uni11o

tl ~ iJ ... .. .. ~-' ... I ... 1 ., a-11 1:nnu'Y1L \Ul'U.~\Uf,fh1n1tlfl111J£ln·Dan~'U.tlfl1~ ') an,ym: fl1~R'l1~LLa: • fl1111Wll~\ufnun'ltlfl1funfl~in n11L1un~£lW11LLfia:ti1:L11'Yl w11Uiin1u111~ n11Lfl1tJ11 n'" ~'"i~ilt~fi1~ 'J "ii1nn1tlfl1fu Elnlian n11LLtJn wa1 u ft'1'l£l'U. vi"U.n'Yln~ittlti1 u,\ ,;A~\~ n1t~ • • • .. ~- u· - ~ ., ... ...1 '1 ..... ~ . I ... I ., T ., ~ ... fl111J elnWJJftn !Jn1tJ1n11LL 'Yl'U.'Yltl1tJ'U.1flft. £) Lnft'Y1~\fLD'l1ft fl1111LLflntl1~fi1'U. Lfl1~W11~'Y11J

~atiafl1111L1fiatl~ffiu1 LLa:tl~ffiu16'U.,£l~£l"'tvi'"1MJ£J~n,.tlfnfunnlftan

1. '41LL'U.nEl"'t~'"1Mtiltlti1~ 'J11El~n1flrnfu£Jn~in LLa:uanfl1111LLtlnth~ti1'U.Lfl7~m~lti ... A ... :T ., ... ~ I .. ~- '1 .,

2. L 1Un~£lLLft:L-n !J'U.~tl'l Lfl1~m1~£l"'t ~'U.1iJJ~tltl1~ ')1J£l~n1flfl111J£lnWJJan Ltl ... .. ...... ... .. . .. ~- _.., ... ~ . ~ .,

3. 1 Lfl71:~ RlllJ fl'Y11~n1 tJ111~,a~ £l"'t~'"lr11£l~n,.ttfl111J~n·Dan lJ"i!"ii tJ'Yl Ln u1-n a~ LLa:

LmuuL fiuul.r

4. L ;j !J'U.U~MtJ1n11Lfl1Ull El"'t ~'U.nLLtla:'JJ\ltl1J£l~n1flfl1f1J£ln~an tJ ~ffiu1 L fl ij~ L ntlrllJ ft'11 I -r tl ~ .. .Y a .... - ..1 A ~ A '1 .,

L~a1'U.LLWfl~ft'1,. 1:nnu'Y1 L"D R1111:1JQn1tJ1 TI1'U.1tJ~fttl~ft'Y1Lnfl Lfl

5. 'l.t1tl~ffitJ1Ltl\fLfl1tJllft'11ti1:L11'Y16~')Lti

CM225 401

I , .• •

e-uw~lf,je"n'fltnfuen'iinLiJ~nallw11~ihJ\1iVf"ni\4ill~~fnu uth~:~ilflii~li . . .. . .. tnfuaitarn"WUtr:nue:fl011~R1l1~l~~1ft1JR" L1t-u X, OCOR, OR. LUil: NR2 ft11nallif' .. . ft1lJ11nLfl1u11lti·;nnR11fl'un1Lilfl~iltlLfltl1nu L~annuunwa1uti1uJ,~:llfW11tiurhLilf1 .. L~3Jnaufi-u -uan~1nd'!T" iiwtnJt\Lt1ihLuu~ilu1nu fi a1a"l 1fi a1Jliffiu1nuil1f'l ile l v4tf~ ~~'Dis (acyl ~roup) a~~\4na"n'flf'l1fuan4inilft'n~m:: 1"'"rn",t1lt.1Lilu

:o: II

...,...C,•• R Z ~

acyl group

L~a z = OH tnnh;nou fie n1ttfl1man'iin =X; 'D'itmliiRI (acid halide)

= OCOR (-.,1a Ar); UD'iflUEJU~li1~J1i (acid anhydride) = OR (-.,1a Ar); 'EJttU'IDf (ester) = NH2, NHR, NR2 ; EJ.:~vl {amide)

10.1 · D\\,\\B!ID\1n'1tlA11uunifin (O.arboxylic Acid· Derivatives) ' . ' Duwuha"n1flfl1fuaniin Li1Utf11~Lfl1u11lti~1nn1flfr1fuon4in LLft:LlJ~vu ' niu\ lfn1t'1ti1fu on 'Bin ltitt1 rn.JLin;u1LUJnRft1 uti1 ull1 lfl uiln1fl~1a LU RL iJut11 L i"

~1a l1i£it11L i"nltl' Li1oLmU1JL nuunu lf'l1-3ft"f1", a"n1flfl1fuon4in ~::L ~\411W1\4~LUU OH ,Eh1fl1fl \]flLL't1Uti1U~~LL'YlU~t"ij"~Ul\Ltfuil1t1R1ol~tf \~o~~utfth" ') ti"if'

0 It

R-C-OH Carboxylic acids

402

f;? ' R-C-CI Acid chlorides

0 0 II II J

R-C-0-C-R Acid anhydrides

0 II

R-C-OR Esters

a· " R-C-NHz

,o R-i-8-NHR Amldes

I~ R-1C-NR2

CM225

L~Eift'111.h·::nEI1JL\U~1\{~~5h'\liLLnU~ L~'" -X, -OH, -OR LLfl~ -NH2 V\;EI -NHR . . ' V\;EI -NR2 Ln1::rl1J'M~UJWft (RCO-) n1l~ft111Jflfl1~Ltliiti1~'1.J',l10L~EIV\~Vf~ni"U.-n\t~ Lfl£J1n'"d\iJLn1:rl1JV\liLLEiflflfl\'\1EILLEI;R

'U

ca; ca; fi'A. I

1 0.2.2 usi~msu llllfl7,{ (Acid anhydrides)

Anhydride V\1J1t.til"thiffi1nJ1 il"t~'"f11itflii'Liifli1nn1flfl1f1Janlian 2la.JL~~~ LiaaJfieH1u19lviin1'nlitnl1aan 1 1aJL~~~ 'V\~Vl"niu,a"ueifl~'DU~lllfl1ffih:na1Jti'1t.t 'V\a.heia 2 'V\a.i ~L~aaJii"nuN1ua:flaaJaan~L1'U

'U 'U

0 0 II r---------- II

R-C-101-:1 + · t1o-c-R1 1 .. .. ·---------- ft~~,o~

acid anhydride ,

UDfflUDU~I1~fl1flij,.f"LL1J1Jft'1J1J1tll 'V\1El simple anhydride ~"U1:nEl1Jti'1t.t'V\a.itDiR 'U

L'V\iJEl'Url'U 2 'V\J.i ('V\1El R = R1) LL~:LLlJlJ~ftlJ (mixed anhydride)~" R LL~: R1 'a.iL'V\iJEl'Url'U 'U . 0.1!!lY.1lf~

A • I II· .I ~ A ... 'I II I ~ simple anhydride •1H1u1:n EllJfl'JtJ'V\~,D·DRL 'V\lJEl'Un'U L 'V\ B1'U-.oEln1tl LL~:LL 'n'U acid

ti'1 tJ anhydride ., ., .. A I ~ I ... 'I II' ... . ~ .. 1 ...

