~ -~-fl1(il A111Jfl rrsan

ft11'tif1 i 111

I • I ,.1 I .. ~ :'1 I*~ .. ~ ~ n~11911lil:noun\I\\Jfl111JEin'"JJaLlJU\I\ijn~n-uu fl1111~1111ntto~n11LLtlnfl1 wn1~

if ~..r-1 _, ~ ~~ .. I ~ n1tlLLft: 't't EJYlLnU'ltl El~ Rli1Jtln1 U111~ fl111JR1JY4U11'1:\I\11~Rli1Jtlfl1~n1 EJ111~ LLa:

lt11~ri1~· RlltJ~Lflii LLa:l11:lu1Ju n11L;vn~on1f1fl1fuon·ln n11Lntnnao n11Lfi;EJll

n1fl fl1f1J El n tfi n 1.1 ~ fl~ EJ1tl a~ n 1ft fl1f1J El n•fi n~\ ~ R11EI"t ~ uf 1.1 ~ n; EJ11 tl EJ orr 1 l 1.1 fl L~U1iD~n1Jm1LLYlUa:fiDll~iiR111~l~fhatJR~tl1UU1flR1ol~tf

~

.,.!'!!! ... ~.,~~ Llla LflflnH11JYlL 1UU1JYlULLft1UnflnH1fl11't:911111ll

1. -;l1LLUn\I\11Yf~niutto~n1tlfl1fuantlnLLa:au ..,uMflth~ 'l lti ~ .

2. aiu1UR111~n1tltta~n1flfl1fuantln iJ'tiu~i1ft'qJ LLa:n.AuuL fiuufl1111911111n \u ~ ar.!! ... ~ • 11 _,

n11LLtlnfl1 LLii:LJJ1U1JLYlU1Jn1J91-1aU Ltl

3. 1Lfl11:~ft'l1Uiin1~n1u.n1v. tta~n1flfl1fuantln iJ'tiu~Lftu1ia~LLa:LtnEJtJLfivult1 4. L;un~oLLa:L;ivuwtl11fl1~m~n1f1tnfuantlnlt1

~ .

5. L ;ivuli~MU1n11Lfi;Ulln1flfl1ftJantfin li~MU1~ LLRfi~Rli1Jil Lflii LLRfi~911U1:n au~ . \,Y R1111:11~MU1 J.JftU~MtJ1~Lntl(u f11U1UJ.JfttlJ.Ja~Lntllt1.

6. \l1li~MU1 11.11. iLfl;Uli911U1:L11Yl~U ') lti

CM225 371

• 1Jt1141

,¥ ..1 " .., • I _,..,. • I' !If " .., .., ..1 . ll •• 1.'!1 . unuL n t.l1, a~n u ft11111:n au nuvuJ fi1'UJ a ~a Ln1~ ~ uli:n u a: tt e111 n w 1l1 v. ~-,.,,au '1.1

~~ tiam~nu-.,~ ~oH fl1fuau,a~-.,~•nfua\tau~m~~uD":nu,u1tt1fl1fuau ft11luun i{~~ii'MlhBfB (acyl group) m-3~'UD':nu 'MJ.i 0H tJ1~SJin~nL:,t1,1JLiJU . '1.1 . • '1.1 .

• 0. • II • .,....C,••

R Z

acyl group

L~El z = OH rrnJ1:nn1J flEl n1ttfl1funniin

mflmfua~inLiiWl1flBU't1;tf il'M~f11f.~~of@ (carboxyl group;- COOH -.,1a-C02H)

Lilu"MliYt~niu n1ttrnfuan~inLLu~tt111-.rJilfl,eJ~f11fuau~ri1~~ucnu"Mlifl1fllDnis LiJu '1.1 ~ '1.1

n1fi,.UfiUDiuwiin (aliphatic acids; RCOOH) LLa:n1~,-\i.ttuDf1LUJin (aromatic acids;

ArCOOH) ttl'Mi''Un1fi,,JJ'U (fatty acid) Lilun1fl,-itf'ILLelftLL~iln 11JitJ11

tf1UiJ1:neJ'U,el~'MJ.ifl1f1JDnf~ ij-.,Jj tllfl1DnfRLn1:LteJ1Jrl'Ufl1f1JDUR R11Utl't11\l . ·--·--~············ ..

LflilLLa:n1tJ1l1~th~~1n"MliLilll,f\IReJ\I ifiLilu"MliM\Iniul"Mli • '1.1 . '1.1

,.... ..carbonyl ,·.·- .. '. ~··

(:' 0'f. ..·hydrOxYl ii II :'--·~·:-:.··· a: : ,· "':'.

R~C.H:011: } \::::·'''·.:.~-,:.·-·"·

amonyl + hydrgg! ~----.. ca~oxyl group

'Mllfl1fllDnfR iJW1JUflLU'U01flfl111\i.tJ1111JJel~L1J7u&JLflfl-R171 011Wa1U~U1J': 0-H '1.1

LiiULL'U'U,J.iW1Jll1fl1 \-.,1tJ1fiDULLft:fJ~fllDni&Rfl tBDDU (carboxylate io~) fl1111ft11111tl,el\l

n11LLflni1 W1l1~n1tlLLa:iJ~ir.JLrlu1io~~='t1nth1lui1io 9.4

~ ~ ·R-C-0-H + H20 ~ R-e-o- + H30+

carboxylic acid carboxylate lon

fnfueJu,o~'Mlifl1fuontal'Jl'oofihia,-\i.tl sp2 ti1~il1iJ't11~LLU'U trigonal planar nn .. . .. ~

o:fiD11'U1L1n&.d'odi1111:U1'UnU iJJJli~UD':~fl1ftJo14lnaLtlU.a .120° fl1111tJ11~U1J': C=O 'IJ I 1

Lfun11 C-0 L~U n1flWBfDn (bmlc aCid)

372 CM225

a- , sp2 :o: ,' II ,' c' H/a~o;~

120 pm lllltiuc H-C=O 124° • 134 pm O=C-0 125°

fl11llt111tium: C=O

C-0 H-C-0 111°

o on~L ~'" i" RD-311 D-3'VI a.ifnfu onttufluL 1JRfl111ibnlJ11 o-3i'J 6 B tt1utnfu a utA" ij .. R1l1?4l~fhRu'ltauni1DDn~L~U ~:£iRil1wf11J1nLLR:£iRlJ1J~LU'UDLRn1fl1lvhfLiULtlU1rl1J luLLaRfilrrtiLLR:fil'nu Li1o-3~1n'VIlifl1fuonttnfiflL1l'JJLLUu41.ti 1hl~fl1fuou11D-3fl1fuoi1R-,. .

Lilus,R'nT,,-twl..tauni1luLLaRillrrtiLLft:fllnu ,,.LUW

iLinltt,\Mi .• 0a-

1 ,,,

' ... , . ...... ,11 '

...,.......c~ ;,H•-----~"'" R a+ -.o~ ..

I a. Ill II ~ fl111J'VIU1LLU\LOLRnfl10UUOU'Y1Rfl •

........ ,u.

