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PHAN 1: NUCLEOPHIL VA ELECTROPHIL
1. NUCLEOPHIL
1.1. Dinh nghia
- Thuat ngit nucleophile c6 thé duge chia thinh "nucleo" bat nguén tir hat nhan va "phile" c6 nghta la yéu.
~ Giiu electron va do d6 “thieh tién Iai gan hat nhan”,
~ Mang dign tich 4m hoe trung tinh: O, N, S.
= Cé kha ning cho cae electron dé tao lién két.
- MOt nucleophile cn duge goi la base Lewis
Bai tap: Tinh base vi tinh Nucleophil khéc nhau nluc thé nao?
°
° °
von e
1.2. So sinh 4} manh ciia ede chat c6 tinh nucleophil
RS" > ArS" > S,0; > (HAN),C-S > I > CN- > SCN" > HO" > D
ArO” > Cl > Pyridine > AcO” > HOH
1.3. Cac yéu té anh hwéng én tinh nucleophil
a. DO Am dign
- Tir (1) dén (4), 46 am dign tang din, tinh nucleophil giam din
b. Dung m
- Trong dung mdi protic (phan cye- ¢6 hydro linh dng nhu alcol, acid, nuée...),
dan dén
- Trong dung méi aprotic (phan cyre- khéng cé hydro linh dng: acetone, DMF, ...), tinh nucleophil tang
tir I den F-,
Tai sao khong ding cdc dung mdi tro hodn todn nine.
c. Cong huéng
- Khi cp electron duge gidi ta trén 1 nguyén tt kha, mat dé electron trén nguyén tir 6 gim, tird6 Kam gidim
tinh nucleophil
fh Nucleophil tir I- giam
can trong cée phan ing ciia cdc tée nhdn nucleophil?
= Cac nh6m thé Ién gan trung tam nucleophil lam gim kha nang tiép can ciia trung tam nucleophil dén trung
im eleetrophil, tir d6 am gidm tinh nueleophil. Chu Van Phong_0373132227
2. ELECTROPHIL
2.1. Dinh nghia
- Thuat ngif electrophile cé thé duoc chia thinh "Electro" cé nghia la dién tir va "phile" c6 nghia la yéu thurong.
- Thigu dign tir va “thich tién lai gan” dign tur
~ Mang dign duong hoie trung tinh.
- Blectrophile con durge goi la acid Lewis.
Bai tap: Hay so sinh kha ning phiin img voi tic nhan nucleophil ciia mét sé tac nhan electrophil sau
1.1 So sinh aldehyde véi ketone
1.2. So sanh giita ketone vi enone lién hyp
1.3. So sanh cdc dan xuat ciia acid carboxylic:
9 9 9 ° L °
vei pbokn don ROH 20 iy
Chloride acid aMhvdride acid ester acid carbamat
1.4. Din xuat halogen (tir F dén 1)
I. PHAN UNG THE
1. Thé nucleophil (Sx)
a. Sy1
Co ché chung
ix dung y b y
Rsolvat héa RoR
(u
Co ché tao carbocation trung gian nén thu duge hén hyp racemic. Mudn so sanh kha nang xay ra ciia 2 phan
mg Sw1 thi ta phai xem xét 46 bin cua carbocation trung gian
Cie logi carbocation
Carbocation thong thing
R
Re R,
Voi cée géc R la cic nhom chite, géc khdc nhau.
whe =p deo.
rbocation nay c6 xu thé chuyén H hay cac géc R dé tao carbocation ben hon. Ngoai ra, chang
thé phan (mg véi alkan dé tao carbocation bén hon.
