Rings, three-membered

Three membered rings are kineticahy easy to form but are rather unstable. Some conventional methods work but are rather capricious. Tliis obvious discoimection on cyclopropyl ketones turns out to be all right  

Three membered rings that contain oxygen are called epoxides At one time epox ides were named as oxides of alkenes Ethylene oxide and propylene oxide for exam pie are the common names of two industrially important epoxides 

Figure 7-2. Strain energies [kj/mol] of three-membered ring systems.

A more general route to three-membered rings is based on a new type of disconnection the removal of an atom 

Analysis We must consider two alternative disconnections of the three-membered ring  

The chief reason why ethylenebromonium ion m spite of its strained three membered ring IS more stable than 2 bromoethyl cation is that both carbons and bromine have octets of electrons whereas one carbon has only six electrons m the carbocation 

Small Rings As Substrates for Ring-opening Reactions 4.03.7.3.1 Three-membered rings 

Unlike most ethers epoxides (compounds m which the C—O—C unit forms a three membered ring) are very reactive substances The principles of nucleophilic sub stitution are important m understanding the preparation and properties of epoxides 

You might reasonably have said stereochemistry, but the best answer is the three membered ring. Which three carbene discormections might we consider (See frames 276-288 if you ve forgotten all tliis ). 

Although epoxides are always considered to have their oxygen atom as part of a three membered ring the prefix epoxy in the lUPAC system of nomenclature can be used to denote a cyclic ether of vanous sizes Thus 

Disubstituted cyclopropanes exemplify one of the simplest cases involving stabil ity differences between stereoisomers A three membered ring has no conformational mobility so the ring cannot therefore reduce the van der Waals strain between cis sub stituents on adjacent carbons without introducing other strain The situation is different m disubstituted derivatives of cyclohexane 

Ethylene oxide is a highly reactive compound, and so is used iudustriaHy as an iatermediate for many chemical products. The three-membered ring is opened iu most of its reactions. These reactions are very exothermic because of the tremendous ring strain iu ethylene oxide, which has been calculated (39). Reviews of ethylene oxide reactions are given iu References 40 and 41. 

The reaction of the vinylcyclopropanedicarboxylate 301 with amines affords an allylic amine via the 7r-allylpalladium complex 302[50]. Similarly, three-membered ring A -tosyl-2-(l,3-butadienyl)aziridine (303) and the four-mem-bered ring azetidine 304 can be rearranged to the five- and six-membered ring unsaturated cyclic amines[183]. 

At temperatures >300° C, substituted pyrroHdines can be obtained by reaction of substituted a2iridines (R = CH, C2H ) and conjugated olefins X = CN, CO2CH2, CH=CH2) with C—C cleavage in the three-membered ring (214—216). 

Tertiary amines have been shown to react with isocyanates ia an analogous fashion to form ureas (41—43). Similarly, a2iridines (three-membered rings containing nitrogen) are found to react with isocyanates to yield cycHc ureas. Tertiary amines have also been shown to form labile dipolar 1 1 adducts with isocyanates reminiscent of salt formation. In contrast, formaldehyde acetal aminals form iasertion products with sulfonyl isocyanates (44,45). 

Rahman and Clapp decomposed dinitromethane derivatives in DMF in the presence of alkenes to obtain 2-isoxazolines. Without any alkene present, an acid and KNO2 were obtained. They proposed a mechanism which proceeded via a three-membered ring or a nitrocarbene which rearranged to a nitrile oxide (76JOC122, 75MI41612). 

Apparent nucleophilic attack on large, fully unsaturated rings may occur by way of attack on a valence tautomer, such as the reaction of oxepin with azide ion. Attack on the oxanorcaradiene valence tautomer leads to ring opening of the three-membered ring, and formation of 5-azido-6-hydroxy-l,3-cyclohexadiene (Section 5.17.2.2.4). 

Bromine and chlorine convert the 1- and 2-butenes to compounds containing two atoms of halogens attached to adjacent carbons (vicinal dihahdes). Iodine fails to react. In this two-step addition mechanism the first step involves the formation of a cation. The halonium ion formed (a three-membered ring) requires antiaddition by the anion. 

Some reactions require the bonds being broken or made in a reaction to be aligned with other parts ti- or free electrons) of a molecule. These requirements are called stereoelectronic effects. Figure 3-6f shows that the bromide ion has to open a bro-monium ion by an anti attack in order that the new bond is formed concomitantly with the breaking of one bond of the three-membered ring. 

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