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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
1. Mt s c im ca cc hp cht hu c: ....................................................................04
2. Gc Hidrocacbon- Nhm th- Nhm chc. ....................................................................04
2.1 Gc hirocacbon ........................................................................................................04
2.2 Nhm th ....................................................................................................................04
2.3 Cacboncation ..............................................................................................................04
2.4 ng ng ..................................................................................................................04
2.5 ng phn ..................................................................................................................04
Cch xc nh ng phn cis-trans ...........................................................................05
Cch vit ng phn ng vi cng thc phn t ......................................................06
3. Mt s gc hidrocacbon v gi tn cn ch : ................................................................07
4. Hiu ng cm ...................................................................................................................08
4.1 Khi nim ...................................................................................................................08
4.2 ng dng .....................................................................................................................08
4.2.1 Dng hiu ng cm so snh mnh yu ca cc axit hu c ..................09
4.2.2 Dng hiu ng cm so snh mnh yu ca cc baz hu c. ...............09
4.2.3 D on sn phm phn ng- kh nng phn ng. .........................................09
5. Cc loi phn ng chnh trong ha hu c. ...................................................................10
5.1 Phn ng th ................................................................................................................10
5.2 Phn ng cng .............................................................................................................10
5.3 Phn ng tch ..............................................................................................................11
5.4 Phn ng oxi ha .........................................................................................................11
5.5 Bng So snh v phn bit mt s phn ng thng gp trong hu c .........................11
6. Hp cht hu c c nhm chc. .....................................................................................12
6.1 Phn loi HCHC c nhm chc. ...............................................................................12
6.2 Bng cng thc tng qut mt s HCHC quan trng ..............................................12
6.3 Bng cc dy ng ng thng gp ng vi CTTQ ( cng thc tng qut ). .......13
6.4 Ha tnh ca mt s cht hu c cn ch : .............................................................13
6.4.1 Ru ................................................................................................................13
6.4.2 Phenol ..............................................................................................................15
6.4.3 Andehit ............................................................................................................16
6.4.4 Xeton ...............................................................................................................17
6.4.5 Axit Cacboxylic ..............................................................................................18
6.5 Cc phng php chnh iu ch mt s cht hu c quan trng: .........................19
6.5.1 Ru ................................................................................................................19
6.5.2 Phenol ..............................................................................................................20
6.5.3 Andehit ............................................................................................................20
6.5.4 Xeton ...............................................................................................................21
6.5.5 Axit cacboxylic ................................................................................................21
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
BI TP ........................................................................................................................34
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
1. Mt s c im ca cc hp cht hu c:
-a s HCHC (hp cht hu c) c lin kt cng ha tr ( cn hp cht v c phn ln l lin kt ion).
-Phn ln HCHC khng bn nhit, bay hi, d chy, thng khng tan trong nc.
-Tc phn ng gia cc HCHC thng rt chm v theo nhiu hng khc nhau nn to thnh hn hp
cc sn phm v thng phi dng xc tc.
*Bn cht s gp chung electron trong lin kt cng ha tr ca HCHC:
-Bn cht ca s gp chung eltectron trong lin kt cng ha tr l s xen ph nhng obitan (xem sch gio
khoa lp 10) gia hai nguyn t t th nng cc tiu.
C hai kiu xen ph:
+Kiu xen ph trc: S xen ph ny xy ra trn trc ni
gia hai ht nhn nguyn t.Lin kt cng ha tr hnh
thnh bng cch xen ph trc gi l lin kt (xch ma).
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
Ru no, n
Ru no, 2 chc
0 Ankan chc, Ete no, n Amin no
este + ru
chc
Axit. Este,
Andehit, xeton,
1 Anken xicloanken Andehit+Ru, Amin khng no
ru, ete cha no
andehit+este
Benzen dn xut
4 Amin thm
ca halogen
Benzen c 1 lin
5 kt (C=C) ngoi
vng.
Xc nh nhm chc (c th c) :
-Da vo cng thc phn t, gi tr c th suy ra cc nhm chc c th c.
V d: Vi hp cht CxHyOzNt nu >0 th:
= tng s lin kt v dng mch vng m HCHC c th c.
Cc lin kt c th thuc ( C=C); (-C C-); (C=O); (C=N-); (-N=O), t suy ra c nhm nh chc
v s ni a trong HCHC.