AL Chu Van Phong_0373132227
sm _
Acylium cation
R-C=O R-C=0*
Oxonium cation
6 —= RO
x YOR, wR,
Allylic cation
NS NA
Carbocation thom
— “ a
a ab
be =
by
BB - Bo:
Cae trong hgp cation @ yj tri dau cau
s ad oly ort
SOF,
Cae tring hgp ngo:
1g (vi tri du cdu nhung van bén virng). Chu Van Phong_0373132227
Bai tap:
1. Khi dun (1-bromo-1-methylpropyl) benzen trong nuée thu duge 3 chat H1, H2, H3. Mét s6 thong tin vé 3
chat d6 durge cho duéi bang sau:
Chat Phan tir khoi (g/mol) Phan trim cdc nguyén to S6 trung tam bat déi
HI 213 %C: 56.36; %6H: 6.15 1
H2 132 %C: 90.85; %H: 9.15 0
HB 150 %C: 79.96; %6H: 9.39 1
Hay xc dinh cu tao etia H1,H2 va H3 va viét co ché tg0 H2 va H3
2. Hay hoan thanh cdc co ché chuyén héa sau, biét ching déu trai qua trung gian cdc carbocation,
».
@ Me
BUH HOH
Br ME ou _H:80, Me HSO,
Z| m4 Br COM
. ol cck
cl
AlCly
> &:
oa
/ ‘
Cpooxa evaotasxe —- vapdg + Or
‘Téc a6 phan img v=k[{Nu}[RX] vi RX 1a dan xudt ban dau.
Do tae nhan nucleophil tan céng 6 phia déi dign so voi X nén phan img Sx2 kim quay céu hinh.
So sinh phan irng Sx1 vA Sx2
SxI Sx2
Yéu t6 quyét dinh ‘D6 bén ciia carbocation Can tro khong gian
Bac alkyl halide 3pD>1 1>2>53
(Electrophil)
DO manh cla tic
nhan nucleophil
Manh (abom tich dign am, CN-,
‘Yéu (nuée, alcol) NH2-, EtO-...)
Dung méi phan eye co nhém O-H hose N- | Dung mdi phan cye khéng cd
Dung mdi H c6 kha ning tao lién két hydro, vi du: | kha nang tao lién két hydro:
aleol DMF, DMSO. Chu Van Phong. 0373132207
Khéng gian san
phim thu duge
Benzylie va allylic
bie 1.2
Benzylic va allylic
bie 3
Arylivinyl halide x x
Racemic Quay cau hinh,
v v
v x
¢. Sxi (cde phan ting Sy gir nguyén edu hinh)
Kinh dién nhat fi phan img thé -OH a sOCh
OH SOCh
R foo Riel
mE wee — for
3
Bai tap: Giii thich tai sao khi str dung SOCI,/Py thi phan img Iai quay céu hinh tuong ty phin mg $x2??
Higu eng nhom ké: phan ting trai qua 2 giai doan la 2 phan img Sx2 lam edu hinh sn phim khdng thay déi
Ga f
Br
Bai tap:
1. Hay giai thich tai sao tir cl
A sang B lai gitt nguyén edu hinh,
xo HNO» ren
oH
NH,
A 8
2. Gia thich hign tuong sau
a
Cc OTS AcONa OAC AcONa oe
OAC AcOH, Ch. AcOH “OAc
OTs ove
_AcONa
i.
4d. Phan tng thé & nh6m allyl
Phan img thé & nhém allyl goi la Sy1” va Sy2’, Sy2 phan tmg nhanh hon Sx2" nén it sin pham Sy2”. Hoa kip
thé Sx2° rat dic thi, nhom Y- tin céng cing huéng véi nhém -X bi tach.
Chi ¥ dén véi cia hop chat cor magie khi 6 mat xiic tae Cu(l) ho&e RoCuLi Chu Van Phong,_0373132227
Bai tap:
1. Hoan thanh chudi phan img sau:
Oo
Monese b 3 OU Cer LID.
0 a ce oO
‘0 CuBr
CaHigOy NHCOs CeIn cusr oH 00
Giai doan khoi mio: Gi
dit dé phan tg.
hinh thinh cae géc tu do ban diu véi sé hrong,
MY — - Mo. ¥
Giai doan phat trién mach: Giai doan nay sé phan tmg dé tao ra sn phim mong mudn cling véri dé Ia lién tue
tao ra gdc c6 thé quay vong duge phan (mg:
Mt .