..e :o: I

.....-. ..,.......c~,H H ep_.

9.2 fl11'L1unn1'ttA14uunian (Nomenclature of Carboxylic Acids)

9.2.1 i1oa1UIJI

4oR11i'ty'VI1a4oLQV.1~111~1nLL'VIa-3n11lJ,,~~-?4tJn1fl,fU'J L~u n1flfl1fuan'Ban

,uflti1" 'l LLR:n1fll111iu \ut1111"~ 9.1 LLR: 9.2 n11rl1'VIUfl.,iLL'VI""'"'4otnlitytio'nl!t1 n1n a, p, y, a,... Lill11nf11fuou~~flrl1J'VIlifl1fuonlDRLflu~1LL'VI14-3usRW1 1ul1Jil" .. -

tl1LL'VI14-3UR1URflflD 1suJn1 (co) • ~

c- --- -c-c-c-c-c-c-oH m E 8 Y p a

CM225 373

I

p 0 p 0 p 0 y a' II H2N~OH rOH CH3-CH:...CH-C-OH

I.· I . Y a . CH30H NH2

a-hydroxy-J3-methylbutyrlc acid y-aminobutyric acid a-aminopropionic acid (GABA) (alanine)

.& t ... ..J ~ -- -et111"f1 9.1 ocrUJqJu.a:YJll1-nEh'ln1flfl1n.JEln'lfanu1-3~Ufl

w1nlnn EJll faruicy .J ff -n12!11rl1111l 1Lfl11 fi71VM1/1lJ

HCOOH Formic acid a:ilu; formica . llfl

CH3COOH Acetic acid a::ilu; acetum J1fll, LtRt11

CH3CH2COOH Propionic acid ... . n1n; protus pnon 'Ll1\W

CH3(CH2)2COOH Butyric ~d a:ilu; ,butyruni LUtl

CH3(CH2)3COOH Valerie acid a:ilu; valeriana ~1n11nm.Ju\,..,

" ana Valeriana

CH3(CH2) 4COOH Caproic acid a:ilu; caper U.Vi:

CH3(CH2) 10COOH Lauric acid a:il'"; taurus tiu bay laurel

HOOC(CH2)2COOH Succinic acid a:ilu; succinum i51..iU

HOOC(CH2)4COOH Adipic acid a:ilu; adip l-nJu

HOOC(CH2)5COOH Pimelic acid n;n; pimelle l,.JuLt.Ja1

C6H5COOH· Benzoic acid D1'V\'nJ; luban jawi = benzoin I .

rht11U (gum benzoin)

COOH

Q--oH Salicylic. acid ;l~ana Salix . "

o-yHCOOH . Mandelic acid Lt101Ju; mandel ~ U.DiliDUtl

OH

!JJ!JJ~.;!."! LiJu.n1tlfl1fuani.Bin l'liu11. lfltl,t1ltJLiJu.l'lifl1-3LLR::~1'U1'Ufnfuau.LiJ\L LR,~ 'nn 4 n-3 30 ElttlElJJ iJtf-3ttr~tl~JJtl1LLR::la.i~JJtl1 n1flttfUtllli6JJtl"l~WltlqJs:i~\Llr::~ 1

n-3 6 ~'Ulrt LLR:nn~'U1ftLU'ULL1J1J Z -.,1a itr (c/s) n1l1'l,JJLRnR,.,~n"a LLfttitltl1L\L1tl~an • ' • 'U

lliLL U\L ni~u.n-:fiuuuim. vh.t4'U';lfl1'lRElJJL 'V\R1';l::ii~~1R-3 (fl.fl111~~ 3.4) 'U • . .. :

n11L1unn1t1l,tTu.iJ 4 1i fia ialfltJ'lJ ia1:uu IUPAC LLa::ia1::uua1-3o-3tA._,£j 2

LLUU tiae1-3D-31'llifnfuani.Ba (COOH-reference) ua::01-3D-3ti1u-.,\L-3 fEJu.Jn1 (ro-reference) 'U . .

.. A ~- --..I ~ t~ ..I .: ~ I ~ ~ ... .. I ..I . L\L,1\L1'U'UJJ 3 11r'Yl1J8n'Yl-3fl11lltl11 ·DLLR:::•t1LL'V\-..-3..,.\L1Jtt) ,Ul81lJqJ Lfl';l1nLL1'lR-3'Yl'VUJJJ1n

..,;a.,uflf-3LL1n iae1-3o-3lf~wa-31::uul,Yti1LR,LLRfl-3fl11llt111l'li n11e1-3D-31'la.ifl1fullni.Ba , 'U

374 CM225

LLRth1'41'U1Ufl1fUEl\4 '41U1ULLft::f11LL~1l-3~Ulf::fi 1fltJL~~Hl1n~1ifl1fuan~ftLi'UL.,tJ1flU .. .. IUPAC LLtlfl1-3flU~Li9l1Lft'!IUElOfl11lltJ1111Ji

i1~i'u1::uu ei1-3e-3f11 LL ~1l-3 fBu1n1 LLRfl-3'41U1Ufl1.fuau ~1u 1u~utr::fi LLft:: .. tl1LL~1.L-3~lniti1LL~1l" TBuJn1ll1n~wfl L~ll~fl1fuaua::flallt1ft1tJ l'Ji fl'l-3-D'1ll~litnfuan~ft

~ ' .. (f11LL~1l-3fBuJn1) Luutl1u~1l-3LL'ln Liu tl1LL~.\L" c.o-3 ~li1Un-3tl1LL~li"~ 3 'll'u·;nnt1ft1u

"" n'lfll'!la7u ro-3 ~-3Lilun'lfll~Ju~ihiur::fi~fl1fuaua::flall~ 3 'll'u~1nUft1tJRfl ~ .. ~

(t) y a

. ~ .~ .. ... " ... ... ~ ...... fl111"fl 9.2 L1J"U.Jt.JLfltJt.Jn11L1tJnn1tl L~l1Ut.J1-3,-Uflfl-3 4 1tr

I --------------------~

_!fJtnVqJ -· IUPAC ____ _j ... _qamo~:.!_~~~~_j ··-·~:.~~!~!!9.!J Palmitic add Hexadecanoic acid I 16:0 I 16:0 I Stearic acid Octadecanoic acid I 18:0 I 18:0 I Oleic acid J 9-0ctadecenoic acid j_ 18:~~-·--J __ 18_:_!_{~_:~L ... ...J

I ! I j ···-~in~~!~~--!~!~·--···-..J --~' 1 ~~~-~-~~.!~.~~--~~ ................ .! .... -~.~.~.?. .. ~~.: ... ~.=··········-·························· •...... !~.~.?. .. ..(~~) ............ . I l I y-linolenic acid I 6,9,12-0ctadecatrienoic acid I 18:3 A6

•9•

12 18:3 (ro-6)

a-linolenic acid I 9,12,15-0ctadecatrienoic acid I 18:3 A9'

12•

15 j 18:3 (ro-3)

oxalic acid (n=O)

glutaric acid (n=3)

malonic acid (n=1) succinic acid (n=2)

·cM22S

adipic acid (n=4) LLft: pimelic acid (n=5)

~ a' J3' y' ~ H-c-c-c-c-c-c-c-c-oH

y J3 a

HO~OH 0 Br

a-bromo-a' -methyladipic acid

375

~LU14fl1flUDf1UViffl4~iitl1f1JElfl~R 2 \'\li~1~L1J141JU L-DU uninuDifl (phthalic acid), .. ta T'lfuninuaifl (isophthalic ·acid) LLR:&n&muninuai~ (terephthalic acid)-

COOH

&COOH phthalic acid

(0-phthalic acid)

9.2.2 ioo'tw"d'

&:OOH lsophthalic acid (m-phthalic acid)

QH COOH

terephthalic acid (p-phthalic acid)

L1tlnLUUEIU~una~n1flUB9nn LUU alkyl "';El arylacetic acid fl1llfl11LL'Y1UltJLfl1L~U • · 11EJ~"li -CH3 lu n1flua9nn L-Du . ..

