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Tng hp l thuyt ha hu c n thi tt nghip - i hc nm 2012

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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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7.0 Mt s dng ton v phng php gii trong ha hu c: .......................................................23

7.1 Phn ng oxi ha kh trong ha hu c: ..........................................................................23 7.1.1 Tnh s oxi ha ca mt nguyn t cacbon (hay Nit) trong phn t hu c: ..........23 7.1.2 Cn bng phn ng oxi ha kh trong ha hu c ..................................................23

7.2 Bin lun tm CTPT t cng thc nguyn (cng thc n gin nht) ...............................25 7.2.1 Phng php tch ring nhm chc: .........................................................................25 7.2.2 Phng php dng s lin kt . ..............................................................................25

7.3 Bin lun tm CTPT t cc d kin phn ng. ...................................................................26 7.4 ng dng nh lut bo ton khi lng gii nhanh mt s bi ton ha hc hu c. 27 7.5 Cc phn ng xy ra kh cho CO2 ( hoc SO2) tc dng vi dung dch baz. ...................29

7.5.1 Cc phn ng xy ra khi cho CO2 (hoc SO2) tc dng vi mt dung dch NaOH. ...29 7.5.2 Cc phn ng xy ra khi cho CO2 tc dng vi dung dch Ca(OH)2 hoc Ba(OH)2. ..30 7.5.3 Ton v s tng, gim khi lng dung dch: ..................................................31 7.5.4 Vit s phn ng, iu ch..........................................................................33

BI TP ........................................................................................................................34


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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). +Kiu xen ph bn: s xen ph thc hin hai bn trc ni gia hai ht nhn nguyn t. Lin kt cng ha tr hnh thnh bng cch xen ph bn l lin kt .

+Th tch xen ph cng ln, lin kt cng bn. Xen ph bn hn lin kt .

2. Gc Hidrocacbon- Nhm th- Nhm chc.

2.1 Gc Hidrocacbon: L phn cn li ca phn t hidrocacbon sau khi mt i mt hay nhiu nguyn t hydro. Nu mt 1 H ta c gc ha tr I, mt 2 H ta c gc ha tr II, thng thng k hiu l R.

V d: Gc no, ha tr I nh: Metyl:(CH3-); etyl:(C2H5-)cn gi l gc ankyl ( cng thc tng qut CnH2n+1- ). 2.2 Nhm th: L nhm nguyn t quyt nh cc tnh cht ha hc c trng ca mt loi hp cht.

V d: Nhm chc cc ru l (-OH), ca axit l (-COOH). 2.3 Cacbocation: L ion ca hidrocacbon, c mt in tch dng nguyn t cacbon ( tuy c th tn ti c lp nhng rt km bn).

V d: Cation metyl CH3- ( Nguyn t cacbon thiu 1 electron nn mang mt in tch dng). 2.4 ng ng: Hin tng cc HCHC c cu to v tnh cht tng t nhau, nhng thnh phn phn t hn km nhau mt hay nhiu nhm (-CH2) gi l cc cht ng ng vi nhau, chugn1 hp thnh mt dy ng ng. 2.5 ng phn: Hin tng cc cht c cng mt cng thc phn t nhng c cu to khc nhau nn c tnh cht khc nhau c gi l ng phn ca nhau.


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*Cc loi ng phn chnh: -ng phn dng mch cacbon ( do thay i dng mch h khng h, c nhnh v dng mch vng):

V d:

-ng phn v tr ( do thay i v tr nhm th, nhm chc, ni i hay ni ba): V d: CH2=CH-CH2-CH3 v CH3-CH=CH-CH3 (but-1-en) (but-2-en)

-ng phn nhm chc ( do cc cht hu c c nhm chc khc nhau). V d: CH3-CH2-OH v CH3-O-CH3 ( Ru etylic) (Dimetyl ete)

-ng phn hnh hc ( hay lp th: Cis Trans): *Nguyn nhn: Do s xp xp trong khng gian khc nhau ca nguyn t hay nhm nguyn t gn vi cacbon mang ni i. *iu kin c ng phn hnh hc: -iu kin cn: HCHC phi c cha ni i. -iu kin : Cc nhm th gn cng mt cacbon mang ni i phi khc nhau.

