[123doc.vn] Ga Dan Xuat Halogen Va h c c Nguyen to Danh Cho Chuyen Hoa

7/25/2019 [123doc.vn] Ga Dan Xuat Halogen Va h c c Nguyen to Danh Cho Chuyen Hoa

1/15

Trng THPT Chuyn Bc Ninh Th/s NgVn BnhCHNG V DN XUT HALOGEN CA HIROCACNON

V HP CHT C NGUYN T

BI 1 DN XUT HALOGEN CA HIROCACBON

I. !" !#"$%& '"(! )*+,& -%!" '"'& /0!# '"(!.1. !" !#"$%.K/n: khi thay th mt hay nhiu nuyn t H trong phn t hirocacbon bng mt hay nhiu nguyn tnguyn t halogen ta thu !c "#n $u%t halogen c&a hirocacbon'(): *H+*l, *H-*l-, *H*l+, **l., **l+0''

1$: ( th2nh ph3n nguyn t, ngo2i *, H ra c4n c5 ch6a c7c nguyn t halogen'. P"(! )*+,.8 )9a 2o b;n ch%t c&a halogen: ng


2/15

Trng THPT Chuyn Bc Ninh Th/s NgVn Bnh(Ey c7c @ng phn c%u t=o c&a "#n $u%t halogen g@m c5

N G@ng phn m=ch *N G@ng phn tr halogen, tr nh7nh'N G@ng phn tr lin kt bi'

b. ng phn lp th.N G@ng phn hLnh h\c

()F: (it c7c @ng phn hLnh h\c c&a *.Hd*l 2 g\i tnf

H

Cl C2H5

C = C

H

H

Cl

C2H5

C = C

H

Cl CH3

C = C

H Cl

C = C

HCH3

CH3CH3

ci?, RQNFNclobutNFNenP tran?, R_QNFNclobutNFNen tran?, RQN-NclobutN-NenP ci?, R_QN-NclobutN-NenCl

H ClH

CH3

H

CH3 H

ci?, RQNFNcloN-Nmetyl$iclopropanP tran?, R_QNFNcloN-Nmetyl$iclopropan()-: (it c7c @ng phn hLnh h\c c&a "#n $u%t iclo$iclohe$an

F,-Niclo$iclohe$an tran?Ra,aQ tran?Re,eQ ci?Ra,eQ ci?Re,aQ

F,+Niclo$iclohe$an ci?Ra,aQ ci?Re,eQ tran?Ra,eQ tran?Re,aQ

F,.Niclo$iclohe$an tran?Ra,aQ tran?Re,eQ ci?Ra,eQ ci?Re,aQN G@ng phn uang h\c'()+: (it c7c @ng phn uang h\c 6ng Ai cCng th6c *.H*l

H

C

Cl

C2H5

CH3H

C

Cl

C2H5

CH3

II. T;!" 6"34


3/15

Trng THPT Chuyn Bc Ninh Th/s NgVn Bnh

N Kh; njng ph;n 6ng c&a c7c "#n $u%t halogen tjng "3n t "#n $u%t *lVrW "o tjng "3n phn c9c ho7 c&a lin ktR phn c9c ho7 tjngkh; njng phn c^t lin kt tjngQ'

N Kh; njng ph;n 6ng tjng "3n t "#n $u%t phenyl, inyl q ankyl, $icloankyl q anlyl, benSylIII.1. P"?! 7!# 4"9 !@6)*'",!.Yng u7t: NN OsNsO ++

O: , *l, Vr, W

s: HN, N, *UHTN, *N, *H*NP H-P H+1, 1H-0'1. C6 )*+, '"?! 7!# 4"9.a. Th X bng nh! "#$.Ot ch& yu Ai "#n $u%t monohalogen'

Yv: HOHNHO - ++Kh; njng ph;n 6ng c&a c7c "#n $u%t tjng theo th6 t9: phenyl, inyl q ankyl, $icloankyl q anlyl,

benSyl' *w thJN )#n $u%t anlyl, benSyl ph;n 6ng "x nh%t chMng c5 thJ ph;n 6ng Ai H - ngay nhiIt th