UD U '11 'fl 1flLL1JlJ~ ft'1J 11h1'V\ lJ' D'71Sfl1"n'U L 'V\ El1'U11Bn1fl't1" ft'El"1f'Ufl fl tJ L 1 t.l" 'U

fl11Jft1i1Jen1Y1 LL~:fl11Jti'1t.t anhydride

fi1Th1fl1 0.2 i1mh~n11L';tJn"Difl"DU 1D1fl1ff1.J1'11ttrilfl

iatUPAC

0 0 II II

CH3-C-O-C-CH3 Ethanoic anhydride Acetic anhydride

Propanoic anhydride Propionic anhydride

Butyric formic anhydride Butanoic methanoic anhydride

• 0 0

o-~-o-~:-Q Benzoic anhydride Benzoic anhydride

404

Benzoic hexanoic anhydride Benzoic caproic anhydride

ueif1UDUtl11fJ1l11ittlLU'U1" (cyclic anhydride) ~"1J1i1nn1fl 1fJf11fuDniin liL";t.tnfl11J~a,a"n'",f'"'1 LLft:fi11Jti'1t.t anhydride Liunu

Q Qo ~o 0 0 0

succinic anhydride maleic •nhydride phthalic anhydride

CM225

10.2.3 &DW&nDf

LDR'L??DnU\lEl\n~~~f!JEh1n,.flfl1f1Jfln4in ~~~a.j --QH nnU'Yl\ltl1tl -OR ~'iEl -OAr 'I .. ..

lfl,.~trn~-na~La«Lnaf~~iJ~lhaiam~W'untfu -OR ~1a -OAr ..

isoamyl acetate

propyl acetate en&L~~

1 0.2.3.1 !J.?J{tii.TJ.t.El.

0 II

R-C-:OR1

L~El R:: H, alkyl 'VI;El aryl R1 = alkyl 'VI;El aryl

ethyl butyrate i1.Jt.l:1fl

methyl butyrate &LD'l.JLi]R

CCOH

COOCH3 methyl salicylate

'u1al'u1:rh

n1,.L1tJnLElRL'YlElfflR1tln1,.L1tJnLnftEl11El~n,.flfl1f1JEln.fin· ltltJL1tJnLU\l ~fl

r,1-3m-3 is /URAC fsruiw 0 II Methyl ~ethanoate Methyl acetate

CHs-C-0-CHs

1?-o CH3CH2-c-o . ~ b . Phenyl• propanoate Phenyl propionate 0 II Butyl methanoate Butyl formate

H-c-0-CH2CH2CH2CH3

0 II

Isoamyl acetate CH3-c-0-CH2CH2CHCHs 3-Methylbutyl ethanoate CHs

0 II

CH3-CH-C-O-CHs I Methyl 2-methylpropanoate Methyl lsobutyrate CHs

0 o-c-0-CH2CH2CHs Propylbenzenecanoe~ate n-Propyl benzoate.

o-0 8-0-yH·CH3 Isopropyl benzenecarboxylate Isopropyl benzoate CHs

1 o.2.a.2 J!ft~fJJJH!tn~fJUf~!11!11P.n.f.~

Ulft'Lnaf-nilfl1~LL'V\1U (cyclic estet~ 'V\;a~~-~.aJ.riY. (lactone) Lnfl~1nu~ffit111l1Vtu

1aJLftnft~El~n1f1JllfJ1Dn4f (hydr~xy acid) 1flt1L~Vn:~ii -OH au\U.,1LL'V\\4~LLn11111 (y) LLft: . ,.. 'f1ftf11 (8) ~a~'V\litnfuan'Ba . ,..

406

~ HO-CH2CH2CH2-C-OH .... 6

(cyclic ester)

d TI1!(i~n.~!.~ft!1~.~-'-4r.t~f. forurtyL;unLilu lactone

~1nfo'Mft'n~a~ntt1 LL'YIU -ic atr:id tuton1tltl1tl -o/acton~:

~U1t11~LL'V\1Url1'V\Utlltlvan~m1nt11li.,,LL'V\\4~tnfuou~Ln1:riu -0- tu1~ L-rlu p, y ~a: 0-actone LUU1.JLalm'Yiof!Ju1t1 4, 5 u.a: 6 o:tloaJ fl11J~1tiu

CM225

Butyric acid P-Butyrolactone

Butyric acid y-Butyrolactone

Valerie acid y-Valerolactone

a600 P a

Valerie acid 5-Valerolactone

y

uJo P4cH y . 3,

Caproic acid 5-Caprolactone

10.2.4 stlJJff (Amides)

D~~J.Jtl LU'Utel'Ut~'UtMJEl~fl1tlfl1ftJan~an ~~'V\3.i OH nnLL'YI'Uttl1tl NH2 'V\;El NHR 'V\;El 1 ~ ~ NR2 LLt.i~tl1llfl11U.'YI'Ut~~l'Ut1fi1L-;J'UtLU'Ut8~~11ff1J~ll1lD D~~JJl'YitltJ1lli LLft::D~~JJffflflt11lD ij .. .. 1 ~ ~ ~'Utlr:: N-C '41'Ut 1'Ut 1, 2 LLft:: 3 ~'UtCtl1ll~1tltJ

0 It

R-C-NH2

~ R-C-NHR Amldes

0 II

R-C-NR2

Li1a R = alkyl ,.,;El aryl

l 'Ut 1 fi1L -;J 'Ut L 'UtD ~ ~V fl,li ii ft'll Ui L iJ 'UtL 1.J ft' L Y411::fi·a Lin tl1 El 'Ut 1 fl fl L ~ tl1 L fl fl L 11 'lJ LL 'Ut 'Ut.f ~

LfliaOUtl1JLOUt1fl1~Ri1~lt1

CM225 407

10.2.4.1 .TJ.J.!(f.!I.TJ'!.EJ.

LtJiu-u ic acid ~;a oic acid ~1nian'l'tlfl1fuan'Bfin Li~J-u amide 'f ... .J.. .J.J ~~ ~I .. ... I"" ~ I ...~~ _,

D~ UJflfUJn11LL 't1'U 't1't1 N L ~ D1'ULLUU Lfl tl1n'U LL911J'Utl1 tl~ll LL 't1'U 't1'Jh1 L n1:nu N '1.1

I ~ I~ 1 I iJ .J.J iJ I iJ .. D1'U1JD~~'U'U-.J tlti1:~11L 'l.L011LL't1'U't1't1 N L 'U D'l'UL 'U N-alkyl ~'l'El N-aryl • ~ ~ ., ... .J

na-u LLft:tl1lltl1ti1JDD:- '11fl't1111~1nn'l'tl

fDIUPAC

Ethanamide Acetamide

Butanamlde Butyramide

9 H-C-NHCH~H3

N-Ethytmethanamtde N-Ethylformamide

0

)lN~

6

408

N,N-Dimethytmethanamide

N-Phenyi-N-propytethanamlde

N-Ethyi-N,2-dim(:ttli'lylpropanamide

2-Ethyl-3-methytpentanamlde

N,N-Oirnethylcyclopenrboxamide

N,N-Dimethylbe~mlde

N,N-Dimethylformamide

N-Phenyi-N-propylacetamide

N-Ethyi-N-methylisobutyramide

a-Ethyt-{3-methylvaleramide

N,N-Dimethylbenzamide

CM225

1 0.2.4.2 .l~ft~!J.fJ.;.l~.{~H!~r!1!~iP.tJ.f.f! a:~vl1filfi1~LL'V\1'U. (cyclic amide) L1vn .L!~!J.L}.r!~ (lactam) Lnfl';l1ntl~mv1l'"

1liLanaLtl!J1tl14 1:'V\11~'V\1i -NH2 LLa: -C00H ttl\l1fiiJJ£J~1~\u1:1J1Jtnajruf11'V\14fiLL1J1JLtl!J1tl1J ~ ~ w LBft'LriBnUfli.JLLVIIU LLfiL1!JnLU'U. lactam L~'"

0

. a.ANH

llY' CH3

rJ-butyrolactam

10.2.5 luln,-if (Nitriles)

a)NH rJU8

y s

e-caprolactam

J.~lr!1; .(R-CN 'V\;EJ ArCN) ii'V\~?f~ni"U. -C=N ~~ti1~';11n£J't~'"f,.t1Ltl-na~n1fl fnfuan~an Lii'U.lfl1~iifl11llill~uilflve1'a1lnua:wl ';)1~n11LivJ,-na~a:wltl13J1lii ... ~

• I"" - 'f 'f _, ., .- =."" ..,. .-..I .I ... 'f 'f .- •-I lJL)n1v1-na~ ,u '"'1R fla1vn1ttfl11U£Jn·JJanLLa:a't~'"1l£J'U.') n11'Yl';lfl '"' '"'1R£J~ L'U.

