The Electrons Circle Around (TECA)
Thermal reactions with an Even number of electron
pairs are Conrotatory or Antarafacial.
A change either from thermal to photochemical or from an even to an odd number of electron pairs changes the outcome from conrotatory/antarafacial to disrotatory/suprafacial. A change from both thermal and even to photochemical and odd causes no change because two negatives make a positive.


Claisen rearrangement - 30.9 A Summary of Rules for Pericyclic Reactions

These selection rules are summarized in TABLE 30.4; knowing them gives you the ability to predict the stereochemistry of literally thousands of pericyclic reactions.


| TABLE 30.4 Stereochemical Rules for Pericyclic Reactions |  |  |
| :--- | :--- | :--- |
| Electronic state | Electron pairs | Stereochemistry |
| Ground state (thermal) | Even number
 Odd number | Antara-con
 Supra-dis |
| Excited state (photochemical) | Even number
 Odd number | Supra-dis
 Antara-con |


PROBLEM Predict the stereochemistry of the following pericyclic reactions:
30-12 (a) The thermal cyclization of a conjugated tetraene
(b) The photochemical cyclization of a conjugated tetraene
(c) A photochemical $[4+4]$ cycloaddition
(d) A thermal $[2+6]$ cycloaddition
(e) A photochemical $[3,5]$ sigmatropic rearrangement


(80) CHEMISTRY MATTERS -


Vitamin D, the Sunshine Vitamin -

Vitamin D, discovered in 1918, is a general name for two related compounds, cholecalciferol (vitamin $\mathrm{D}_{3}$ ) and ergocalciferol (vitamin $D_{2}$ ). Both are derived from steroids (Section 27.6) and differ only in the nature of the hydrocarbon side chain attached to the five-membered ring. Cholecalciferol comes primarily from dairy products and fish; ergocalciferol comes from some vegetables.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1106.jpg?height=489&width=771&top_left_y=631&top_left_x=674)


Vitamin D, the Sunshine Vitamin -

FIGURE 30.17 Here are the sunbathers, again, with their chemical work complete. (credit: "Tanning" by Meraj Chhaya/Flickr, CC BY 2.0)
The function of vitamin $D$ in the body is to control the calcification of bones by increasing intestinal absorption of calcium. When sufficient vitamin $D$ is present, approximately $30 \%$ of ingested calcium is absorbed, but in the absence of vitamin D, calcium absorption falls to about $10 \%$. A deficiency of vitamin $D$ thus leads to poor bone growth and to the diseases rickets in children and osteoporosis in adults.


Vitamin D, the Sunshine Vitamin -

Actually, neither vitamin $D_{2}$ nor $D_{3}$ is present in foods. Rather, foods contain the precursor molecules 7-dehydrocholesterol and ergosterol. In the presence of sunlight, both precursors are converted in the outer, epidermal layer of skin to the active vitamins, hence the nickname for vitamin $D$, the "sunshine vitamin."
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1106.jpg?height=590&width=1478&top_left_y=1502&top_left_x=321)


Vitamin D, the Sunshine Vitamin -

Pericyclic reactions are unusual in living organisms, and the photochemical synthesis of vitamin $D$ is one of only a few well-studied examples. The reaction takes place in two steps, an electrocyclic ring-opening of a cyclohexadiene to yield an open-chain hexatriene, followed by a sigmatropic [1,7] H shift to yield an isomeric hexatriene. Only the initial electrocyclic ring-opening requires irradiation by so-called UVB light of 295 to 300 nm wavelength. The subsequent sigmatropic [1,7] H shift occurs spontaneously by a thermal isomerization.


Vitamin D, the Sunshine Vitamin -

Following synthesis under the skin, further metabolic processing of cholecalciferol and ergocalciferol in the liver and kidney introduces two additional -OH groups to give the active forms of the vitamin, calcitriol and ergocalcitriol.


Key Terms -

```
- antarafacial • lowest unoccupied molecular orbital (LUMO)
• conrotatory • pericyclic reaction
- cycloaddition reaction
- photochemical reaction
- disrotatory
- sigmatropic rearrangement
- electrocyclic reaction
- suprafacial
- frontier orbitals
- symmetry-allowed
- highest occupied molecular orbital (HOMO)
```

- conrotatory
- cycloaddition reaction
- disrotatory
- electrocyclic reaction
- frontier orbitals
- highest occupied molecular orbital (HOMO)
- lowest unoccupied molecular orbital (LUMO)
- pericyclic reaction
- photochemical reaction
- sigmatropic rearrangement
- suprafacial
- symmetry-allowed
- symmetry-disallowed


Key Terms -


Summary -

A pericyclic reaction takes place in a single step through a cyclic transition state without intermediates. There are three major classes of pericyclic processes: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. The stereochemistry of these reactions is controlled by the symmetry of the orbitals involved in bond reorganization.


