70, 85... 

A number of methods have been proposed for particle shape analysis these include verbal description, various shape coefficients and shape factors, curvature signatures, moment invariants, solid shape descriptors, the octal chain code and mathematical functions like Fourier series expansion or fractal dimensions. As in particle size analysis, here one can also detect intense preoccupation with very detailed and accurate description of particle shape, and yet efforts to relate the shape-describing parameters to powder bulk behaviour are relatively scarce.10... 

Often it is necessary to convert numbers from one base to another. The above examples illustrate the ease of converting from octal to binary and vice versa. Consider the following examples ... 

Air passed for 1 hr. through a soln. of 10-methyl-JU9)-octal-2-one pyrrolidine enamine in benzene-methanol containing FeClj 10-methyl-JU9)-octalin-2,8-... 

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