I .I ... • ... .. .. ...... ., ..I nalllfl1lJ1:n auLa'lfR'V\1£1 au ~'UlliJJ a~n1flfl111J an-uantt1 v L 14£J~';l1n ~ ~

1. ~tl1'U.:aan~Lfl-i'U.-n£J~fl1fua'"l'""'li -e=N Lii'U. +3 L Yhnufl1fua'"~"'lifl1f ~ ~

uaila 'V\;a,aiR 1 l"U.a14~14fl1a~n1ttfl1fuan~an ~

2. fl1fua'"~"'li -e=N ij~UiL'V\ila14fl1fua'"-na~'V\liLaiR fiarhtJnn~hnnuil1f'1a ~ ~ :..1

la L ~a1iLL1J1J_Lii !J1tl'U.

3. nnLtr1fi1Ltufl~ntflflTf1Jan•anL~'"n'" ~

... ..I 10.2.s.1 DJ.1.~1.~.n~.rJ.

~;~!J .. HJ.P-~.9. L1!Jnfi13Jan~m:n11LL 'YI'\4 ~Ltf 1tt1L ';1\LIJJ£)~ 1fl1~ rn~'V\ an .r~d

"'1l'li"'an ~ii"'li eN ~

~1'"1'U.fl1fua'"l'"1fl1~m~"'anll'u113Jfl1fu£J'U.-n£J~ eN ti1v

a~'ri1!J~EILtr1fl1fl1fua'U.~Lii'U.1fl1~rl1~'V\ant11!J -nitrile L1vnLiJ'U. alkanenitrile, alkenenitrile 'V\;EJ alkynenitrile LLa1LLtin1m

fl1fuawtm~ CN Lil14fi1LL'V\\i~~· 1 Lliti£J~1:uLa-nfi1LL'V\1-i~l'"~a ~

CM225 409

.n:n:~!P.n!lJ.~1JJ;:~!.lnro1 L1vnLih~ alkyl cyanide

~;£lft-\Jli'1Vtl1V -carbonitrile L~O~ai -CN Ln1:~1-\JLL~1'U . 'U

~-~.'-J.~Jll L1vnfl11Jn1flfnfuen4Bnn lflvLl.Jiv" -ic acid li'1v~en1fl LU'U -onitrile

ethane nitrile 'M;O

acetonitrile

~~N 6

5 4 2

5-methylhexan•nltrile 'M;B

4-methylpen~l cyanide

cyclopentanecarbonitrile

'M;O cyclopentyl cyanide

Q-c=N benzonitrile

Q-cH;zCE:N phenylethanenitrile

'M;B phenylacetonltrile

~-10.3 ftiJ1Jtlfl1\1fl1fJ111ft

LL1-\11:~11-\J 111Lftnft~El-\JEl'U~'UfuEl-\Jn'Jflfl1f1JDn'BnnLiJ'ULL1-\11:~11-\Jlfll Wft lfiVL\\?41: • • •

D:'~11~1.Jt1JTiiiLLft:flfiVTiiilS-\Jii~'Ulr.: N-H '11'U1'U 2 US: 1 ~'UlJ: n1l~Lfifl~'UCltrlfl1L';l'U • 'U • 'U

1:,.,11-\1 l1JLftn a ~-\Jij';) fl~SEllJL ,_,S1LLS:';lflLtlflflft'-\Jn11811~'U ,.t1 l1.J~U1~\l'n 11JLSn SL ti1 ')n'U • • • 'U . •

lfl v L\\ w1:a:-~vll.J:ilJTI iitS"~"';)fl~ a ElliL ~ s1"a:';l fiLtl Elflft'-\Jn11n1flfnfu an•n n 81~ ruD:-~vl ..; 'U • • 'U

- ... -~ " " !M ~ I .. - J! ~ ~ ...... ....f ~~.. .. flflVTI11LLS:ft'l~lJ1:nau 'u '"1SJJft'm'Vftl1fl ElU111-\Jft'-\JUJElLTtVUnue'U V-4'UD'El'U ') r11 L~';lflLfl Elfi&N

'U 'U • • 'U

L-D"n"

410 CM225

.. ., .. - - ., ., .. - i1 ... .J r ... .., ::. ""· ~ LEJft'Lt1EJ1, EJ:' UJfl'Yiflli1UJ LLa: UUt11fi1J1~~'"fl L '"fi1T11ft:ft1ti&EJ W1flnV"I'Yifl L-D'" ~ v .

ethyl acetate, dimethylformamide (DMF) LLR: ~nitrile

alp~''"f-na~n,.flfl1f1Jan~anw1'"\~qtftijfl1f1Ja'"'~Ln'" 5 a:flalJ s:a1uJ1Liia~·;nn Lflfl~'"1f:,ULfl1L,-,'"n1JJ1'~ ff~\fi~'\t1J1111UEJifJflREJ~1flLLa:LLEJU~l1~fl1fl;A~'1flEltl~n1tJ1tl1J "' (( \bLLR:LLaanEltiElR

.. ,,";t 10.& LmuuLiluuthfl~ftn,~n1ll1l1~~o~n~flflTfuon~anuft:au~ul ua:ft1,.th:nou tJ1~~uflftiiJ,"',rn ta.nana \niLf\u~nu ~ •

WUC',IJlfl1LiU • rf)1"rn" l..f1~LnYIB11 uu. YflLflDfl n11R~R1t.1J'1 TJJLRnR 1~wi1" TJJLRnR (c~ . •

CH3(CH2hCOOH .. ... ...

88 ...

164 ... n1tlfl1,.tJ £m'Jfan 11 tlll1n

CH3(CH2)2CONH2 a: '11 lt1•11nii 87 ....

216-220 a::a1vttr lJ • 'II

CH3CH2CONHCH3 \lJ.. ... ... 87 ... 205-210 a::a1vttr a: fl'YltllllllJ lJ • 'II

CH3CON(CH3)2 ' .. ... ... 87 '~ii 166 ... a: lJfl9l9llltllJ tlll1n 'II HCON(CH3)CH2CH3 a: 'lJ titl ilunii 87 '~ii 170-180

... tlll1n 'II

CH3(CH2hCEN ''"'n,.a- 83 ~ii 141 . ...

Lan'"av

HC02COCH3 LLa~fl LL£lU 't'J'tl,.t)' 88 ' .... . lJlJ 105-112 orhtJ~ffirnnuJ1 CH3CH2C02CH3

.. 88 '~ii 80

. ... L £l ftL 'Yl 0,. Lan'"av CH3C02C2H5

.. 88 '~ii 77 t.h'"na1.:1 L£l m 'Yl a,.

CH3CH2COCI ... ' .. LL£l'Jftlflaa ,.tl 92.5 '~ii 80 n1tJ~ffirnnuJ, CH3(CH2)3CHO , uaail,ul 86 ~ii 103 •

... Lan'"ev

CH3(CH2)2COCH3 f\tnu 86 'liii 102 • ...

Lan'"av

CM225 411

~a :Q:J

I.e' •• R-c-z . I~

Nu

.•• :o

II ,.....c, .+ r R Nu

Z = leaving group; Nu = il'lflRln,vhf

10A.2 .. ~, ... l-n.Jfimu1!1o"o'tft'"tfmo"n,.tttt1i'uonian

fl11lll 111Eh'lll~ffitn("nul-11i z ~-3SiJ.Jafien..J~ffiv1R£h'ILL1J1J .r"d' "\

.~., · - • ~ 1w .. 1 0.4.2.1 !1.~1l!J~.?..t!~.~f1Jf{).!.ff!J.'JiJ1!~! ..... ~

l"a"~"i'-na-3n1t1fl1fuan~~n z a'l-;,-;,:LiJ'U LLD1RL-;J'U, o -na-3£DBU?Df LLa:uaifl "

uau1111,,; LLa: N L'Ua:-1111 4"£ifiaLanfl1a'Ult1t1L~!.I1Yhl~l-11ifl1fua\ta£iLwflv1n1w

: D:-111{

1 0.4.2.2 .f!.3J.Y]1!!J~.l!J.tAY.{IJ9.9t9.'!P..