Summary -

Electrocyclic reactions involve the cyclization of conjugated acyclic polyenes. For example, 1,3,5-hexatriene cyclizes to 1,3 -cyclohexadiene on heating. Electrocyclic reactions can occur by either conrotatory or disrotatory pathways, depending on the symmetry of the terminal lobes of the $\pi$ system. Conrotatory cyclization requires that both lobes rotate in the same direction, whereas disrotatory cyclization requires that the lobes rotate in opposite directions. The reaction course in a specific case can be found by looking at the symmetry of the highest occupied molecular orbital (HOMO).


Summary -

Cycloaddition reactions are those in which two unsaturated molecules add together to yield a cyclic product. For example, Diels-Alder reaction between a diene (four $\pi$ electrons) and a dienophile (two $\pi$ electrons) yields a cyclohexene. Cycloadditions can take place either by suprafacial or antarafacial pathways. Suprafacial cycloaddition involves interaction between lobes on the same face of one component and on the same face of the second component. Antarafacial cycloaddition involves interaction between lobes on the same face of one component and on opposite faces of the other component. The reaction course in a specific case can be found by looking at the symmetry of the HOMO of one component and the lowest unoccupied molecular orbital (LUMO) of the other.


Summary -

Sigmatropic rearrangements involve the migration of a $\sigma$-bonded group across a $\pi$ electron system. For example, Claisen rearrangement of an allylic vinylic ether yields an unsaturated carbonyl compound, and Cope rearrangement of a 1,5-hexadiene yields an isomeric 1,5-hexadiene. Sigmatropic rearrangements can occur with either suprafacial or antarafacial stereochemistry; the selection rules for a given case are the same as those for cycloaddition reactions.


Summary -

The stereochemistry of any pericyclic reaction can be predicted by counting the total number of electron pairs (bonds) involved in bond reorganization and then applying the mnemonic "The Electrons Circle Around." That is, thermal (ground-state) reactions involving an even number of electron pairs occur with either conrotatory or antarafacial stereochemistry. Exactly the opposite rules apply to photochemical (excited-state) reactions.


Additional Problems -


Visualizing Chemistry -

PROBLEM Predict the product obtained when the following substance is heated:


30-13 -


30-13 -

PROBLEM The ${ }^{13} \mathrm{C}$ NMR spectrum of homotropilidene taken at room temperature shows only three peaks. 30-14 Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1108.jpg?height=305&width=451&top_left_y=300&top_left_x=417)


Mechanism Problems -

PROBLEM The following rearrangement of $N$-allyl- $N, N$-dimethylanilinium ion has been observed. Propose a
30-15 mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1108.jpg?height=198&width=818&top_left_y=795&top_left_x=488)
$N$-Allyl- $N, N$-dimethylanilinium ion
o-Allyl-N,N-dimethylanilinium ion
PROBLEM Plastic photochromic sunglasses are based on the following reversible rearrangement of a dye 30-16 inside the lenses that occurs when the lenses are exposed to sunlight. The original dye absorbs UV light but not visible light and is thus colorless, while the rearrangement product absorbs visible light and is thus darkened.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1108.jpg?height=540&width=979&top_left_y=1264&top_left_x=405)
(a) Show the mechanism of the rearrangement.
(b) Why does the rearrangement product absorb at a longer wavelength (visible light) than the original dye (UV)?


Mechanism Problems -

PROBLEM The sex hormone estrone has been synthesized by a route that involves the following step. Identify
30-17 the pericyclic reactions involved, and propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1108.jpg?height=345&width=1080&top_left_y=2061&top_left_x=409)


Mechanism Problems -

PROBLEM Coronafacic acid, a bacterial toxin, was synthesized using a key step that involves three sequential 30-18 pericyclic reactions. Identify them, and propose a mechanism for the overall transformation. How
would you complete the synthesis?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1109.jpg?height=659&width=1381&top_left_y=256&top_left_x=410)


Mechanism Problems -

PROBLEM The following thermal rearrangement involves two pericyclic reactions in sequence. Identify them, 30-19 and propose a mechanism to account for the observed result.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1109.jpg?height=212&width=615&top_left_y=1035&top_left_x=408)


Electrocyclic Reactions -

PROBLEM Do the following electrocyclic reactions take place in a conrotatory or disrotatory manner? Under
$\mathbf{3 0 - 2 0}$ what conditions, thermal or photochemical, would you carry out each reaction?
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1109.jpg?height=237&width=890&top_left_y=1448&top_left_x=479)
(b)
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Electrocyclic Reactions -