* Cch xc nh ng phn cis v trans: -Bc 1: mi C mang ni i, chn mt nhm th ln. -Bc 2: Nu hai nhm th ln cng pha -> dng cis. Nu hai nhm th ln khc pha -> dng trans.

V d:


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*Cch vit ng phn ng vi cng thc phn t: -Bc 1: Xc nh bt bo ha () v nhm chc c th c.

bt bo ha (): cho bit s lin kt (ni i, ni ba) hoc dng mch vng, hoc c hai m HCHC c th c.

Cch tnh gi tr (): Vi HCHC dng CxHyOzNtXu (X l halogen) ta c: 2 2 ( )

2

x y u t

Bng gi tr v loi HCHC tng ng ( c th c )

CxHy CxHyO CxHyOz CxHyNt

0 Ankan Ru no, n

chc, Ete no, n chc

Ru no, 2 chc este + ru

Amin no

1 Anken xicloanken Andehit, xeton,

ru, ete cha no

Axit. Este, Andehit+Ru,

andehit+este Amin khng no

2 Ankin, ankadien,

xicloanken Andehit, xeton c

cha ( C=C) Axit, este cha no,

andehit 2 chc

4 Benzen dn xut

ca halogen Amin thm

5 Benzen c 1 lin 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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3. Mt s gc hidrocacbon v gi tn cn ch :

Gc Cu to Gi tn

CH3CH2CH2- n-propyl

CH3-CH- | CH3

Iso-propyl (iso: nhm CH3 gn vo v tr C th 2 t ngoi mch m vo)

CH3CH2CH- | CH3

Sec-butyl (Sec: -CH3 gn vo v tr C th 3 t ngoi mch m vo )

CH3 | CH3 C | CH3

Tert- Butyl No

CH3 | CH3 C CH2 | CH3

Neo-pentyl

CH2=CH- Vinyl

CH3-CH=CH- Propenyl Khng no CH2=C

| CH3

Iso- propenyl

C6H5- Phenyl

C6H5 CH2 Benzyl Thm

CH3 C6H4 p-Tolyl


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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:

3 2 5

3 2 2 5 2

C H OH Cl CH

C

CH OH H OH COOH

CH NH H NH

2

3 3 3 2

H Cl

Cl CH

NH

CH NH CH CH COOH 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: Cp electron cha tham gia lin kt ca nguyn t oxi do cch cc

electron ca vng benzen ch mt lin kt nn tham gia lin hp vi cc electron ca vng benzen lm cho mt electron dch chuyn vo vng benzen. iu dn n h qu sau:

+Lin kt O-H tr nn phn cc hn, lm cho nguyn t H linh ng hn. +Mt electron vng benzen tng ln, nht l v tr ortho v para( v tr

ortho-v tr cacbon th 6 v 2,para-cacbon th 4, meta -cacbon th 3 v 5 .. xem


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SGK Ha hc 11 nng cao trang 187), lm cho phn ng th d dng hn so vi benzen v ng ng ca n.

+Lin kt C-O tr nn bn vng hn so vi ancol, v th nhm OH phenol khng b th bi gc axit nh nhm OH ancol

4.2.1 Dng hiu ng cm so snh mnh yu ca cc axit hu c:

Trong phn t axit hu c O

R C O H , do s c mt ca nhm cacbonyl ||

O

C nn lin kt O- H vn

phn cc tr nn phn cc rt mnh. Kt qu l phn t RCOOH d dng phng thch H+, th hin tnh axit. Axit hu c cng mnh th n phng thch H+ cng d. iu ny xy ra khi trn R c cc nhm th gy

hiu ng cm m. V d: So snh tnh axit ca ru etylic vi nc: Trong phn t ru etylic v nc xy ra cc hiu ng cm

