Primary alcohols derivatives

Ester hydrolysis occurs to a larger extent with the trans and primary alcohol derivatives as compared with the corresponding cis and secondary alcohol derivatives, respectively (Fig. 2). The chirality (1 S or 1R) at the acid moiety of phenothrin [9], tetramethrin [10], and permethrin [11] does not significantly affect ester hydrolysis. 

The investigations of Rossini on the heats of combustion of the aliphatic hydrocarbons and of primary alcohols derived from these have proved the existence of some remarkable deviations from the additivity rule. They can be expressed by a steady decrease of the substitution heats... 

Dytol [Rohm Haas], TM for aliphatic primary alcohols derived from natural fats and oils (C10 to C18). 

From isopentyl alcohol (3-methyl-l-butanol), acetylene, and any required straight chain primary alcohols, derive a practical synthesis for 2-methylheptadecane, the sex-attractant for the Tiger moth. 

The general reactivity of oxidized Ni anodes in various f-butanol/H20 mixtures was followed by cyclic voltammetry. " The coulombic and organic product yields of aldehyde and acid were determined for various primary alcohol derivatives. Substituent effect on the anodic oxidation rates of a series of benzyl alcohols were evaluated. Attempts were made to relate the oxidation rates to the Hammett cr parameter for substituent properties. 

Scheme 4.40 DKR of primary alcohols derived from tropic acid ethyl ester with Shvo s catalyst.

The phenolic primary alcohols derived in this way from phenylalanine (Phe, F) and in some systems from tyrosine (Tyr, Y) are incorporated into structural plant materials by linking carbohydrates (Chapter 11) together to form Ugnins. The same alcohols give rise to phenylpropenes, such as eugenol and safrole, which are commonly referred to as essential oils, while further oxidation and double-bond isomerization of p-coumaric acid leads to umbeUiferone (Figure 12.6). 

In the same area, Atuu and Hossain have developed the DKR of a series of other primary alcohols derived from tropic acid ethyl ester. Indeed, these substrates led to the formation of the corresponding acetates in good yields and moderate to high enantioselectivities when submitted to a combination of lipase PS and Shvo s catalyst in the presence of isopropenyl acetate, as shown in Scheme 8.46. These products constituted precious precursors of... 

Esters derived from the primary alcohols are the most stable and those derived from the tertiary alcohols are the least stable. The decomposition temperature is lower in polar solvents, eg, dimethyl sulfoxide (DMSO), with decomposition occurring at 20°C for esters derived from the tertiary alcohols (38). Esters of benzyl xanthic acid yield stilbenes on heating, and those from neopentyl alcohols thermally rearrange to the corresponding dithiol esters (39,40). The dialkyl xanthate esters catalytically rearrange to the dithiol esters with conventional Lewis acids or trifluoroacetic acid (41,42). The esters are also catalytically rearranged to the dithiolesters by pyridine Ai-oxide catalysts (43) ... 

Alkylation of aluminum with ethyleae yields products that fiad appHcatioa as iaitiators and starter compounds ia the productioa of a-olefias and linear primary alcohols, as polymerization catalysts, and ia the syathesis of some monomers like 1,4-hexadieae. Triethyl aluminum [97-93-8] A1(C2H3)2, is the most important of the ethylene-derived aluminum alkyls. 

It is possible to introduce this group selectively onto a primary alcohol in the presence of a secondary alcohol. The derivative is stable to KMn04, w-chloro-peroxybenzoic acid, LiAlH4, and Cr03 Pyr. Since this derivative is similar to the p-methoxyphenyl ether it should also be possible to remove it oxidatively. The GUM ethers are less stable than the MEM ethers in acid but have stability comparable to that of tlie SEM ethers. It is possible to remove the GUM ether in the presence of a MEM ether. 

The conversion of the BOC group to other carbamates is achieved by heating the alcohol, Ti(0-/-Pr)4 in toluene. Teoc-, Cbz-, and Alloc-pro-tected primary amines have been prepared in this fashion. The reaction is selective for a primary BOC derivative. ... 

The thermolysis of xanthates derived from primary alcohols yields one olefin only. With xanthates from secondary alcohols (acyclic or alicyclic) regioisomeric products as well as fi/Z-isomers may be obtained see below. While acyclic substrates may give rise to a mixture of olefins, the formation of products from alicyclic substrates often is determined by the stereochemical requirements the /3-hydrogen and the xanthate moiety must be syn to each other in order to eliminate via a cyclic transition state. 

Acid halides are among the most reactive of carboxylic acid derivatives and can be converted into many other kinds of compounds by nucleophilic acyl substitution mechanisms. The halogen can be replaced by -OH to yield an acid, by —OCOR to yield an anhydride, by -OR to yield an ester, or by -NH2 to yield an amide. In addition, the reduction of an acid halide yields a primary alcohol, and reaction with a Grignard reagent yields a tertiary alcohol. Although the reactions we ll be discussing in this section are illustrated only for acid chlorides, similar processes take place with other acid halides. 

The homology between 22 and 21 is obviously very close. After lithium aluminum hydride reduction of the ethoxycarbonyl function in 22, oxidation of the resultant primary alcohol with PCC furnishes aldehyde 34. Subjection of 34 to sequential carbonyl addition, oxidation, and deprotection reactions then provides ketone 21 (31% overall yield from (—)-33). By virtue of its symmetry, the dextrorotatory monobenzyl ether, (/ )-(+)-33, can also be converted to compound 21, with the same absolute configuration as that derived from (S)-(-)-33, by using a synthetic route that differs only slightly from the one already described. 

Intermediate 10 must now be molded into a form suitable for coupling with the anion derived from dithiane 9. To this end, a che-moselective reduction of the benzyl ester grouping in 10 with excess sodium borohydride in methanol takes place smoothly and provides primary alcohol 14. Treatment of 14 with methanesulfonyl chloride and triethylamine affords a primary mesylate which is subsequently converted into iodide 15 with sodium iodide in acetone. Exposure of 15 to tert-butyldimethylsilyl chloride and triethylamine accomplishes protection of the /Mactam nitrogen and leads to the formation of 8. Starting from L-aspartic acid (12), the overall yield of 8 is approximately 50%, and it is noteworthy that this reaction sequence can be performed on a molar scale. 

---