H'O I II

H-C-C-OH I H

H+ acetic acid trlrnethylacetic acid

9.2.3 is1tU,).i IUPAC

9.2.3.1 DJ~#.flft"r!.~D. (Aliphatic acids)

La en 11Ji"9n 4~LiJullfifl1fue'l4tienuo11~RflLLa:ii"IJ -eooH . - . .. fl1f1JEIU'IIEI~ -COOH B!hJa1u Llfi ii.,1LL\1\\W 1 l1JtiEJ~1:1JLU~El .. . £hU~EJLIJi\'\Rntl1ll'lfilfl11El~lDLfl1tl1f1JEIU Lt.Jiuufin~1 -e' n1ufeLiJU -oic .acid

0 II

H-C-OH

rnethanoic acid

yH3 ~ CH3-C-CH2-CH-C-OH

I 1 I CH3 CH2CH3 .

0 Q-cH2-8-oH ·phenylethanoic acid

Q~ CH3-qH-C-OH

propanoic acid

2-ethyl-4,4-dimethylpentanoic acid 2-cyclohexylpropanoic acid 2-pentenoic acid

F 0 I II

F-C-C-OH I r

F 2,2,2-trlfluoroethanoic acid

376

~ ~-CH3-yH--<(H-C-OH

CH3 OH 2-hydroxy-3-methylbutanolc acid 4-amlnobutanoic acid

CM225

QOOH cyclohexanecarboxylic acid 5-methyl-3-cyclohexene

CH(CH3)2

3-isopropylcyclopentane carboxylic acid carboxylic acid

9.2.3.2 !l1.~M~J1.~~~Q. (Aromatic carboxylic acids)

LUUtn'1flii,_,1i -COOH ·m~~uD:ntJ1~U.£ll1U.lltln LiU n1tlLtJUliJfan (benzoic acid) • • ,.,1a benzene carboxylic acid ~~Lilun1tlUtll1u.uiin~J1ti~Rfl n11L1un~an1lti1:t1u •

COOH

6- ~OH benzene carboxylic acid ma benzoic acid

0 3-formylbenzoic acid 2-methyl-5-nitrobenzoic acid

3-methylbenzoic acid (m-toluic acid)

2-hydroxybenzoiC acid (salicylic acid)

9.2.3.3 n1t1 ~,,,fvsniin ..... , ......................... . ..liiT~iJ .. .,. t~., ...... I 'YlL \h-nL fl L,.,LRan -n,.,Rn 'Ylll -COOH 2 ,.,ll •

COOH.

~COOH

v benzene-1,2- .

dicarboxylic acid (phthalic acid)

~COOH

~S03H

o-sulfobenzoic acid

¢~ COOH

benzene-1 ,4-dicarboxyllc acid

(terephthalic acid)

L1tlflfl1~ltrlfl.1fl1ftJ£lU~iifl1ftJ£lUL Yhnu U.R::tian1Utl1tl dioic acid fl1ftJ£lU 11a~ -eooH ti1u~lnft',.,liu.'Ylu~111nni1 Lilu.,,u.,.,u~fl 1 . ..

0 0 II II

HO-C-CH2-CH2·CH2-C-OH

pentanedioic acid

OtOH4

~ 2~oH

Br 3-bromohexanedioic acid

CM225 377

tl1LUU cyclic dicarboxylic acids llfiifrl1l-U.i -COOH ff'lft'El'ILUU,.UlLL'YIU~lu1'1 ~ ~

LL1'\1U L~U

QOOH &:OOH COOH

1,3-cyclopentanedicarboxylic acid 1,3-benzenedicarboxylic acid

.. ... .. ~--9.2.4 n11'L1'tJnLnaD!ID"n,.tttt11'Uiln'llan

Lnaa11a'ln1tlfnfuen'Bin LU'ULnaa,.a" la'V\: ,Lnaaua11 lJJ\ilr.Ju ua:Lna·aa~iiu n11

L1~n~Elfi1ltittlr.JL1r.JnUflfltDDDULLL'l::fl1lltl1r.JUDUtaaau

Uflfl taaau ltiLLrl laaau1JEl'l la'V\::, LLElll l~L ilt~11leaau ua::a:-iiulaaau

uau taaau 111~1n~an;t1 LtJ5r.~uan~1 ic acid ,;,r.J~an1tlLUu ate

~Lflfllaaau I + ,, uaulaaau (ic acid·-+ ate~

0 ·~aQl

. ONH4

common name: ammonium butyrate IUPAC: ammonium butanoate

~- ~ ~-9.3 ftJJtJtln1lii11Yt!Uh1n1tttl1'11JBn'llan

common name : sodium propionate IUPAC: sodium propanoate

C=O LLR:: 0-H LUU~UtJ::ii~1 fl1llfn1tlfl1fuan'BinLnflU1'11::1'\i1'1ltll~altiil LLR::

Lnfl~'UD":lu lfl1L~U1:1'\11'1 l11L&naii111n LL1'11:1'\i1'1 l11Lanal un1tlfl1fuan'Bin lflr.JLQ~1: ' . . ... ' , 1 fit I .. ..1 al l ... ... V.UC lJ tl1L~ULL1J-3LL1'1n111110'U') 'Yl~JJ'YI1'1·LLfl:ll1& liLRf1Rflt'l1r.JnU

n1flfl1fuan'Binff'IRCl1U::1Ja-3.L1'\R"HLR:,.a'ILL;i-3 Lnt~~un-:lt~lfl1L~u1:1'\i1'1nu 2

lliLRnR lt~r.Jiunu\u-,tJtflUJDf (dirner) tfiL~flfl ~tl1'\RflliL'KR1 LLR:n11R:R1r.Jtl1~'1R'Ini1 . ~ . . . ' . ~

111BU'Y11U~U~li1R lliLRnaL fi1 ')nU . . '

378 CM225

~ --Jl OH 0

~ ~OH alkene ketone alcohol carboxylic acid

,fiL~Bfl 31°C 80°C ggoc 141°C

.. ~.¥ 1 ~ 1!111 .... I ,¥ ... ... ~fiLtHlflL YUJ1J'Ufl1li1.1'U.1fl 2JLSfllU~'U.Ltl tl1fl1Jft'11£l~ LLfl,fll·U~ £llJL 'V\ 611J'Ufl1Jfl1·1~fl

tl11.1Eh1 l2.1Lant=t lou 1tl~9nti1 u n1t1~1..,1n 11ifl1"~iif1Tfu EJ'U.LU'U.Lt=t1Jtiii~fl'V\t=t EllJL 'V\t=t1w"ni1 "'U ...... 'U

..1 iJ ..1 ~ ... .. 1 .. ,., 1 ~ _, A . t -! ..,,nnL 'U.LR1.1fi'JJ"llfi11U£l'U.2J1nn11'V\1B""'Btln11 1 EJ:flEJll -n"w:'YlB'U.fl"fl11liLLflnfl1" L'U.

