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Alicyclics Aliphatic compounds containing rings, cycloalkanes, cycloalkyl halides, cycloalkyl alcohols, cyclic ethers, cycloalkenes, cycloalkadienes, etc. Cycloalkanes. cyclopropane cyclobutane cyclopentane cyclohexane . methylcyclopentane 1,1-dimethylcyclobutane.

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Alicyclics

Alicyclics

Aliphatic compounds containing rings, cycloalkanes, cycloalkyl halides, cycloalkyl alcohols, cyclic ethers, cycloalkenes, cycloalkadienes, etc.


Alicyclics

Cycloalkanes

cyclopropane cyclobutane cyclopentane cyclohexane


Alicyclics

methylcyclopentane 1,1-dimethylcyclobutane

trans-1,2-dibromocyclohexane


Alicyclics

cycloalkenes

3

4

2

5

1

6

cyclopentene 3-methylcyclohexene 1,3-cyclobutadiene



Alicyclics

  • Cycloalkanes, syntheses:

  • Modification of a ring compound:

  • 1. reduction of cycloalkene

  • 2. reduction of cyclic halide

  • a) hydrolysis of Grignard reagent

  • b) active metal & acid

  • 3. Corey House

  • B. Ring closures


Alicyclics

A. Modification of a cyclic compound:

H2, Ni

Sn, HCl

Mg; then H2O


Alicyclics

Li

CuI

+ CH3CH2-Br

CH2CH3

must be 1o

Corey-House


Alicyclics

  • ring closures

  • CH2=CH2 + CH2CO, hv 

  • Br-CH2CH2CH2CH2CH2-Br + Zn 

  • etc.


Alicyclics

Cl2, heat

+ HCl


Alicyclics

exceptions:

H2, Ni, 80o

CH3CH2CH3

Cl2, FeCl3

Cl-CH2CH2CH2-Cl

H2O, H+

CH3CH2CH2-OH

conc. H2SO4

CH3CH2CH2-OSO3H

HI

CH3CH2CH2-I


Alicyclics

exceptions (cont.)

+ H2, Ni, 200o CH3CH2CH2CH3

??????????


Alicyclics

internal bond deviation heat of

angles from 109.5 combustion

60o-49.5o 166.6

90o-19.5o 164.0

108o -1.5o158.7


Alicyclics

Cyclopropane undergoes addition reactions that other cycloalkanes and alkanes do not. This is because of angle strain in the small ring. Because the bond angles are less than the optimal 109.5o for maximum overlap, the bonds are weaker than normal carbon-carbon single bonds and can be added to.

Cyclobutane has angle strain that is less than that for cyclopropane, reacts with H2/Ni at a higher temperature, but does not react like cylcopropane in the other exceptional reactions.


Alicyclics

internal bond deviation heat of

angles from 109.5 combustion

60o-49.5o 166.6

90o-19.5o 164.0

108o -1.5o158.7

120o +11.5o157.4

128.5o +19o158.3

135o +25.5o158.6


Alicyclics

Cyclohexane does not have any angle strain! It isn’t a flat molecule. By rotating about the carbon-carbon bonds, it can achieve 109.5o bond angles.


Alicyclics

conformations of cyclohexane flat molecule. By rotating about the carbon-carbon bonds, it can achieve 109.5

chair twist boat

boat


Alicyclics

The flat molecule. By rotating about the carbon-carbon bonds, it can achieve 109.5chair conformation of cyclohexane is free of both angle strain and torsional strain (deviation from staggered). This is the most stable conformation.


Alicyclics

The boat conformation is free of angle strain, but has a great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:


Alicyclics

a = great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:axial positions in the chair conformation

e = equatorial positions


Alicyclics

great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:

CH3 in axial position CH3 in equatorial position

is more stable


Alicyclics

  • Cycloalkenes, syntheses great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat::

  • Modification of a ring compound:

  • 1) dehydrohalogenation of an alkyl halide

  • 2) dehydration of an alcohol

  • 3) dehalogenation of vicinal dihalides

  • (B. Ring closures)


Alicyclics

KOH(alc) great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:

H+, Δ

cyclohexene

Zn


Alicyclics

  • Cycloalkenes, reactions: great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:

  • addition of H2 8. hydroboration-oxid.