N-X ———+ N + MX
: M-Y .
N N-Y so!
Giai doan tat mach: giai doan nay cae géc ty bat c§p véi nhau dé tao cae phan tur trung hoa.
Noo+ Mo ——* NM
N + yh NY
Cha y: Giai doan phat trign mach phai tao ra géc cé thé quay vong phan tmg va san phim cua cia phan img
phai duge sinh ra trong giai doan phat trign mech
4 hv . R :
Xe 2x 5. BusSnH > BuySn
“RH
On . . .
2 Her + B+ Hoo 6 ROOR
Dé bén ciia géc trung gian durge danh gid bing sé lugng nhom thé gan vao carbon d6, khéng quan trong nhom
thé hat electron hay day electron, cang nhiéu nhém thé thi géc cng bén. Tuy nhién, néu géc cé thé gidi toa Chu Van Phong._0373132227 . | . . .
dign tich bing cae nhom thé phi hgp thi cing bén. Mot s6 géc, dé tang d6 bén ca ge, c6 thé gin thém céc
nh6m chiém kh6ng gian lén, kim gidm kha nang phan (mg cua géc, vi du:
EL, OH
Khi cae géc R ¢é chiéu dai va vi tri thich hop, ¢6 thé xay ra phan img chuyén vi géc tu do:
Ge
rai tap:
1 Viet co ché cho 2 phan ting sau?
Om CE"
AIBN ech, Ce
2. Hay xée dinh sin phim cho phan img sau va viét co ché phan img?
BuySnH
= — A
AIBN
Br Caste
3. Khi dun néng hgp chat A s& chuyén thanh B,C,D. Phan ing dugc thic day khi chiéu xa. Hay xdc dinh edu
tgo cia B,C,D va diing co ché phan img dé giai thich suv thanh cac san phim nay.
2 Nx ea 8 cake GO + CyHt,,c10
B c D
4, Viét co ché cho phan img sau?
1 °
A, ZO GHy
al ie ‘0
COOSnBuy ale
CaHe
3. Thé electrophil
Co ché téng quat: khi nhc dén phan img Se, ngudi ta thuong nghi ngay dén phan img thé vong thom. Tuy
nhién, thy té.c6 rat nhiéu loai phan ing Se ma khéng c6 vong thom, nhung phan ing dac trung cia vong thom
1a phan ing Se
Mt s6 tae nhan E* va cach digu ché
STT | Tac nhan ET Dieu che
1 [NOx HNO3 +2 H:S0; NO® +2HSOy + 1307
2 Brz hay Br)-MLy Bro +) MLa = Br-MLa
3_| Brion HOBr + H’ > BrHOH
4 Ch hay Cl-MLi Ck + Mla 2 Ch-MLa
5 CIHOH™ HOCL + H => CIHOH Chu Van Phong_0373132227
6 SOs nSO3. HoSOs
7 RSO} RSO2CI_+ AICh > _RSO.*
8 Ra R3C-OH + HO > RC
RCX + AIC > RC
9 R2C-CHR2 R2C=CR:_ + H’ > RaC'-CHR:
10 | RCH2X-ML, RCHbX + MLy > RCH2X-MLa
1 [RCSO" RCOCL + AICh > RC=O*
2 | HX, HiSOx
13 [| RsC=OH” RC-O + HW
14 [| HC=NH* HCN + H
15 [NO™ NaNO: + HY
16 | ArN= AINH; + NO® > ArN=N™
1-7: cae téc nhan phan img tot vai cde vong bi bat hoat.
8-13: cdc tac nhan phan img tét voi cic vong khéng bi bat hoat
14-16: ede te nhin phan img t6t v6i cde vong duge hoat hod.
