f i t h dition
`
`y
`
`PGR2020-00009
`Pharmacosmos A/S v. American Regent, Inc.
`Petitioner Ex. 1060 - Page 1
`
`

`

`Fundamentals of
`Organic Chemistry
`
`Fifth Edition
`
`John McMurry
`Cornell University
`
`THOMS ON
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`BROOKS/COLE
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`
`PGR2020-00009
`Pharmacosmos A/S v. American Regent, Inc.
`Petitioner Ex. 1060 - Page 2
`
`

`

`THOMSON
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`PGR2020-00009
`Pharmacosmos A/S v. American Regent, Inc.
`Petitioner Ex. 1060 - Page 3
`
`

`

`rt(cid:173)
`en
`od
`
`th
`
`1-
`n
`1-
`
`.e
`;s
`·e
`lf
`e
`
`1
`
`4.9
`
`(cid:127) Addition of Radicals to Alkenes: Polymers
`
`119
`
`Enzyme-catalyzed reactions are usually much more chemically selec(cid:173)
`tive than their laboratory counterparts. Fumarase, for example, is com(cid:173)
`pletely inert toward maleic acid, the cis isomer of fumaric acid. Neverthe(cid:173)
`less, the fundamental processes of organic chemistry are the same in the
`living cell and in the laboratory.
`
`4.9
`
`Addition of Radicals
`to Alkenes: Polymers
`
`No other group of synthetic chemicals has had as great an impact on our
`day-to-day lives as polymers. From carpeting to clothing to foam coffee cups,
`we are surrounded by polymers.
`A polymer is a large (sometimes very large) molecule built up by
`repetitive bonding together of many smaller molecules, called monomers.
`As we'll see in later chapters, nature makes wide use of biological poly(cid:173)
`mers. Cellulose, for example, is a polymer built of repeating sugar units;
`proteins are polymers built of repeating amino acid units; and nucleic acids
`are polymers built of repeating nucleotide units. Although synthetic poly(cid:173)
`mers are chemically much simpler than biopolymers, there is an immense
`diversity to the structures and properties of synthetic polymers, depending
`on the nature of the monomers and on the reaction conditions used for
`polymerization.
`Many simple alkenes undergo rapid polymerization when treated with
`a small amount of a radical as catalyst. Ethylene, for example, yields poly(cid:173)
`ethylene, an enormous alkane that may have up to several thousand
`monomer units incorporated into its long hydrocarbon chain. Ethylene
`polymerization is usually carried out at high pressure (1000-3000 atm)
`and high temperature (100-250°C) with a rallical catalyst such as benzoyl
`peroxide.
`
`Ethylene
`
`A section of polyethylene
`
`Radical polymerization of an alkene involves three kinds of steps: initi(cid:173)
`ation, propagation, and termination. The key step is the addition of a radi(cid:173)
`cal to the ethylene double bond in a process similar to what takes place in
`the addition of an electrophile to an alkene (Section 3.7). In writing the
`mechanism, a curved half-arrow, or "fishhook," is used to show the move(cid:173)
`ment of a single electron, as opposed to the full curved arrow used to show
`the movement of an electron pair in a polar reaction.
`
`PGR2020-00009
`Pharmacosmos A/S v. American Regent, Inc.
`Petitioner Ex. 1060 - Page 4
`
`

`

`F
`
`120
`
`CHAPTER 4
`
`Reactions of Alkenes and Alkynes •
`
`' I
`
`1
`
`I I
`I i1 1
`
`l ,
`., '
`! :
`I :
`,,
`
`:
`
`i
`
`;!
`
`STEP 1
`
`Initiation: Reaction begins when a few radicals are generated by the cata(cid:173)
`lyst. For example, when benzoyl peroxide is used as initiator, the 0-0 bond
`is broken on heating to yield benzoyloxy radicals. The benzoyloxy radical
`then adds to the C=C bond of ethylene to generate a carbon radical. One
`electron from the carbon-carbon double bond pairs up with the odd electron
`on the benzoyloxy radical to form a C-0 bond, and the other electron
`remains on carbon.
`
`Heat --
`
`Benzoyl peroxide
`
`0
`
`II a c'---
`
`2
`
`:::::---.
`
`O·
`
`BzO ·
`
`Benzoyloxy radical
`
`STEP 2 Propagation: Polymerization occurs when the carbon radical formed in
`step 1 adds to another ethylene molecule. Repetition of this step for hun(cid:173)
`dreds or thousands of times builds the polymer chain.
`
`Repeat
`ma ny times
`
`STEP 3 Termination: Polymerization eventually stops when a reaction that con(cid:173)
`sumes the radical occurs. For example, combination of two chains by chance
`meeting is a possible chain-terminating reaction:
`
`Many substituted ethylenes, called vinyl monomers, undergo radical(cid:173)
`initiated polymerization, yielding polymers with substituent groups regu(cid:173)
`larly spaced along the polymer chain. Propylene, for example, yields
`polypropylene when polymerized (although a nonradical method of poly(cid:173)
`merization is used industrially).
`
`+ CHs CH3 CH3 CHi
`
`I
`I
`I
`I
`CH2CHCH2CHCH2CHCH2CH
`Polypropylene
`
`Propylene
`
`Table 4.1 shows some commercially important vinyl monomers and
`lists some industrial uses of the different polymers that result.
`
`PGR2020-00009
`Pharmacosmos A/S v. American Regent, Inc.
`Petitioner Ex. 1060 - Page 5
`
`

`

`4.9
`
`Addition of Radicals to Alkenes: Polymers
`
`121
`
`Monomer name
`
`Formula
`
`Trade or common
`name of polymer
`
`Uses
`
`Ethylene
`
`H2C=CH2
`
`Polyethylene
`
`Propene (propylene)
`
`H2C=CHCH3
`
`Polypropylene
`
`Chloroethylene
`(vinyl chloride)
`Styrene
`
`H2C=CHC1
`
`H2C=CHC6H5
`
`Poly(vinyl chloride),
`Tedlar
`Polystyrene, Styron
`
`Tetrafluoroethylene
`
`F2C=CF2
`
`Teflon
`
`Acrylonitrile
`
`Methyl methacrylate
`
`H2C=CHCN
`CH3
`I
`H2C=CC02CH3
`
`Orlon, Acrilan
`
`Plexiglas, Lucite
`
`Vinyl acetate
`
`H2C=CHOCOCH3
`
`Poly(vinyl acetate)
`
`Packaging, bottles,
`cable insulation,
`films and sheets
`Automotive
`moldings, rope,
`carpet fibers
`Insulation, films,
`pipes
`Foam and molded
`articles
`Valves and
`gaskets, coatings
`"• Fibers
`
`Molded articles,
`paints
`Paints, adhesives
`
`Practice Problem 4.5 Show the structure ofpoly(vinyl chloride), a polymer made from H 2C=CHCl,
`by drawing several repeating units.
`Strategy Mentally break the carbon-carbon double bond in the monomer unit, and
`form single bonds by connecting numerous units together.
`Solution The general structure ofpoly(vinyl chloride) is
`
`Vinyl chloride
`
`Poly(vinyl chloride)
`
`•• ••• •••••••••• • •• ••••••••oooee• •• • •••e•
`
`Problem 4.11
`
`Show the structure of Teflon by drawing several repeating units. The monomer unit
`is tetrafluoroethylene, F 2C=CF2 •
`
`•••••••••••••••••e•••••••••••••••••• •• o•
`
`PGR2020-00009
`Pharmacosmos A/S v. American Regent, Inc.
`Petitioner Ex. 1060 - Page 6
`
`