4/15

Trng THPT Chuyn Bc Ninh Th/s NgVn Bnh. C 6"9 '"?! 7!# 4"9 !@6)*'",! Nh;n 6ng th nucleophin c5 thJ $;y ra theo mt trong hai cD ch ]1F Rth nucleophin Dn phn tQhoc ]1- Rth nucleophin l~ng phn tQa. &5 ch 6178 l4 c5 ch ch9 -*y 0a !:t g,a, ;on th


5/15


R-X l& CH3X R-CH2-X R2CH-X R3C-X

T'c () th*+N, t ng

T'c () th*+N gi.$

() : Yh9c t R*H+Q+*NO h3u nh ch $;y ra theo cD ch ]1F, khCng theo cD ch ]1- "o 7n ng[ khCnggian r%t lAn

N Bc anlyl 2 benSyl l2m tjng tc th ]1F, ]1- "oZ tr=ng th7i chuyJn tip !c l2m bn nh< ?9 $en ph& c&a ` Ai ` c&a tr=ng th7i

chuyJn tipZ *acbocation ?inh ra !c l2m bn bi hiIu 6ng Z * c&a c7c nh5m th n2y l2m cho iIn tch

RZQ !c gi;i to; trn hI lin h!pN Bc phenyl 2 inyl l2m gi;m tc th ]1F, ]1- "o hiIu 6ng Z* c&a c7c nh5m th n2y ln lin ktAi halogen l2m cho lin kt n2y c5 tnh ch%t c&a mt ph3n lin kt Ci n5 ng^n l=i njng lDnglin kt tjng kh5 b ph7 ~ kh5 ph;n 6ng'8 V;n ch%t c&a halogen']9 tjng phn c9c ho7 c&a lin kt *NO t n W ph;n 6ng th ]1F chim u th "o kh; njng

t7ch halogenua t=o cacbocation tjng ln']1F : W | Vr | *l ||Rh3u nh trDQ8 Y7c nhn 1u 2 "ung mCiZ Y7c nhn 1u m=nh l2m tjng kh; njng cD ch ]1- RHN, N, *N0'Q(): 1u tjng n@ng HNhAng ]1- ? u tin hDn 1u gi;m n@ng HNR"ung "ch kim longQ hAng ]1F ? u tin hDnZ )ung mCi: "ung mCi phn c9c c5 kh; njng ?onat ho7 tt ? l2m n nh tr=ng th7i chuyJn tip ]1F Rcacbocation Q hDn tr=ng th7i chuyJn tip ]1-'() *H+Vr H,a$eton - RcD ch ]1-Q *H+Vr /$ica$it RcD ch ]1FQ

III.. P"?! 7!# 46" "%)*#!. C 6"9 E()F: *H+N*H-*l Z KH t,H *H-X*H-Z K*l Z H-

R*hM nu "ung mCi l2 H- ? $;y ra ph;n 6ng th *H+N*H-*lZKH b

- t,H *H+N*H-HZK*lQYv: |*HN*Oq Z KH t,H |*X*q Z KO Z H-

()-: Ho2n th2nh phDng trLnh ph;n 6ng*H+N*H*lN*H-N*H+Z KH

t,H f

t,H *H-X*HN*H-N*H+R?ppQ Z *H+N*HX*HN*H+R?pcQ @, 4J6 46" K%,': 1guyn t Hal u tin t7ch Ai H c&a nguyn t * bn c=nh c5 bEc cao hDnt=o th2nh anken c5 nhiu nh5m ankyl hDn ni Ci Rlin kt Ci nm trong m=chNc5 nhiu hiIu 6ng Hnh%tQN Kh; njng tham gia ph;n 6ng t7ch tjng "3n t "#n $u%t W

