Rearrangements 2- bromid

An alternative view of these addition reactions is that the rate-determining step is halide-assisted proton transfer, followed by capture of the carbocation, with or without rearrangement Bromide ion accelerates addition of HBr to 1-, 2-, and 4-octene in 20% trifluoroacetic acid in CH2CI2. In the same system, 3,3-dimethyl-1-butene shows substantial rearrangement Even 1- and 2-octene show some evidence of rearrangement, as detected by hydride shifts. These results can all be accoimted for by a halide-assisted protonation. The key intermediate in this mechanism is an ion sandwich. An estimation of the fate of the 2-octyl cation under these conditions has been made ... 

The first-formed carbocation is secondary. It is possible for this carbocation to become a more stable tertiary carbocation via rearrangement, in which a methyl group with its pair of electrons migrates from one carbon to the adjacent positive centre. Now the rearranged tertiary carbocation can yield SnI- and El-type products in much the same manner as the original secondary carbocation. A rearranged bromide is formed, together with two alkenes from an El... 

Various unsubstituted solid alkenes are able to quantitatively add gaseous halogenohydrides. Prominent examples are the cholesterol esters 128 that give stereospecifically the bromides 129 at -30 °C [75,75al and camphene (130) that gives stereospecifically the rearranged bromide 131 or the elusive camphene hydrochloride (132) with 100% yield [11] (Scheme 15). The quantitative solid-... 

The primary alcohol 16 reacts with HBr to give the rearranged bromide 19 (reaction 5.16). Protonation will give the oxonium ion 17 as the water molecule leaves in the second step, the methyl group migrates so that the tertiary carbocation 18 is formed, which adds a bromide ion to give the final product. 

An interesting example of the formation and reaction of a /7-silylcarbonium ion was reported independently by Eaborn61 and Jarvie62. Reaction of the dideuterio-/Miydroxy-silane 3 with phosphorus(III) bromide gave the directly substituted bromide, 6, together with the rearranged bromide, 5. 

Myrtenol (203 X = CH2OH) may be obtained most efficiently from the more stable secondary allylic alcohol (+)-trans-pinocarveol (30 enantiomer) via bromination with PBra to the rearranged bromide (203 X = CH2Br) [(30) (203 X = CH20H)/85 15] ester thermolysis and isomerization-oxidation were less effective, and the direct acid-catalysed isomerization was not observed. Intramolecular cyclization of (206), which is readily synthesized via trifluoroacetic anhydride cyclization of 4-methylcyclohex-3-enylacetic acid to (186), affords (207) which is cleaved to (208 X = NH2) in a synthesis of ( )-a-... 

Synthesis of (A) started with the combination of 2,4,6-trimethylphenol and allyl bromide to give the or/Ao-allyl dienone. Acid-catalyzed rearrangement and oxidative bydroboration yielded the dienone with a propanol group in porlactone ring were irons in the product as expected (see p. 275). Treatment with aqueous potassium hydroxide gave the epoxy acid, which formed a crystalline salt with (R)-l-(or-naphthyl)ethylamine. This was recrystallized to constant rotation. 

The 5-oxohexanal 27 is prepared by the following three-step procedure (1) 1,2-addition of allylmagnesium bromide to an a, / -unsaturated aldehyde to give the 3-hydroxy-1,5-diene 25, (2) oxy-Cope rearrangement of 25 to give 26, and (3) palladium catalyzed oxidation to afford 27. The method was applied to the synthesis of A -2-octalone (28), which is difficult to prepare by the Robinson annulation[25]. 

In the alkylative cyclization of the 1,6-enyne 372 with vinyl bromide, formation of both the five-membered ring 373 by exn mode carbopalladation and isomerization of the double bonds and the six-membered ring 374 by endo mode carbopalladation are observed[269]. Their ratio depends on the catalytic species. Also, the cyclization of the 1,6-enyne 375 with /i-bromostyrene (376) affords the endo product 377. The exo mode cyclization is commonly observed in many cases, and there are two possible mechanistic explanations for that observed in these examples. One is direct endo mode carbopalladation. The other is the exo mode carbopalladation to give 378 followed by cyclopropana-tion to form 379, and the subsequent cyclopropylcarbinyl-homoallyl rearrangement affords the six-membered ring 380. Careful determination of the E or Z structure of the double bond in the cyclized product 380 is crucial for the mechanistic discussion. 