Leaving group ~fll-1RfiJ1tJ 1ufiaLShfl1a.'Ult1fi~R:LiJUL1Jft'ela'U LslaLtntJULfltJUn11 " v .

~II A ... 1 "··' .. ~ I ~ .. ~- . ~ .. .. I LL't1'U't1fl1tJ'U1fiR a LnR't1\-13J£D"'llnEl-3n1flfi11UEln~anLLR::ft11a'UW'U1r ';Jt(\-1'U11ft'1l1WL1Jcntel-3 v "

• :'1 ~ ,¥ leavmg group LlJ'Ut1-3'U

1'1l1ViL1JI'

ft e_......c, e e < 0 . R < OR1 Tl1flf11WDnfan > D:-J11/

412 CM225

t.l .. t.l I .~ ~ ~ ~ ~.,_ 10.4.3 n11'L Rti\UL a"-stM~1"nM!ID"OMWM6\l1nn'lflft1"SUDn'Dan • (lnterconversion of Acid ~es)

Liia~-;nnalt~\uf~a~n1tlfl1f1Jent&njjfl1111l1t1~n1u1ti1.:niu alt~un~~l1tia tJ~mu11nnn11~~LtJ~uu1.~alt~ufrll1tietJ~mmll'aun11lt1 LLa:'ln~itflvhtJ~ffiu1ntJtl1 ~;annlDLtl1lad\~n1tlfl1ftJan~in . ' .

-

I

CM225

-

NH3 ,.;u RNH.2_

111; 0 R2NH

acid anhydride

carboxylic acid

ester

413

10.4.4.1 y_D_ryj_lJ.J.ffJ..M'.~!!.'if]#.~H.~~-~~J:~

"D'ifl"tJ~al fhtJ~ffiu1nuntflfnfu an'i~n ,.,;a Lni a-n a"n1flfnfu an'i~n laj.;' a" 'l " ... • If "' f'l ,.J.. .. • ,. - .. ., -"" • ... ,.J - t¥ L41Jff11L1" LVi11:::"1J 'Sf) 'DDDULu14 leaving group 'Ylfl L14uLJn1EJ13J 'W1flUL~a-;,tJn1fi'YILnf11J14

acid, chforide

0 II

0 g pyridine._ R( 'oH carboxylic acid

0

acid anhydride

0 0 ' c +

CHf 'c1 "-Q Na•-oc ~ A ~ II 11-o CH3-c-o-c ~ !J + NaCI acetyl chloride acetic benzoic anhydride

0 II

- 0 H 0 0

CH3(CH2)s-C-c1 + HO-C-(CHvsGH3 pyridine • C.H3(CHvs-C-O-C-(CHvsCH3

414

heptanoyl chloride heptanoic acid heptanoic anhydride

u·- m., .. 10.4.4.2 · ... D.Q.1.lJ.!..!l •• MJ.~'-~!1P.l UEU~naDaR'VI1aw14aft LiJ14il1flRlalv.JlfLi1n1tJ~ffiEJ1n1JLLa~f1LLlflfttf lt1Laft'L 'Yiaf

0 0 II •• ~ridine II c + HO-R .. I c + HCI

R/ 'ct •• 1 R~ 'oR1 acid chloride

.!T:u:J~J~l-Jjjm!.JJ. 0 II O"C'CI 0 II

CH3CH{"C'CI

propanoyl chloride

+

alcohol ester

pyridine (CH3)3COH · ._

ten-butyl alcohol

ten-butyl benzoate

0 pyridine .. g n +

CH3CH{" '0/--'

cyclobutanol cyclobl.ityl propanoate

HCI

HCI

CM225

0 II . c +

R,....... 'ca •• NH3

ammonia

0 II •• /c,. +

R Cl R2NH

2° amine

.!i1tl~J~'='~mP.J. 0

~CI hexanoyl chloride

stearoyl chloride

o-9 C-CI + piperidine

1° amide

HCI

I RNH2 ~ R~H3C~

0

~NH2 + hexanamide

0 II

C H ,...,c,N ... CH3 + 17 35 . I _

H N-methylstearamide

0 NaOH ., Q-8-NJ + NaCI

1 0.4.5 t.lfi M!J1!1il\1UBWfJUBHliJ y,,., Lft ufi'1 lutl~mtl1~ Eh1UDifJUDU tlitfJ1iflR1UntJUDifJUIJtsl fi eni1U~ffit11ntJ\t 1t1S

1a l ~a &t1oul'V\ qjl.,ulliti a~ liti1L i~tl~mr.n LLtit111aJl1u~ffiu111'aun11ue~fJu11~sl.

0 0 II II C C + H-Nu

R/ 'o/ 'R ••

CM225

.. 0 II c

R/ 'Nu +

415

uDiflUDU t,tfl1lla.ili'Lfl'iulluDif1flflD t,-l Lrta"~nn leaving group (RCOO- ) LiJ'U LlJMLrifli1 C( ~"'VIftfltnnni1 •

1r .. - m-- .. 1 0.4.5.1 .. !ll.TJ.1.11.1.r! • .'J!d.lJJ!.ffl.FJ.1. UDiflUDU tlT tfl1fffl1t.J ~ fl; U1 n 1) LL a Rna lJ £J a 'VI1 a~ 'U £J R £i fl1 f11 D ni' fl fl tD D D U

(RCOO-) Li]'U leaving group l1-tL£Jft'Lflaf ·

.. + H-OR ••

acetic anhydride

acetic anhydride salicylic acid

cQO

0 HO~

. 0

· propan-1-ol

phthalic anhydride

10.4.5.2 JJ.D.QJ.I/J.~.M'.EJ;.~~~

•

0 II c

R/ 'oR ester

COOH

+

~ &o'c~o , I · CH3

acetylsalicylic acid (aspirin)

Lil~t.Jilmv1nu NH3 'VI~aD:-iiu VuRtlilmu,uuuLilu1nuuDiflu11tt~l fi1"n~~ leaving group LiJ~tnfvsnfu~fl1BBBU 4"Ld£JLOtlUQM!J1tlUNH3 'VI1£JB:iiu1::ltl'LnR£J

0

~ R-H-NH2 + RCoo- NH.t +

416' CM225

.fT:HJ~J~,)~fJl'JJ.

0 0 0 II II II

H3C/c,

0/c'CH

3 + 2 NH3 __..., H3C-C-NH2

acetamide

00, 0-o-cll c

11 H N-o-~ CH(CH ) pyridine.., H3c-c11-o ~-~~ CH.(CH3)2 / ' / ' + 2 32 H3C 0 CH3 - .

......... .. 10~4.6 u!J n"IU1!10"&Bif&fJB1

11 .. - m ~ ~ 1 0.4.6.1 .. {l).TJ.1llJ.rl .. Y!tFJ.~~rJ.FJ.1. tl~mtnii'tia n11u.JRuuLEHJU1Df ~;a transesterification Lil14tl~ffirnn11LL'Yl~~~

~ajLa:Ua~a-3LDBL nDf fl'1uu~an at~aaan~\t"~\1-3 t ~Latn, af~\t" t~a.i Lil~nTnll; u~~a.i ~ . ~

R1 L~L£lftL'Yl£lfL~11 nu~a.i R2 ·;nnLLaanaDaftl~aj 1fluiin1fl~LL~-3 L~~ H2S04 ~;£) HCI(g) ~

'V\;£lLtJRLLEJSfJEJn!'lfff (RO-) Lil~tl'1Li-3

.!11!J.~J~Y~m.'J.'J. 0

~OCH3 + HO~ methyl acrylate t;lutan-1-ol

methyl benzoate

· o a· o- 11-o-11--o o-c ~ 11 c-o dicyclobutyl terephthalate

HCI

...