L1El"fl11-i'fl1liLRnaL'U1U~ftn &tl'V\~1Jfl1fll-nJ'U.lli~iJtl1 :j"'"'"lr:flLU'U.LLUU Z 'Vl'iElift' rhL~ " 'U 'U

1liLRnt=tifltl1L'U1U~ftnltl\liLL\L'U ~tl'V\RB2JL'V\R1SfiR"L~B'"'U.CflLLU1Jift'L~ll;f'U. (fl111" 3.4) " 'U " . 11

t.,,.un1.:~ '41'Ut 1'Uttl1'fu El'Ut mp bp n11a:a1 ml1

"' {oCl tel {S n1fl/U1100 mq

HC02H 1 8.4 101 ...

a:a1tJflaJ1n

CH3C02H 2 16.6 118 ...

a:a1tJflaJ1n

CH3CH2C02H 3 -20.8 141 ...

a:a1tJflaJ1n

CH3(CH2)2C02H 4 -5.5 164 ...

a:a1tJflaJ1n

CH3(CH2)3C02H 5 -34 186 4.97

CH3(CH2)4C02H 6 '-4.0 205 1.08

CH3(CH~)5C02H 7 -7.5 223 0.24

CH3(CH2)8C02H 8 16.3 239 0.07

CH3(CH2)rC02H 9 12.5 254

~COOH (aromatic acid) 122 250 0.34 ~

o5 . (aromatic acid) 160 300 'bia:a1t1

~

n11'ata1s

CM225 379

. ~ ~" 9.4 A111JLL1\1!JD"n1'tlfl11'UUn'DiU'I

n1flfl1fuan'BiinLiJUn1fiEien.t. (PI<,. > 0) iith PKa ~ 4 - 5 LLfiLiJUn1fiLLrin11~'U.ElL'l

(PI<a ~10) LLL'l:LLaL'lnauatf (PI<a -16) fl113Jft'11111nlun11LLflnt11l'V\Lthflau 4unuumv1n1~ ., -....... . - •. ~1 t ..

~El-3UDU 'DDDU A '.D'-311n11n1:~11tJElL·anfi~El:'U. 'tH fltl inductive effect LLL'l:l1,'11UUU'11

.. .. . H20 .. -e H3o+ R....,O,H + • R-0: + ••

alcohol alkoxicle ion

cr~H •• e

+ H20 .. o-2= + H3o+ .. )< y.:

G G .

phenol phenoxicle ion

-----------·--------------------------------------------------------------------------------.I

tP' R-C +

bH carboxylic acid

~-'1/ R-C"~ ~ . b9

~-~e -l R-C · + ,, 0

carboxylate anion ·

I ....... ~ I .

9.4.1 NR!I£h1M~LLfi\U1fiNfU1.n1ftn1fl

9.4.1.1 !;l.~-;rJ.n.!nf!YQt!¥!!.f!.ftf!.f!!. · - tl 1 ,.,.. -11 •••• ~ " .. - fit Lnfl11nn11n1:-;t1tJ 1:1au tltJEl.:fiEl11flllft1l1·~ ~nn111Jft-3 tl1ttn11fi-3ElLL'lnfi1El'U. . ~

N1u~un-:'Bn111 .Yh\~unu tnnnuihmtt11l1~111n4~ fl1.}11LiJUn1fl~~ll;fu (fh pKa afla-3)

inductive effect 4unu1:tt:.:'J:'V\~1-3'V\~tl-3DLinfi1El'U.n1J'V\~fnfuan'Bati1tt Wl'V\i'u'V\~LLaaila 1:ii~atiaftll1~n1fl,~ll1n"n

"~-~iLinttTBU

¢::::::3 0 ¢::::1 0 II . . II e

z~c-C-OH :.ii•i=::=:l.,!:' z-c--:-C-0 + H+ c:::::) r::::::::>

"IJ\~LinttTD'Il .

380 CM225

110 H-C

o· HcJ

H 0 ·~- 1.~+ II

CI ........ C-C

~-

~· 0 ~- . T ~+ II \ 0-H

3 \ 0-H

I \ H 0-H

Cl ........ £~c,

Cl 0-H ~-

P.~a 3.75 4.74 2.86 0.64

0 H2 H~+ ·/;

H c-c -!-c 3 \

. I ~- 0-H

P.~a 4.52 4.06 2.84

-•"" -~ ... I ..a 40io ..1 ... I I ... ..1 'Sufi 9.2 L1J'UJ1JL'YlU1J~&11£h1~2JLL'Yl\lflWfl inductive f.llJflOfl1LLflnfl1f\~'Yl1JO~n,-tl • v .

' ~· _. • ' •• I 9.4.1.2 fli111Ln~n:-DB"V11JB~fiB1JflfJ11JJDUfi1UVIU"UDAn1 ........................... .., ................................................... .

lfl1~.rn~~t.\m~.Y\nJJ~. Acetic acid

'V\a.iLLDl&LiiU.ytthLL 'V\U~UDRW1'th \~Ril1l'm1fiL ~ll;f\4 ................................................. ~····················· Iodoacetic acid

Bromoacetic acid

Chloroacetic acid

Fluoroacetic acid

Trichloroacetic acid

Trifluoroacetic acid

1 .. - - .. t ..I..J \-~ ..:. ~ 'V\llfl~manfl,-ouou flU inductive effect 'Ylll1 l'\Ril1l'4n,.tlL l'4lJ11\l ........................................................................................... Methoxyacetic acid

· Cyanoacetic acid

Nitroacetic acid

·cM225

r,,,m,

CH3COO!:!

ICH2COO!:!

BrCH2COOf:!

CICH2C00t!,

FCH2COOf:!

CI3CCOO.tl

F3CCOO.tl

CH30CH2COP.t!

NECCH2COO!:!

