Alkene formation

The above simple process cannot be applied to the preparation of the homo-logues a higher temperature is requir (di-n-amyl ether, for example, boils at 169°) and, under these conditions, alkene formation predominates, leading ultimately to carbonisation and the production of sulphur dioxide. If, however, the water is largely removed by means of a special device (see Fig. Ill, 57,1) as soon as it is formed, good 300 of ethers may be obtained from primary alcohols, for example ... 

In the reaction of a substituted ylide (r CH—PPh ) with an aldehyde R CHO, a stereochemical problem arises. Much work has been carried out in order to achieve control of either cis- or rrans-alkene formation. This work has been reviewed several times with always changing viewpoints (A. Maercker, 1965 L.D. Bergelson, 1964 M. Schlosser, 1970 H. Best-mann, 1979). 

Alkene synthesis via alcohol dehydration is complicated by carbocation rearrangements A less stable carbocation can rearrange to a more sta ble one by an alkyl group migration or by a hydride shift opening the possibility for alkene formation from two different carbocations... 

The stabilization reactions of alkylcarbenes were used preparatively in some cases. The diazirine derived from adamantanone gave the dehydroadamantane (2l7) thermally in 96% yield 73ZOR430). Alkene formation was reported for a steroid with its C-3 atom part of a diazirine ring. At 140 °C a A-2-unsaturated steroid was formed 65JA2665). 

It was demonstrated that when a better leaving group than lithium oxide (Li20) is present at the a-position (e. g., epoxide 125 Scheme 5.27), alkene formation occurs with retention of the alcohol moiety [44]. 

The variation of enantioselectivities with temperature and pressure was investigated. The effects of these two factors are very substrate dependent and difficult to generalize even in a single substrate serie. However, it seems that enantioselectivities are shghly better at 25-40 °C than at lower temperatures (0 °C or less). The stereoselectivity can be inverted for specific alkenes (formation of the S or R enantiomer preferentially). For several substrates, the reactions tend to proceed to completion with optimal ee s when performed at lower hydrogen pressure (2 bar) instead of 50 bar (Fig. 13). Pronoimced variation of enantioselectivities with hydrogen concentration in solution may indicate the presence of two (or even more) different mechanisms which happen to give opposite enantiomers for some substrates. 

The linear appearance of the plot shows that this reaction obeys a first-order rate law. Additional mechanistic studies suggest that alkene formation proceeds in a two-step sequence. In the first step, which is rate-determining, the C — Br bond breaks to generate a bromide anion and an unstable cationic intermediate, hi the second step, the intermediate transfers a proton to a water molecule, forming the alkene and H3 ... 

The transformation of CF3CH2CI was studied at 320 C in a pulse flow reactor. Indeed, in a dynamic reactor, the agnificant alkene formation leads to a rapid deactivation of the catalyst. The reaction is carried out in absence of HF in order to favour the dehydrofluorination reaction. Products distribution is shown in Fig. 1. 

Catalytic activity for the fluorination of CF3CH2CI and for the alkene formation after 5 hours of CF3CH2CI pulses over chromium oxide with different degree of fluorination... 

The nickel addition in chromium oxide decreased the formation of alkenes which was smaller than the one observed in the presence of just chromium oxide. It is to be remarked that the decrease of alkene formation was independent of the quantity of nickel in the catalyst. However, the catalytic activity for the fluorination reaction decreased when the nickel content increased. Thus the addition of nickel in small quantities allowed to increase the selectivity for the fluorination reaction. We could suggest that nickel substitute... 

Oxidation of (3-silyl and (3-stannyl acids leads to loss of the substituent and alkene formation.283... 

Monocyclic Phosphoranes. - Further studies on the mechanism and stereochemistry of the Wittig reaction have been conducted by a combination of 1H, 13C and 3 P n.m.r.2k 25. The results show that at -18°C both ois and trans diastereomeric oxaphosphetans (e.g. 17 and 18) may be observed and their decomposition to alkenes monitored by n.m.r. Evidence was presented to suggest that during this process oxaphosphetan equilibration involving the siphoning of (17) into (18) occurred in competition with alkene formation. 

Table 4.2. Effect of y-Substituents on Alkenal Formation from Cyclohexanones...

Here too, a second alkylation can be made to take place yielding RC=CR or R C=CR. It should, however, be remembered that the above carbanions—particularly the acetylide anion (57)—are the anions of very weak acids, and are thus themselves strong bases, as well as powerful nucleophiles. They can thus induce elimination (p. 260) as well as displacement, and reaction with tertiary halides is often found to result in alkene formation to the exclusion of alkylation. 

The dianion derived from methyl 3-nitropropanoate is formed on treatment with LDA, and it is alkylated by alkyl halides exclusively at the 2-position (Eq. 5.6). Elimination of HN02 with DBU in THF furnishes methyl a-methylenealkanoate (see Section 7.3, which discusses alkene formation).12... 

Similar alkene formations via dealkoxycarbonylation and denitration have been reported for the synthesis of novel heterocycles. Heterocyclic nitro compounds such as 4-nitroisoxazole undergo the Diels-Alder reaction subsequent dealkoxycarbonylation and denitration give the products, which are regarded as the Diels-Alder adducts of five-membered heterocyclic arynes (Eq. 7.142).121... 

Preparation of all four diastereomers of /3-hydroxydiphenylethyl spirophosphoranes 72 via deprotonation of hydrospirophosphoranes 70 (R = H) with BuLi facilitated a subsequent mechanistic study on stereospecific alkene formation <1997TL7753, 2002CL170>. Three of the diasteromers could be formed by reacting 70 (R = H) with BuLi, followed by treatment with cis or /ra/w-stilbene oxide at room temperature (Scheme 12). 

Our analysis of literature data will focus on two closely related questions about the influence of changes in the relative thermodynamic driving force and Marcus intrinsic barrier for the reaction of simple carbocations with Bronsted bases (alkene formation) and Lewis bases (nucleophile addition) on the values of ks/kp determined by experiment. 

Side reactions are exchange of organic groups, followed by homo coupling, P-hydrogen elimination with alkene formation, isomerisation followed by coupling, or benzene formation and alkene liberation. Examples are shown in Figure 13.22. 

The positive slope for ether formation found on alumina (series 47), which contrasts with the negative one for alkene formation, has been interpreted by Knozinger as evidence of different mechanisms for these two, often in parallel proceeding transformations of alcohols. It has been suggested that the first step of the dehydration to an ether is the formation of a surface alkoxide, which is then attacked by a weakly bonded alcohol molecule. 

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