C2H5 O H H O H Kt qu l lin kt O H trong nc linh ng hn trong ru nn nc c tnh axit mnh hn ru. V d 2: So snh tnh axit ca:

a) axit fomic; axit axetix; axit propionic b) axit axetic; axit monoclo axetic; axit iclo axetic.

a. Trong phn t axit trn xy ra cc hiu ng cm :

C

|| O

H O H

3 2 5 || || O O

CH C O H C H C O H

Kt qu l lin kt O H trong axit formic linh ng nht, ri n axit axetic v axit propionic. Vy tnh axit ca axit formic > axit axetix> axit propionic.

b. Trong cc phn t axit trn xy ra hiu ng cm:

3 2 Cl CH Cl CH || || || O

CH C O H C O H C O H

O Cl O

Kt qu l lin kt O H trong axit iclo axetic linh ng nht ri n axit monoclo axetic v n axit axetic. Do tnh axit ca axit iclo axetic > axit monoclo axetic > axit axetic.

4.2.2 Dng hiu ng cm so snh mnh yu ca cc baz hu c. Cc amin u c tnh baz. Tnh baz cng mnh th kh nng thu nhn H+ cng d. iu ny xy ra khi cc gc R gn trn nguyn

t N ca amin l cc gc gy hiu ng cm dng mnh. V d: So snh tnh baz ca metylamin vi amoniac v imetylamin. Trong cc phn t amin trn xy ra cc hiu ng cm:

3 2 2 3 3 H CH (I) (II) (III)CH NH NH NH CH

Kt qu l mt in tch m trn nguyn t N ca (III) > (I)>(II). 4.2.3 D on sn phm phn ng- kh nng phn ng. Da vo s ht hoc y electron ca nhm th X, ta c th d on c sn phm phn ng, hoc kh

nng phn ng ca mt cht. V d:D on sn phm phn ng ( sn phm chnh ) ca phn ng: CH3 CH =CH2+HCl .

Do CH3 l nhm y electron nn trong phn t propen xy ra s phn cc: . Kt qu l phn cation ca tc nhn tn cng vo nhm CH2, cn phn anion ca tc nhn kt hp vo

nhm CH nh sau:


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CH3 CH =CH2 + HCl CH3 CHCl CH3 V d 2: D on kh nng phn ng ca benzen v toluen vi Br2 ( bt st xc tc). Trong phn t toluen, do CH3 l nhm y electron lm tng mt electron trong vng thm khin

phn ng th Brom xy ra d hn so vi benzen. 5. Cc loi phn ng chnh trong ha hu c. 5.1 Phn ng th L phn ng trong mt hoc mt nhm nguyn t phn t hu c b thay th bi mt hoc mt

nhm nguyn t khc .

Tn Ankan Aren Ankin

CH4+Cl2 CH3Cl +HCl C ch gc t do

+ Br2 +HBr C ch ion

HC CH + 2 AgNO3+3 NH3 Ag C C Ag +2NH4NO3+NH3 Th ion kim loi

Cc loi phn ng th thng gp: Halogen ha, nitro ha.Ankyl ha ankan, aren. Th H ca axit, andehit, xeton, este ha, thy phn, trng ngng.

5.2 Phn ng cng. L phn ng trong phn t tc nhn tch thnh 2 phn, gn vo phn t phn ng, phn ng xy ra

ch yu lin kt . bt bo ha phn t gim ( nh ngha theo SGK11 Nng cao trang 130: Phn t hu c kt hp thm vi cc nguyn t hoc phn t khc ).

HC CH + 2H2 H3C -CH3 Cc phn ng cng thng gp: Cng H2 (kh H2), cng H2O (hyrat ha), cng halogen, cng halogenua hiro, trng hp *Quy tc cng Mc- cp-nhi cp.(SGK 11 nng cao trang 162) Khi cng mt tc nhn bt i xng ( cng axit hoc nc HA, H2O) vo lin kt C=C ca anken bt

i xng, H ( phn mang in tch dng) u tin cng vo C mang nhiu H hn (cacbon bc thp hn), cn A (phn mang in tch m) u tin cng vo C mang t H hn ( cacbon bc cao hn).