0 2NCH2COO.tl

pKa

4.74

3.10

2.90

2.85

2.59

0.9

0.23

3.6

2.5

1.7

381

9.4.2 n1'tUtlntl1!1D"n1flUDf1'LLIIin

U';JitJ~L~tJ1-lfl~ ltiLLri'

9.4.2.1 !i.ft?!ll~!J.?!JJ!Y1lfli (Hybridization effect)

.. ... ..... .. ..... .t!t 2 .... fit . ... ...... • .. 3 .. ... fl11tJfl~,fl~1~LtJ~'111h'lfflfl1tJ'Y1a'Jfl4t1 sp tl~flLanfl1fl~ Ltltl011'Jf~t1 sp L ~a~;,1n3J

in~m::,f.i~aafih1a s lnnn11 L-rl~ n1tutn4f'lfenLiJ~n,.fiLLrin11n1tluD9nn Ltia~';J1nl'lli - ..

fl1fuanlgaLn1:nutnfua~'Jfitfl sp2 lflEJtl1-J ~~LLflnfi'1iln11l'l~fl1fuanlga~Ln1:nufl1fua~

.. 3 'Jf'Utl sp

PKa

sp'l \ 0

' II

·etC,~ benzoic acid

4.2

• .J . .J ~ 9.4.2.2 #JR'JJD.JM1/U'YIU'YI'Yii.JUJU"DU ··············v····························

COOH COOH COOH

sp3 \

\~ 1!0 H3c~c,

0-H - acetic acid

4.74

¢ 6 ' 0 · N02

9H OCH3 . N02

p-methoxy benzoic acid m.nltro p.nitro-

P.~ 4.46 4.19 3.47 3.41

OH N02 '

~

a-nitro

2.16

'nJfl9.3 J.II,.S-3'MlJLL 'n\L~~~fien1nLftni1,.8-3n1fiU8 f 1UUfin .. . .

382 CM225

., .. ~- ... I t • a ~ ... -., ..;... I ..

n1fl 'flf1111JEJn·D6n1Jfl1 pK8 2 fl1 L1JEIL1J'UJ1.JL flti1Jn1J pK8 ~El-3n1fi'YUJ'V\11fi111JEln 'U

'Ba 1 'V\3.i~iifl1fua14L Yhn'\4 fh pK1 ,El-3n1fl ~,,,.funn'iinii~11l'aun11 'V\Jjf11fuantaaLLfi 'U 'U

a :'V\ 3.i L il '"'V\ 1i ~"aLi~ n fl1 El '", El-3 ii n 'V\ li'V\ it" W1 'V\ ~1J n1fl LL 1J1.J H02C-(CH2)n-C02H fl1111 'U 'U 'U

I t • .! ,¥ LLflnfi1-31:'V\11-3 pK1 LLa: pK2 afla-3UJO n LYUJ'il'\4

.a • ... ""' If .. ~.. .. fi1Tl"fl 9.5 fl1LLtlOtl1fl~'t101fllf.l£l~ 'fJn1flfl11lJDn"DBnU1~'UUfl

rfl,.,m.,

HOOC-COOH

HOOC-CH2-COOH

HOOC-(CH2)2-COOH

HOOC-(CH2~-COOH

HOOC-(CH2)4-COOH

():COOH COOH

qCOOH ~

COOH

.. ~ ~~ 9.5 fl11Lt11UaJfl1tlfl11tJDfl'Ditfl

fan1fl

Oxalic acid

Malonic acid

Succinic acid

Glutaric acid

Adipic acid

Phthalic acid

lsophthalic acid

Rh3+

HI 30-60 atrn 150-200 °C

9~5.2 Lfl;tJuTtatJUDMtJ1ooniLtti\6

pK1 pK2

1.2 4.2

2.9 5.7

4.2 5.6

4.3 5.4

4.4 5.6

2.9 5.4

3.5 4.6

9.5.2.1 ffltJn11DEJn'i~fiBUD6nEJliEJtfl.ltvnii U6~UD6~~ll~ .............................................. _ .. ..,. ....................... . (~11ia 6.6.1.5 ua: 8.6.3.1)

CM225 383

~ •'1 .. 0 .. ~" .. ~· ~ a'l .. ...~ I 'YI:3LUlf4fl Lllfl LLC'4: 1 LL£lf40£ltUlft .vnaan-n Lflftfl1[Jfl1£l£lO'lf Ltlft'YILL1:3 L'Jf'U KMn04,

K2Cr201, H2Cr04 llfn1flfnfuan'iin i1~i'uLL£lfttlLtrfinnaan'ilflRlflvi1aan'ilfltfarh:3 ~ .

Eiau L~u Ag20 ua: Ag(NH3}/ OH- llfn1tlfl1fuan~anl.i

'~ 0 oxidize ~ II

R,....C,H R,....C,OH

aldehyde carboxylic acid

OH 0 0 I oxidize II oxidize II

R-C-H R-C-H R-C-OH I H

1° alcohol ald•hyde carboxylic acid

e 1) KMn04 • OH, A

2) H3c9l

9.5.2.2 IftP111!~fl!J.'P.!ftl.ijf!_,_~HM.,EM.'J.'!J!l.tf (~1-ia 3.7.9.4 LLft: 3.8.2.7)

LL£lftflU1J1:3'Jf;lfl LLa:uaa ltnf f111Jimv1n1Jltl1a:a~ vi'au, a:3 KMn04 Lnfl n11 LLtlnin~uctiua:~uctnJJllfn1flfl1fuan41n

384

~

R • R . \ I I

,c::;::q + KMn04 H H

I I I I

R-C!C:C-R + KMn04 I I I I

H3C, : ,CH2CH3 ,c::;::q

H H

R H~o .. C=O ..

Hd carboxylic acid

H30$ NaOH, H20 .. A

+

R +

I O=C

bH carboxylic acid

R R I

C=O + O=C Hcf

- \

C~CH3 o=c OH

propionic acid

OH

CM225

I I I

CH3-C$C-CH2CH3 KMn04

NaOH~~ 4

H30ED H3C\ __..;;...-~~ C=O

Hc:f acetic acid

~ ... ~ ., ... IBu ... ., 9.5.2.3 .. ~J!OJ!~Ul!J.! .. !!~~R.~.~UUY.H ..... (Y\1,0 4.10.~) I

propionic acid

LLoaileuu"U~'U~ii,u1fl1L~"Uti1LL\IlU-3LtJ"Uta nnoon,,flR~1tJ KMn04 L~\llaj -COOH ~ ~

R Q-C-R· - H R, R' = alkyl, aryl, H .

propylbenzene

e KMno ... oH ..

A

benzoic acid

~ I .,tl .. _ ... L w ., ... ., 9.5.2.4 .. ~JL~ .. D.n~J!J.rrr!.~nfl.'!V..§ ... tl!N. (\1\1-no. a.7.4)

LU'UU~mtJ1-n0-3,1/naffTnu ntJLLD1tU~'U (CI2 \1\10 Br2) L'U R11l'4:~1tJ NaOH l~n1fl

fnfu on,~n

carboxylate anion haloform

Br2 (excess) .. H o• 3 .. '

' ... ... f': - ... ~ 9.5.3 LCA1'UIJ~1nft1'Su1::notJ nn1::D\6rl'SU

.• 1 ... .. .. ~ ... ... ., .. 1 ... .. ..t ···- ... tn1lJ1:nou a'V\:OWY11tJ Lll'U n1tlJ111£EJUJUfl ua:oo1LLn 'Ul'IL'YitJ11 Tl1lJ~n1t.nnu

·,r,u;j"u~" (C02) LLa:,D1fl1,aRL"URil11:n1tl ~:l~n1flfnfuon,in~"ii1-rlfnfuo"Ulnnn11 tn1U1:nouuulat1Lii11 1 o:t1o11

CM225 385

a- a+ a+~ •• r •• a-R-MgBr + O=C=O __.....