-Bc 2: Vit mch cacbon c th c, t mch di nht ( mch thng) n mch chnh ngn nht, bng cch
bt dn s nguyn t cacbon mch chnh to nhnh ( gc ankyl).
-Bc 3: Thm ni a(i, ba), nhm chc, nhm th vo cc v tr thch hp trn tng mch cacbon.
-Bc 4: Bo ha gi tr cacbon bng s nguyn t Hidro sao cho .
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
3. Mt s gc hidrocacbon v gi tn cn ch :
Gc Cu to Gi tn
CH3CH2CH2- n-propyl
CH3-CH- Iso-propyl (iso: nhm CH3 gn
| vo v tr C th 2 t ngoi mch
CH3 m vo)
CH3CH2CH- Sec-butyl (Sec: -CH3 gn vo v
| tr C th 3 t ngoi mch m
CH3 vo )
CH3 Tert- Butyl
No |
CH3 C
|
CH3
CH3 Neo-pentyl
|
CH3 C CH2
|
CH3
CH2=CH- Vinyl
CH3-CH=CH- Propenyl
Khng no CH2=C Iso- propenyl
|
CH3
C6 H 5 - Phenyl
Thm C6H5 CH2 Benzyl
CH3 C6H4 p-Tolyl
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
4. Hiu ng cm
4.1 Khi nim.
Hiu ng cm (I) l s phn cc ca lin kt gy nn s do s chnh lch v m in ca 2 nguyn
t hay 2 nhm nguyn t to nhm lin kt. ( ni cch khc hiu ng cm l s dch chuyn cp electron
trong ni n do nhm th X ht hay y cp electron ).
Hiu ng cm c biu din bng hng theo chiu di chuyn ca i in t dng chung.
V d:
CH 3 OH C2 H 5 OH H OH Cl CH COOH
CH 3 NH 2 C2 H 5 NH 2 H NH 2 Cl
CH 3 NH CH 3 CH 3 COOH Cl CH 2 COOH
Nu nhm th X y electron, ta ni X gy ra hiu ng cm dng (+I). Nu nhm th X ht electron, ta
ni X gy ra hiu ng cm m. ( -I).
V d: Nu ta ly lin kt n ( -C-H) lm chun. Nu nguyn t hay nhm nguyn t ht e mnh hn H
th s gy hiu ng cm m. Nu nguyn t hay nhm nguyn t y e mnh hn H th s gy hiu ng cm
dng.
Sau y l nhm th X gy ra hiu ng cm thng gp:
(-I): -NO2 > -F > -Cl > -Br> -I > -OH
(+I): -C(CH3)3 > -CH(CH3)2 > -C2H5 > -CH3> -H
4.2 ng dng
Hiu ng cm dng gii thch v so snh tnh axit hay tnh baz ca cc cht hu c hoc dng gii
thch c ch ca phn ng.
V d: So snh tnh linh ng ca nguyn t H trong nhm (-OH) ca Phenol v ru?
Trong khi nhm Phenyl ht e th gc ankyl trong phn t ru y e v pha nguyn t O. Do vy mt d
e trn nguyn t O tng ln, s phn cc ca lin kt trong nhm (-OH) gim i, tnh linh ng ca nguyn
t H gim theo:
R O H , C6H5 O H
Hoc theo sch gio khoa Ha Hc11 nng cao trang 231 c gii thch nh sau ( theo chng trnh phn
ban- Khoa hc t nhin).
V sao phenol c lc axit mnh hn ancol? V sao phn ng th vo nhn thm phenol d hn benzen?
l do nh hng qua li gia gc phenyl v nhm hydroxyl nh sau:
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
H OH
| |
CH 2 CH CH 3 CH 2 C CH 3
| | |
H Cl CH 3
( sp Chnh) CH 2 C CH 3 HOH ( Sp chnh)
CH2=CH CH3 + HCl ; |
CH 2 CH CH 3 CH 3 OH H
| | | |
Cl H CH C CH
(Sp Phu.) 2
|
3
CH
(sp phu. ) 3
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
Andehit R(CHO)x x 1
Andehit no CnH2n+2-x(CHO)x x 1, n 0
Andehit n chc R CHO hay CxHyCHO x 0, y 2x+1
Andehit on chc, no CnH2n+1CHO hay CmH2mO n 0, m 1
Axit n chc R COOH hay CxHyCOOH x 0, y 2x+1
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
i axit no CnH2n(COOH)2 n0
Axit n chc, no CnH2n+1COOH hay CmH2mO2 n 0, m 1
Este n chc R COO R R H
Este n chc, no CnH2nO2 n2
Amin n chc CnHyN y 2x+3
Amin n ch, no CnH2n+3N n1
Amin bc I, no, n chc CnH2n+1 NH2 n1
iu kin chung: x, y, z, t, u, n, m u N
(R ) l gc hidrocacbon no hay khng no
V d: ( Ru benzylic)
( p-Crezol)
Ru thm c phn ng th trn gc (C6H5-):
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
Natri etylat
* Tc dng vi Cu(OH)2: Ch phn ng vi ru a chc c t nht 2 nhm OH k nhau cho dung dch
c mu xanh lam.
