Dehydration of trans

Dehydration of trans dihydrohumulinic acid with polyphosphoric acid yields dehydrated dihydrohumulinic acid or 2-(3-methylbutyl)-5-(1-hydroxy-3-methyl-butylidene)-2-cyclopentene-1,4-dione (138, Fig. 66) with a melting point of 75-76°C and UV absorption maxima at 240 nm and 266 nm (50). When polyphosphoric acid or a mixture of hydrogen chloride and acetic acid were used, the isomeric 2-(3-methylbutanoyl)-5-(3-methylbutylidene)-3-hydroxy-2-cyclopentenone (139, Fig. 

In addition to being regioselective alcohol dehydrations are stereoselective A stereo selective reaction is one m which a single starting material can yield two or more stereoisomeric products but gives one of them m greater amounts than any other Alcohol dehydrations tend to produce the more stable stereoisomer of an alkene Dehydration of 3 pentanol for example yields a mixture of trans 2 pentene and cis 2 pentene m which the more stable trans stereoisomer predominates... 

Hydnde shifts often occur during the dehydration of primary alcohols Thus although 1 butene would be expected to be the only alkene formed on dehydration of 1 butanol It IS m fact only a minor product The major product is a mixture of cis and trans 2 butene... 

Sulfurane reagent lor conversion of trans diols to epoxides, generally for dehydration of diols to olefins or cyclic ethers, and as an oxidizing agent... 

Calcium hexacyanoferrate (II) (IIH2O) [ 13821 -08-4] M 490.3. Recrystd three times from conductivity H2O and air dried to constant weight over partially dehydrated salt. [Trans Faraday Soc 45 855 1949.] Alternatively the Ca salt can be purified by pptn with absolute EtOH in the cold (to avoid oxidation) from an air-free saturated aqueous soln. The pure lemon yellow crystals are centrifuged, dried in a vacuum desiccator first over dry charcoal for 24h, then over partly dehydrated salt and stored in a dark glass stoppered bottle. No deterioration occurred after 18 months. No trace of Na, K or NH4 ions could be detected in the salt from the residue after decomposition of the salt with cone H2SO4. Analyses indicate 1 Imols of H2O per mol of salt. The solubility in H2O is 36.45g (24.9 ) and 64.7g (44.7 ) per lOOg of solution. [J Chem Soc 50 1926.]... 

The use of mesyl chloride for the dehydration of C-11 alcohols has already been mentioned, and mesylates can certainly be intermediates at least in the a-series. The preference for a coplanar trans arrangement is demonstrated by the well-known elimination reactions of tosylates of epimeric 20-alcohols (ref. 185, p. 616), although this does not restrict the usefulness of the reaction, and in some cases (sulfonates of 1 la-alcohols, for example) cw-elimination occurs (ref. 216, p. 293 ref. 224, 225, 226). 

The stereochemistry of the product resulting from the reaction of a 17-keto steroid with ethylidenetriphenylphosphorane is different from that of the 17-ethylidene steroids obtained by dehydration of 17a-ethyl-17/ -hydroxy compounds, Wolff-Kishner reduction of A -20-keto steroids or by sodium-alcohol or sodium-ammonia " reductions of 17-ethynyl carbinols. These latter products have generally been assumed to possess the trans configuration (C-21 methyl away from the bulk of the ring system) because of anticipated greater stability. The cis configuration for... 

Hydrogenation of alkynes to alkenes using the Lindlai catalyst is attractive because it sidesteps the regioselectivity and stereoselectivity issues that accompany the dehydration of alcohols and dehydrohalogenation of alkyl halides. In tenns of regioselectivity, the position of the double bond is never in doubt—it appears in the carbon chain at exactly the sane place where the triple bond was. In tenns of stereoselectivity, only the cis alkene forms. Recall that dehydration and dehydrohalogenation normally give a cis-trans mixture in which the cis isomer is the minor product. 

Subsequent dehydration of /3-hydroxybutyryl ACP by an ElcB reaction in step 7 yields trans-ciotonyl ACP, and the carbon-carbon double bond of crotonyl ACP is reduced by NADPH in step 8 to yield butyryl ACP. The doublebond reduction occurs by conjugate addition of a hydride ion from NADPH to the /S carbon of fraus-crotonyl ACP. In vertebrates, the reduction occurs by an overall syn addition, but other organisms carry out similar chemistry with different stereochemistry. 

In addition to the synthetic applications related to the stereoselective or stereospecific syntheses of various systems, especially natural products, described in the previous subsection, a number of general synthetic uses of the reversible [2,3]-sigmatropic rearrangement of allylic sulfoxides are presented below. Several investigators110-113 have employed the allylic sulfenate-to-sulfoxide equilibrium in combination with the syn elimination of the latter as a method for the synthesis of conjugated dienes. For example, Reich and coworkers110,111 have reported a detailed study on the conversion of allylic alcohols to 1,3-dienes by sequential sulfenate sulfoxide rearrangement and syn elimination of the sulfoxide. This method of mild and efficient 1,4-dehydration of allylic alcohols has also been shown to proceed with overall cis stereochemistry in cyclic systems, as illustrated by equation 25. The reaction of trans-46 proceeds almost instantaneously at room temperature, while that of the cis-alcohol is much slower. This method has been subsequently applied for the synthesis of several natural products, such as the stereoselective transformation of the allylic alcohol 48 into the sex pheromone of the Red Bollworm Moth (49)112 and the conversion of isocodeine (50) into 6-demethoxythebaine (51)113. 

