Unsaturated Aliphatic Alcohols

As demonstrated by the example in Eq. 66, propargylboron reagent 93 affords allenic alcohols in very high enantioselectivities. Although this reagent has not been widely employed, the selectivity it provides with all classes of aldehydes is truly remarkable (>99% ee for model aliphatic, unsaturated, and aromatic aldehydes). 

The partial oxidation of alcohols, to afford carbonyl or carboxylic compounds, is another synthetic route of high industrial interest For this, scC02 was investigated as a reaction medium for the aerobic oxidation of aliphatic, unsaturated, aromatic and benzylic acids with different catalytic systems, mainly based on the use of noble metals, both in batch [58-64] and in continuous fixed-bed reactors [65-70]. In this context, very promising results have been obtained when studying the catalytic activity of supported palladium and gold nanoparticles in the oxidation of benzyl alcohol to benzaldehyde these allowed conversions and selectivities in excess of 90% to be achieved [71-73]. 

For the manufacture of non-crosslinked ionomer polymer mixtures ethylene, butene-1, isobutylene, vinyl chloride, vinylidene chloride, aliphatic carboxylic acids of vinyl esters (C2-C18), aliphatic unsaturated mono and di carboxylic organic acid esters (C3-C8) with mono aliphatic saturated alcohols (C2-C12) and unsaturated aliphatic mono and di carboxylic organic acids (C3-C8) can be used as raw materials. 

Vinyl chloride can be copolymerized with a series of monomers Vinylidene chloride, trans-dichloroethylene, vinylesters of aliphatic carboxylic acid (C2-C18), acrylic acid esters, methacrylic and/or maleic acid as well as fumaric acid with mono-functional aliphatic saturated alcohols (Cj-C18), mono-functional aliphatic unsaturated alcohols (C8—C18), vinyl ethers from mono-functional aliphatic saturated alcohols (C i-Cis), propylene, butadiene, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid (total < 8 %) and N-cyclohexylmaleinimide (< 7 %). 

Three-component reactions of aldehydes, amines, and allyltributyltin also proceeded smoothly in micellar systems with Sc(OTf)3 as Lewis acid catalyst, to afford the corresponding homoallylic amines in high yields (Eq. 19) [68]. Not only aromatic aldehydes but also aliphatic, unsaturated, and heterocyclic aldehydes worked well. The procedure is very simple—merely mixing an aldehyde, an amine, and allyltributyltin in the presence of Sc(OTf)3 and SDS in water no homoallylic alcohol (an adduct between an aldehyde and allyltributyltin) was produced. It was suggested that imine formation from aldehydes and amines was very fast under these conditions, and that the selective activation of imines rather than aldehydes was achieved. 

Applicability Particularly accurate for the following families acetates, aliphatic ethers, halogenated compounds, dicarboxylic acids, ketones, aliphatic alcohols, aliphatic acids, propionates and butyrates, and unsaturated aliphatic esters. 

Twenty-two pheromones and kairomones and two synthetic analogues are now listed in The Pesticide Manual (Tomlin, 2000). Most of them are long aliphatic unsaturated compounds, with substituents containing oxygen, e.g., esters, alcohols, ketones, and aldehydes. 

A. Linear and branched-chain aliphatic, unsaturated, unconjugated alcohols, aldehydes, acids and related esters... 

In the presence of a strongly basic amine, rhodium complexes are found to catalyse selective hydrogenation of cinnamaldehyde to cinnamyl alcohol. Hydrogenation of aliphatic unsaturated aldehydes under the same conditions gives poor selectivity. ... 

Oxygen-containing heterocycles are abundant in nature and are important in fine chemicals. The addition of alcohols across unsaturated C-C bonds represents an atom-economical and direct route for the synthesis of these cyclic ethers. Hydroalkoxylation transformations mediated by a wide range of transition-metal and alkali-metal catalysts yield a variety of vinyl ethers. Organolanthanide complexes offer an alternative agent for the efficient and highly selective synthesis of both aliphatic and vinyl ethers with selectivities often complementary to those of transition-metal catalysts. 

Because of their structural diversity, the C-9 compounds occupy first place among the aliphatic alcohols and carbonyl compounds. Cucumber 164, 296, 619) and various melon fruits 293, 294, 297, 298) seem to be particularly rich in derivatives having this number of carbon atoms. In addition to nonanal and the corresponding alcohol, their unsaturated analogs (16) to (25) were also found in these Cucurbitaceae fruits. ( ,Z)-2,6-Nonadienal (23) and ( )-2-nonenal (17) constitute the organoleptic principle for cucumber flavor Cucumis sativus L.) (164, 296). Although it is present in a concentration of only 0.9 ppb (about 45 times its threshold value) (295), (Z)-6-nonenal (21) is the essential... 

The simplest aliphatic unsaturated alcohol, allyl alcohol (prop-2-en-l-ol), is formed from alliin during high temperature processing of garhc. AUyl alcohol was found to be one of the major degradation... 

Description. This class of surfactants essentially covers ethoxylated derivatives of lanolin (wool fat) and castor oil. Lanolin is the generic name of a wax containing a complex mixture of esters and polyesters of high-molecular-weight alcohols (aliphatic, steroid, and triterpenoid) and fatty acids (saturated, unsaturated, hydroxylated, and non-hydroxylated). The ethoxylation is carried out on fractionation products of lanolin (lower aliphatic alcohols and sterols). 

Secondary aliphatic alcohols 3625-3620 (s) 1350-1260 (s) 1125-1085 (s) See comments under primary aliphatic alcohols Also for a-unsaturated and cyclic tertiary aliphatic alcohols... 

Composition. Shellac is primarily a mixture of aUphatic polyhydroxy acids in the form of lactones and esters. It has an acid number of ca 70, a saponification number of ca 230, a hydroxyl number of ca 260, and an iodine number of ca 15. Its average molecular weight is ca 1000. Shellac is a complex mixture, but some of its constituents have been identified. Aleuritic acid, an optically inactive 9,10,16-trihydroxypalmitic acid, has been isolated by saponification. Related carboxyflc acids such as 16-hydroxy- and 9,10-dihydroxypalmitic acids, also have been identified after saponification. These acids may not be primary products of hydrolysis, but may have been produced by the treatment. Studies show that shellac contains carboxyflc acids with long methylene chains, unsaturated esters, probably an aliphatic aldehyde, a saturated aliphatic ester, a primary alcohol, and isolated or unconjugated double bonds. 

Lower aliphatic primary alcohols including octanol, halogeno alcohols, and benzylic alcohols yield only alkyl fluorides [81, 82 The reaction of higher primary alcohols gives a mixture of fluorides and alkyl 2,3,3,3-tetrafluoropropionates [S3] and 2-nitro alcohols, alcohols branched at C-2 [82, 84 and unsaturated alcohols [55] give 2,3,3,3-tetrafluoropropionates exclusively... 

Corey used a chiral bromoborane 75 (1.1 equiv.) to promote the addition of tert-butyl bromoacetate (76) to aromatic, aliphatic, and a,P-unsaturated aldehydes to give the halo alcohols 77 with high enantio- and diastereoselectivities (Table 1.10) [35]. 

---