CH 2 OH HO CH 2
| |
2CH 2 CH CH 2 Cu (OH )2 CH O Cu O CH 2 H 2O
| | | | |
OH OH OH CH 2 OH HO CH 2
ng (II) glixerat, mu xanh lam
Phn ng ny dng nhn bit glixerol v cc poliancol m cc nhm OH nh vi nhng nguyn t
C cnh nhau, chng hn nh etylen glicol.
*Tch nc to ete:
*Tch nc to lin kt .
Khi un nng vi H2SO4 c 1700C, c mi phn t ancol tch 1 phn t nc to thnh 1 phn t
Anken.
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
*Este ha:
R CH CH 3
R CH =CH2 +H2O |
OH
* Phn ng c bit:
M gO ,Zn
2 C2H5OH to
CH2 = CH CH = CH2 + 2 H2O + H2
Phenolat natri
+Tc dng vi NaOH.
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
R C OH
ROH < H2O < < H2CO3 < ||
O
6.4.3 Andehit:
-Andehit l nhng hp cht hu c m trong phn t c nhm (CH=O) lin kt trc tip vi nguyn t
cacbon hoc Hiro. Nhm CH=O c gi l nhm chc ca andehit, n c gi l nhm cacbanehit.
Vd: HCH=O ( fomandehit); CH3CH=O( axetandehit)
*Phn ng cng H2( phn ng kh):
Khi c xc tc Ni un nng, andehit cng vi hiro to ra ancol bc I:
RCHO +H2 RCH2OH
CH3CH=O + H2 CH3CH2 OH
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
6.4.4 Xeton.
-Xeton l hp cht hu c m phn t c nhm >C=O lin kt trc tip vi hai nguyn t cacbon
V d: H3C CO CH3
*Xeton cng tham gia phn ng cng hiro khi c mt Ni xc tc, un nng to thnh ancol bc (II):
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
CH 3 C CH 3 H 2 CH 3 CH CH 3
|| |
O OH
*Phn ng cng nc, cng hiro xianua:
CN
|
CH 3 C CH 3 H CN CH 3 C CH 3
|| |
O OH
(xianohidrin)
*Phn ng gc hirocacbon
Nguyn t hiro bn cnh nhm cacbonyl d tham gia phn ng.
V d:
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
*Phn ng th gc no.
Khi dng photpho xc tc, Cl ch th cho H cacbon bn cnh nhm cacboxyl
P
CH3CH2 CH2COOH +Cl2 CH 3CH 2CHCOOH HCl
|
Cl
*Phn ng th gc thm.
Nhm cacboxyl vng benzen nh hng cho phn ng th tip theo vo v tr meta lm cho phn ng
kh khn hn so vi th vo benzen.
xt, t0, P
nCH2=CH COOH CH 2 CH n
|
COOH
6.5 Cc phng php chnh iu ch mt s cht hu c quan trng:
6.5.1 iu ch ru:
* Ln men tinh bt:
enzim
(C6H10O5)n +nH2O nC6H12O6
enzim
C6H12O6 2C2H5OH + 2CO2
*Hirat ha anken xc tc axit
H+
CnH2n +H2O CnH2n+1OH
H2SO4, 3000C
CH2=CH2 + H2O CH3CH2OH
* T andehit v xeton.