PROBLEM The following thermal isomerization occurs under relatively mild conditions. Identify the pericyclic 30-21 reactions involved, and show how the rearrangement occurs.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1109.jpg?height=270&width=679&top_left_y=2017&top_left_x=414)


Electrocyclic Reactions -

PROBLEM Would you expect the following reaction to proceed in a conrotatory or disrotatory manner? Show
$\mathbf{3 0 - 2 2}$ the stereochemistry of the cyclobutene product, and explain your answer.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1110.jpg?height=172&width=673&top_left_y=188&top_left_x=414)


Electrocyclic Reactions -

PROBLEM Heating ( $1 Z, 3 Z, 5 Z$ )-1,3,5-cyclononatriene to $100^{\circ} \mathrm{C}$ causes cyclization and formation of a bicyclic
$\mathbf{3 0 - 2 3}$ product. Is the reaction conrotatory or disrotatory? What is the stereochemical relationship of the two hydrogens at the ring junctions, cis or trans?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1110.jpg?height=202&width=554&top_left_y=536&top_left_x=558)
(1Z,3Z,5Z)-1,3,5-Cyclononatriene
PROBLEM ( $2 E, 4 Z, 6 Z, 8 E$ )-2,4,6,8-Decatetraene has been cyclized to give 7,8-dimethyl-1,3,5-cyclooctatriene.
$\mathbf{3 0 - 2 4}$ Predict the manner of ring-closure-conrotatory or disrotatory-for both thermal and photochemical reactions, and predict the stereochemistry of the product in each case.


Electrocyclic Reactions -

PROBLEM Answer Problem 30-24 for the thermal and photochemical cyclizations of 30-25 (2E,4Z,6Z,8Z)-2,4,6,8-decatetraene.


Electrocyclic Reactions -

PROBLEM The cyclohexadecaoctaene shown isomerizes to two different isomers, depending on reaction $\mathbf{3 0 - 2 6}$ conditions. Explain the observed results, and indicate whether each reaction is conrotatory or disrotatory.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1110.jpg?height=576&width=904&top_left_y=1222&top_left_x=410)


Cycloaddition Reactions -

PROBLEM Which of the following reactions is more likely to occur? Explain.
30-27
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1110.jpg?height=256&width=1281&top_left_y=1924&top_left_x=411)


Cycloaddition Reactions -

PROBLEM The following reaction takes place in two steps, one of which is a cycloaddition while the other is a
$\mathbf{3 0 - 2 8}$ reverse cycloaddition. Identify the two pericyclic reactions, and show how they occur.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1110.jpg?height=223&width=917&top_left_y=2312&top_left_x=409)

PROBLEM Two sequential pericyclic reactions are involved in the following furan synthesis. Identify them, and 30-29 propose a mechanism for the transformation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1111.jpg?height=213&width=960&top_left_y=300&top_left_x=409)


Sigmatropic Rearrangements -

PROBLEM Predict the product of the following pericyclic reaction. Is this [5,5] shift a suprafacial or an
30-30 antarafacial process?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1111.jpg?height=117&width=690&top_left_y=706&top_left_x=414)

PROBLEM Propose a pericyclic mechanism to account for the following transformation:
30-31
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1111.jpg?height=232&width=615&top_left_y=895&top_left_x=411)

PROBLEM Vinyl-substituted cyclopropanes undergo thermal rearrangement to yield cyclopentenes. Propose 30-32 a mechanism for the reaction, and identify the pericyclic process involved.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1111.jpg?height=112&width=418&top_left_y=1256&top_left_x=466)

Vinylcyclopropane Cyclopentene
PROBLEM The following synthesis of dienones occurs readily. Propose a mechanism to account for the results,
30-33 and identify the kind of pericyclic reaction involved.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1111.jpg?height=142&width=820&top_left_y=1555&top_left_x=411)


Sigmatropic Rearrangements -

PROBLEM Karahanaenone, a terpenoid isolated from oil of hops, has been synthesized by the thermal reaction
30-34 shown. Identify the kind of pericyclic reaction, and explain how karahanaenone is formed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1111.jpg?height=274&width=725&top_left_y=1820&top_left_x=407)


Karahanaenone -


General Problems -

PROBLEM What stereochemistry-antarafacial or suprafacial-would you expect to observe in the following
30-35 reactions?
(a) A photochemical $[1,5]$ sigmatropic rearrangement
(b) A thermal $[4+6]$ cycloaddition
(c) A thermal $[1,7]$ sigmatropic rearrangement
(d) A photochemical [2 + 6] cycloaddition