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CH2=CH CH3 + HCl

2 3

2 3

| | H Cl( Chnh)

| | Cl H(Sp Phu.)

CH CH CH

sp

CH CH CH

; 2 3

3

| CH

CH C CH HOH

2 3

3

2 3

3

H OH | |

| CH( chnh)

H | |

| CH(sp phu. )

CH C CH

Sp

OH

CH C CH

5.3 Phn ng tch. L phn ng trong mt vi nguyn t hoc nhm nguyn t b tch ra khi phn t.

2 2 | | H OH

H C CH H2C=CH2 + H2O

Cc phn ng tch thng gp: hiro (tch H2); hyrat ( tch H2O); Crackinh ankan; tch ihalogen; tch halogennua hiro. 5.4 Phn ng oxi ha: L phn ng trong tc nhn cung cp oxi, phn t cht phn ng c s tng s oxi ha. +Oxi ha hon ton: phn ng chy ca HCHC vi oxi. +Oxi ha khng hon ton (oxi ha chm): tc nhn oxi ha thng l KMnO4, CrO3, K2Cr2O7, O2, c

xc tc bng Cu, Pt, NO, ************So snh v phn bit mt s phn ng thng gp trong hu c*************

Cng Trng hp -L phn ng 1 ln gia 2 phn t to thnh mt phn t mi -Cht phn ng phi khng no ( hoc c cha lin kt ). V d: CH2=CH2+HBrCH3 CH2Br

-L qu trnh cng hp lin tip nhiu phn t nh ging nhau hay tng t nhau to thnh phn t ln hay cao phn t. -Cht phn ng v tc nhn phi u khng no. V d: nCH2=CH2 (-CH2 CH2 -)n

Trng hp Trng ngng

-Qu trnh cng hp lin tip nhiu phn t nh (monome) to thnh phn t ln(polime) c gi l phn ng trng hp. -c im cu to cc monome tham gia phn ng trng hp l phi c lin kt kp. V d:CH2=CH2 ; C6H5 CH=CH2 ; CH2=CH Cl ; CH2=CH CH=CH2 ; nCH2=CH2 (-CH2 CH2 -)n

-Qu trnh nhiu phn t nh (monome) kt hp vi nhau thnh phn t ln (polime) ng thi gii phng nhng phn t c khi lng nh (nh H2O, NH3, HCl,) c gi l phn ng trng ngng. -c im cu to cc monome tham gia phn ng trng ngng l phi c t hai nhm chc tr ln. V d: H2N CH2 COOH ; H2N (CH2)6 NH2 ; HOOC (CH2)4 COOH ; H2N (CH2)5 COOH ;

nH2N CH2 COOH 2 2( ) + nH

|| O

nHN CH C O


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Hyrat ha Thy phn

-Cht phn ng c lin kt cn tc nhn l H2O. -Phn ng xy ra 1 chiu. V d: CH2=CH2 +H2O CH3 CH2 OH

-Cht phn ng l este, ete, dn xut halogen ca CxHY, cn tc nhn l nc. -Phn ng thun nghch. V d: CH3Cl+H2O CH3OH + HCl

X phng ha Thy phn -L phn ng thy phn este ca axit hu c trong mi trng kim (NaOH, KOH, ) to mui ca axit cacboxylic. -Phn ng mt chiu.

RCOOR +H2O ROH+RCOONa +H2O

-Cht phn ng l este, ete, dn xut halogen ca CxHY, cn tc nhn l nc. -Phn ng thun nghch. V d: CH3Cl+H2O CH3OH + HCl

6. Hp cht hu c c nhm chc.

6.1 Phn loi HCHC c nhm chc. -Thnh phn: Gc hyrocacbon + nhm chc. -Cng thc tng qut: CxHy-kAk (iu kin k y).

n chc a chc Tp chc 1 nhm chc ( k=1) 2 nhm chc cng loi tr ln (k 2) 2 nhm chc khc loi tr ln

(k 2) Gc CxHy no (CnH2n+2-kAk) HCHC no. Gc CxHy khng no (CnHy-kAk) HCHC khng no.

