Professional Documents
Culture Documents
T Ha hc
CHUYN : HIN TNG CHUYN V TRONG PHN NG HU C Trong hu ht cc phn ng ha hc hu c, trung tm phn ng l cc nhm chc v ch c s bin i v cu to (cu trc) . Tuy nhin, nhiu phn ng c s bin i khng ch v tr nhm chc m c s tham gia ca c gc hidrocacbon to ra nhng sn phm khc d kin, l hin tng chuyn v trong phn ng hu c. Chuyn v gm 3 loi ch yu: + Chuyn v 1,2 (Thuc dy no). + Chuyn v 1,3 (Thuc dy khng no no). + Chuyn v t nhm chc vo vng thm (Thuc dy thm). I. CHUYN V 1,2 I.1. Chuyn v 1,2 Nucleofin L s chuyn v m nhm nguyn t hoc nguyn t chuyn i mang theo c cp electron. I.1.1. Chuyn v n nguyn t Cacbon a. Chuyn v Vannhe-Mecvai: Chuyn v nguyn t Hidro, gc Ankyl, Aryl n v tr C+ (To cacbocation bn hn). Loi chuyn v ny thng gp : Ancol/H+(P th, phn ng tch nc), dn xut/Ag+, amin/HNO2, hidrocacbon (Anken/H+)... VD:
CH3 CH3 C CH3 + HCl CH2OH - H2 O CH3 CH3 C CH3 CH2Cl
Pinacol
T Ha hc
CH3
CH3
NH2
c th lp th: Do to ra cacbocaction trung gian dng cu ni nn chuyn v Vanhe-Mecvai v chuyn v Pinacol-Pinacolon u lm quay cu hnh sn phm (C). Hng chuyn v: + Nhm dch chuyn mang theo c cp electron (Nh mt tc nhn Nu) nn nhm no c tnh y electron mnh hn s b chuyn dch. VD:
CH3C6H4 C6H5 C OH C6H4 CH3 C C6H5 OH +H - H2O
+
Chuyn v
-H+
SPP
+ nh hng khng gian: o-Anizyl kh nng dch chuyn km p-Anizyl 1500 ln. c. Chuyn v Vonfer Chuyn ha -diazoxeton thnh xeten, tc dng vi H2O (Ancol) to ra axit (este). VD:
RCOCHN2 +Ag2O -N2 RCOCH Cacben
..
Chuyn v
R-CH2COOH R-CH2COOR'
+SOCl2
R-COCl
+CH2N2
RCOCHN2
O
+Ag2O
+CH2N2
CV
Trng THPT Chuyn Lo Cai d. Chuyn v benzylic (Chuyn v Benzyl-axit benzilic) L s chuyn ha -dixeton/HO- thnh -Hidroxi axit.
ArCOCOAr HOAr Ar - C - C - OH
O O
-
T Ha hc
Ar O CV Ar - C - C - OH
O-
H3O+
Ar O Ar - C - C - OH
OH
I.1.2. Chuyn v n nguyn t Nit a. Chuyn v Hopman: Amit chuyn ha thnh amin di tc dng ca BrO-/HO-. .. CV -BrHOBrOR-CO-NH2 R-CO-NHBr R-CO-N Br R-CO-N :
R-N=C=O
+ H2O -CO2
R-NH2
b. Chuyn v Curtius
R-CO-N3 -N2, to R-CO-N : CV R-N=C=O + H2O -CO2 R-NH2
(Azit) Nu phn ng trong dung mi khng c hidro linh ng, phn ng dng li giai on to isoxianat. c. Chuyn v Lotxen
R-CO-NH-OH + HO-H2O R-CO-N - OH -HOR-CO-N : CV R-N=C=O + H2O -CO2 R-NH2
Nh vy, cc chuyn v Hopman, Curtius, Lotxen v Schmitdt u qua h/c isoxianat, ch khc iu kin v cht ban u. e. Chuyn v Backman Chuyn ha xetoxim (V cc dn xut O-Axyl ca chng) thnh cc amit th. Xc tc thng axit nh: H2SO4; PCl5; RSO2Cl; BF3; P2O5... C ch:
R C
N OH
R' +H
+
R' +C
N
HO + H2 O -H
+
R' C
N
O C
NH
R'
-H2O, CV
V mt lp th: Trong chuyn v Backman, vi cc xetoxim khng i xng (c phh), nhm b chuyn v v tr anti (i) vi nhm -OH. VD:
T Ha hc
PCl5 O C - NH p-CH3OC6H4
O C6 H 5 C - NH C6H4OCH3 - p
C6H5
OH
ete
PCl5 ete
I.1.3. Chuyn v n nguyn t Oxi a. Chuyn v Bayer-Viliger Nm 1899, nh ha hc c Baeyer v nh ha hc Thy S Villiger trong lc nghin cu v phn ng m vng hp cht Xeton vng bng peroxi axit hoc hydro peroxit, h pht hin ra Xeton s c chuyn ha thnh este v Xeton vng chuyn ha thnh lacton hoc hydroxi axit tng ng. V vy loi phn ng ny c dt tn l Phn ng oxi ha chuyn v Baeyer-Villiger
Xeton C ch phn ng
Este
Xeton
Lacton
Phn ng Baeyer-Villiger c nhng c im sau: + S chuyn v u tin xy ra so vi nhng phn ng khc. VD: Hp cht , bt bo ha xeton cho phn ng oxi ha chuyn v vi nhm carbonyl thay v oxi ha ni i. + Nhm tham gia chuyn v thng theo th t: alkyl bc 3> xyclohexyl> alkyl bc 2 > aryl > alkyl bc 1 > metyl. + S chuyn v xy ra c lu gi cu hnh lp th ca nhm chuyn v. + Nhiu loi tc nhn oxi ha c th s dng cho phn ng ny vi hot tnh gim dn tng i nh sau: axit CF3COOH >axit monopermaleic > axit monoperphtalic > axit 3,5-dinitroperbenzoic > axit p-nitroperbenzoic > axit mclo peroxi benzoic ~ axit performic > axit perbenzoic >axit peracetic >> H2O2. + Vi -dixeton c th b oxh B-V thnh anhidrit axit, cn -dixeton th khng. a. Chuyn v Hidropeoxit: Chuyn v ny xy ra khi phn hy hp cht peoxit, bn cht tng t chuyn v Bayer-Viliger. VD:
T Ha hc
CV (CH3)2C+-O-C6H5 + H2 O (CH3)2C=O + C6H5OH
-H2O
CH3
C 6 H5 C O+ CH3
I.1. Chuyn v 1,2 electronfin, ng li Nhm chuyn v khng mang theo cp electron lin kt (ng vai tr nh tc nhn electronfin), to lin kt mi vi cp eletron ca nguyn t chuyn n. a. Chuyn v Steven:
+ Z-CH2-N(CH2)2 R HO-H2O Z-CH-N(CH2)2 R
R: Anlyl;
Benzyl...) b. Chuyn v Wittig: Chuyn ha ete di tc nhn baz mnh: C6H5Li; NaNH2... VD:
CH3 - O - CH2C6H5 + C6H5Li -C6H6 CH3 - O - CH C6H5
CV
O - CH C6H5 CH3
+ H2O -HO-
HO - CH C6H5 CH3
Kh nng chuyn dch ca cc gc: Anlyl, benzyl > metyl; etyl > phenyl. c. Chuyn v 1,2 Halogen ( Chuyn v 1,2 ng li ) t-C4H 9OCl CH3CHClCH2Br (SPP) + CH 3-CBr(Cl)CH3 (SPC) VD: (CH3)2CHBr (Sn phm chnh u tin hng to ra gc t do bn hn) II. CHUYN V 1,3 a. Chuyn v Anlylic Trong phn ng th ca dn xut Anlyl: RCH=CH-CH2X /NaOH VD:
CH3CH=CHCH2OH (40%) CH3CH=CH-CH2Cl + NaOH CH3CH(OH)CH=CH2 (60%) CH3CH=CHCH2OH (15%)
(CH3)2C=CH-CH2Cl + Na2CO3
H2 O
CH3CH(OH)CH=CH2 (85%)
b. Chuyn v Xeton-Enol (Hin tng Tautome) Xut hin hp cht c H linh ng: Hp cht Cabonyl; hp cht cha nhm: -NH-CO- ; > CH-NO2 ; > CH-NO ... Nhng s chuyn ha Xeto-Enol c nhiu ngha hn c. Di xc tc H+ hoc HO-, hp cht Cacbonyl b Enol ha nhanh to ra mt cn bng. T l Xeto/Enol trng thi cn bng ph thuc vo nhit , nng , dung mi v c bit l cu trc. Nu trong phn t c nhm gy -C mnh lin hp vi h Enol th dng Enol chim t l ln. VD: Phm Duy ng - Chuyn hu c 5
T Ha hc
Cn bng Xeto-Enol
Xeto ha xt axit
Enol ha xt axit
Enol ha xt bazo
III. CHUYN V VO VNG THM Chuyn v vo vng thm ch yu l cc phn ng mang c th th Electronfin vo vng benzen (Nhm chuyn v ng vai tr nh mt tc nhn elctronfin). Cc chuyn v vo vng thm thng t cc nguyn t d t nh Oxi, Nit. III.1. Chuyn v t nguyn t oxi vo vng thm a. Chuyn v Frai (Fries) Chuyn v nhm axyl trong este ca phenol vo vng thm di xt axit Lewis (AlCl3, ZnCl2, FeCl3...) nhit thp, u tin chuyn v vo v tr Para. Khi vng hm c sn nhm y e (Hot ha vng) th chuyn v Frai cng d thc hin.
T Ha hc
OCOCH3
AlCl3, 165oC
OH CH3CO
CH3 CH3CO
80%
CH3
95%
CH3
b. Chuyn v Claizen Khi un nng ete Anlyl chuyn ha thnh o-Anlyl phenol.
OCH2CH=CH2
200oC
OH CH2CH=CH2
90%
III.2. Chuyn v t nguyn t Nit vo vng thm a. Chuyn v nhm Ankyl un nng mui Halogen ca Aryl ankyl amin, nhm ankyl s chuyn dch n v tr o- hoc p- ca nhn thm. VD:
NR2
HHal, to
NHR
NHR
R
NHR
HHal, to
NH2
NH2
b. Chuyn v Octon (Chuyn v nguyn t Halogen) un N-Clo axetanilit vi HCl (HBr), thu c o- hoc p- Clo (Brom) axetanilit.
N(Cl)COCH3
HHal, to
NHCOCH3
NHCOCH3
Hal
Hal
c. Chuyn v nhm Aryl azo Chuyn v nhm Aryl azo ca diazo aminobenzen thnh p-aminoazobenzen
T Ha hc
N=N-Ar
NH2 Nu v tr p- c nhm th, s chuyn v vo v tr od. Chuyn v Fis - Hep(Chuyn v nhm Nitrozo ) Cho hp cht c nhm Nitrozo ca amin thm tc dng vi HCl, to.
N(NO)CH3
HHal, to
NHCH3
NHCH3
NO
NO
-NH-NH-
H2N
NH2
(70%)
Trng THPT Chuyn Lo Cai T Ha hc IV. BI TP VN DNG Bi 1: Hy d on sn phm to thnh trong cc qu trnh chuyn v sau: Xiclo heptanon. a. Xiclo hexanon + CH2N2 b. Xyclohexanon + 1. H2N-OH; 2. H+ Caprolactam (CH3)3CCH2NH2 c. (CH3)3CCH2CONH2 + NaOBr
H3C
-NH-NHH+
CH3
H2N
NH2
d.
CH3
H3C
H
+
(C6H5)2C-C(CH3)2
e.