  • addition of X2 9. addition of free radicals

  • addition of HX 10. addition of carbenes

  • addition of H2SO4 11. epoxidation

  • addition of H2O,H+ 12. hydroxylation

  • addition of X2 + H2O 13. allylic halogenation

  • oxymerc-demerc. 14. ozonolysis

  • 15. vigorous oxidation


Alicyclics

H great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:2, Pt

Br2, CCl4

trans-1,2-dibromocyclohexane


Alicyclics

HBr great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:

H2SO4

H2O, H+

Markovnikov orientation


Alicyclics

Br great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:2 (aq.)

H+, dimer.

HF, 0o


Alicyclics

HBr, peroxides great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:

polymerization

CH2CO, hν

Peroxybenzoic acid


Alicyclics

KMnO great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:4

cis-1,2-cyclohexanediol

HCO3H

trans-1,2-cyclohexanediol

Br2, heat


Alicyclics

stereoselective great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:


Alicyclics

cyclic alcohols, halides, ethers great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:as expected:

PBr3

Na

H+

CH3COOH +

NaOCl


Alicyclics

NaOH great deal of torsional strain (eclipsed). To relieve the strain, it twists slightly to form the twist boat:

2o alkyl halide => E2

Mg

H2O

conc. HI, heat

conc. HBr, heat

2 Br-CH2CH2-Br

1,4-dioxane


Alicyclics

Alicyclic compounds are chemically like their open chain analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.


Alicyclics

Epoxides: analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

ethylene oxide propylene oxide cyclopentene oxide

(oxirane) (methyloxirane)

Synthesis:

C6H5CO3H

cis-2-butene

β-butylene oxide


Alicyclics

  • epoxides, reactions: analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

  • acid catalyzed addition

OH

CH2CH2

OH

H2O, H+

OH

CH3CH2-O-CH2CH2

CH3CH2OH, H+

OH

CH2CH2

Br

HBr


Alicyclics

2. Base catalyzed addition analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

OH

CH2CH2

OH

CH3CH2-O-CH2CH2-OH

H2N-CH2CH2-OH

CH3CH2CH2CH2-OH


Alicyclics

mechanism for acid catalyzed addition to an epoxide analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.


Alicyclics

mechanism for base-catalyzed addition to an epoxide: analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.


Alicyclics

acid catalyzed addition to analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.unsymmetric epoxides?

OH

+ H2O, H+ CH3CHCH2

OH

which oxygen in the product came from the water?

18OH

CH3CHCH2

OH

+ H218O, H+


Alicyclics

CH analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.3

O

+ CH3OH,H+ CH3CHCH2

OH

Br

+ HBr  CH3CHCH2

OH


Alicyclics

Base? analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

18OH

+ Na18OH, H218O CH3CHCH2

OH

OCH3

+ CH3OH, CH3ONa CH3CHCH2

OH

NH2

+ NH3 CH3CHCH2

OH


Alicyclics

Acid: analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

Z

+ HZ CH3CHCH2

OH

Base:

Z

+ Z-, HZ CH3CHCH2

OH


Alicyclics

“variable transition state” analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

Z

acid: — C — C —

OH

Bond breaking is occurring faster than bond making, making the carbon slightly positive. C δ+ : 3o > 2o > 1o

δ+

δ+

base:

Z

— C — C —

O

Bond breaking is occurring at the same time as bond breaking, there is no charge on the carbon. Steric factors are most important: 1o > 2o > 3o

δ-


Alicyclics

Acid: analogs. The exceptions are for small ring compounds where angle strain may give rise to reactions that are not typical of other molecules.

Z

+ HZ CH3CHCH2

OH

Cδ+: Z to 2o carbon

Base:

Z

+ Z-, HZ CH3CHCH2

OH

steric factors: Z to 1o carbon