6.2 Bng cng thc tng qut mt s HCHC quan trng.

Hp cht hu c Cng thc tng qut iu kin Hp cht cha C, H, O Hp cht cha C, H, O, N Hp cht cha C, H, O, X (X l halogen)

CxHyOz CxHyOzNt CxHyOzXu

y 2x +2 y 2x +2 +t y 2x +2 u

Ru , no Ru n chc Ru bc I, n chc Ru n chc, no, bc I

R(OH)x hay CnH2n+2-x(OH)x CxHy OH CxHy CH2OH CnH2n+1(OH) hay CnH2n+2O CnH2n+1 CH2OH

x,n 1 x 1, y 2x+1 x 0, y 2x+1 n 1 n 0

Andehit Andehit no Andehit n chc Andehit on chc, no

R(CHO)x CnH2n+2-x(CHO)x R CHO hay CxHyCHO CnH2n+1CHO hay CmH2mO

x 1 x 1, n 0 x 0, y 2x+1 n 0, m 1

Axit n chc R COOH hay CxHyCOOH x 0, y 2x+1


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i axit no Axit n chc, no

CnH2n(COOH)2 CnH2n+1COOH hay CmH2mO2

n 0 n 0, m 1

Este n chc Este n chc, no

R COO R CnH2nO2

RH n 2

Amin n chc Amin n ch, no Amin bc I, no, n chc

CnHyN CnH2n+3N CnH2n+1 NH2

y 2x+3 n 1 n 1

iu kin chung: x, y, z, t, u, n, m u N (R ) l gc hidrocacbon no hay khng no

6.3 Bng cc dy ng ng thng gp ng vi CTTQ ( cng thc tng qut ).

CTTQ C th thuc dy cc ng ng iu kin

CnH2nO

+ Andehit no, n chc ( ankanal) + Xeton no, n chc. +Ru n chc, khng no (c mt ni i phn gc hidrocacbon)

n 1 n 3 n 3 n 3

CnH2nO2 +Axit hu c no, n chc. +Este no, n chc.

n1 n 2

CnH2n+2O +Ru no, n chc (ankanol) +Ete no, n chc

n 1 n 2

6.4 Ha tnh ca mt s cht hu c cn ch : 6.4.1 Ru: *Ru l hp cht c nhm OH lin kt vi gc hyrocacbon. Bc ca ru bng bc ca C mang

nhm OH *Nu thay th H on mch nhnh ca hirocacbon thm bng nhm ( -OH) ta c ru thm. Cn phn bit ru thm vi cht thuc loi phenol:

V d: ( Ru benzylic)

( p-Crezol) Ru thm c phn ng th trn gc (C6H5-):


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*Tc dng vi natri : +Ancol tc dng vi kim loa kim to ra ancolat v gii phng kh hiro.

2( ) ( )2

x y z x y z

zC H OH zNa C H ONa H

CH3 CH2OH +Na C2H5ONa + 21

2H

+Ancol hu nh khng phn ng c vi NaOH, m ngc li, natri ancolat ( RO Na) b thy phn hon ton:

RO Na +H OH RO H +NaOH 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.

2 2

2 2 2 2

CH HO | | 2 ( ) 2 |

OH CH

CH CH CH Cu OH CH O Cu O CH H O

2 2

| | | | OH OH OH CH HOOH CH

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 170

0C, c mi phn t ancol tch 1 phn t nc to thnh 1 phn t Anken.

Hoc ankadien nu cht phn ng co 1 lin kt :

CH3OH khng c phn ng tch nc to anken Hng ca phn ng tch nc tun theo quy tc zai-xp: Quy tc zai-xp (Zaitsev): Nhm OH u tin tch ra cng vi H nguyn t C bc cao hn bn cnh to thnh lin kt i

C=C. V d:


15

*Este ha:

Axit + Ru Este +H2O

(RCOOH + ROH RCOO R + H2O) *Oxi ha: +Ru bc (I) b oxi ha cho andehit.