N Yu theo iu kiIn 2 t7c nhn ph;n 6ng m2 ph;n 6ng t7ch "ixn ra theo mt trong hai cD ch ?au: cDch t7ch Dn phn t _FP cD ch t7ch l~ng phn t _-'a. &5 ch tch l?ng phn t@ A7.]D @: ph;n 6ng "ixn ra theo mt giai o=n t=o th2nh tr=ng th7i chuyJn tip tDng t9 ]1-'

sN Z HN* * O s0H0'* *0O Hs Z ON Z |*X*qpX k'*NO'*s

h;n 6ng t7ch nucleophin bao gi< czng km theo ph;n 6ng th ]1b. &5 ch tch ;5n phn t@ A>.]D @ : cD ch "ixn ra theo - giai o=n

Biai o=n F : t7ch nucleophin t=o cabocation, y l2 giai o=n chEm uyt nh tc ph;n 6ng

|*HN*Oq |*HN*Z

q Z ON

Biai o=n - : t7ch HZ"Ai t7c "wng c&a nucleophin, giai o=n n2y "ixn ra nhanh|*HN*Zq Z sN |*X*q Z Hs

pX k'*NO

Chng II DN XUT HALOGEN Trang 5


6/15

Trng THPT Chuyn Bc Ninh Th/s NgVn Bnh() : R*H+Q+*NVr

bt,H,KH R*H+Q+*Z Z VrN

R*H+Q+*Z *H-X*HR*H+Q- Z HZ

&h' (8 N )ung mCi nAc thL ph;n 6ng ]1chim u th, ph;n 6ng t7ch $;y ra tN )ung mCi ancol thL ph;n 6ng _ chim u th t=o th2nh ?;n ph{m t7ch c5 l#n t ?;n ph{m

th'N h;n 6ng t7ch _F, _-u theo hAng tran? R?;n ph{m bn hDnQ

+ C2H5O-

HCH3

Br

H

HH H H

HCH3 H

Br

C2H5O

CH3

H H

H

tr=ng th7i chuyJn tipN Yc ph;n 6ng t7ch gi;m khi bEc c&a "#n $u%t gi;m WWW | WW | WN *D ch _-chim u th khi n@ng baSD cao, c4n cD ch _ Fchim u th Ai c7c "#n $u%t

c@ng knh c5 ;nh hng khCng gian lAn' (Ai c7c "#n $u%t c@ng knh 2 t7c nhn nucleophin ancol

czng c@ng knh thL ph;n 6ng theo _Fchim u th 2 nhiu khi ?;n ph{m khCng tun theo ui t^cai$ep()

CH3

Br

CH3-CH2-C-CH3(CH3)3CONa

E1CH3-CH2-C(CH3)=CH2(72%) + CH3-CH=C(CH3)2(28%)

*D ch _Fth


7/15


Z Yh 2o m=ch nh7nh: ]Ra?ktQZ GJ iot ho7 nhn thDm ph;i "ng ch%t o$i ho7 nh HW+, H1+*UHT' Z W- *UHTW Z HWHW Z HW+ W- Z H-

. P"?! 7!# 6!# HX


8/15


liti0

R-H

R#COCl

R-OH

+ X2

(RCO)2

O

O

R-CH=O

2/ H2O

R-X

R#-X

R3C-OH

R-CHO

R-R#

RCH2CH2OH

H2O

CH(OC2H5)3 H2O

R--H

1/ O2 2/ R-X 3/ H2O

+ '/ee *ha$

R-'-X

+ HX H-OH H-OR

H-NH-R H-OOCR

R-X

CH2- CH2RCOOH

CO2 H2O

2/ H2O

RCOR

RCOOR#

R2CH-OH

2/ H2O

2/ H2O R3C-OH

R-'-X

' Ynh ch%t 2 6ng "wng c&a h!p ch%t cD magi

():*-HTN*l Z g khan,ete *-HTNgN*l

N *-HTNgN*l Z H- *-HUZ g*lRHQN *-HTNgN*l Z W- *-HTW Z gW*lN *-HTNgN*l Z *H+*l *-HTN*H+Z g*l-N *-HTNgN*l Z - *-HTNg*l

*-HTNg*l Z *-HT*l -*-HTg*l *-HTg*l Z HO *-HTH Z g*lON *-HTNgN*l Z *- *-HTN*g*l *-HTN*g*l Z HO *-HT*H Z g*lO