General Problems -

PROBLEM Bicyclohexadiene, also known as Dewar benzene, is extremely stable despite the fact that its 30-36
rearrangement to benzene is energetically favored. Explain why the rearrangement is so slow.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1112.jpg?height=174&width=440&top_left_y=257&top_left_x=433)


General Problems -

PROBLEM Ring-opening of the trans-cyclobutene isomer shown takes place at much lower temperature than
30-37 a similar ring-opening of the cis-cyclobutene isomer. Explain the temperature effect, and identify the stereochemistry of each reaction as either conrotatory or disrotatory.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1112.jpg?height=175&width=1172&top_left_y=601&top_left_x=411)

PROBLEM Photolysis of the cis-cyclobutene isomer in Problem 30-37 yields cis-cyclododecaen-7-yne, but
30-38 photolysis of the trans isomer yields trans-cyclododecaen-7-yne. Explain these results, and identify the type and stereochemistry of the pericyclic reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1112.jpg?height=184&width=677&top_left_y=946&top_left_x=410)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1112.jpg?height=177&width=676&top_left_y=1223&top_left_x=413)


General Problems -


General Problems -

PROBLEM The following rearrangement was devised and carried out to prove the stereochemistry of $[1,5]$ 30-40 sigmatropic hydrogen shifts. Explain how the observed result confirms the predictions of orbital symmetry.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1112.jpg?height=179&width=1104&top_left_y=1816&top_left_x=410)


General Problems -

PROBLEM The following reaction is an example of a $[2,3]$ sigmatropic rearrangement. Would you expect the
30-41 reaction to be suprafacial or antarafacial? Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1112.jpg?height=162&width=742&top_left_y=2136&top_left_x=410)


General Problems -

PROBLEM When the compound having a cyclobutene fused to a five-membered ring is heated,
30-42 ( $1 Z, 3 Z$ )-1,3-cycloheptadiene is formed. When the related compound having a cyclobutene fused to an eight-membered ring is heated, however, ( $1 E, 3 Z$ )-1,3-cyclodecadiene is formed. Explain these results, and suggest a reason why opening of the eight-membered ring occurs at a lower
temperature.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1113.jpg?height=199&width=1163&top_left_y=258&top_left_x=416)


General Problems -

PROBLEM In light of your answer to Problem 30-42, explain why a mixture of products occurs in the following 30-43 reaction:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1113.jpg?height=222&width=1064&top_left_y=599&top_left_x=411)


General Problems -

PROBLEM In nature, the enzyme chorismate mutase catalyzes a Claisen rearrangement of chorismate that
30-44 involves both the terminal double bond and the double bond with the highlighted carbon. What is the structure of prephenate, the biological precursor to the amino acids phenylalanine and tyrosine?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1113.jpg?height=297&width=692&top_left_y=1055&top_left_x=413)


CHAPTER 31 <br> Synthetic Polymers -


CHAPTER 31 <br> Synthetic Polymers -

FIGURE 31.1 If you ride a bike, wear your helmet! Most bike helmets are made of two different polymers, a hard polycarbonate shell and an inner layer of polystyrene. (credit: modification of work "View from the top" by Gene Bisbee/Flickr, CC BY 2.0)


CHAPTER CONTENTS -


CHAPTER CONTENTS - 31.1 Chain-Growth Polymers

31.2 Stereochemistry of Polymerization: Ziegler-Natta Catalysts
31.3 Copolymers
31.4 Step-Growth Polymers
31.5 Olefin Metathesis Polymerization
31.6 Intramolecular Olefin Metathesis
31.7 Polymer Structure and Physical Properties


WHY THIS CHAPTER? Our treatment of polymers has thus far been dispersed over several chapters, but it's also important to take a comprehensive view. In the present chapter, we'll look further at how polymers are made, and we'll see how polymer structure correlates with physical properties. No course in organic chemistry would be complete without a look at polymers.


Polymers are a fundamental part of the modern world, used in everything from coffee cups to cars to clothing. In medicine, too, their importance is growing, with uses as diverse as cardiac pacemakers, artificial heart valves, and biodegradable sutures.