·o: • .. ee R-C-0 MgBr

H·o· 3 •

:o: II

. R-C-OH . ..

Li pentane

Mg .... dry ether

·~· 9$ R-C-0 Li

VCH2U

organolithium

H o• 3 •

:oz II

R-C-OH

\/ 1. C02 \/ ~MgCI 2. H30~ -. ~COOH

:Z,2-c:timethylpropanoic acid

9.5.4 Lt~1sa.a\l1flft11"tl1tnou luln1l

n11lultt1latflutn1lf (nitriles) LUW11a:a1vn1tt ~:lti'n1ttfnfuen'iin LLa:LnsoLLell LlJL iltJll n1LUUU~MtJ1' UL1Jn: ltl'LnR O'lle-3n1tttl1fuen-iin LLli:LLell LliL ilu

H3o• R-COOH M1o Ar-COOH

+ NH/ R-C:N M1B Ar-C:N

H20 R-eo& M1B Ar-C009

OH

+ NH3

LLeRLL~~n Jutn,.,( Ltt1ulllti~ntJ~mrme-3 UBftflftUliJsl nu NaCN .IJ1-3LUUU~MU1 ... "' - ... 1 ........ m1LLfiUfltt1tJU1flli e Lnli

KCN. I ~CN

386

2-bromobutane

Br~B; 1,3-c:tibromopropane

2-methylbutanenitrile

Hao• J M1e .. COOH

1. N.OH 2-methylbutanoic acid 2. H3o•.

H·o• 3 • HOOC~COOH

glutaric acid · (dlcarboxylic acid)

CM225

ttwriuuD T1uvin ~u ~r11l ltl'·;nnn1.,...R81Jfl1tu,D1s'lfs Tvliln (arylsulfonic acid) ... • ... • " r ... ... ~ ..r " r :-~ .. " .., ,. .. nu NaCN ~1ElLtt1tiiJ';J1nLnaa LflD!''~'uvvntJ CuCN 'lh1LIJEl Ll1Lfl1 LftR';J: Lfi01flLLEl L1LLIJfln

~S03H

~CH3 arylsufonic acid

NaOH ~

diazonium salt

CJ:sEO,Nf -~-~-: ...... o:c=N , CH3 CH3,

aromatic nitrile

aromatic nitrile

9~6 tJfin'!l1!1ih1n"ttlA1411onian (Carboxylic Acid Reactions)

t.l --- ..a rJ 9.6.1 !Jn"I!J1fiLLftfh1fl111JL '14n1'fl

9.6.1.1 yj_ljj_fi.J.ff.1J.f~U,.; l ~Lna £) UR:LLfi RlD 1fl1L ';1\l

Lnaa11a~ 1a~:LLaatnlaa:a1uli'1lfl' Ltl~'iuLnaa11a~ 1a~:~un L~u Ag, Hg. Pb i.i ... 1 .. .~ ·' 1 • iJ • ""... .. ROMnL: flL 1Lft\lfiiJ1fl11\l n11R:R1ti"K1ftflft~ fltiL~~1:LIJElL ULnREl11El~01fi'YliJfl111JEl\l

~. .~,._, fi~Ufl 4 O:fl£11111\l LlJ

CM225

0 0 II II

2 R-C-OH + Zn ~ (R-C-0)2Zn + H2

0 II

2 CH3-C-OH + Zn ~

0 II

R-C-OH + NaOH ~

lJJa:I1UU1

i1~u11~JJnm~n 0

o-8-0H + NaOH --

lala:111u11'1

0 II

R-e-o- Na• + H20

1:11u1f1

387

0 II ~·

R-C-OH + NaHC03 --... R-c-o-.Na+ + C02 + H20

i.1~u!:l~J.J!imP.:t . 0

Q'-8-oH

"

0 I

+ NaHC~ - Q'-8-o-Na• + C02 + H:z()

.. 1•- ., T ., • ., t" • 1 ,.. • • ,.. 9.6.1.4 J:I.D.TJ.1.(l!J1Y.U.J.~Hfli!J!l.Ul.'='..Yl.1f.l.EJ.;.~Y, -v\LntUlLLElll liL lUJll -v\1BLnaea:li'U

f11ll~1i1J

0 0 II - II~$ R-C-OH + NH3

__.... R-C- NH4

\ala::11u1l'1 mi~LLBII laJL ilua~

0 ~ $ II •• R-C-~ N(CH3h R-C-OH + N(CH3h __.... . I

H \ala::11u1l'1 3°amlne 'nlae::llu

a::11u1l'1

-·-~ ........ 9.6.2 ul)n1'!11'tflntf16

n1flfl1fuan'Bin~n;t;,Lfti1u LIAIH4 (~11ia 6.5.4.2) -.,;a 11D,1U (BH3) t~

LLBftnBDElftUJllllii. (lliLfifiU~MU1L~at,Y NaBH4 LiJ'Uft1ntl1R) ~ .

388

0 II LIAIH..

R-C-OH --et~he~r~..,~

carboxylic acid

0

R-g-OH _B_H.;;..3 -• THF

LIAIH4 ether

H o• 3 ...

H o• 3 ..

' H I

R-C-OH I H

1° alcohol

H I

R-C-OH I H

CM225

9.6.3 tlfimu1t~itiA1fuoM1ttoun lwtf (Decarboxylation reaction)

iJ -·-- .., .. ., 1,1 ... ~ f' ... ... f' I .. L -ulJnnnnn L-ufl11111EI\Uf~ LViE:rnflfl111JEI'U LflElEin L'lfflVln'V\11 -COOH 'V\1EI COONs ~ . .

lttu'V\aEl11Lnial'lfLfiu11t~a~n1tt n1J f'l1fJ1tau (soda lime) ~~LiJUft'11~Rllt~EI~ l'lfLtlullltrfl1an

l'lfti' ua::ufla L'lu11a an l'lftf

0 0 II II

R-C-OH Mo R-C-ONa IOdallrile .., R-H + Na2C03 (decarboxylation)

0 Q-8-oH soc:taUme .., 0'

(decarboxylation) ~ b +

9.6.4 tlfimu1 Heii-Volhard-Zellnaky'

LiJUn11LL nufilu lfl1L~Uti1LL'V\U~UBIW1 (a-H) 1.1EI~'V\lifl1f1Jonlia tl1 ULLlJ laL~'U .. (Br2 ,.,;o C~) Jj~omorw ,.,;o PX3 (X= Cl, Br) LfJ\li1Li~ ltl' a-haloacids

,r1R~J~.1JnmP.:t CH30 I II

CH3·CH-C-OH + Br2

isobutyric acid

p ...

p ..

