D,/-2-Octanol

Determined after hydrolysis to give the acid and esterification with d-2-octanol b Determined after transesterification with <7-2-octanol/Ti(0-n-Bu)4. 

In agreement with these findings, the product of hydrolysis of D-2-octyl acetal is D-2-octanol, with an unchanged optical configuration [172]. 

Removal of the unreacted diene, bp 45 °C/20 torr, followed by distillation, bp 123 °C/0.2 torr, gave /-menthyl chrysanthemate (4.7 g, 76%) whose GC analysis showed the following composition d-trans, 89.9% l-trans, 2.7%, and the cis isomers, 7.4%. The cis/trans ratio was 7/93 and ee of the trans isomer was 94%. Complete hydrolysis of the /-menthyl ester with potassium hydroxide in aqueous ethanol followed by esterification with d-2-octanol in the presence of thionyl chloride and pyridine gave the corresponding d-2-octyl ester. GC analysis revealed the following composition d-trans, 90.4% l-trans, 4.7% d-cis, 3.6%, and... 

Sample preparation Acidify 5 mL solution with concentrated HCl, extract with two 5 mL portions of dichloromethane. Combine the organic layers and evaporate them to dryness, reconstitute the residue in 1 mL d-2-octanol toluene sulfuric acid 2 100 0.1, heat at 40°for 19 h, neutralize with 1 mL 20 mM sodium bicarbonate. Remove the organic layer and dry it over anhydrous sodium sulfate. Remove a 200 pL aliquot and evaporate it to dryness, reconstitute with 10 mL mobile phase, inject an aliquot. 

RESOLUTION OF sec.-OCTYL ALCOHOL (d/-2-OCTA-NOL) INTO ITS OPTICALLY ACTIVE COMPONENTS (d- AND f-2-OCTANOL)... 

Stability constants of metal complexes of 9-hydroxy-4//-pyrido[l,2-n]pyrimidin-4-one [Ni(II), Co(II), Zn(II), and Cd(II)] were determined by potentiometric and polarographic investigations (93JCC283). The distribution coefficient of risperidone (11) in H20- -octanol at pH 7.4 (log D — 2.04) was determined by an RP-HPLC method (01JMC2490). 

Figure 15.11 (a) Total ion clnomatogram of a Grob test mixture obtained on an Rtx-1701 column, and (b) re-injection of the entire clnomatogram on to an Rtx-5 column. Peak identification is as follows a, 2,3-butanediol b, decane c, undecane d, 1-octanol e, nonanal f, 2,6-dimethylphenol g, 2-ethylhexanoic acid h, 2,6-dimethylaniline i, decanoic acid methyl ester ], dicyclohexylamine k, undecanoic acid, methyl ester 1, dodecanoic acid, methyl ester. Adapted from Journal of High Resolution Chromatography, 21, M. J. Tomlinson and C. L. Wilkins, Evaluation of a semi-automated multidimensional gas chromatography-infrared-mass specti ometry system for initant analysis , pp. 347-354, 1998, with permission from Wiley-VCH. 

Burkhard, L.P. and Kuehl, D.W. -Octanol/water partition coefficients by reverse phase liquid chromatography/mass spectrometry for eight tetrachlorinated planar molecules, Chemosphere, 15(2) 163-167, 1986. 

In Section 8.14 of the text we are told that optically pure (S )-( I )-1-methylheptyl /Holuenesulfonate is prepared from optically pure (S)-(+)-2-octanol having a specific rotation [a]o +9.9°. The conversion of an alcohol to a p-toluenesulfonate proceeds with complete retention of configuration. Hydrolysis of this /Holuenesulfonate with inversion of configuration therefore yields optically pure (R)-(-)-2-octanol of [ ]d -9.9°. 

The infrared absorption spectra of four octyl alcohols, using a cell length of 0.1 mm., are shown in Fig. 3 (a) 1-octanol, (b) 9.2 vol. % solution of 1-octanol-d in 1-octanol, (c) 1 octanol-2-d, (d) l-octanol-2-d exposed to ketone-synthesis conditions. 

Frankland and Price 17 were the first to attempt the resolution of alcohols (and acids) by fractional crystallization of their solid esters. The isomeric solid esters formed from Z-s-butylcarbinol and di-dibenzoyl-glyceric acid failed to separate on crystallization the corresponding di-alcohol-i-acid ester was liquid. Marckwald and McKenzie 18-19 effected partial resolutions of dl-mandelic acid and related acids with 1-menthol and d-bomeol, and of di-2-octanol with d-tartaric acid, but did not develop a satisfactory method for resolving alcohols. Later investigators, however, have employed the following resolving agents in several more or less successful resolutions of certain alcohols (a) i-menthyl isocyanate, (6) d-camphoric acid, (c) d- or i-mandelic acid, (d) d- or... 

Table 5.1 Repeatability (mean Ax/Ai.s. value of 5 data) for some compounds in a young Gewiirztraminer wine adsorbed by HS-SPME in a 1 cm PDMS fiber and analysed by GC-MS using a PEG capillary column. Values referred to Ax/Ai.s. ( m/z 45) with 2-octanol as internal standard. S.D. standard deviation.

Fig. 3. The stereochemical course of the 2-aminooctane -> 2-octanol transformation with 1.6 M NaNO 2S °C, pH 4, vs. Fm. Open circles correspond to runs in HCIO4 solid circles correspond to runs in HQ. [Reproduced from Moss, R. A., Talkowski, C. J., Reger, D. W., Powell, C. E. J. Am. Chem. Soc. 95, 5215 (1973). ...

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