We've seen on several occasions in previous chapters that a polymer, whether synthetic or biological, is a large molecule built up by repetitive bonding of many smaller units, or monomers. Polyethylene, for instance, is a synthetic polymer made from ethylene (Section 8.10), nylon is a synthetic polyamide made from a diacid and a diamine (Section 21.9), and proteins are biological polyamides made from amino acids. Note that polymers are
often drawn by indicating their repeating unit in parentheses. The repeating unit in polystyrene, for example, comes from the monomer styrene.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1115.jpg?height=215&width=524&top_left_y=299&top_left_x=795)


Styrene
Polystyrene


Synthetic polymers are classified by their method of synthesis as either chain-growth or step-growth. These categories are somewhat imprecise but nevertheless provide a useful distinction. Chain-growth polymers are produced by chain-reaction polymerization in which an initiator adds to the carbon-carbon double bond of an unsaturated substrate (a vinyl monomer) to yield a reactive intermediate. This intermediate reacts with a second molecule of monomer to yield a new intermediate, which reacts with a third monomer unit, and so on.


The initiator can be a radical, an acid, or a base. Historically, as we saw in Section 8.10, radical polymerization was the most common method because it can be carried out with practically any vinyl monomer.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1115.jpg?height=459&width=1399&top_left_y=979&top_left_x=363)


Acid-catalyzed (cationic) polymerization, by contrast, is effective only with vinyl monomers that contain an electron-donating group (EDG) capable of stabilizing the chain-carrying carbocation intermediate.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1115.jpg?height=139&width=1521&top_left_y=1535&top_left_x=302)
where $E D G=$ an electron-donating group
Isobutylene (2-methylpropene) is a good example of a monomer that polymerizes rapidly under cationic conditions. The reaction is carried out commercially at $-80^{\circ} \mathrm{C}$, using $\mathrm{BF}_{3}$ and a small amount of water to generate $\mathrm{BF}_{3} \mathrm{OH}^{-} \mathrm{H}^{+}$catalyst. The product is used in the manufacture of truck and bicycle inner tubes.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1115.jpg?height=180&width=643&top_left_y=1883&top_left_x=741)


Vinyl monomers with electron-withdrawing groups (EWG) can be polymerized by basic (anionic) catalysts. The chain-carrying step is a conjugate nucleophilic addition of an anion to the unsaturated monomer (Section 19.13).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1115.jpg?height=137&width=1601&top_left_y=2211&top_left_x=262)
where EWG $=$ an electron-withdrawing group
Acrylonitrile $\left(\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCN}\right)$, methyl methacrylate $\left[\mathrm{H}_{2} \mathrm{C}=\mathrm{C}\left(\mathrm{CH}_{3}\right) \mathrm{CO}_{2} \mathrm{CH}_{3}\right]$, and styrene $\left(\mathrm{H}_{2} \mathrm{C}=\mathrm{CHC}_{6} \mathrm{H}_{5}\right)$ can all be polymerized anionically. The polystyrene used in foam coffee cups, for example, is prepared by anionic
polymerization of styrene using butyllithium as catalyst.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1116.jpg?height=283&width=1338&top_left_y=254&top_left_x=388)


An interesting example of anionic polymerization accounts for the remarkable properties of "super glue," one drop of which can support up to 2000 lb . Super glue is simply a solution of pure methyl $\alpha$-cyanoacrylate, which has two electron-withdrawing groups that make anionic addition particularly easy. Trace amounts of water or bases on the surface of an object are sufficient to initiate polymerization of the cyanoacrylate and bind articles together. Skin is a good source of the necessary basic initiators, and many people have found their fingers stuck together after inadvertently touching super glue. So good is super glue at binding tissues that related cyanoacrylate esters such as Dermabond are often used in place of sutures to close wounds.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1116.jpg?height=264&width=1253&top_left_y=860&top_left_x=439)


Dermabond <br> (2-ethylhexyl $\alpha$-cyanoacrylate) -

PROBLEM Order the following monomers with respect to their expected reactivity toward cationic
31-1 polymerization, and explain your answer:


$$
\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCH}_{3}, \mathrm{H}_{2} \mathrm{C}=\mathrm{CHCl}, \mathrm{H}_{2} \mathrm{C}=\mathrm{CH}-\mathrm{C}_{6} \mathrm{H}_{5}, \mathrm{H}_{2} \mathrm{C}=\mathrm{CHCO}_{2} \mathrm{CH}_{3}
$$


PROBLEM Order the following monomers with respect to their expected reactivity toward anionic 31-2 polymerization, and explain your answer:
$\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCH}_{3}, \mathrm{H}_{2} \mathrm{C}=\mathrm{CHC} \equiv \mathrm{N}, \mathrm{H}_{2} \mathrm{C}=\mathrm{CHC}_{6} \mathrm{H}_{5}$
PROBLEM Polystyrene is produced commercially by reaction of styrene with butyllithium as an anionic 31-3 initiator. Using resonance structures, explain how the chain-carrying intermediate is stabilized.