0

R00H + HBr

Br

CH30 I II

CH3·C-C-OH I Br

2-bromo-2-methyl propanoic acid

C1 H3011 1) N OH 2) H 0E& CH301 3 I I CH3·C-C-OH aq. a .. -..:......:::.......-...; ... ~ CH3·C-C-OH I I ~ OH

r

2-hydroxy-2-methylpropanolc acid

1 tJ-- .r ... ~ ~ ... ...t I iJ ~ • 1Jn1UlUli'IStnliUnLflll 3 Tt1U llN?l1ULL1nL UL!JQ1lJU flO Call Magnus \G'J Hel (flfl. 1849-1926) LLR:

Jacob VolhsrrJ (flfl. 1834-1910) anu'ti1Uflrtll Nicolay Zeinsky (flfl. 1861-1953) LiJuunLfliifm.fu

CM225 389

•

s.a.4.2 ~.!!l~NJ:~~mtiJ9..1!q!g

CH3 0 I II

CH3·C-C-OH . I Br

CH o " I 3 ii

CH -C-C-OH 3 I

Br

CH3 0 I II

H2C-C-C-OH I I H Br

NaCN,_

ale. KOH

CH3 0 I II 1) aq. NH3

2) H,tf • CH3·C-C-OH I NH2

2-amino-2-methylpropanoic acid

CH3 0 I II

CH -C-C-OH 3 I

c=N

e CH3 0 H 0 I II ~ CH3-C-C-OH

I

COOH 2,2-dimethylmalonic acid

CH3 0 I II

H2C=C-C-OH

. methacrylic acid

9.6.5 tJfiins1n11'LLfiHrflllf"1'L\JHif1\1LtJHiHtiD\1n1'fUUJf1'LLIIin

'VIli -COOH LiJ'U'VIliti~~Lftnfl1EI'U LL~:LiJ'U meta director DLRn Lfl1lvhf~~Li1LL'Y1'U .. .. lDLfi1L~ou\utl1LL'VI"-3'1/f11~El~'VI~fl1f1JEin'i~ (i1iEl 4.7.2)

0 II C-OH

6~ . cone. H2S04 ,.., + cone. HN03 ---~~

0 II ;(oH ~NO . 2

m-nltrobenzoic acid

acyl group', ____ ---· ',i o:

• II : : R-CiOH ·-------

Ntf3

Carboxylic acids

390 CM225

0 II

R-C-CI Acid chlorides

0 0 II II

R-C-0-C-R Acid anhydrides

0 b

. II

II R-C-OR Esters

R-C-OH Carboxylic acids 0

II R-C-NH2

0 II

R-C-NHR Amides

0 II

R-C-NR2

11·- .. IB ~ .. 9.6.6.1 .. !l1.1J.1.1:1.!.11111Qfl.LJ..(J. •• !J1~'-•• ~.!!

n1tlf'l1fuen~anrhtl~ffit11 nu~nfDUSflSD~1~ (thionyl chloride; SOC~) ,_,7£1 SOBr2 . . .... ~ ., .. . .. ., .. ~~ ,_,1£1 PCI3 ,_,1£1 oxalyl chloride L,_, UD'"llfiLLll 'Sfl ,.,1£1 'D'lfSLLll 'Sfl (acyl harldes) tl-\1'\.l

0 II

R~C-OH soc~

0 II

R-C-OH + CIHO 0 Cl

oxalyl chloride

,r1.~.tt1~.Y!lmP.1 0

Q-g-OH N02

CM225

soc~ ...

... 0 II

R-C-CI + HCI + S02

acid chloride

ft R-C-CI + HCI + CO + C02

acid chlorid~

0

Q-g-CI + HCI + S02

N02

2-nitrobenzoyl c~loride

0 II

,/'y. · C. 'Br L_j + H3P03

cyclopentanecarbonyl bromide

391

' . .. n11Lfl1ttll acetic anhydride l14~flR1\'\n11lll,Yn1'nliflu1~1nn1flLUl'Anntl'1uf111ll .

i'EI'\4~~ lflttii trtethyl ·phosphate LU'\4tl1Li~ lti ketene ~~n1tl~ffitt1tlEill1nun1flLLEl'Annl~ acetic anhydride tl~ffiu1it'~EI ketene process

0 II

CH3-C-OH 750°C

0 II

CH2=C=O + CH3-C-O-H

ketene

ketene

n11Lfl1ttlll14\fa~tl~uf1n11li'ti~Mt11111111ifiJ1fl~m\'\1Jli"~ n-:tl~n1flf11fuEin4 fin 2111Lanan1Jn'\4LLa::iin1'T21ifiJ1EIEin 11aJLana • •

0 0 II r-.--------~ II

R-c:~~ ___ ~ __ 110-C-R .acid anhydride

trifluoroacetlc acid

t'llflinusu t,.tfJ7lflii,141fl1~ 5 ..,;EI 6 o::t1E11J Ltl1EJ11,1nn1nJitlJ,·;nnn1fl tfJ~f usniin

392

9.6.6.3 y!i_fi1.~.1.U11.\0fl.'.~ft'~11~f. (Esterification) (~11To 6.6.1.2) I

n1flrnfuon'iinLuiuwihuomfloiV 2 ii ;~d' (1) Fischer esterification tl~mr.n1:wli~n1flrnfuEin'iinnuLLoanorJEia l,Yf111a.Ji'EI14

ua::lin1fl L'Jt'\4 ~4 ..,;o H3P04 Lilt.~.t11Li.;

CM225

ho R-c1

~------------, ~ 9.:::1:1 __ +_ _ -~::-o-:-R1

carboxylic acid \

ho R-c1

\ O-R1 + H20

carboxylate ester

(2) tJ~ffitnn11LL n~~ LL1.J1.J ~2 ltuJLtJa v~n1flfl1ftJon~snLiJ~fl1fvaniLsf1uau ~DDDU :A~LiJ~it1flaLol~a L~1LL'Yim:tLLOt'lflt'lLLlJlatftJ13J11ii ~1DL3JnaLLDlatf

~.o R-c

1 \ 0-H

carboxylic acid

+ NaOH

~!.~.tb~J:J!imP-1 0 II

CH3-C-OH

acetic acid

0 Q-C-oH + NaOH ------~ .. -..

...

u·- .... ~ ~ 9.6.6.4 .JJJ.TJ.1ltJ.TJ.11.VJflll.; .. ~.fJ.