Additional evidence for carbocation intermediates in certain nucleophilic substitutions comes from observing rearrangements of the kind normally associated with such species For example hydrolysis of the secondary alkyl bromide 2 bromo 3 methylbutane yields the rearranged tertiary alcohol 2 methyl 2 butanol as the only substitution product... 

Unbranched primary alcohols and tertiary alcohols tend to react with hydrogen halides without rearrangement The alkyloxonmm ions from primary alcohols react rap idly with bromide ion for example m an Sn2 process Tertiary alcohols give tertiary alkyl halides because tertiary carbocations are stable and show little tendency to rearrange... 

When It IS necessary to prepare secondary alkyl halides with assurance that no trace of rearrangement accompanies their formation the corresponding alcohol is first converted to its p toluenesulfonate ester and this ester is then allowed to react with sodium chloride bromide or iodide as described m Section 8 14... 

Clearly the temperature at which the reaction occurs exerts a major influence on the product composition To understand why an important fact must be added The 1 2 and 1 4 addition products interconvert rapidly by allylic rearrangement at elevated tempera ture m the presence of hydrogen bromide Heating the product mixture to 45°C m the presence of hydrogen bromide leads to a mixture m which the ratio of 3 bromo 1 butene to 1 bromo 2 butene is 15 85... 

The rearrangement of carbonium ions that readily occurs according to the thermodynamic stabiUty of cations sometimes limits synthetic utility of aromatic alkylation. For instance, the alkylation of ben2ene with / -propyl bromide gives mostly isopropylben2ene (cumene) much less... 

Other Reactions. Primary amyl alcohols can be halogenated to the corresponding chlorides by reaction with hydrogen chloride in hexamethylphosphoramide (87). Neopentyl chloride [753-89-9] is formed without contamination by rearrangement products. A convenient method for preparing / f/-amyl bromide and iodide involves reaction of / f/-amyl alcohol with hydrobromic or hydroiodic acid in the presence of Li or Ca haUde (88). The metal haUdes increase the yields (85 —95%) and product purity. 

The S ->N rearrangement of pyridazinethione glycosides proceeds smoothly under the influence of mercury(II) bromide. For example, 3-(tetraacetyl-l-/3-D-glucosylmer-capto)pyridazines rearrange to 2-(tetraacetyl-l-/3-D-glucosyl)pyridazine-3(2//)-thiones. 

Alkylation of 3-methyl-4-phenylisoxazolin-5-one with allyl bromide gave a mixture of N- and C(4)- alkylation in a 2 1 ratio. Heating the mixture changed the ratio to 1 99 and this conversion is believed to take place by an amino-Claisen rearrangement (Scheme 91) (69TL543). 

Electrophilic attack on the sulfur atom of thiiranes by alkyl halides does not give thiiranium salts but rather products derived from attack of the halide ion on the intermediate cyclic salt (B-81MI50602). Treatment of a s-2,3-dimethylthiirane with methyl iodide yields cis-2-butene by two possible mechanisms (Scheme 31). A stereoselective isomerization of alkenes is accomplished by conversion to a thiirane of opposite stereochemistry followed by desulfurization by methyl iodide (75TL2709). Treatment of thiiranes with alkyl chlorides and bromides gives 2-chloro- or 2-bromo-ethyl sulfides (Scheme 32). Intramolecular alkylation of the sulfur atom of a thiirane may occur if the geometry is favorable the intermediate sulfonium ions are unstable to nucleophilic attack and rearrangement may occur (Scheme 33). 

Neopentyl (2,2-dimethylpropyl) systems are resistant to nucleo diilic substitution reactions. They are primary and do not form caibocation intermediates, but the /-butyl substituent efiTectively hinders back-side attack. The rate of reaction of neopent>i bromide with iodide ion is 470 times slower than that of n-butyl bromide. Usually, tiie ner rentyl system reacts with rearrangement to the /-pentyl system, aldiough use of good nucleophiles in polar aprotic solvents permits direct displacement to occur. Entry 2 shows that such a reaction with azide ion as the nucleophile proceeds with complete inversion of configuration. The primary beiuyl system in entry 3 exhibits high, but not complete, inversiotL This is attributed to racemization of the reactant by ionization and internal return. 

Joly s method (or modifications) is the best procedure for preparing A " -3-ketones and can be extended to the elimination of hydrogen bromide from a-bromo ketones of all types. Rearrangement is sometimes observed but is not often serious. Selectivity can be improved in some instances by lowering the reaction temperature. The method has been found useful for the preparation of A" -3-ketones from 6-halo-A" -3-ketones ... 

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