Z-Octanol

Preparation of Sec.-Oclyl Hydrogen Phihalate.—A mixture of 130 g. (i mole) of 5ec.-octyl alcohol (Org. Syn. 1, 61) and 148 g. (i mole) of phthalic anhydride is heated for twelve to fifteen hours in a flask surrounded by an oil bath at 110-115° (Note i). During the heating the mixture should be mechanically stirred 

The octyl hydrogen phthalate is filtered, washed with water, ground thoroughly with water in a mortar and finally filtered and dried. For complete purification it may be crystallized either from petroleum ether (b.p. 60-70°) or glacial acetic acid from which it separates as needles melting at 55°. The crude material, however, is perfectly satisfactory for the following experiments. The yield is nearly quantitative if the ec.-octyl alcohol is pure (Note 2). 

The crystals (A) are dissolved in a minimum amount of hot ethyl alcohol and decomposed by pouring the solution into dilute hydrochloric acid. The weight of the ester thus obtained is about half of that originally taken and its rotation in absolute alcohol is about ( ) , ,-t-47 ( )n+44°- 

Optically pure I- and d-sec.-octyl alcohols are obtained by distillation in a current of steam of the -octyl hydrogen phthalate and 2 moles of sodium hydroxide in 30 per cent solution. The alcohols are practically insoluble in water and are separated, dried with potassium carbonate and distilled. Each boils at 86 /20 mm. and has a rotation (0)5461-1-11.8°, (a) -1-9.9° ( )546i (0)0 9-9°- The yields of alcohol from the sec.- 

If this temperature is exceeded the yield of octyl phthalate is reduced and the color of the product is very dark. The color is carried through with the /-fraction, making it difficult to read rotations. 

---

Lipophilicity in particular, as reflected in partition coefficients between aqueous and non-aqueous media most commonly water (or aqueous buffer) and Z-octanol,has received much attention [105,141,152,153,176,199,232,233]. Logic )W for the octanol-water system has been shown to be approximately additive and constitutive, and hence, schemes for its a priori calculation from molecular structure have been devised using either substituent tt values or substructural fragment constants [289, 299]. The approximate nature of any partition coefficient has been frequently emphasized and, indeed, some of the structural features that cause unreliability have been identified and accommodated. Other complications such as steric effects, conformational effects, and substitution at the active positions of hetero-aromatic rings have been observed but cannot as yet be accounted for completely and systematically. Theoretical statistical and topological methods to approach some of these problems have been reported [116-119,175,289,300]. The observations of linear relationships among partition coefficients between water and various organic solvents have been extended and qualified to include other dose-response relationships [120-122,160,161,299-302]. 

Figure 8.9 The pH dependence of the /z-octanol-water distribution ratio of pentachlorophenol (PCP, pKj = 4.75), 4-chloro-a-(4-chlo-rophenyl) benzene acetic acid (DDA, pKb = 3.66), 2-methyl-4,6-dinitrophenol (DNOC, pKia = 4.46), and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T, pKia = 2.83). (from Jafvert et al., 1990).

Die Reduktion mit Lithiumalanat hangt von der Loslichkeit der Metallsalze im ange-wendeten Losungsmittel ab. Bei Natriumsalzen kann in den iiblichen Losungsmitteln durch zwei Hydrid-Aquivalente reduziert werden3 4, Natrium-octanoat und Natrium-ben-zoat z. B. in Tetrahydrofuran (quantitative Ausbeute an Octanol bzw. Benzylalkohol)4. 

Analog lassen sich Carbonsaure-ester mit 1,5- Mol-Aquiv. Natriumboranat in Gegenwart von 1 Mol-Aquiv. Benzanilid in 2-Methyl-pyridin bei 100°in 5-6 Stdn. zu Alkoholen reduzieren" [z.B. Herstellungvon Octanol (74% d.Th.), Nonanol (87% d.Th.) und 4-Cyano-benzylalkohol (89% d.Th.)]. 

Molnar, L, Keserii, G. M., Papp A., Gulyas, Z., Darvas, F. A neural network based prediction of octanol-water partition coefficients using atomicS fragmental descriptors. Bioorg. Med. Chtm. Lett. 2004, 14, 851-853. 

The Level I calculation proceeds by deducing the fugacity capacities or Z values for each medium (see Table 1.5.3), following the procedures described by Mackay (2001). These working equations show the necessity of having data on molecular mass, water solubility, vapor pressure, and octanol-water partition coefficient. The fugacity f (Pa) common to all media is deduced as... 

Kralj, F. and Sincic, D. Mutual solubilities of phenol, salicyaldehyde, phenol-salicyaldehyde mixture, and water with and without the presence of sodium chloride and sodium chloride plus sodium sulfate, J. Chem. Eng. Data, 25 (4) 335-338,1980. Kramer, C.R. and Henze, U. Partitioning properties of benzene derivatives. 1. Temperature dependence of the partitioning of monosubstituted benzenes and nitrobenzenes in the n-octanol/water system, Z. Phys. Chem., 271(3) 503-513,1990. Krasnoshchekova, R.Ya. and Gubergrits, M. Solubility of paraffin hydrocarbons in fresh and salt water, Neftekhlmlya, 13(6) 885-888, 1973. 