O

CH2- CH2- R-'(-X + RCH2CH2O'(Cl

*H-*H-g*l Z HO *H-*H-H Rancol tjng -*Q Z g*lO

OCH3

CH2- CH-

CH3- R-'(-X + RCH2CHO'(Cl

CH3

RCH2CH-OH + '(ClX

CH3

RCH2CHO'(Cl + HX

N NgN*l Z H*HX N*H-Ng*l N*H-Ng*l Z H- N*H-NH Z g*lRHQ

CH3

CH3- CH=O- R-'(-X

RCH2CH-OH + '(ClX

CH3

RCH2CHO'(Cl + HX

CH3

RCH2CHO'(Cl

Chng II DN XUT HALOGEN Trang 8


9/15


O

CH3- C - CH3- R-'-X

+ HX

CH3

RCH2C - O'Cl

CH3

CH3

RCH2C - O'Cl

CH3

CH3

RCH2C - OH + 'ClX

CH3

R1COR+ RCOOR#- R1-'-XOR#

R1- C - O'ClR

+ R#O'Cl

R1COR+ RCOCl- R1-'-XCl

R1- C - O'Cl

R

+ 'Cl2

N NgN*l Z HN*R*-HTQ+ N*HR*-HTQ- Z *-HTg*l N*HR*-HTQ- Z H- N*HX Z -*-HTH RphDng ph7p n2y "ng

J iu ch anehitQ

Chng II DN XUT HALOGEN Trang


10/15


BI TcPDN XUT HALOGEN

K4, >(it *Y*Y c&a t%t c; c7c @ng phn monoclo l2 "#n $u%t c&a !"#$%n&an, toluen, nN 2 i?obutan'B\i tn c7c @ng phn 5 theo "anh ph7p th


11/15


K4, >2 ]^p $p theo trEt t9 gi;m "3n kh; njng ph;n 6ng theo cD ch ]1F c&a c7c h!p ch%t ?au:VenSylcloruaP $NclobenSylclorua $Nmeto$ibenSylclorua $NmetylbenSylclorua 2 $NnitrobenSylclorua'Bi;i thch ?9 ?^p $p 5'

K4, >LHai "#n $u%t halogen c5 cng cCng th6c phn t *THFFVra' Khi t7ch lo=i mt phn t HVr t ` 2 ?au 5 thu phn oSonit c&a ?;n ph{m t7ch HVr ngomanehit 2 anehit i?obutiric'

b' Khi thu phn "#n $u%t halogen V cho ancol bEc + 2 khi lo=i HVr cho trimetyletilen'Hy $7c nh cCng th6c c%u t=o c&a ` 2 V'K4, >MVa "#n $u%t halogen c5 cng cCng th6c phn t * UHF+Vr' Khi un n5ng Ai "ung "ch kimancol thu !c hai ole>in c5 c%u t=o kh7c nhau nhng c5 cng cCng th6c phn t *UHF-' 1u cho haiole>in 5 t7c "wng Ai HW ? thu !c hai ?;n ph{m -NiotN+Nmetylpentan 2 +NiotN+Nmetylpentan' Hy$7c nh cCng th6c c%u t=o c&a ba "#n $u%t halogen' (it c7c Y'

K4, >NHai h!p ch%t h[u cD ` 2 V c5 cng cCng th6c phn t *dHU*l-2 u !c oSon ho7 chooSonit' ]au khi thu phn oSonit, ` cho >omanehit 2 anehit -,+NiclopropionicP V cho anehitcloa$etic' O7c nh *Y*Y c&a ` 2 V' (it Y iu ch ` 2 V t a$etilen 2 c7c ch%t C cD c3nthit'