Mt sé nguyén tie thé trong vang benzen:
= Néu 1 nhém hoat héa manh canh tranh véi 1 nhém hoat héa yéu hodc nhém bat hoat, nhhém hoat héa
‘manh la nhom dinh huréng phan img: NHz, OH, NRo, O-> OR, OCOR, NHCOR > R, Ar > halogen >
nhém dinh huéng -m
- Nh6m thir 3 gn nhu sé khong tan c6ng vao vj tri 6 gitta 2 nhém thé
tuong tac khong gian
~ Khil nhém dinh huéng -m 6 vj tri meta so véi nhém dinh huéng -o/-p, thi nhém thé di
tri-o so v6i nhom dinh husng meta thay v
vi tri -m ¢6 sin trong vong do
thurdng 6 vi
1% » 20 u
= Trong cae chudi tng hop, cae nhom hit electron (ma trong chudi khong bj chuyén héa-ton tai tir dau dén
cui) thi thudng khong cho phan ting dau do gidm higu suit phan img SE phia sau. Cc nh6m hat electron
thuéng cho vio cudi cde phan tng
knongnén Xo, No, Noy
HNO, Oo Mot a Met
H,S0, AICI, AIC
Nen | Mel/AICl,
Mel
AlCl,
thich sy Iya chon nitro héa trong hgp chat sau?
HNO, Chu Van Phong_0373132227
HNO
OO ‘
HO,
2. Toluene, tert-butyl benzen va anisole (methoxybenzen) déu chira nhém thé hoat héa, dinh huéng nhém thé
tip theo trong phan img Sr vio vj tri -0 va -p ciia nhin benzen. Giai thich ly do tao thnh sin phim -o, -p cua
cae phan img Chlor héa xiic tac voi ti 1 % nhu sau?
Me Me Me teu yee
ch cl cb
AICI, AlCl
a cl
Toluene 64% 26% tert-Butybenzen ~100%
ome ome OMe
ce cl
AlCl,
1
Anisole °
35% 65% Chu Van Phong_0373132227
PHAN 2: PHAN UNG CONG VA PHAN UNG TACH
I. PHAN UNG CONG
1. Phan ing céng electrophil (Ar)
Trong co ché nay, dién tich duong (chat electrophil) tién dén lién két d6i hodc lién két ba va trong bude dau
tién hinh than lién ket bang cach lién két déi/ba tang cap electron 2p cho dign tich duong (chat electrophil)
Giai doan 1 a giai doan cham, do vay la giai doan quyét dinh téc 46 cua phan tg.
Tuy nhién, khéng phai tit ca cdc co ché Ar déu tuan theo co ché téng quat trén, vi dy nhu céng brom vao alken
théng qua co ché vong 3 canh.
Yéu t6 lip thé trong phan tng Ar. Xét 1 cis-aken ABC=CBA. Qué trinh cOng Y-W vao alken thu duge san
pham nhu sau:
+ Truang hgp 1: Phan img cOng cis (Y va W huéng cing | phia trong khong gian)
w w
yar
‘ AT
A Preece te
B
asp
cexythro dl pair
y
y
A
yO ‘7s
: 5 ———
B
ey
+ Tring hyp 2: Phan img cng trans (Y vi W hurdng nguge phia trong khéng gian)
yA Ai
'
ey —— y/W
va
a's
"
os 8
:
As
Déng phan trans sé cho két qua nguge lai. Trong trvéng hop Y=W, erythro sé tao hop chat meso
threo al pair Chu Van Phong._0373132227
X4 CoHsOs phan img durge v6i dung dich NaHCOs (co nhém -COOH) va phan ting mau véi . X4 phan img
v6i OsOs thu duge 1 cap déng phan lgp thé threo XS (CoH 100s). XS phan mg véi H1Os r¥i cho sin pham phan
img véi m-CPBA va thay phan bing KOH thu duge X6 (CsH«O2) khéng phan eye va dé bi oxy héa trong
khéng khi. Xac dinh cu trite cc chat chua biét?
