SENJU EXHIBIT 2042
`LUPIN v SENJU
`IPR2015-01105
`
`PAGE 1 OF 6
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`

`
`THIRD EDITION
`
`- Introduction to
`Organic Chemistry
`
`Andrew Streitwieser, Jr.
`Clayton H. Heathcock
`
`UNIVERSITY OF CALIFORNIA, BERKELEY
`
`Macmiilan Publishing Company
`
`New York
`
`Collier Macmilian Publishers
`
`London
`
`PAGE 2 OF 6
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`PAGE 2 OF 6
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`

`
`Copyright © 1985 Macmillan Publishing Company, a division of Macmillan, Inc.
`Printed in the United States of America
`
`All rights reserved. No pan of this book may be reproduced or transmitted in any form or by any
`means, electronic or mechanical, including photocopying, recording, or any information storage and
`retrieval system, without pennission in writing from the Publisher.
`
`Earlier editions, copyright © 1976 and 193] by Macmillan Publishing Co., Inc. Selected illustrations
`have been reprinted from Orbital and Electron Densiry Diagrams: An Application of Coinpurer Graph-
`ics. by Andrew Streirwicser, Jr., and Peter H. Owens. copyright © 1973 by Macmillan Publishing
`Co., Inc.
`
`Macmillan Publishing Company
`866 Third Avenue, New York. New York 10022
`
`Collier Macmillan Canada. Inc.
`
`Library of Congress Cataloging in Publication Data
`
`Streitwieser. Andrew.
`Introduction to organic chemistry.
`Includes index.
`
`I. I-leathcock. Clayton H.
`
`I. Chemistry. Organic.
`II. Title.
`54?
`I935
`QD25l.'2.S?6
`BBN001M3hm4(HmmmwrBmmm
`ISBN Cl-O2-946720-9 (Intemational Edition}
`
`84-15399
`
`Printing:
`
`|2345673
`
`Year: 567890|1'3
`
`ISBN l]-[IE-ll]iEu1.'-ll]-Ll
`
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`
`456 "
`
`Chan 17
`Carboxylic
`Acids
`
`.
`
`becomes less important than the nonpolar hydrocarbon tail (R). Consider the reaction
`of a carboxylic acid such as dodecanoic acid with hydroxide ion,.
`K
`
`CH3(CH2)mCO0H + OH* ——d- H20 + CH3(CH2)mCO2‘
`
`.
`(17-3)
`
`The equilibrium constant for reaction (17-3) may be derived as follows.
`
`= iCH3(CH2)1oCO2‘iiH+]
`[CH3{CH2) NCOOH]
`
`0'
`
`= 1.3 x 10-5M
`
`Kw = lH*l[0H‘l = 10'“ M2
`
`Rear-ranging (17-5), we have
`
`+
`__ 10-14
`[H ]_[OH_}M
`
`Substituting (17-6) into (17-4) and expanding, we have
`
`a
`lCHa(CH2)roC02‘l
`_
`K _ = 1.3 x 109M ‘
`
`(17.4)
`
`(17-5)
`
`_
`(17 6)
`
`(17-7)
`
`Equation (17-7) is merely the equilibrium expression for reaction (17-3). The large
`value of K shows that the reaction proceeds to completion; dodecanoic acid is con-
`verted by aqueous sodium hydroxide completely into the salt, sodium dodecanoate.
`Note that the anions of carboxylic acids are named by dropping -ic from the name of
`the parent acid and adding the suffix -ate. Although dodecanoic acid is a neutral
`molecule, sodium dodecanoate is a salt. Dissolution of this salt gives an anion and a
`cation, which can be solvated by water. It is not surprising that the solubility of sodium
`dodecanoate (1.2 g per 100 mL) is much greater than that of dodecanoic acid itself
`(0.0055 g per 100 mL).
`
`EXERCISE 17.5 Equation (17-7) can be used to calculate the ratio of ionized and
`nonionized dodecanoic acid at a given pH, by inserting the proper value for [OH‘]. Calculate
`
`this ratio for pH = 2, 4, 6, and 8.