Ni
R CHO +H2 R CH2OH ( ru bc I )
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
Ni,t o
R CO R R CHOH R ( Ru bc II)
CH 2 CH CH 2 3 NaOH CH 2 CH CH 2 3 NaCl
| | | | | |
Cl Cl Cl OH OH OH
6.5.2 Phenol:
*T C6H6:
CH2=CHCH3 , H+ 1)O2(kk); 2)H2SO4
C6 H 6 C6H5CH(CH3)2 C6H5OH + CH3COCH3
Benzen Cumen (isopropyl benzen) axeton
Fe
C6H6 +Cl2 C6H5Cl +HCl
to, p
C6H5Cl + NaOH C6H5OH +NaCl
*T natri phenolat:
C6H5ONa +HCl C6H5OH + NaCl
C6H5ONa + CO2 +H2O C6H5OH + NaHCO3
* Oxi ha iso propyl benzen:
6.5.3 Andehit:
*Oxi ha ru bc (I):
to,
R CH2 OH +CuO R CHO +Cu +H2O
to,
CH3OH +CuO HCHO +Cu +H2O
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
HgSO4,to
*C2H2 +H2O CH3CHO
6.5.4 Xeton:
*Oxi ha ru bc (II):
Hoc t CH3COONa:
to,
2CH3COONa CH3 CO CH3 +Na2CO3
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
*T dn xut halogen:
KCN H O+,t0
R X R C N 3 R COOH
+Thy phn dn xut 1,1,1 trihalogen.
Cl
| t0
CH 3 C Cl 3 NaOH CH3COOH +3NaCl + H2O
|
Cl
*T metanol
to, xt
CH3OH +CO CH3COOH
*T mui natri ca axit cacboxylic:
R COONa +H2SO4() R COOH +NaHSO4
7. Hp cht hu c tp chc.
7.1. CACBOHIDRAT.
+isaccarit l nhm m khi thy phn mi phn t sinh ra 2 phn t monosaccarit .vd : saccaroz , mantoz
+Polisaccarit l nhm m khi thy phn n cng mi phn t sinh ra nhiu phn t monosaccarit . vd : tinh bt ,
xenluloz .
7.1.1 GLUCOZ
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
a/ Tc dng vi Cu(OH)2: nhit thng to phc ng glucoz (dd mu xanh lam- nhn bit glucoz)
a/ Oxi ha glucoz:
AgNO3 / NH 3
C6H12O6 2Ag
+ Bng Cu(OH)2 mi trng kim: natri gluconat v Cu2O gch (nhn bit glucoz)
3/ Phn ng ln men: C6H12O6 2C2H5OH + 2CO2 ( Khi gii bi tp ch n Hiu sut phn ng)
7.1.2. Fructoz:
ng phn ca glucoz
+ CTCT mch h:
CH2OH-CHOH-CHOH-CHOH-CO-CH2OH
+ Tnh cht ancol a chc ( phn ng Cu(OH)2 nhit thng to dd xanh lam)
OH
Fructoz
glucoz
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
+ Trong mi trng baz fructoz chuyn thnh glucoz fructoz b oxi ha bi AgNO3/NH3 v Cu(OH)2 trong
mi trng kim.
CTPT: C12H22O11
a) Phn ng vi Cu(OH)2
2C12H22O11+Cu(OH)2(C12H21O11)2Cu+2H2O
( - glucoz) ( fructoz )
c, Phn ng vi sa:
AgNO3 / NH 3
C12H22O11 2 Ag
a) Phn ng vi Cu(OH)2
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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012
2C12H22O11+Cu(OH)2(C12H21O11)2Cu+2H2O
mu xanh lam
( - glucoz) ( glucoz )
7.1.4.TINH BT XENLULOZ
I. TINH BT
1. Tnh cht vt l:L cht rn, dng bt v nh hnh, mu trng, khng tan trong nc lnh, tan trong nc nng (
600C)
2. Cu trc phn t:
Tinh bt thuc loi polisaccarit, Phn t tinh bt gm nhiu mt xch -glucoz lin kt vi nhau.
CTPT : (C6H10O5)n .
-Dnh l xo: bng lin kt -1,4 - glucozit khng phn nhnh (amiloz) .
-Dng l xo bng lin kt -1,4 glucozit v -1,6 glucozit phn nhnh (amilopectin).
b) Phn ng mu vi iot:To thnh hp cht c mu xanh tm (phn ng dng nhn bit Tinh bt)
II. XENLULOZ
-Xenluloz l cht rn dng si, mu trng, khng tan trong nc v dung mi hu c, nhng tan trong nc
Svayde (dd thu c khi ha tan Cu(OH)2 trong amoniac) .
2. Cu trc phn t:
- Xenluloz l mt polisaccarit, phn t gm nhiu gc -glucoz lin kt vi nhau bng lin kt -1,4 glucozit
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