' 0 h /; r\-C

'oe carboxylate anion

... "'

ethyl acetate

~.o R-c1

\ O~CH2R1 ester

butyl benzoate

., ~ !'I ~ .. ~ ... ll !1" .. .. .. I ~ .. ... •

a~ '1/fl Lu~a~~~tr'YILfl1li1J Lfl Lflllfl1~·;nnn1flfl11lJEln'lfan v1nn11 au~utr-nufl au ~ ~

...1 1 .,. .., !'I ...1 .1 tJ • •• ~ .- • • ll .., • L 'U.El~';J1n LLEl3J 1J L ~ll LLt'l:D~1/UL u'U.LlJ W LlJ El 111 !Jn1ll1 n1.Jn1fl fl111.J Eln'lfa n-;J: Lfl L n tHl

tJ~ffiv,d\fLfl1li3JD:wt1u1~-nitfllu~flft'1~nnlllti LLtilliL~ll1:ntJn11Lfl1li1JLu,.;o~tJ~u~n11 (~1-ia 10.4.3.3)

tJ1iffiv11:~1,~n1flfl1fuan~snnuLLall lllL itv, a~i7ut11llnii~1onilvnii LnfiLnaa w ... "' ~ "'

1 ... .. .. .., ,.._ • .. ... ... ... .r ll ... ., ~ ~ ~ LLEllJ lJL ~llll ~1ElLnaOD~1/U 'JJ~LlJEl L~fl111J1El~';J:La'lll\1LLa: LfiD~ '1/fl fl-3~

0 0 0 II II fl11lli'ou II

R-C-OH + NH3 .. R-c-o-NH"+ R-C-NH2. + H20

ammonium salt amide

0 0 9@

0 II II fl11lli'ou II

R-C-OH + R1NH2 R-C-0 NH3R1 R-C-NHR1 + H20

1° amine amine salt amide

CM225 393

394

i.1RP.1~.lli\mP.:1 0 H-8-oH · + o-{H3

N-methylbenzenamlne ~amine

toluene

1100C

N-methyi-N..;phenylformamlde

CM225

Fumimycin

3. ft111fl~:~1tltl1fl~Rfl • (1) CH3CH2CH2COOH

(2) CH3CH2CH2COO-~

CH3CH2CHCOOH I

(3t CH3

O COOH (4)

CM225

1'!11 II; .cl LLVtiRD\llfl 'Vflfl 9

Cefaclor (antibiotic)

395

4. n11L'1th1~1iuwn1~n1fi11El-3W11t.h::naufialt.Jdialfltu1 . .

N02 0 .·dOH UOH (YloH UOH ~

A B c D

(1) C > B > D >A (2) B > C >A> D

. (3) A > C > B > D (4) D > B > C >A

5. 1 .. ' iJ ·-' fl1-3RTl-3 fiL 14n1fiLLn't1Rfl • o-CH2·COOH 0-9-cooH

(1) .(2) Cl

Cl Q-CH2·COOH 0-¢-cooH

(3) Cl (4) Cl

6. ' ... I -' n1fl flllfl1 pKa R-3'YIRfl • • COOH COOH

¢ qN02 ~

(1) N02 (2) N02

COOH COOH

H3C*CH3 ~ I~ N02 .

(3) CH3 (4) N02

1. R11'L11:nau A, B, c ua: o £ifi1 pKa -na-31'L11f1El14 J:i_lu1fl1-3n1-3LiJu 25,.23, 8.8

ua: 4.2 f11lJa1iu iafl11lllfllajtn'ltia-3

396

.... .., ......... . 0

~~H Utt

A, pKa = 25 8, pKa = 23

(1) B LiJ14Ti1fiUfin11 A

(2) B Lilun1fiDEl14n11 c (3) o Lilun1fl~urln11 c

(4) A, B LLI: C LU14n1f1Ufin11 0

C, pKa = 8.8

~9 Utt D, pKa =4.2

CM225

(1) 2-methylbutanal

(3) 3,3-dimethylbutanoic acid

s. tn1ti£JltJdti£Jtn1Lfl 0 II

· CH3-CH2-CH2-CH2-CH-C-OH . I CH3-CH2

(1) 2-ethylpentanoic acid

(2) 3-methylpentan-2-one

(4) 3-ethylpentanoic acid

(2) 2-butylbutanoic acid

(3) 2-ethylhexanoic acid (4) 1-ethylhexanoic acid

10. CH3CH2C(CH3)2CH2CH2COOH flDft11Lfl

( 1) 4-methylhexanoic acid

(2) 3,3-dimethylhexanoic acid

(3) 4,4-dimethylpentanoic acid

(4) 4,4-dimethylhexanoic acid

11 .. tn1dti £l tn1Lfl

(1) 4,4-dimethyl-3-hexanoic acid

(2) 2-ethyl-3,3-dimethylpentanoic acid

(3) 3,3-dimethyl-2-ethylpentanoic acid

(4) 4,4-dimethyl-3-carboxylhexane

CM225 397

13. 1f11~rn~1flfi~ 2-hexen-4-ynoic acid 0 '

~ JoH ~OH ~ «OH (/ {H

(1) (2) (3)

14. ft11~1:nau1flnnaan,,flal~n1flfl1fuan'ftn .. (1) methanol (2) propan-2-ol

(3) H-C:CCH2CH2CH3 ~

(5) 'YI~ a, b, c LLS: d

16. ~~m[J11fl~1~n1flf11fuan,ftni1Lil[J1ri'" 0

A o-CH~-H

8 o-CH2CH2Br Mg C02 • .. ether

o-CH2CH3 KMn04 H o+

3 .. Ho-c

o-CH20H K2Cr20 7 .. H2S04

D

0 .. ~

(1) 1. BriAIBr3 ; 2. Mg/ether ; 3. 002 ; 4. H30

(2) 1. CH3CHCICHJAICI3 ; 2. KMn04, H30 +

+ (3) 1. (CH3)3CCI/AICI3 ; 2. KMn04, H30

(4) ,jg 1 LLS: 2

398

H o+ 3 ..

+

(4)

CM225

~0 (2) OH

0

+ H)l_OH

~0 (3) OH

~0 (4) OH

0

~OH Br

~0 0

0

~OH OH

(1) (2) (3)

<4> lliLnt1t.l~ffiv1 20. i1LaBnlfliifl11aJL1tiBn11Li1fht.l~ffiv1~B-3it1flalBl~&fann~~.,

(1) (2)

... ~ -(4)' ?4B ')n'Ut'Yl-3 3 -uutl

21 .. LBRL nBf'Y11-3ti1U~11111';'11nn1flLtl 0

CM225

(1) HO~ ('YCOOH'

<a>v

~ OH

d'OH

(3)

0

(2) HO~ ~COOH

<4>v

,.cj' ........ _ ...... o .. :~J i :

t ............................................ .J

399

400

22. LLtift::iatia,tJd'LiJoutl1tt13JLL1.J1.Jttn-Nfl ia~~"l~annu~1aLLrf'L~l~nnti'Eh1 .. ' .. ( 1) R1tl1.Jfl112J LiJoun1fl~ a"n1flfnfu an 'Bin

0 0 Cl .o 0

~OH > ~OH > A)l_OH .> CI~OH Cl

............................................................................... ·~ .......... .

0 0

~o~>~H ' · > /".../'oH > /"o...-.....,.

....... -......................................................................... • ......... .

(3) ~EJ~EJ"r11d' fia 2,2-dibromopropanedioic acid

0 0

HoVoH Br Br -

' ................. •·• ...................................................................... .

CM225

'\