1.1. Phan ting eng HX vio alken duéi xic tie acid (X 1A hagogen, -OH)
HX
x
RS
Ht R
x
slow Ry A R
R
Dé xc dinh san pham nao li sin pham chinh, san pham nao Ia san phim phy, Markovnikov dé ra nguyén
tiie nhu sau; Khi eng HX vao alken, nguyén tr hydro s& sé giin véi nguyén tir earbon nao ¢6 it nhom thé g6e
alkyl hon (nguyén tir cacbon bic thip) con nhém halogenua (X) s€ gin voi nguyén tir carbon nao cé nhiéu
nh6m thé géc ankyl hon (nguyén tir carbon bac cao).
cl 1
~ HCI SA ¢
Sin phim chinh Sin phém phy
1.2. Phan tng c6ng halogen (X-Y)
Co ché
Ore q
RAR SN, AC yO y PN
Pee hy, hs
x x
° Roy y Rox
x — x.
® RAR Ry AR,
y
Co ché vong 3 canh trung gian va co ché cng la cong trans,
YE kha ning phin tng cua halogen (X=Y) thi Fs > Cl > Br: > I, New ta hay sir dung Ch vi Bro hom fi
4 thip, do d6, rit kho dé khéng ché phan ing
ciing nhwr thu duge sin phim mong mudn, Ngoai ra, nguy co chay né cing nhur van dé an toan khi sir dung
F. vi le vi F2 c6 kha ning phan img manb ligt ngay ca 6 nhi Chu Van Phong_0373132227
F2 ding khién phan img nay khéng duge sir dung, Cdn I2 khi phan img v6i alken, dn xuat thu duge thirdng
bj tach I2 dé tr6 Iai chat ban dau:
a
on a SH
1
Voi X khée Y, thi kha ning phan tmg cla cde chét nhur sau:
L Br Bry Ia BrCl
1 3000 10000 100000» 4 000000
Néu str dung dung méi c6 tinh nucleophil nhu nude thi co thé xay ra canh tranh gidta H2O vi Y
a a
a,
a HO"
H,0
Vai acid hypohalogen thi Y la nhom -OH. Cac hgp chat HO-X c6 thé thu duge bang cach cho X> vao nude,
H a
HOX —= HO 4 x
Tuy nhién HO-I rat kém ben va thye té khéng ton tai. Ching ta c6 the sir dung xitc tac Io/NaHCOs dé thyre
hign phan tng tuong tw HO-I. Diéu dic biét la phan img nay rat hay duge sir dung trong cdc chat ma ¢6 nhom
-COOH c6 thé tg0 duge vong 5 canh voi -OH.
!
b - BU
NaHCO, . a 2 ro)
coon
‘ ‘o
3. So sinh tc d6 phan img
a. 2-phenylpropen hay 4-(1-methylethenyl) benzoic acid véi acid sulfuric trong nude.
x
c. Trong 2 chit sau, chit ndo dé hydrat héa hon?
("3 if 4
1 2
4, Sp xép kha ning phan img tng din trong phan tmg hydrate hoa trong méi trxéng acid ctia ethene, propene,
2-eyclopropylpropene, 2-methylpropene, 1-cyclopropyl-1-methoxyethene
1.4. Cong boran vio alken Chu Van Phong_0373132227
a
COng boran li cng cis, -OH va -H duge thém vio alken cling hung véi nhau
Co ché cng boran vao alken theo ev ehé vong 4 canh, Sau khi hinh thinh sin phdm (1), (1) tiép tue phan img
vi alken du cé trong hon hgp phan img dé tao cdc san phim cOng 1:2 va 1:3.