0

~ ~+ CH30H 0 butyl acrylate

cyclopentyl benzoate

diethyl terephthalate

10.4.6.2 !!nffl.~.rl~l~P.;'.~~?f (Amin~lysis of Esters)

LDBLnDi'bfi atl~ffiu1\l'auni1LLDifJLur!sl ua:uDifJuEJu !a!fJ,.; uc;i.Yhtl~mu1n~ LL£l11111LittJ'V\;£lEJ~iiuLtlEJ~!vff L~~n~

CM225 417

0 II ••

R-C-OR1 + NH3 0 II

R-C-NH2 + H-OR1

.II 1-\' 0 • 0 ... . " .. 0 '0 1f_. .. .I ... WD'"D 1 'M10 2 D:IJU LLYI14 NHs 1:: Lfl 2 LL&:: 3 D: Wfl tni.Jat1fl1J

.!T:uuJJ:'l1Jjjffi!IJ. 0 .

Q-cH:z8-ocH2CH3 + NH3 . 0 .. Q-cH:z8-NH2 +

ethyl phenylacetate phenylacetamide

0

CH3CH20H

.. . II H-o FCH2-c-N . + CH3CH20H A

N-cyclo~exyi -2-fluoroacetamide

10.4.7 t.lfimEntJINS~W,(

s:~umiJua't~'"~'si•~~1tien.J~mu1\l'au~~" LLfiLntltl~ffiu1n11LLEJnwtnut1'1u LLDRnDDOS (alcoholysis of amides) L\fLDRLYlQf1tl tl~ffimiin1flflLL\f" L~\1. HCI(g) 'V\;D ~04 1iJui1Li" lflutio"t\ffl11~i'auua::liL1R1~1u Li1a"\l1nff"s:~umLa::uoanouosLi1uaLin. T :-1 •• 1 .- ..,. .-T 111 •• 1 .-.1 • ~ .., ~ • ~fl1 LnftLLR::\1.1fla LD LnaYlO£l'U.fl1EJn'U.Yl"fl ..

0 o-Il CH3CH20H C-N(CH3)2 H~O,. N,N-dimethylcyclopentane

carboxamide

+

e~hyl cyclopentanecarboxylate

10.4.8 n111at .. ,laafo'twwf!lo\1n1~tni'uanian

tl~ffiu1il'LiJun11LLunwa1ua't~'"na"n'"fl1f1Jen•int1•uJ,.t"Liluil•flalol~a ~LiJuna1" H20 Li1~1tl1iffiu1~fl1f1Jou-nth1'V\ahsf• ua::ou~ufYln1fitflnnlulfl1lai'l~ w .. .. " .. 01flfl1f1J an 'Bin

1 o.4.8.1 .m!l'-T.fl!l«l.i!fl~!l~!!.llfi

LiJUn11LLYlUflfl1"'Vl1J&sfai1lJ\l1ffLiJUi11flRlal~L(ftLfJuna1" UBfflui'~Blflii . .. . J,Mtl'nlliLRflR~1~1tl~mr.nl~n1tttnftJentinltl'L;1llltia"l-it11Li-a, ~1nftJ,Mtl'nlliLafla ""'::l1ti otl~mm\l'oun11 tlMiiJtl~fflu1ft'n" \ uL1Jft!11t1snt.,.r (HO -> f-aLilu il1t1ale .. . . l ~~~ LL '" tl~ffiEJ1\l::L n4uu:: LiLnRD-nD-3n1f\tnfuon4in

418 CM225

0 II

R-C-CI +

acid chloride

0

Ar-8-ct +

acid chloride

H20

,r,

H20

\1'1

0 II

---~•~ R-C-OH + H-CI

carboxylic acid hydrogen chloride

0 . 0 NaOH.. Ar-8-o-Na+ ~ Ar-8-oH

carboxylate salt

0 Q-cH)\-CI + H~

0 Q-c~8-0H + H-CI

phenylacetyl chloride phenylacetic acid

0

Q-H-c1 0 0

:~.r Q-H-o-Na• ~ Q-H-oH sodium benzoate

1 o.4.a.2 .O.?!l'-T.~!l@f.~P.!!!~!R.~J.v.J.~!ff

n11LLtln"a1uusi~JusuYrTYfl,.,r tt1tl,i',l,.;'n1t~fnfuontin 2LaJLafla LLa:~atJ~mu1 '11n t~flinusu Yl1Yfl1llt1n1tl t~Jf'nfusniin tJ~mti1Lnfl lt~ulliti o"lii1Li" usiflusu Y11 y,,.,r~,i','V\\l'n L11Lafl a\1"'1: l1ti etJ~mm\toua" LLa:n1iin1t1LiJ~i1L i"tJ~ffim'l:Ln fiL ;,;f~ ·

ft ft ft ft C C + H20 ... C + C

R/ 'o/ 'R R/ 'oH HO/ 'R acid anhydride

..

cyclic anhydride

carboxylic acid

¢:: 0

dic8rbo)(ylic acid

carboxylic icid

.!T.1fJ.~J~1-J~m.FJJ. 0 0 II II c c

H3C/ •'o/ 'cH2CH3

acid anhydride ·

CM225

0 II c

HO/ 'cH2CH3

propionic acid

419

Q+ 0

succinic anhydride

1 o.4.a.a .tJJ.!Iv.f.fJ.!II!mf!!!.U1!!.f

¢: 0

succinic acid

· n11ltJ 1fl1lSRlDRl nDnflfli1 tJ~ffitJ1LflflltiLil Ell ifl113Ji'El'U '1fl !JUfl1fi~1ElL1J RL iJu fl1 L i"tJ~ffit11 ltin1flfl1f1J Eln,nn~1Elfl1flJ Eln,Lftfl lEJElEl'U LLS:LLElftnEltiElft'~1El~'UElft

0 0 0 II H-OH II II

R-C-OR1 R-C-OH "'1e R-e-o- + H-OR1 H• "';u,. Ho-ester carboxylic acid

\14ntfl

.YT:ut~J~!llim.FJJ. 0 II H2S04

CH3-C-OCH2CH3 + H20

ethyl acetate

0 0 .

carboxylate ion

\14UJI

0

CH3-H-oH + HOCH2CH3

(CH3)2CH,0~0 ... CH(CH~2 o~ o HO~OH

diisopropyl pimelate heptanedioic acid +

2 (CH3)2CH-OH

tl~ffitt1~iiL1JSLiJui1Li" L';vn saponificat!on (JJ1~10il1Wlft:ilu: ~3J1E.Jn" soap making ~1Eln11f11SU) liLlJS 11aJft tlElLElBLYlElfLLfift:13Jft 1fltttlJJl-ua!uifl{~1all13JU~11 .. lur11a:a1vLusLLri (NaoH ~;El KOH) HO Liluil1flalalwa~iiL-i1n1tJ~mv1~fl1fuEJu -nEJ"~llmfuEJ\ta ltifiufi l~ 9U4"Lilt4LnREJ-uEJ~n1fl l-uJu. 41"Lilun1flfl1fuEJnlinn l'lim1 .. ' ..