Li, L., Wang, L., Han, S., and Zhang. Z. Comparison of four methods of predicting newly measured octanol/water coefficients (log Ko ) for heterocyclic nitrogen compounds and the partition mechanism. Environ. Toxicol. Chem., 18(12) 2723-2728. 1999. 

Liao, Y.-Y., Wang, Z. T., Chen, J.-W.. Han. S.-K.. Wang. L. S.. Lu. G. Y.. and Zhao. T.-N. The prediction of soil sorption coefficients of heterocyclic nitrogen compounds by octanol/water partition coefficient, water solubility, and by molecular connectivity indices. Bull Environ. Contam. Toxicol, 56(5) 711-716. 1996. 

SANEX 3 used the 2,6-Z) -(5,6-dialkyl-1,2,4-triazine-3-yl)pyridine family of extraetants eontaining the propyl group, whieh are able to selectively extract trivalent actinides from Imoldm EINO3 [53,78]. The extractant was 0.04mol dm in a mixture of 70%/30% TPH/octanol. A flow sheet based on this solvent has been tried and is shown schematically in Fig. 12.21 the results are given in Table 12.13. The feed was an... 

The plots of log k vs. log P w and the plots of log k (v) vs. log k (z) were studied for seven cephalosporins. A linear relationship was obtained in micellar solution and in microemulsion solution (Tables 3 and 4). The results obtained indicate that the capacity factor determined by EKC could be used both as parameter to characterize the partition behavior of drugs in ME and MC and as hydrophobic parameter instead of log Pow. k appears to be an evident parameter, and it shows a better diversification than P w. In the 1-octanol/water system, we did not found high values of the partition coefficients. In contrast, the ME systems used provide a better characterization of the drugs according to their hydrophilic/lipophilic properties. 

Jia, Z., Mei, L., Lin, F., Huang, S. and Killion, R.B. (1007) Screening of octanol-water partition coefficients for pharmaceuticals by pressure-assisted microemulsion electrokinetic chromatography. Journal of Chromatography A, 2003, 203-208. 

Die Konfiguration optiseh-aktiver sekundarer Alkohole wird hierbei umgekehrt so erhalt man z.B. aus (Sj-2-Octanol in 48% Gesamtausbeute (Rj-2-Amino-octan2 ... 

Elderberry (Sambucus nigra) is cultivated on small scale in Europe. The fruits have a high concentration of red and purple anthocyanins and a relatively low concentration of sugars, organic acids and aroma compounds, which make this juice attractive as a natural colour ingredient in other red fruit products [126-129]. The fresh green odour of elderberry juice is associated with volatile compounds with typical green notes such as 1-hexanol, 1-octanol, (Z)-3-hexen-l-ol, ( )-2-hexen-l-ol, hexanal and ( )-2-hexenal, whereas the floral aroma is mainly due to the presence of hotrienol and nonanal [127-130]. 

Figure 10.15 Plot of log 1 /LCi50 for guppies versus (a) log octanol-water distribution ratio (log Z),ow, Eq. 10-41), and (b) log liposome-water distribution ratio (log Z),lipsw, Eq. 10-41) at pH 7 for a series of chlorinated benzenes (o) and chlorinated phenols ( ) as well as for the herbicide 2-.9ec-butyl-4.6-dinitrophenol (dinoseb) (v). The liposomes used were L-a-dimy-ristoyl-phosphatidylcholine (chlorinated benzenes) and L-a-dioleyl-phosphatidylcholine (chlorinated phenols and dinoseb). The pH dependence of D/ow and D,lipsw of pentachlorophenol (PCP) and dinoseb is shown in Fig. 10.14. Data from Saarikoski and Viluskela (1992), Gobas et al. (1988), Escher and Schwarzenbach (1996), and Gunatilleka and Poole (1999).

The octanol-water (pH 5) partition coefficients of 1,2,3,4-tetrahydro-and 1,2,3,4,6,7,8,9-octahydro-llH-pyrido[2,l-Z>]quinazolin-l 1-ones and their 6-, 7-, 8-, and 9-methyl derivatives were determined and the Hansch it values of the methyl substituents were also calculated (84MI5). The oc-tahydro derivatives were more hydrophilic than the tetrahydro compounds. 

Kramer, C-R., Henze, U. (1990) Verteilungseigenschaften von Bensenderivaten. 1. Zum temperatureinfluss auf die verteilung von monosubstituierten benzenen und nitrobenzenen im system w-octanol/wasser. Z. Phys. Chemie—Leizing 271, 503-513. Krasnykh, E.L., Vasiltsova, T.V., Verevkin, S.P., Heintz, A. (2002) Vapor pressures and enthalpies of vaporization of benzyl halides and benzyl ethers. J. Chem. Eng. Data 47, 1372-1378. 

Wang, W., Wang, L., Tian, L., Zhang, Z., Qiu, J. (1987) Partition coefficients of the intermediate of pyrethroid in n-octanol/watcr system. Huazhong Gongxueyuan Xuebao 15, 135-137. 

Chen, J.W., Hamer, T., Schramm, K.-W., Quan, X., Xue, X.Y., Wu, W.Z., Kettrup, A. (2002) Quantitative relationships between molecular structures, environmental temperatures and octanol-air partition coefficients of PCDD/Fs. Sci. Total Environ. 300, 155-166. 

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... 

---