(C6H5)2C-C(CH3)C 6H5
f.
g.
h. p-CH3OC6H4-COCOC6H5
i. 2,2-dimetyl propan-1-ol + H+ k. Xiclopentyl metanol + H+ Bi 2: Hy gii thch 1 . 3-metylbuten-1 tc dng vi axit clohidric to ra cc sn phm, trong c A l 2-clo-3-metylbutan v B l 2-clo-2-metylbutan. Bng c ch phn ng, hy gii thch s to thnh hai sn phm A v B. 2 . 2-metylbuten-2 phn ng vi axit clohidric. Trnh by c ch ca phn ng, cho bit sn phm chnh v gii thch? 3. But-3-en-2-ol tc dng vi dd HBr to thnh 3-brombut-1-en v 1-brombut-2en. Hy gii thch? 4. Ho tan hexa-1,4-dien-3-ol (A) trong H2SO4 ri sau mt thi gian pha long dd th thu c A v 2 ancol ng phn cu to ca n. (BT1,2 HS t gii) Bi 3. Cho ancol A c CTCT:
H3C CH3 C CH3 OH
Khi ehiat ha ancol A thu c 3 ankaien lin hp. Vit CTCT, gi tn 3 ankaien lin hp? Trnh by c ch phn ng? HD: Phm Duy ng - Chuyn hu c 9
OH
OH
OH
H+
OH
OH
OH
HO-
T Ha hc
-H+
-H+
Bi 4. Tin hnh phn ng gia 3,5,5-trimetyl xiclohex-2-enon v n-butyl magi ioua. Sau , thu phn hn hp bng dung dch HCl 4M thu c hp cht B. B b chuyn thnh nm ng phn, k hiu t D1 n D5 c cng thc phn t C13H22. Vit cng thc cu to ca cc ng phn D1, D2, D3, D4, D5 v gii thch s hnh thnh chng? HD:
O
1 .BuMgBr 2. H 2 O
Hb HO H+
- H2O
Ha
- Hb - Ha
D2
D3
CV
D1 H+
- H O 2 +
D5
D4
Bi 5. X l - halogen xeton Vi baz mnh to thnh cc sn phm chuyn v. S chuyn v ny gi l phn ng Favorski. - cloxiclohexanon s chuyn v thnh metylxiclopentancacboxilat khi c mt CH3ONa trong ete. Hy xc nh c ch ca phn ng ny.
O Cl CH3ONa ete COOCH3 NaCl
HD:
10
T Ha hc
OCH3 H2O OH
OCH3
Bi 6. Hy vit cu to cc cht t A n E:
O COOH OH
(CH3CO)2O CH3COOH (CH3)3CNH2 HBr
C H3C
COOH
Br 2 H+
OH
HD:
COOH
OOCCH3
COOH
OH
COOH
OH
A:
; B
CH3CO
COOH
OH
;C
BrCH2CO
CH2OH
OH
D: (CH3)3CNHCH2CO ; E: (CH3)3CNHCH2CH(OH) Bi 7. Anlylmagie bromua (A) phn ng vi acrolein to thnh cht B, sau khi thy phn B s c sn phm C duy nht. un nng C nhn c cht D. Cho D phn ng vi C6H5Li thu c sn phm E. un nng E khi c vt iot th c F c cng thc C12H14. 1 . Hon thnh s dy phn ng trn (vit cng thc cu trc ca cc cht hu c trn t C n F). 2 . Ghi k hiu c ch cc giai on ca phn ng di dng cc mi tn trong s , tr giai on to thnh F. HD:
11
T Ha hc
CH2=CH-CH2-CH2-CH=CH2-OMgBr B
tautome ho H3O+
CH2=CH-CH2-CH2-CH=CH-OH C
CH2=CH-CH2-CH2-CH2-CH=O D
Hoc:
CH2=CH-CH2-MgBr AN H2O + CH2=CH-CH2-CH-CH=CH2 CH2=CH-CH2-CH-CH=CH2 cng 1, 2 -MgBr(OH) CH2=CH-CH=O B OMgBr C OH
t Chuyn v 3, 3
o
H bin
H D O
OH
OH
H2O
xeto-enol
C6H5Li AN
C6 H 5 H OLi
C6 H 5 H E OH
Vt iot, to - H2O
C6 H5
TI LIU THAM KHO [1] C s l thuyt ha hc hu c - GS.TS Trn Quc Sn - NXBGD 1979. [2] Bi tp ha hu c - GS.TSKH Ng Th Thun - NXBKHKT 2001 v 2008. [3] thi HSGQG cc nm. [4] Advanced Oganic Chemistry - Part B - Reactions and Synthesis - Kluwer Academic Publishers - New York - 2002. [5] Name Reactions - Phil S.Baran - La Jollan - 2006
12