0

o-Na• sodium dodecanoate

1 o.4.a.4 n1!7!!.Tt!!7J!.tf.ll~Jy_fl'

D= ~11~ LiJUEl't~UnEJ"n1~fl1fu&n4fln~1 El'"l1fi otJ~MU1\\'El tJ~ ~fl. ~~ mU1Lflfllti ti1jjn1fl~1EJLumiJui1L i"

420 OM225

0 II

R-C-NR2

.!T:u.t~J~1:l~m1:1J. 0 II H-o

CH3-C-:-N ~ !J

N-phenylacetamide

,(

~~. ~oi( 1.~ 'o

0 H+ II

::--;..,;,._~..,• R-C-OH + H ·~ R-N-H

Carboxylic acid

0 II _e

R-C-0

I R

mloLLoaJ tan iluaJ 'M~o mloo:ilu

H + R-N

R carboxylate ion LLDJJlaJLilU

'M~O o:ilu

L~El R = H ..,;El alkyl ..,;El aryl

0 II

+ H20 NaOH .. CH3-c-o- Na• + H2N~

b. sodium acetate aniline

~OH ~o· + HO[f' + ·/""N~ .. I~ 0 H 1 o.4.8.5 m!l'!.Ifl!ltj.tf(f}.~f!Y.~YJn1.l (~1-n a 9.5.4 >

n11lu lt11ltuftu 1fl,.,( (R-C=N) Lil~tl~ffitnllin1~nau tl~ffitnLntl ~1~D: 111ff\~ ·R1l11::n1fl \,.; n1tlfnfuan'iinLLa::LLalJ 1lll \hJlllaaa~ R1~1'1l11::Lua-lti f)1fvDnilsfJ 1DDDU

LLa::LLalJ 1aJL itu

CM225

R-C:N 'M~o Ar-C:N

CH3(CH2)9CN

undecanenitrlle

1. H20, KOH fl11JJiau 2.H+

R-COOH "~o Ar-COOH

+ NH.-+

R-cocf "~o Ar-co&

CH3(CH2)gCOOH

undecanolc acid

421

t.l """ ... -· ~ " .. ~ 1 0.5.1 lJn"S!11nlJ81"1u"S=notJLRM=BM't1"S!J

u·- lB t ~II; n1 fl .. • ~ 1 0.5.1.1 . .'Jl!11Y11!fl~Hfl ... ~~ftfl . .1!J.T.U!!!'J .•.. l;.TJ.~'d .. tj.M~(J.M1'J.!I!. EJEJf"n f U"flfU£illV LLR:ns"vu1,Ell iU{fi11J~fl;u1n1JUEJfflflSEJ t 1/ ltl'~f J?U

(i1iD 8.4.8)

1 0.5.1.2 !/.Dfii.t[J'!!.IJ:~~!l.'f}JlP.fff.ll.trJW~flY.fHYJ~~H.~if. ci1io 6.5.5.3)

lEJR,nEJfua.:Jn1flviDfiin ..,;oLon-L n$f.no.:Jn'Jflf11fuonliin~u Yi11J~mu1nun1m1f ;,EJ,iUff 2L11ft fl111tl1Un11lD1fl1lRLf-ltiLLDftnDDOa'Yltl!Jilij 'Vl;DflflU115i~ii'Vlli R L'Vliiounu ············· ' " ... ... ... WO.:J'Vlli ...

0' II

H-C-0-R + 2 R'-MgBr ethef ..

LBI'Lnaf!Ja~ formic acid

0 II

R-C-0-R" + 2 R'-MgBr

LDI'L nof!l~n,flmftJon•ino14, I

OH I

R-C-R' . I

R' 3° alcohol

OH I /

H-C-R' + ROMgBr I R'

+ HOMgBr

+ R"OMgBr + HOMgBr

EJEJf"n Tui' ntJV";l;l1ti otJ~n;U1lnnn1~n1w1n'EJ' vul Ldon11J ~n;u,~: 1 ~ LLDRnDtJOa'YltlUilii 'Vl;DfltlUilDL'liYLtlt.l1nY " ... ...

0 II

R-C-0-R" + R'-Li

n1ty1n'EJ' vul uR:sEJfun Tui,ntJutl1tJ~mu1nu'Vl~ ...;.caN ~~tl o111\ln lu lt11lR Lf oth.:J11flL11lti~fnu .

422 CM225

nitrile

R\ 1Mgl

H20~ ~ c=N

I •• R

~+ ~-

R-c=N + R'-MgX ---1..,..

.!T:u:t~J~,)~f)1FJJ.

Q-c-N + CH3Mgl

benzonitrile

H3c, ,Mgt ---~....... c=N d ..

R' H R' 'c=N' H o• \ 3 ~ c=o I .• r{ R imine ketone

acetophenone

... - .. .. .e• ... .. .. -- - - ., .. UAJH4 1fl1Rn'l'tlfl11tJEJn·Danua:a14~141MJEJ-3n1flfl11tJEln'lfannni!Jf14fl LLEJ!IflfiREJ ,1, ' '

LLEJ'ifiLLEJU !a~f11ff LLa~LEJft'L rJEJf nn1ti1tfl~LLElROEJlf£la'lht1111 ij ft114D: !11/ LLR: ~ U! r11R';l: Ltl ~ Q ~

R11th:naue:ii14

Ql~~lj (diisobutyl aluminum hydride) LU'\4ft1nii1wtA-3l1'll'auni1 LiAIH4 tn1111tl ..... .. .. ~ .. .. iJ ... , .. ... ~ 1f11RLLD'lfflflREJ 1fl LLR:L£lRL'YlEl1L 14LLEJRfl lffl ('V\1~£) 8.4.8)

0 H II LiAIH4 H o• . J R-C-OH 3 ~ R-C-OH + H20 ether I

H carboxylic acid 1° alcohol

0 H II LiAIH4 H o• I R-C-CI 3 ~ R-C-OH + ·Hct ether I

H acid chloride 1° alcohol

0 0 H II II LiAIH4 H o• I R-C-0-C-R

ether 3 .. R-C-OH + H20

I H

carboxylic acid .1° alcohol

0 H ll liAIH4 HaO+ I R-C-OR'

ether .. R-C-OH + R'OH

I H

ester 1° alcohol

0 0 II DIBAH H o• II

R-C-OR' toluene

3 ~ R-C-H + R'OH

-70°C ester aldehyde

CM225 423

·.tl1tt~.1~1J~fJl!JJ. 0 II

~CH2-C-OCH~H3

LIAIH.4 .... H o• 3 ... ~

ethyl phenylacetate

~ ~CH2~C-OCH2CH3 DIBAH

V toluene · -700C

H o• ~

0 " .. ... _til Ill 0 .. 1 B~ UJfl fl01tl1ftL" 1 8~1/U .,

octanamlde

LIAfi.t. ~

N,N-dlmethylbenzamlde

10.5.2.2 OJnft1!r1YJr.t!l,

~CH2-CH2-0H

~ +. CH3CH20H

2-phenylethanol

0 II

~CH2-C-H + CH3CH20H

.

2-phenytacetaldehyde

H~ ~

~NH2 octan-1-,mlne

CH3-CH2-NH-o

N-ethylbenzenamine

(~amine)

N,N-dimethylbenzylamlne (3° amine)

YuYrnl an1il1ll~ 1°EJ:uu Jl1a1Laa~lutf ;f"ntmil9rllfl-311nil1lf Lda\,Y LiAIH4 1t ., . ltl'1° B~iiu LLthi1;il1ft1'1EJ DIBAH 1::ltiuaaifllmtf .

424 CM225

R-C:N UAIH1 ... · ~0

~ R-CH2NH2

nitrile 1° amine

H20 0

DIBAH ... II R-C:N .. R-C-H nitrile akdehyde

!Y~tJ-~J~)JDmiJJ.

VC:N LiAIH4 ... H20 VCH2NH2 ~ .