Bloodworth, A. J., et al., J. Chem. Soc., Perkin Trans. 1, 1983, 471-473 Attempted thermal dehydration of benzeneseleninic acid, formed by oxidation of diphenyl diselenide with hydrogen peroxide, gave a solid which exploded at 53-55°C. The solid may have been the complex of the acid with hydrogen peroxide. 

Neither has oxidation, with lead tetraacetate, of the sirup obtained by dehydration of the D-galactose condensate VIII so far resulted in isolation of the expected dialdehyde. On the other hand, when the anhydride from the D-glucose condensate (XXXIV) was oxidized with lead tetraacetate, an appreciable amount of dialdehyde (XXXVI) was isolated. This discrepancy in behavior is probably attributable to the trans position of the hydroxyl groups of the anhydride derived from D-galactose as compared with the cis configuration for the anhydride from D-glucose. 

Norman, W. S. Trans. Inst. Chem. Eng. 23 (1945) 66. The dehydration of ethanol by azeotropic distillation. Ibid. 89. Design calculations for azeotropic dehydration columns. 

PRATT, H. R. C. Trans. Inst. Chem. Eng. 25 (1947) 43. Continuous purification and azeotropic dehydration of acetonitrile produced by the catalytic acetic acid-ammonia reaction. 

In order to determine whether trans elimination may occur also in the removal of elements of water from alcohols, the dehydration of menthol... 

From the similarity of the activation energy of dehydration of the aliphatic alcohols and of some of the cyclohexanols it can be assumed that the mechanism of the dehydration of the two groups of alcohols is identical. The presence of a neopentyl-type carbon atom as in 2,2-dimethylcyclohexanol diminishes the reactivity only slightly, but among stereoisomeric alkylcyclohexanols the cis isomer reacts much faster than the trans. The distinct dissimilarity in activation energies of the two... 

The geometry of the cis-alkylcyclohexanol is favorable for trans elimination since the hydroxyl and the neighboring trans hydrogen are coplanar, but this is not true for the l,i-trans isomer hence the molecular conformation has to flip over, to set the hydroxyl group in the axial position for the trans elimination to occur. This would require a few kilocalories of energy and for frans-lert-butylcyclohexanol it would be more difficult to achieve than for IroMs-methylcyclohexanol. It is, therefore, possible that the trans elimination from a boat conformation, or possibly even an epimerization from the trans to the cis isomer which then undergoes a trans elimination reaction. Such an epimerization was found to occur under conditions of dehydration of certain alcohols over alumina, as will be seen under 1,4-cyclohexanediol. The more facile elimination of the cis-i-tert-butylcyclohexanol system as compared with the trans system in solution was also reported in the literature 63). 

The rate of dehydration of the cis diol was about fifty times slower than that of the trans diol and the product of the reaction consisted mainly of cyclohexenol. The 1,4-epoxycyclohexane formed in the reaction was formed after a prior epimerization of the cis to the trans diol this was demonstrated by means of tritium tracer technique. When irons-1,4-cyclohexanediol was dissolved in ieri-butyl alcohol-T having the hydroxyl hydrogen marked with tritium (C4H,OT) the 1,4-epoxycyclohexane produced in this reaction had a very low tritium content. A similar reaction carried out with cis-1,4-cyclohexanediol produced a highly tritiated 1,4-epoxycyclohexane. The insertion of tritium in the 1,4-epoxycyclohexane produced from the cis diol can be explained as follows ... 

The faster rate of dehydration of 2-ea o-bornanol over that of 2-endo-bornanol can be attributed in part to the anchimeric assistance of the C(l)-C(6) bonding electrons which are trans to the electrons bonding the OH group to C(2) carbon, as with solvolytic reactions 74), The occurrence of tricyclene as the primary product of dehydration of 2-ea o-bornanol can best be explained by an elimination reaction which takes place within the submicroscopioal pores of the aluminas. 

The dehydration of the title alcohols was made over alumina in the presence of piperidine (84). The experimental results listed in Table VII give the primary products. In all experiments the cis-olefins predominate over the trans-. 

The primary products obtained from 2-butanol are of mechanistic. significance and may be compared with other eliminations in the sec-butyl system 87). The direction of elimination does not follow the Hofmann rule 88) nor is it governed by statistical factors. The latter would predict 60% 1-butene and 40% 2-butene. The greater amount of 2-alkene and especially the unusual predominance of the cis-olefin over the trans isomer rules out a concerted cis elimination, in which steric factors invariably hinder the formation of cis-olefin. For example, the following ratios oicisjtrans 2-butene are obtained on pyrolysis of 2-butyl compounds acetate, 0.53 89, 90) xanthate, 0.45 (S7) and amine oxide, 0.57 86) whereas dehydration of 2-butanol over the alkali-free alumina (P) gave a cisjtrans ratio of 4.3 (Fig. 3). 

In the dehydration of alicyclic secondary alcohols the cis-olefin predominates over the trans-, and greatly exceeds the equilibrium con-centration. 

There is a strong parallel between elimination reactions in solution and the dehydration of alcohols over alumina. The trans elimination reactions and the anchimeric assistance of alcohols over aluminas suggest that the dehydration must occur within either the submicroscopical pores, or crevices, or channels of the aluminas. The aluminas therefore must surround the alcohol molecules providing acid sites to act as proton donors or electron acceptors and basic sites to act as proton acceptors or electron donors. For that reason the aluminas seem to act as solvating agents and therefore may be considered as a pseudosolvents for dehydration reactions. 

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