Basicity alkenes

More recent measurements related to carbocation stabilities in strongly acidic media have involved rates of reaction rather than equilibria.52,54,72 75 Application of the X0 function to the correlation of reaction rates as well as equilibria mirrors the use of structure-based free energy relationships. Of interest is the access this gives to rate constants for (a) protonation of weakly basic alkenes and (b) acid-catalyzed ionization of alcohols to relatively unstable... 

A great variety of organic compounds are emitted by vegetation. These biogenic compounds are highly reactive in the atmosphere. They are basically alkenes or cycloalkenes, and their atmospheric chemistry is generally analogous to that of alkenes. Because of the presence of C=C double bonds these molecules are susceptible to attack by 03 and N03, in addition to the customary reaction with OH radicals. 

Scheme 2.1 (a) The basic alkene metathesis mechanism and (b) alkene metathesis reactions. 

The focus of this chapter is the polymerization of relatively simple alkenes with metallocene catalysts. As Figure 1 illustrates, this particular intersection of basic alkenes with relatively complex catalysts lies in a region where the catalyst significantly multiplies the value of an inexpensive alkene -resulting in intricate and highly engineered polymers. Thus, it is easy to understand the great interest with which chemists -especially industrial chemists - have developed metallocene-based catalysts, which are a subset of the broader... 

Later work by Fischer and Wan > demonstrated that meta (37 and 38) and para (39) hydroxy-substituted styrenes are also active towards photohydration ( = 0.22, 0.24 and 0.1, respectively). Evidence for formation of quinone methide intermediates was provided by nanosecond LFP. Both steady-state and time-resolved fluorescence quenching of 37 by water showed a cubic dependence on water concentration. This was attributed to an initial ESIPT process in which a three-water-molecule bridge mediates a proton transfer from the phenol to the basic alkene. 

The proton chemical shifts of the protons directly attached to the basic three carbon skeleton are found between 5.0 and 6.8 ppm. The J(H,H) between these protons is about -5 Hz. The shift region is similar to the region for similarly substituted alkenes, although the spread in shifts is smaller and the allene proton resonances are slightly upfield from the alkene resonances. We could not establish a reliable additivity rule for the allene proton shifts as we could for the shifts (vide infra) and therefore we found the proton shifts much less valuable for the structural analysis of the allene moiety than the NMR data on the basic three-carbon system. 

Alkylation can also be accomplished with electrophilic alkenes. There is a dichotomy between basic and acidic conditions. Under basic conditions, where the indole anion is the reactive nucleophile, A-alkylation occurs. Under acidic conditions C-alkylation is observed. The reaction of indole with 4-vinylpyri-dine is an interesting illustration. Good yields of the 3-alkylation product are obtained in refluxing acetic acid[18] whereas if the reaction is done in ethanol containing sodium ethoxide 1-alkylation occurs[19]. Table 11.2 gives some examples of 3-alkylation using electrophilic alkenes. 

Experimental measurements of dipole moments give size but not direction We normally deduce the overall direction by examining the directions of individual bond dipoles With alkenes the basic question concerns the alkyl groups attached to C=C Does an alkyl group donate electrons to or withdraw electrons from a double bond d This question can be approached by comparing the effect of an alkyl group methyl for exam pie with other substituents... 

Step 3 IS new to us It is an acid-base reachon m which the carbocation acts as a Br0n sted acid transferrmg a proton to a Brpnsted base (water) This is the property of carbo cations that is of the most significance to elimination reactions Carbocations are strong acids they are the conjugate acids of alkenes and readily lose a proton to form alkenes Even weak bases such as water are sufficiently basic to abstract a proton from a carbocation... 

In general, hydroboration—protonolysis is a stereoselective noncatalytic method of cis-hydrogenation providing access to alkanes, alkenes, dienes, and enynes from olefinic and acetylenic precursors (108,212). Procedures for the protonolysis of alkenylboranes containing acid-sensitive functional groups under neutral or basic conditions have been developed (213,214). 

The synthesis of dehydro-hnalool (28) rehes on the basic chemicals acetone and acetjiene. Addition of a metal acetyUde to acetone yields methylbutynol (33). Semihydrogenation affords the alkene (34) which is reacted with /-propenylmethyl ether. A Cope rearrangement of the adduct yields methyUieptenone (35). Addition of a second mole of metal acetyUde to dehydro-linalool (28) is followed by a second Cope rearrangement to yield... 

Dimethylsulfonium phenacylide (574) underwent C-alkylation with a-chloronitroso compounds such as (575). The intermediate (576) immediately cyclized to the isoxazoline (577). With a more basic ylide such as dimethylsulfonium methoxycarbonylmethylide the initial alkylation product underwent elimination of the sulfonium group to an alkene rather than its displacement (72T3845). 

Rate differences observed between the same bromophenylcarbene (241) when prepared by two different routes, diazirine photolysis and the reaction of benzylidene dibromide with potassium r-butoxide, vanish when a crown ether is added to the basic solution in the latter experiment. In this case the complexing potassium bromide is taken over by the crown ether, and selectivity towards alkenes reaches the values of the photolytic runs (74JA5632). 

Which addition is more favorable thermodynamically Assuming that the difference is entirely due to different 7t-bond energies, then which contains the stronger % bond, the alkyne or the alkene What flaws might there be in the basic assumption ... 

A more promising procedure for the formation of alkenes from tosylhydrazones is represented by the Shapiro reaction It differs from the Bamford-Stevens reaction by the use of an organolithium compound (e.g. methyl lithium) as a strongly basic reagent ... 

In addition to the oxymercuration method, which yields the Markovnikov product, a complementary method that yields the non-Markovnikov product is also useful. Discovered in 1959 by H. C. Brown and cailed hydroboration, the reaction involves addition of a B-H bond of borane, BH3, to an alkene to yield an organoborane intermediate, RBH2. Oxidation of the organoborane by reaction with basic hydrogen peroxide, H2O2, then gives an alcohol. For example ... 

When an alkene reacts with BH3 in THF solution, rapid addition to the double bond occurs three times and a tricilkylborcme, R3B, is formed. For example, 1 molar equivalent of BH3 adds to 3 molar equivalents of cyclohexene to yield tricyclohexylborane. When tricvclohexylborane is then treated with aqueous hydrogen peroxide (H2C>2) in basic solution, an oxidation takes place. The three C-B bonds are broken, -OH groups bond to the three carbons, and 3 equivalents of cyclohexanol are produced. The net effect of the... 

Treatment of an or.jS-unsaturated ketone with basic aqueous hydrogen peroxide yields an epoxy ketone. The reaction is specific to unsatnrated ketones isolated alkene double bonds do not react. Propose a mechanism. 

I The order of topics remains basically the same but has been changed to devote Chapter 3 entirely to alkanes and Chapter 4 to cycloalkanes. In addition, epoxides are now introduced in Chapter 7 on alkenes, and coverage of heterocyclic chemistry has been moved to Chapter 24. 

Ketosilanes react with alkyl lithiums in a diastereoselective manner (7), the preferred diastereoisomer being the one predicted on the basis of Cram s Rule acidic or basic treatment provides a stereoselective route to trisubstituted alkenes. 

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