~

benzonitrile phenylmethanamine

Oc=N H~ 0

DIBAH.~ 0" ~ C-H cyclohexanecarbonitrile cyclohexanecarbaldehyde

10.5.3 tJfimu1n1nt~i"l1\1aiLLUUIJstl&i"uu (Hofmann rearrangement)

a:111ltJ~11nDn1tJ1iffit.nnulu,ij1J. ~1aflaa11J.LlJ.ft11a::a1u NaOH 'Vl1a KOH L1J.J1 ... 'U w

.. • ... - ~ .1 .. " ... I .. ... --.. I iJ ., ., ., ., •• ~ .. " 0 LnfllllJn1U1'YlTI1 LV\Lft'lJ'V\~fl111.1EllJ.a LlJL lJ.fJ11lJB,Ufl 'BBBU LLa::a: '1/fJ~nLlJalJ\h~ 1 D: "" ..( ... .. " 1/U 'JJ~llfl111JEllJ.lJ.ElUa~ 1 El::flElll

0 II

R-C-NH2

.!i.1fJ.~J~):Ilim!JJ.

CM225

JJN~ 3-methylpentanamide

0 II

()'C'NH2 N nicotinamide

X2, NaOH

2-methylbutan-1-amlne

()NH2

pyridin-3-amine

4:25

ni 'UQ'" n"Jfl l -n ai'" l '"l111Touu~::,r ,,r ouLil "n"Jfll'll u11 Lil ouft'1ou1.h::n au i1ti ty-n £N~1l11 Lftn ft 'I ' 'I

n1t1a::Dl'" LwtJl ntf Uft:: ltJ~il-u (i1,Ya 13.3) Liloun1flfnfuan~iinLLft::a'twufa~~11flL'U ln11J'Jf1tl

· n1flua~nnl-uJ,illtnU'Jflti';l1nm1~Jin ~'1an11aan'Bltuf,a~1uaa t1i'Lilouf11n1 - "'

~ ~- t., ... ~ ... ... ft::ft1U n"n1fiUE1""Dt7nLLft:: acetic anhydride 'JfLfi1U1Jft11L1'1::fi1J£lfl«1~n11ll~ft1U'Jf'Ufl . 'I

1fiULQ'r41::LaRL'naf-na"nfi1LL£l~fln L,.'U l1faaTstrua'ilnfl, vinyl acetate monomer (VCM), . v

,ansuald'n" uft:: l1i'Lfl1uliLLawlw;-u Liloutl'-u

n1fl ~naflain (glycolic acid) ~1a hydroxyacetic acid .wuLanll'aul-uel'au i1~nn1fl aJouLLft::~ft lmj-u Cl LiJoun1fiUDBJ\h ~11fl1Dn9 (a-hydroxy acid ~1a AHA) 111LftnftLan~Rfl

'I J 'I 'I

lin,"n11LLwnuuft::~iiflnm-ti'i'nM-1~1 ';l'Ui)"~iiflnmttfn1fl11llw::a1fl1::iuaflft1~n11ll 'I

n1fiE1~~wn (adipic acidl lin1louft,£l'U 66, n1f1Vit77Tu6n (butanoic acid) LLft::n1fl

urn'111Tu6n (hexanoic acid) LiJ'Ui1L~ni~louLiiflu11::ti1U, n1fl111in (malic acid) Ufl::n1t1 inm (citric acid) wul-u~n~ftlli~~1u'Jf\tfl ilft'1oun1L~1RLtAU1

0 1)- .q HXCOOH HOOCXH H~OH HO·· O OH OH 0 0 H COOH H COOH 0

malic acid citric acid maleic acid fumaric acid malefc anhydride

111lBDnuau~IJ~f11l (maleic anhydride), n1fl111lf1Dn (maleic acid) ua::n1flrl111 v

1n (fumaric acid) utift:: 1uLftnath"il~lifl'1fuaila 2 \1\li ua::~-un-::fi1::\'\11"i'" ~nlaDn 'I "' "' "'

uau~JJ~fl1mLft:n1fl111lfiDn Ltlou~flqilutuitylou~flfti\'\n11liL1'Bou'Jfilflfi1" 'J L,.ou l'fiuuaa flfl, L'fiU'WE1RlE1tflt1E1f. ~fl&n~nnll'r4£lRLllllf UR:fti1LflJj't11"n11Ln~1

n1flrl1111n LiJ~la 1'lfLll£lfLt"LT!J1flmfl,£l"n1flli1LR~n W1JL'U~'Jf\'\ft1U'Jfilfll-Kl~ v '

1R'LtJi'U1L 'U£l1~11LLR:Lfl1fl"~ll LfJ'ULn1L;'-Itl'U L 'U011't11l 1iu 'WBilDBl t7.D-flli~lltl1 \1\iin LL~"L;1 ,f'1li'ULflftfl1JL"1 LLR::LiLtt1Ull01tlfl:;1ilouuaft'J'nfin

~ua1iu (niacin) ~;a itt1iluil-a Li1oun1flfl1fuan•iin'Jfilttua11ulliln, ua-ulaao-u

';l1nn1fl ~wpn (pyruvic ackt) LfJU&n1t"lti'lllun1:tJ1Un1nn"t1Lflii ltl'';l1nn11RR1Un~ lflw LLft:n1flfflin (cholic acid) LiJUn1fl,{1fim-3(U~tl1Jt1nfl8U9W't781Bfi

426 CM225

~COOH

ll&.~ N

nicotinic acid (niacin)

0

'a~ methyl butyrate

iut.J:1fl

pyruvic acid ·

0

'-../'a~ propyl acetate

(pear)

COOH

cholic acid

0

yo~ IY isobutyr' propionate isopentyl acetate

(rum) na'lu

0

~0~ octyl acetate

ill

0

~0~ 0

CM225

benzyl acetate (peach)

isopentyl pentanoate (apple)

~0/ UNH2

methyl 2-aminobenzoate f)~"

0

~0/ UOH me.thylsalicylate

u1iu1:ri1

427

428

Cefaclor (antibiotic)

OH 0 CH3CH2 :

Camptothecin

m ~ .. "vv ll"" vnn 10

.il

Fumimycln

Oaeltamivir

CM225

(3) CH3CH2-0-CH2CH3

5. 1fl'l\1rn"Lflfl£lUfJiflUDU ~~~~fl1l

Go (1) 0

0

0

(2) Co Go

(4) 0

0 II

(2) H-C-OCH2CH3

0 . II

(4) CH3-C-OH

0 0

~0~ (2)v

0 0

(4)~

0 0

(3) Cro (4)~0~ • 7. Lactam flO .•...

( 1) cyclic acids

(3) cyclic amines .

(5) cyclic amides

8. Lactone ti a ..... . (1) cyclic acids

CM225

(2) cyclic esters

( 4) cyclic anhydrides

(2) cyclic esters

429

(3) cyclic amines

(5) cyclic amides

(4) cyclic anhydrides

9. fa IUPAC 1JB~ft'11tialt.Jif fia .....

Rei ( 1) 2-hydroxy-3-bromo-4-ethylhep.nyl chloride

(2) 3-bromo-4-ethyl-2-hydroxyhept~noyl chloride

(3) 3-bromo-4-ethyl-2-hydroxyhept~noic acid . (4) 3-bromo-2-hydroxy-4-propylhe~anoyl chloride

10.lfl1~rn~\tlfiB ethyl p-hydroxyben~oate

430

(1)

..........,o0...,.o OH '~ j

0~ (3) ~. OH

I

(2) ~OH _r[ O'U

(4) · ~ OH

11. cyclopentyl cyclohexanecarboxylat• fiaia\tl

·(1)do ca>oJ-oD

12. lfl,~rn~tialt.Jd'ia ..... 0 II

6~HCH2CH3

(1) 1-ethylbenzamide

(3) N-ethylbenzamide

(2) do' .(4) cfoD

(2) ethylaminobenzoic acid

· (4) ~,N-dlmethylbenzamide

CM225

13. 811 \t1ti a N-ethylacetamide

.~NH2

(1) 0

0 0 )l)(__

(2) ~ l ~Ny

(4) 0

(1)15 (2)7 (3)5 (4)8

15. ~Btl1li1::1J1J IUPAC ,.8~811\\Lia 14 fia ..... ( 1) phenylmetnyl-2,4,4-trimethylpentanoate