`
`D. Soaps
`
`The sodium and potassium salts of long-chain carboxylic acids (“fatty acids") are
`
`obtained by the reaction of natural fats with sodium or potassium hydroxide. These
`
`salts, referred to as soaps, have the interesting and useful ability to solubilize nonpolar
`organic substances. This phenomenon can easily be understood if one considers the
`structure of such a salt.
`
`CH3CH2CH2CH2CH2CH2CH2Cl-IZCI-l2CH2CH2CH2CH2CH2CH2CO3- K+
`
`The molecule has a polar ionic region and a large nonpolar hydrocarbon region. In
`aqueous solution a number of carboxylate ions tend to cluster together so that the
`hydrocarbon tails are close to each other, thus reducing their energy by the attractive
`van der Waals forces enjoyed by normal hydrocarbons. The surface of the sphere—lil<e
`cluster is then occupied by the highly polar CO2‘ groups. These polar groups face the
`medium, where they may be solvated by H30 or paired with a cation. The resulting
`spherical structure, called a micelle, is depicted in cross section in Figure l7.3. The
`wavy lines in the figure represent the long hydrocarbon chains of the salt molecules.
`Organic material such as butter or motor oil that is not normally soluble in water may
`“dissolve” in the hydrocarbon interior of a rnicelle. The overall process of soap
`solubilization is diagrammed schematically in Figure 17.4.
`
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`CO’
`
`H30
`
`FIGURE 17.3 Cross section of a micelle.
`
`grease,
`insoluble in H20
`
`soluble in H30
`
`solubllized grease
`
`FIGURE 17.4 Schematic diagram of soap solubilization.
`
`Certain bacteria can metabolize soaps. This degradation 15 most rapid when there are no
`branches in the hydrocarbon chain of the soap molecule. Since the naturally occurring
`fatty acids are all unbranched compounds, soaps derived from natural fats are said to be
`biodegradable. Before 1933 all cleaning materials were soaps. In that year the first syn
`thetic detergents were marketed. Detergents have the useful property of not forming the
`hard “scum" that often results from the use of a soap with hard water. This scum is
`actually the insoluble magnesium and calcium salts of the fatty acid. The first detergents
`were alkylbenzenesulfonates. Like soaps. they had a large nonpolar hydrocarbon tail and
`a polar end.
`
`R,—</¥ \>v—SO3‘ K+
`
`R —_- branched allryl chain
`
`However, being branched compounds, these early detergents were not rapidly biodegrad-
`able. Since the materials could not be completely metabolized by the bacteria that operate
`in sewage treatment plants, they were passed into natural waterways with the treated
`sewage and often reappeared as foam or suds on the surface of lakes and rivers. After an
`
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`458
`
`Chap. 17
`
`Corboxylic
`Acids
`
`L
`
`intensive research project, the detergent industry in 1965 introduced linear alkanesul-
`fonate detergents (Section 25.5.3).
`
`cHgcHg4ngm%—K+
`
`
`
`Since the new detergents are straight—cha.in compounds,
`bacteria.
`
`_.
`
`_.
`
`they can be metabolized by
`
`._J
`
`17.5 Spectroscopy
`
`A. Nuclear Magnetic Resonance
`
`The resonance positions for various types of hydrogens in carboxylic acids are summa-
`rized in Table 17.5. I-Iydrogens attached to C-2 of a catboxylic acid resonate at roughly
`the same place as do the analogous hydrogens in aldehydes and ketones. The very
`low—field resonance of the carboxy proton is associated with the dimeric hydrogen-
`
`bonded structure discussed in Section 17. l. The spectrum of 2-methylpropanoic acid is
`shown in Figure 17.5.
`The CMR chemical shifts of carboxylic acids are similar to those seen with alde-
`hydes (Table 14.4), except that the carbonyl carbon itself resonates at much lower
`field. Representative data are summarized in Table 17.6.
`
`TABLE 17.5 Chemical Shifts of
`
`Carboxylic Acid I-Iydrogens
`
`Type of Hydrogen
`
`Chemical Shift. 5, ppm
`
`CH3C00I-I
`
`RCHZCOOH
`
`RQCHCOOH
`RCOOH
`
`2.0
`
`2.36
`
`2.52
`about 10-13
`
`
`
`FIGURE 17.5 NMR spectrum of Zmethylpropanoic acid, (CH3)3Cl-ICOOH.
`
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