Cae sin phim c6ng 1:1, 1:2, 1:3 cia alken véi boran khi phan tmg déu cho cing | sn phim. Tuy nhién, trong
thuc té, cdn phai tinh ché tach loai cdc san phim phu nén viée c6 3 chit trong mét hén hop khién vige nay tro
nén phite tap. Do dé, ching ta cin cae dan xuat khie cia boran dé thyc hién phan img chon Ige hon:
TR be che
Disiamylboran Thexylboran o-nDN
Cée din xuat trén déu chi cdn duy nhit 1 nguyén tir hydro nén chi e6 thé cOng theo ti Ié 1:1
Bai tap:
1. Hydrobo héa ~ oxy héa 1 4-ditertbutyl cyclohexene thu durge 3 alcol: ©.77%; D 20%, E 3%. C oxy héa cho
ketone F. F dé ding bi ding phan héa thanh ketone G trong méi trudmg acid hoZe base. G la sin phim duy
nhat ctia qué trinh oxy héa D va E. Hay xa dinh céu tric cdc chat chia biét?
1.5. Phan tng céng mudi kim loai
Dién hinh cho phan ting nay la phan tg c6ng mudi thuy ngan vao alken, Co ché cua phan img nay twong tye
hu phan ting cong X-Y vio alken, déu tgo thanh cu carbocation:
io
i Hgoac NaBiy H
a ~/0Ac Ret R, Ho“Ny Hoy’
2 ‘OH, 2 2
R
Uu diém: Khdng e6 qua trinh chuyén vi carbocation trong qué trinh nay, Khée hiin ede qua trinh hydrat hoa
bing acid
1.6.Phan ting eng vio h¢ alkin
- Noi chung, cfc ankin c6 phan phan tmg kém hon cae anken trong cdc phan tmg Ax. Mét ly do chinh cho sy
khac biét vé kha nding phan img nay li vé ning long ctia chit trung gian cation vinyl duge tao thanh béi mat
cudc tan céng electrophin vao mét alkyne. Ngudi ta ude tinh ring cdc cation vinyl kém bén hon mét alkyl
khoang 10 keal / mol
~ Déi véi cde phan ting Ag tién hanh thong qua chat trung gian theo kiéu bic edu, ede alkyne eting it phan tg
hon vi c6 thém site cing trong chat trung gian, Chu Van Phong_0373132227
Table 5.10. Relative Reactivity of Alkenes and Alkynes"
‘Alkene/alkyne pair Bromination, Chlorination, Acid-catalyzed
HOAc HOAc hydration
T-Hexene/I-hexyne 18x 53x10) 36
EAHerene/heryne 34x ~ 1x 108 166
Styteneiphenlethyne 26x 72x10 065
1.7.Phan ting véi hg allene
- Allene khi phin img véi acid sé thu duge 2 loai cation, vé mat ly thuyét, c6 vé nhur allylic eation (1) sé chiém
uu thé do kha nang céng hung va giai toa dién tich
woe He + sH Tee
oS Ss
1 2
Tuy nhién, két qua thye té lai cho két qua nguge lai, 46 chinh la vinyl cation la trung gian chinh. Gidi thich cho
két qua nay, ngudi ta nhan thay, trong qua trinh tao allylic cation, 6 trang thai trung gian, AO p tréng cita cation
khong song song vii cae true AO p cia lién két doi, do vay, khong e6 syr xen phi va giai toa dign tich
Vay tai sao dang vinyl cation lai due wu tién???
1.8.Phan tig cOng vao hé lién hop
‘Voi hé dien lién hgp, trong phan img Ap, sin phim e6ng 1,2 thurdng 1a san phim chinh, tuy nhién trong 1 sé
trudng hop, sin phim cng 1,4 la'sin pham chinh,
2, Phin tng cOng nucleophil (Sé day k¥ hon & chwong hop chit carbonyl)
Ban chat ciia céc tac nhan nucleophil 1a c6 mat 46 electron cao, nén nd phai tin céng vao vi tri cé mat do
electron thap. Nhung c: két béi cing 14 noi c6 mat d6 electron cao, vi thé, can c6 cic nhom thé hat Chu Van Phong_0373132227, . .
