Oxidation 2-decanol

Oxidation of tridecylborane gives 1 decanol The net result is the conversion of an alkene to an alcohol with a regioselectivity opposite to that of acid catalyzed hydration... 

NMR using liquid crystal solvents is now a well-established tool for the investigation of molecular structure. Selenophene was studied in a liquid crystal composed of sodium sulfate, decanol, deuterium oxide, and sodium decylsulfate.12 The refined direct couplings were obtained iteratively with the help of a computer. The ratios of the interproton distances were calculated from the direct couplings and found to be in good agreement with corresponding values calculated from the microwave data. 

Kroutil et al. have recently reported [18] an elegant one-pot oxidation/reduction sequence for the deracemization of a chiral secondary alcohol using a single biocatalyst. LyophiUzed cells of a Rhodococcus sp. CBS IVJ.Ti converted racemic 2-decanol into the (S)-enantiomer in 82% yield and 92% enantiomeric excess (e.e.). via a non-specific oxidation followed sequentially by an (S)-selective reduction (Scheme 6.5). Acetone was used as the hydrogen acceptor in the first step and isopropanol as the hydrogen donor in the second step. 

Primary alcohols were oxidised to aldehydes and (less readily) secondary alcohols to ketones by Ru(N0)Cl(salen = )/03//UV (incandescent or halogen lamp), hi competitive experiments between 1- and 2-decanol or benzyl alcohols only the primary alcohol was oxidised [827]. With Ru(NO)Cl(salen )/(Cl2pyNO) or TMPNO or Oj/C H /UV (TMPNO=tetra-methylpyridine-iV,iV -oxide) racemic secondary alcohols were asymmetrically oxidised to ketones [828]. A Ru(NO)(salen " ) complex was used as Ru(N0)Cl(salen " )/02/UV/CgH3Cl to oxidise racemic secondary alcohols to the ketones in the presence of l,3-bis(p-bromophenyl)propane-l,3-dione e.e. of 55-99% were achieved [829], Chiral Ru(NO)Cl(salen ) complexes were made... 

Cosolvents Isopropanol butanol hexanol octanol decanol Rewopal HV5 (nonylphe-noxy) pentaethylene oxide... 

Diols are faster oxidized than the corresponding monoalcohols as the voltammetric-ally determined relative rates have already indicated. In preparative electrolysis 1,10-decane diol is about five times faster oxidized than 1-decanol. 

As can be seen from current-voltage curves the lower amines are about 10 times faster oxidized than the corresponsing alcohols In a competitive preparative electrolysis (0.3 M potassium hydroxide in 50% t-butanol 50 % water, 40 °Q 1-decylamine is 5.3 times faster oxidized than 1-decanol The electrochemical kinetics have been investigated . ss.es.es) following mechanism proposed... 

Decanol Geranial Neryl acetate ct s-Linalool oxide P-Caryophellene ... 

Unfortunately, even using this optimized procedure, we were not able to improve the conversion of primary alcohols into the corresponding aldehydes. However, close examination of the oxidation behavior of several primary aliphatic alcohols revealed intriguing features (Table VII). Whilst poor conversion of 1-decanol 23 to decanal 24 was achieved (Table VII, Entry 1), dibenzyl leucinol 25 and Boc-prolinol 27 were quantitatively transformed into the corresponding aldehydes (Table VII, Entries 2 and 3). The enhanced reactivity of 25 and 27 could be due either to an increased steric effect at the a-carbon center, to an electronic influence of the a-nitrogen substituent or to a combination of both. To test the importance of steric hindrance, the aerobic oxidation of cyclohexane methanol 29 and adamantane methanol 31 was carried out. Much to our surprise, oxidation of 29 afforded 30 in 70% conversion (Table VII, Entry 4) and transformation of 31 to 32 proceeded with 80% conversion (Table VII, Entry 5). Clearly increased substitution at the a-position favors the oxidation of primary aliphatic alcohols, although the conversions are still not optimum. 

In order to improve this transformation, a variety of selected additives were tested in the aerobic oxidation of 1-decanol 23. The high... 

Rationalizations of hydroboration stereoselectivity using models with dimeric boranes are thus not viable. Recent secondary isotope-effect measurements may suggest a model (Mann et al., 1986). Addition of a chiral dialkyl borane to 3-deuterio-cw-3-pentene, followed by alkaline oxidation, yields equal amounts of 3- and 4-deuterio-3-hexanols showing that the secondary isotope effects at these alkene sites are vanishingly small. Deuterium substitution at the allylic sites has a much larger effect. Thus similar treatment of 4,4-dideuterio-cw-5-decene yields a 2.86 1 mixture of 4,4-dideuterio- and 6,6-dideuterio-5-decanols. 

