Side exclusion

In the presence of an axial la-hydroxyl group methylmagnesium iodide reacts with 3-keto-5a-steroids from the j5-side exclusively to yield the 3f -methyl isomer. ... 

Here m = 4 and the number of degrees of freedom m—1 = 3. For a two-sided exclusion domain, a 95 percent confidence interval corresponds to a = 2.5 percent. From standard statistical tables (e.g., Spiegel, 1975), we obtain r97 s3 = 3.18. Let us calculate the sample mean... 

Combinatorial chemistry has an unusual patent history. No single company or individual has control of any one strategic patent and there is no single strategic patent that defines the field. Many companies have patents that enable them to pursue unique chemistries, and this provides investors with many choices. On the other side, exclusivity is reduced. 

Introduce a solution of 100 g. of sodium bisulphite in 200 ml. of water and continue the stirring, preferably for 10 hours with exclusion of air. A thick precipitate separates after a few minutes. Collect the bisulphite compound by suction filtration, wash it with ether until colourless, and then decompose it in a flask with a lukewarm solution of 125 g. of sodium carbonate in 150 ml. of water. Separate the ketone layer, extract the aqueous layer with four 30 ml. portions of ether, dry the combined organic layers over anhydrous magnesium sulphate, remove the ether at atmospheric pressure, and distil the residual oil under reduced pressure from a Qaisen flask with fractionating side arm (Fig. II, 24, 5). Collect the cyclo-heptanone at 64r-65°/12 mm. the yield is 23 g. 

Synthesis You will see that there are problems in both the routes found by the analysis. For route a it is known that malonate attacks exclusively the less hindered side of some Michael acceptors ... 

Step 2 of the mechanism m Figure 6 12 is a nucleophilic attack by Br at one of the carbons of the cyclic bromonium ion For reasons that will be explained m Chapter 8 reactions of this type normally take place via a transition state m which the nude ophile approaches carbon from the side opposite the bond that is to be broken Recall mg that the vicinal dibromide formed from cyclopentene is exclusively the trans stereoisomer we see that attack by Br from the side opposite the C—Br bond of the bromonium ion intermediate can give only trans 1 2 dibromocyclopentane m accordance with the experimental observations... 

Even though ketones have the potential to react with themselves by aldol addition recall that the position of equilibrium for such reactions lies to the side of the starting materials (Section 18 9) On the other hand acylation of ketone enolates gives products (p keto esters or p diketones) that are converted to stabilized anions under the reaction conditions Consequently ketone acylation is observed to the exclusion of aldol addition when ketones are treated with base m the presence of esters... 

The reaction of dihalocarbenes with isoprene yields exclusively the 1,2- (or 3,4-) addition product, eg, dichlorocarbene CI2C and isoprene react to give l,l-dichloro-2-methyl-2-vinylcyclopropane (63). The evidence for the presence of any 1,4 or much 3,4 addition is inconclusive (64). The cycloaddition reaction of l,l-dichloro-2,2-difluoroethylene to isoprene yields 1,2- and 3,4-cycloaddition products in a ratio of 5.4 1 (65). The main product is l,l-dichloro-2,2-difluoro-3-isopropenylcyclobutane, and the side product is l,l-dichloro-2,2-difluoro-3-methyl-3-vinylcyclobutane. When the dichlorocarbene is generated from CHCl plus aqueous base with a tertiary amine as a phase-transfer catalyst, the addition has a high selectivity that increases (for a series of diolefins) with a decrease in activity (66) (see Catalysis, phase-TRANSFEr). For isoprene, both mono-(l,2-) and diadducts (1,2- and 3,4-) could be obtained in various ratios depending on which amine is used. 

Delignification Chemistty. The chemical mechanism of sulfite delignification is not fully understood. However, the chemistry of model compounds has been studied extensively, and attempts have been made to correlate the results with observations on the rates and conditions of delignification (61). The initial reaction is sulfonation of the aUphatic side chain, which occurs almost exclusively at the a-carbon by a nucleophilic substitution. The substitution displaces either a hydroxy or alkoxy group ... 

Waferboard is made almost exclusively from aspen wood and the flakes are roughly square in shape, up to 2 in. (5 cm) on a side. They are used for low end stmctural sheathing appHcations. 

Preventive Explosion Protection The principle of preventive explosion protection comprises the reliable exclusion of one of the requirements necessary for the development of an explosion. In pictorial terms, therefore, at least one of the sides of the hazard triangle shown in Figure 26-33 will be broken open. 

Since the side chains of consecutive amino acids of a p strand are on opposite sides of the P sheet, every second residue of the p strands contributes to this hydrophobic shell. The other side chains of the P strands point inside the barrel to form a hydrophobic core this core is therefore comprised exclusively of side chains of P-strand residues (Figure 4.3). 

Casing The vertical enclosing side- or endwall of a tower, exclusive of the air inlet louvers. 

This chapter will deal exclusively with three-membered rings containing the hetero atoms O, S and N, and fused to the steroid skeleton. Because of the conformational requirements in steroids, not all of the usual methods of synthesis of three-membered rings are applicable to the fused ring system. For the synthesis of steroids to which an aziridine, oxirane or thiirane is attached either in the side chain or at a ring position but not directly fused to the nucleus, the methods discussed in this chapter, as well as others, are applicable. 

In general, epoxidation of steroids with trans-anti-trans ring fusions leads to exclusive formation of the a-oxirane. Steroid Reactions lists examples of exclusive a-epoxide formation from 2-, 4-, 6-, 7-, 8(9)-, 14-, 16- and 17(20)-unsaturated steroids. Further examples of a-epoxidation of steroid 1-enes, 3-enes, 8-enes, 9(ll)-enes, 8(14)-enes and 16-enes have been reported. The preferred attack by the reagent on the a-side of the steroid nucleus can be attributed to shielding of the -side of the molecules by the two angular methyl groups. 

Another unusual directive effect has been observed in the epoxidation of A -double bonds, which in most cases takes place predominantly on the a-side, e.g. 23. However, when carbon-17 is sp hybridized, epoxidation gives exclusively the -epoxide e.g., 25). 

When applied to A -pregnenes, 17a,20-glycols are produced exclusively, because of rear-side attack by the reagent. 

Styragel columns are compatible with most solvents commonly used in size exclusion chromatography. Exceptions are found on both sides of the polarity scale the use of standard general-purpose Styragel columns with aliphatic hydrocarbons or with alcohols (except hexafluoroisopropanol) and water is generally not recommended. However, it is possible to pack columns in special solvents for special-purpose applications. The interested user should contact Waters for additional information. 

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