electron manh dé kim gidm dang ké mat do electron etta lién két boi dé céc te nhan nucleophil e6 thé tn cong
dé dang. Cae nhém thé hut electron manh cé thé ké dén; COR, CN, NO2, SOSH.
y Y
‘aaa
x x
Cac nhém X hat electron manh cing gép phin lam bén carbanion trung gian. Phin phan tmg c6ng nucleophil
8 durge ban ki hon & phan carbonyl véi cdc nhém chite va tae nhan cy thé:
3. Phan tg cong géc (xem phiin tg thé géc)
X=COR, CN, NO,, SOsH. Chu Van Phong,_0373132227 . _, |
PHAN 3:PHAN UNG TACH
1. Phan logi phan ng tach
a, Theo vj tri tieh
Tach a
H
H
aa u .
RRO on
la
RSX
X la halogen
Xie tic cho phan tg nay thuéng 1a mét base manh: BuLi, t-BuOK...Carben sau cling cé thé tham gia cic
phan tng dong vong, tao lién két di...
Phan img nay ciing co img dung dé ting hop alkin dau mach,
Bai tap
a. Hay viét co ché cho cae chuyén héa sau?
1. CH,Br,, LITMP,
OOEL
O70 a. Buti
‘OH
3. EtOH, HCL
Biét LiTMP la 1 base manh,
b
Br Buli R
Se Bg
er
Tach B
(x
RY — RAR,
a “
y
Day la loai phé bién nhat trong céc loai phan img tach.
Ung dung chit yéu dé ting hop alken, méi truéng cita phan ting tuy thude vao ban chat nhom X
b. Theo eo ché tach
‘Tach E2
oY
tt R “1
wy AR gr
i
x
Xiic tic cho phan img thug ki mdi trurdg base.
Hod lap thé phan teng téch E2
- Tach theo kiéu trans, tic li tich nhuyén tir H nim 6 vi tri trans so véi X trén truc H-C-C-X.
= Muédn tach duge thi true X-C-C-H phai nim trén cing 1 mit phing. Chu Van Phong_0373132227
n Ys Me Me
ZL —_-
“HX,
x
Theo ding nguyén tac Zaistev, hop chat B sé dugc hinh thanh véi higu suat cao hon. Tuy nhién, thuc té, chit
A lai la san phim chinh. Diéu a6 dugc giai thich bing viée H-C-C-X trong co ché tao A nim trén | mat phing
cén tao B thi khOng,
M6t vi du khéc vé hing s6 téc d6 cua phan tg tich E2 khi vj tri nhOm thé thay doi
41x10 80x 106
Bai tip:
1. Xée dinh cau tric san phim ciia 2 phan ting tach sau va so sinh t6e d6 phan img cua 2 phan tng do.
Kon KOH
tBu tBu
2. Cho cis-2-aminoxiclohexanol phan img véi dung dich NaNO2/HClI, thu duge chat A va chat B déu e6 céng
thie phan tir + CoH 00. ‘Cho trans-2- aminoxiclohexanol phan (mg véi dung dich NaNO2/HCl, thu duge chat A,
Ca A va B déu phan img voi thude thir 2,4-dinitrophenythidrazin, Xac dinh cng thite cau tao ciia A va B. DE
xuat co ché giai thich su tao thanh A va B,
3. Dy dodn sin phim cia 2 phin img sau va giai thich?
Br
= A CyHieOe
‘COOH
Br
base
“COOH
Phan tmg E1 tao ra carbocation trung gian nén nhém R 6 vi tri alpha sé anh huémg lén dén co ché tich c6 di
theo huéng tach E1 hay khéng (D6 bén carbocation xem phin thé electrophil). Ngoai ra, trang thai carbocation
trung gian c6 thé chuyén vi, sip xép lai cde nhém thé hay bj cic nhém nucleophil khdc tan cong.