Newman, Underwood, and Renoll (48) studied the reduction of 1,2-epoxydecane. Over Raney nickel the product was 1-decanol. In the presence of alkali, however, the main product was 2-decanol. Chemical reduction also leads to 2-decanol. It is interesting to note that, when styrene oxide is reduced over Raney nickel, the primary alcohol is received as the main product whether or not alkali is present. 

Marko and coworkers [195, 196] reported that a combination of Cu2Cl2 (5 mol%), phenanthroline (5 mol%) and di-tert-butylazodicarboxylate, DBAD (5 mol%), in the presence of 2 equivalents of K2C03, catalyzes the aerobic oxidation of allylic and benzylic alcohols (Fig. 4.68). Primary aliphatic alcohols, e.g. 1-decanol, could be oxidized but required 10 mol% catalyst for smooth conversion. 

Bis(tetrabutylammonium) dichromate is a neutral oxidant which at reflux in dichloromethane acts as a selective oxidant for allylic and benzylic alcohols.Only 10% of oxidation products are obtained after treatment of n-decanol with bis(tetrabutylammonium) dichromate for 24 h. 

Similar results are obtained with copper permanganate octahydrate, Cu(Mn04)2 8H20. Addition of this salt to a solution of 2-decanol in di-chloromethane results in an exothermic reaction and boiling of the mixture for 5 min. After 10 additional minutes at room temperature, 2-decanone is isolated in 93% yield [894. Allylic alcohols are oxidized in 84-85% yields to a, 3-unsaturated ketones after boiling in dichloromethane for 24 h [894]. 

The structure of the western corn rootworm sex pheromone is 8-methyl-2-decanol propanoate (] 6) and four stereoisomers are possible (Figure 7). In our synthesis (3), we coupled a chiral 5-carbon unit to a 6-carbon fragment that had the requisite substitution to allow resolution at the oxygenated carbon. As mentioned earlier, (S)-2-methylbutyric acid was available to us from the alcohol. D-Isoleucine served as a source for the (R)-acid. Nitrosation, followed by decarboxylative oxidation of the intermediate hydroxyacid led to the (R)-2-methylbutyric acid in 96% ee. The process of fractional crystallization was... 

For the synthesis of sulfobacin A (158) and flavocristamide A (160), TBS ether of (f )-3-hydroxy-15-methylhexadecanoic acid was necessary, which was synthesized from 10-bromo-l -decanol (A) as shown in Figure 6.20. Chain elongation of A under the Schlosser conditions gave B, which was oxidized with PCC to give aldehyde C. ( )- 3-Hydroxy ester D was prepared from C by treatment with ethyl acetate and LDA. The corresponding ( )-acid was acetylated with vinyl acetate in the presence of lipase PS to give enantiomerically pure (R)-hydroxy acid and the acetylated (S )-acid. The former was converted to its TBS ether E. 

Figure 4.8. The GC/MS-EI (70eV) SCAN mode chromatogram of compounds formed by acid hydrolysis of a Raboso grape skins extract. Peak 1. frans-furanlinalool oxide peak 2. cfs-furanlinalool oxide I.S.l, internal standard (1-octanol) peak 3. (Z)-ocimenol peak 4. ( )-ocimenol peak 5. a-terpineol I.S.2, internal standard (1-decanol) peak 6. 2-exo-hydroxy-l,8-cineol peak 7. benzyl alcohol peak 8. P-phenylethanol peak 9. actinidols A peak 10. actinidols B peak 11. endiol peak 12. eugenol peak 13. vinylguaiacol peak 14. p-menthenediol I peak 15. 3-hydroxy-P-damascone peak 16. vanillin peak 17. methyl vanillate peak 18. 3-oxo-a-ionol peak 19. 3-hydroxy-7,8-dihydro-P-ionol peak 20. homovanillic alcohol peak 21. vomifoliol.

KADOX -25 (1314-13-2) see zinc oxide. KALCOHL 1098 or KALCOHL lOH (112-30-1) see decanol. 

DECANOL, n-DECANOL, or 1-DECANOL (112-30-1) Combustible liquid (flash point 180°F/82°C oc). Reacts, possibly violently, with oxidizers, acetaldehyde, alkalineearth, alkali metals, strong acids, ammonium persulfate, strong caustics, aliphatic amines, benzoyl peroxide, boranes, bromine dioxide, chromic acid, chromium trioxide, dialkylzincs, dichlorine oxide, ethylene oxide, hypochlorous acid, isocyanates, isopropyl chlorocarbonate, lithium tetrahydroaluminate, nitric acid, nitrogen dioxide, pentafluoroguanidine, perchlorates. 

Fluoro-l-decanol is converted by chromium(vi) oxide in glacial acetic acid into the corresponding fluoro carboxylic acid in 93% yield.478... 

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