Strain, ring

The strain energies of these five-membered heterocycles are relatively small with values of 23.5, 24.8 and S.SkJmoF estimated for tetrahydrofuran, pyrrolidine and tetrahy-drothiophene respectively (74PMH(6)199). The closeness of the values for the two former compounds reflects the almost identical covalent radii of oxygen (0.66 A) and nitrogen (0.70 A) atoms. The sulfur atom with a much larger covalent radius of 1.04 A causes a 

Structure of Five-membered Rings with One Heteroatom 

The effect on strain energy of introducing unsaturation into these rings has been evaluated in the cases of 2,3- and 2,5-dihydrothiophene, where the additional values are 18 and 15.8 kJ mol  

If we assume that in fully saturated carbocyclic rings each carbon is sp hybridized, then each bond angle would ideally be 109.5 . However, in a planar ring, the carbon atoms don t 

These data are best presented as a graph, and the ring strain per carbon atom in planar rings for ring sizes up to 17 are shown on the next page. Whether the bonds are strained inwards or outwards is not important so only the magnitude of the strain is shown. 

From these figures (represented in the graph on p. 368), note  

Heats of combustion for some straight-chain alkanes 

Number of atoms in ring Internal angle In planar ring 109.5°— internal angle  

Cycloalkane properties depend on ring size. Strained molecules, i.e., moleeules with distorted geometries, tend to be more reaetive in ring-breaking ehemieal reaetions. For example, eombustion of a strained eyeloalkane should release more energy per CH2 group than eombustion of an unstrained moleeule. 

Examine and eompare eleetrostatie potential maps for the eycloalkanes. Is there any evidenee of earbon-carbon bonds being espeeially eleetron rieh (subject to electrophilic attack), or of CH bonds being espeeially electron poor (subject to deprotonation)  

Electrostatic potential map for cycloheptane shows negatively-charged regions (in red) and positively-charged regions (in blue). 

Exocyclic unsaturation can stabilize small ring heterocycles. In three-membered rings it is difficult to separate the contributions from increased angle strain and from electronic interactions between the unsaturation and the heteroatom. In four-membered rings such separation has been done (74PMH(6)199, p. 235). The CRSEs change from oxetane (106 kJ mol-1) by -11 kJ mol-1 to oxelan-2-one (95 kJ mol-1) (corrected for electronic effects) and 4-methyleneoxetan-2-one (95 kJ mol ). In contrast, an increase of 10 kJ mol 1 over the value for cyclobutane (111 kJ mol-1) is observed on going to both methylenecyclobutane and l,3-bis(methylene)cyclobutane. 

Strain enormously influences the tendency for ring formation to give azetidines. Within the homologous series of azaheterocycles, the tendency for cyclization is smallest for the nitrogen-containing four-membered ring (5 3 6 7 = 4) (85JCS(P2)1345). 

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Although reasonably stable at room temperature under neutral conditions, tri- and tetrametaphosphate ions readily hydrolyze in strongly acidic or basic solution via polyphosphate intermediates. The hydrolysis is first-order under constant pH. Small cycHc phosphates, in particular trimetaphosphate, undergo hydrolysis via nucleophilic attack by hydroxide ion to yield tripolyphosphate. The ring strain also makes these stmctures susceptible to nucleophilic ring opening by other nucleophiles. 

The four-membered oxetane ring (trimethylene oxide [503-30-0]) has much higher ring strain, and irreversible ring-opening polymerization can occur rapidly to form polyoxetane [25722-06-9] ... 

Because of the high ring strain of the four-membered ring, even substituted oxetanes polymerize readily, ia contrast to substituted tetrahydrofurans, which have tittle tendency to undergo ring-opening homopolymerization (5). 

The chemistry of polymerization of the oxetanes is much the same as for THE polymerization. The ring-opening polymerization of oxetanes is primarily accompHshed by cationic polymerization methods (283,313—318), but because of the added ring strain, other polymerization techniques, eg, iasertion polymerization (319), anionic polymerization (320), and free-radical ring-opening polymerization (321), have been successful with certain special oxetanes. 

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. 

Calculation of group increments for oxygen, sulfur and nitrogen compounds has allowed the estimation of conventional ring-strain energies (CRSE) for saturated heterocycles from enthalpies of formation. For 1,3-dioxolane, CRSE is about 20 kJ mol . In 2,4-dialkyl-l,3-dioxolanes the cis form is always thermodynamically the more stable by approximately 1 kJ mol" . 

Ring expansion of small rings is once again favored by ring strain, and many 3 5 conversions are known. Four-membered rings can expand to five- or six-membered ones. Examples are given in Scheme 13. 

Bond Lengths, Bond Angles, Ring Strain... 

The N—CO distance of 1.38 A in (58) is rather greater than that of a normal amide (ca. 1.32 A) this has been attributed to ring strain and to inhibition of normal amide resonance by interaction with the N-aryl substituent. This inhibition of resonance is more pronounced in the N-tosyl-4-thioxoazetidin-2-one (59), which exhibits very short C=0 and C=S distances as well as the unusually long C—N bonds (80TL4247). NMR investigations... 

Azabicyclo[2.2.0]hexa-2,5-diene, pentakis-(pentafluoroethyl)-synthesis, 2, 304 2-Azabicyclop.2.0]hexadiene reactivity, 7, 360 thermal isomerization, 7, 360 2-Azabicyclo[2.2.0]hexa-2,5-diene synthesis, 2, 304 1 -Azabicyclo[3.2.0]hexadiene synthesis, 7, 361 1 - Azabicyclo[2.2.0]hexane reactions, 7, 344 ring strain... 

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