(2) benzyl 2-methyl-4,4-dimethylpentanoate

(3) benzyl 2,4,4-trimethylpentanoate

(4) benzyl. 2,4,4-trimethylbutanoate

16. ~Btl1li1::1J1J IUPAC ,.a~~U~r11Rfla ..... . &N v

(1) benzyl nitrile (2) phenyl cyanide

(3) benzene cyanide (4) benzonitrile

17. 811\tltialtlii'Lntl~\L1J::lllltl1L~\Ln1JJ} LLtilliLfifln1J81T!fUtlLfl!J1n\LLB~ (1) CH3CH20CH2CHa

(2) CH3CH2COOH

(3) (CH3CH2hCHOH

(4) CH3CH2NHCH2CH3 --~ ..1 ..e.... ... ... tl I "tl.r 18. 11htlfiLV\ll1::~ tV\11Jn11Ltl1Ull811 1::naut1a L '"

0

~CI (1) hexanal + Cl2, LLR~ (2) 1 ;-ehlorohex~ne + Cr03

(3) hexanoic acid+ SOCI2 (4) hexanoic acid anhydride + cf

CM225 431

... ..1 1 .., .. .. ~- -~ .. . • .. .. 19. UJ£1 Ltlrt Z L14£l14Yi141MJEI-3n1tlfl1'1lJOO"Dftn R-C(O)Z Ln1JLfttUJ1111WJJEI-3'V\1Jfl111J014ft

. • v

(1) L~O Z iiR111Yil~Yl1ft1Jft-3111n v

(2) L~Oti1ftti1Yil~ff1R1J1JEI-3 Z \taf,J 20. d1tl1Jfl1111l1fiat.J~ffiu1n11LLrt14fiA'Vl~L£l•ft1Ja~&n1t.l7:n£Jufialt.Jd' Liluath"l'

0 0 0 0 0 II II II II II

CH3-C-CI CH3-c-0pH3 CH3-C-NH2 CH3-C-O-C-CH3

(A)

(1) A 1¥B > C > 0

(2) C > 8 >/ 0 > A

(3) D > 8 >'A> C

(4) A> 0 > 8 > C

(B) (C) (D)

,. ···- ,. 1 ,. .- • L.... T • ..lf~t • ..1 • 21. fl1111 L11J£jfl1U1fl11 Lll tl1 Lfttn11ffC9UUt'U187110-3n1tlL1J14L'lf£lnrtiJ'V\~LLftUftfl1" ')

432

(Y) ~tl1LL'V\U-3W111 L14ft1111:L1JftLfJ11.L~ULtl 0 II

QOCH~ Ho-

y

• (1) Lll a Y = N02 > 8r > H > CH3 > OCH3 . ' . (2) LliD Y =·OCH3 > N02 > Br > H > CH3

• (3) LlJD Y = OCH3 > CH3 > H > Br;. N02 • (4) LliD Y = H > OCH3 > CH3 >,Br > N02

22. L14rt1""'"i1llntJn11ltrltl1latfLamrtafL~oiin1tlLil:Uti1Li-3 L14fttl11:~iiLuft ..... (1) Lu14t.l~ffiu1-uittlrt114nau (2) Li1utl~ffiu1llirt1unau

(3) lliLnt1t.J~ffiu1 (4) t.l~ffitJ1Lntlu1nn11 23.1LDL~uf1fl\,jl14n"l1Lt.Jau\ULUft-3&n1tiQltJtff1a'Ji£lLfl

0 0

d'o~ (1) H2so ... so3

(3) H20

0

? '" d'OH (2) NH3 .

(4) 1. LiAIH4, ether 2~ H20

CM225

24. ft1iufl11ll1eJ~l1tieJtJ~ffiv1n~ti',,e~eJ"t~"lfueJ~n,"fl1fueJn'BanLiJl.I.LLuuifl (1) acid halide > ester > acid anhydride > amide

(2) acid anhydride > amide > acid halide > ester

(3) amide> ester> acid anhydride/> acid halide

(4) acid halide > acid anhydride >ester> amide.

25. ti'T;J:Ltla u1.1.! u !n1miJl.l.n1tlfl1futn'Ban ';1: i -Ktl~mt11 '" ( 1 ) oxidation

(3) dehydration

(5) addition

(2) reduction

(4) hydrolysis

... wtil-r .. -- n 26. LEJWL 'YIEJ191El L \l.ll1';11nn1tlfl111Jeln'1JanLLa:LLeJSneJDElft tl

1. HBr, peroxide

2. Mg, ether

3.C02

4. H3o+, 5. SOCI2, pyridine

o (Yoy )lo~ o

(YCOOH

(2) HOOC~ . ~OH · (YCOOH

(4) HOA_/ )__OH

?

(1) carboxylic acid (2) Grignard reagent

(3) acid chloride (4) alkyl halide

28. ~afl~a'V\sn-;J1n.tl~ffiu1tialtJd' flEJW11Lfl

CM225

KMn04~0H fi111Jfau

SOCb .. CH3CH20H .. ?

433

(1) acetaldehyde

(3) acetyl chloride

(2) acetic acid

(4) acetamide

30 ... tl~mu1tioltJdfl11ltl'Nifl~alfl

'11 CCOH I ~ ~CI + I 'A pyridine

(1). I ~, () C2l yJo~ · ~

(3) ltl'lf-3 1 ua: 2

31. tJ~rnu,fioltJdi.tl'R1'''" 0 II

CH3-CH2-C-OH + CH3-180H ?

18~ ~ . (1) CH3-CH2-c-OCH3 (2) CH3-CH2-C-

18.0CH3

18~ ~ (3) CH3-CH2-C-

180CH3 (4) CH3-CH2-c-OCH3

32. L~o lu Lfl1laLfLoRL noftio ltJd'~:ltl'Nifl~afl1a.J'Jio '" 0 II

CH3CH2CH2C-OCH2CH3

(1) propanoic acid ua: propan-1-ol (2) butanoic acid ua:: ethanol (3) ethanoic .acid ua:: butan-1-ol (4) propanoic acid ua: ethanol

33. o:l2Jtl~Lfifl~1nn1fiL1J~L'JJDnnu CH3CH2NH2 flO

'--'~00 ,~

(1) A

0

HN~

.(3)6

434 CM225

34. tJ~ffiU1tl El 'tJ\i' \LT;J: \ TiL£JL1Utffe \tt 0

cY~/ ... (1) 1. NaBH4 ; 2. H30+ (2). H2N-NH2/KOH (Wolff ... Kishner reduction)

(3) 1. BHafTHF ; 2. H30

0 . II

H-C-NHCH2CH3

N-ethylformamide

0

+ + (4) 1. ~iAIH4 ; 2. H30

0 . II G)

(1) H-c-o- Na+ + CH3CH2NH3 II

(2) H-c-o- Na+ + CH3CH3 + NH3

0 II +

(3) H-c-o- Na + CH3CH2NH2

37. tJ~ffiu1fialud\L,1:'ti~afl~alfl vcN cH3CH2MgBr ,..

0

H o• 3 ...

0 II

(4) H-C-OH + . CH3CH2NH2

(1)~ (3)~ v N,OH

(2) ()'("

(4) v~ ........... 38. U~MU1fl £) 'tJd\ ,r,L£) L 1Utli £) '"

(2) H2f'Ni +

(3) 1. DIBAH/toluene ; 2. H30

CM225 435

0

~OH ~H d'OH

(1) (2) (3) ... ~

(4) YHl')1lUYh1 1, 2 LLft:: 3 40. ~a~~ft~~n~a~u~n;u,~nlun~oial~

~Jl-~ Ho• V 0 · + CH3MgBr (exc;ess) _____.... 3 ..

(3) ft11~nlud tin 3-methylbutanoyl2-methylbutanoate.

DU . 0. . .

••••••••••••••••••••••••••••••••••••••••••••••• 'II ••••••••••••••••.••••••••••••••••••••••••.••

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -. ........................................ .

436 CM·225