‘Tach Eleb
Elcb ki sy két hgp gitta 2 co ché El va E2 Chu Van Phong_0373132227
R — ATR
x) x
Co ché nay ban chat a sy két hop gitta 2 co ché El va E2, tach nhan necleophil tn céng H 6 vi tri beta nhumg
khong tach X lun theo eo ché E2 ma to carbanion (co ché E1 thi tao carbocation). D6 bén carbanion phy
thuge vao nhom R, néu nhom nay hut electron manh c6 kha nding gidi toa dién tich thi co ché dé xay ra theo
huéng nay va nguge lai,
2. Quy tic tach
Quy tae Zaitsev: trong phan iing tach E1, nhom thé duge tach vé phia c6 it nguyén tir H nhat, tite Ta cing nhigu
nhom thé gin vao lién két déi thi san phdm dé cang al
x
A x on
x Ww
NOS
Sin phém chinh Sin phim phy
\Véi phan ting £2, néu nh6m bi téch khong mang dign tich eting nhur khong €6 «in ngit khong gian thi efing teh
theo quy tic Zaitsev. Tuy nhién, khi str dung cac base céng kénh nhu t-BuOK hay LDA thi lai tach theo huéng
nguge Iai (quy te Hoffinan).
tBuOK Jw
sin phim phy Sin phém chinh
H
Khi tach E2 voi nhom thé céng kénh va mang dign tich (thuéng mang dién tich dong) thi phan img tach tuan
theo quy tae Hoffman, tire la tich vé phia ¢6 nhiéu nguyén ti H hon,
xe,
HO" CH ‘San phdm phy ‘San phém chinh
Bat Iudn tach theo co ché nao thi néu trong phan tir c6 sn lién két bdi thi huéng tach tao hé lién hgp sé duge
wutign,
9
Oo x 9
4 BLO" Sy
woh A BoA
‘Sin phém chiah 'Sbn phim phy
NS
Bat ludn tich theo co ché nao, sin phim khéng bén s
Ae bb
Hop chat A khéng durgc hinh thanh do néi d6i 6 vi tri cdu lim thay ddi khung cé dinh ciia phan tir nén khong
bén mic dit vi tri cau c6 nhiéu nhém thé hon.
khong duge wu tién, Chu Van Phong._0373132227
3. Phan img tach bing nhigt
Thuong dién ra trong ra khi theo co ché vong 4,5,6 canh
Vidu:
Te R RR RR
yal + RCOOH + RS ‘ot -
R, nf Hr
R R
R °
HR 11,0, gs Ron
~
RS
M6t s6 dan xuat trong diéu kign nhiét 46 cao ¢6 thé tach hydro 6 vj tri beta theo co ché ving va tach kiéu cis.
Ba sé cde phan tig xay ra theo co ché vong hod va theo kiéu cis. Dic biét, tach loai Ph-S-OH durgc sit dung
nhigu trong téng hgp dudng-carba (carbasugar) theo so dé sau
on on Ho, 2 Vi
Ho, mCPBA HO, Q PhsH HO, mCPBA 2
ot lo
HO” HO" 4 HO” O “sPh aR i,
on
on on
we HO, on
Ho" ‘on
on on
Bai tap:
1. Trong 2 hop chat sau, hop chat nay khi xt ly trong méi trudng base sé thu duge din xuat epoxide?
= “Br C4
:
AH
A 8
2. So sanh toc d6 phan img ciia 3 phan img sau:
HO 6 A
Ho. NaOH °
oo 7, >
2
Hoa A
3. So sinh tc d6 phan img ciia 2 phan img sau:
OTs SPh OTs Ph
O PhSNa PhSNa .
‘Bu tBu
tBu Bu Chu Van Phong_0373132227 . a .
4. Téc d6 phan img thay phan ciia céc hop chit dusi day duge sip xép theo thir ty ting din nhur sau: A <
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