HP CHT C NGUYN TK4, > a' (it c7c Y c&a c7c "#n $u%t ibrom cho ?au y Ai g trong ete khan: F,-NibrometanP F,.NibrombutanP F,+NibrompropanP pNibrombenSenP F,-Nibrombutan' b' 1h[ng h!p ch%t n2o thu !c khi cho c7c h!p ch%t ?au ph;n 6ng Ai g R"Q trong ete: FNcloN.N

brombenSenP -NbromNFNmeto$ibutan 2 F,.,TNtribromhe$an'K4, 7(it c7c Y c&a *UHTgVr Ai tng h!p ch%t ?au: H*H, *H+*H, *H+**l, *-, *-HTH, W-,-, gVr' (it cCng th6c c%u t=o c&a c7c ?;n ph{m thu phn'

K4, 2*ho $eton *THF RWQ ph;n 6ng Ai *-HTgVr, ?au khi thu phn ?;n ph{m trung gian thu !cancol' Y7ch nAc t ancol thu !c anken RWWQ' Khi oSon ho7 RWWQ cho ietyl$eton R*-HTQ-*X 2 anehit a$etic'(it *Y*Y c&a RWQ 2 RWWQ' 1u phDng ph7p tng h!p RWQ t etan 2 c7c ch%t C cD c3n thit'

K4, LKhi cho h!p ch%t ` 2o "ung "ch *H+gW trong ete th%y c5 kh *H.tho7t ra 2 t=o th2nh h!p ch%t V'*h%t ph;n 6ng Ai "ung "ch Hg].trong mCi tr


12/15


ph;n 6ng iu ch h!p ch%t cD magie th


13/15


bQ *ho F,.Nibrombutan t7c "wng Ai g R"Q trong ete' )ung "ch ete c&a h!p ch%t thu !c choph;n 6ng Ai etyl a$etat theo t lI mol l2 F:F, ?au 5 Ai H -' (it c7c phDng trLnh ph;n 6ng$;y ra'

cQ (it c7c phDng trLnh ph;n 6ng gi[a anhirit propionic R*H+*H-*Q- Ai *UHTgVr tronghai tr


14/15

*H+*H-*H N * N *-HT*H+ H

*H+


K*1 *H+R*H-Q-*HR*1Q*H+

+H/HQ-gVrH*QF -T- *H+R*H-Q-*HR*H+QN*N*-HT

+H/HQ-gVr*HQF -+

eQ *UHT*H+ *UHT*H-*l

1a/ete*UHT*H-*H-*UHT

g/ete*UHT*H-g*l

H-]."

Fo*

FQ *H+*H

-Q H-/HZ

gQ

H-]."

Fo*

FQ *H+**-HT

-Q H-/HZ

Vr+ g/ete

"" 1aH

Kn.

*l-/a?

*UHT*H-N*HN*H+

H

*H+*H*-HTH

*H+*H*-HTVr

*H+*H*-HTgVr

*-HT*H N *H N *H*-HT

H*H+ *H+

*-HT*X *N *H*-HT

*H+ *H+

*-HT* N *H N *H*-HT

H *H+

*H+ *H+*H+*H+

H

*UHT*HX*HN*H+

B, 1.(it c7c phDng trLnh ph;n 6ng c&a *l+, Hg*l-, *"*l-Ai *UHTgVr trong hai iu kiIn:N Yheo t lI mol F:FN %y " *UHTgVr'

T0* l,

*UHTg*l Z *l+ F:F *UHTb*l- Z g*l-+*UHTg*l " Z *l+ R*UHTQ+ Z +g*l-

*UHTg*l Z Hg*l- F:F *UHTHg*l Z g*l--*UHTg*l " Z Hg*l- R*UHTQ-Hg Z -g*l-*UHTg*l Z *"*l- F:F *UHT*"*l Z g*l-

-*UHTg*l " Z *"*l- R*UHTQ-g Z -g*l-B, 12.Khi cho h!p ch%t ` 2o "ung "ch *H+gW trong ete th%y kh *H.tho7t ra 2 t=o th2nh h!p

ch%t V' *h%t ` ph;n 6ng Ai "ung "ch Hg].trong mCi tr


15/15


*H+*H-*RHQR*H+Q- *H+*HX *R*H+Q-

[123doc.vn] Ga Dan Xuat Halogen Va h c c Nguyen to Danh Cho Chuyen Hoa

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