RCH2OH +CuO RCHO +Cu +H2O +Ru bc (II) b oxi ha cho xeton.

' | OH

R CH R +CuO

2' || O

R C R Cu H O

*Cch chuyn ru bc (I) sang bc (II):

R CH2 CH2 OH R CH =CH2 +H2O

R CH =CH2 +H2O 3

| OH

R CH CH

* Phn ng c bit:

2 C2H5OH ,

o

M g O Z n

t CH2 = CH CH = CH2 + 2 H2O + H2

_ivinyl(buta -1.3 - ien) 6.4.2 Phenol. -Phenol l nhng hp cht hu c m phn t c cha nhm hiroxyl (-OH) lin kt tc tip vi nguyn

t cacbon ca vng benzen. *Tnh axit. Phenol c lc axit mnh hn ancol ( khng nhng tc dng c vi kim loi kim m cn phn ng

c vi NaOH), tuy nhin n vn ch l mt axit rt yu (b axit cacbonic y khi phenolat). Dung dch phenol khng lm i mu qu tm.

+Tc dng vi Na

Phenolat natri +Tc dng vi NaOH.

* Phn ng th vng thm. Phn ng th vng thm phenol d hn benzen ( iu kin m du hn, th c ng thi c 3

nguyn t H cc v tr ortho v para)


16

+Tc dng vi dung dch Brom.

+Tc dng vi HNO3 c:

*Tc dng vi CH2O (HCHO, anehit formic):

Ch : Tnh linh ng Ca H trong OH tng dn nh sau:

ROH < H2O < < H2CO3 < || O

R C OH

Nn: + Na2CO3 Khng phn ng Ngc li:

+H2O +CO2 +NaHCO3 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


17

*Phn ng cng nc, cng hiro xianua: -Lin kt i C=C fomandehit c phn ng cng nc nhung sn phm c hai nhm OH cng nh

vo 1 C nn khng bn, khng tch ra khi dung dch c:

2

OH |

| OH

HCH O HOH H C

-Hiro xianua (H C N)cng vo nhm cacbonyl xy ra hai giai on, anion NC phn ng giai on u, ion H+ phn ng giai on sau:

3 3

3 3

CH CH O | C N

| | C

N C CH CH O

CH CH O H CH CH OH

N C N

*Phn ng brom v kali pemanganat: Andehit rt d b oxi ha, n lm mt mu nc Brom, dung dch kali pemanganat v b oxi ha thnh

axit cacboxylic. RCH=O +Br2+H2O RCOOH + 2HBr * Tham gia phn ng trng gng (Phn ng trng bc). RCHO +2 AgNO3+3NH3+H2O RCOONH4+2NH4NO3+2Ag. V d:OHC CHO + 4 AgNO3+6NH3+2H2O NH4OOCCOONH4 +4NH4NO3+4Ag Ch : HCHO khi tc dng vi dung dch AgNO3/NH3 s to t l mol l 1:4 trong khi cc andehit n

chc khc ch to bc theo t l mol 1:2 HCHO + 4 AgNO3+6NH3+2H2O (NH4)2CO3+4NH4NO3+4Ag *Phn ng vi Cu(OH)2 trong mi trng kim, nhit : RCHO+2Cu(OH)2+NaOH RCOONa+Cu2O +3H2O V d: CH3CHO + 2 Cu(OH)2+NaOH CH3COONa+Cu2O +3H2O *Phn ng trng ngng vi phenol:

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):


18

3 3 2 || O

CH C CH H 3 3 | OH

CH CH CH

*Phn ng cng nc, cng hiro xianua:

3 3 3 3

C N |

|| CH C CH H CN CH C CH

|

O OH (xianohidrin)

*Phn ng gc hirocacbon Nguyn t hiro bn cnh nhm cacbonyl d tham gia phn ng. V d:

6.4.5 Axit (axit cacboxylic) -Axit cacboxylic l nhng hp cht hu c m phn t c nhm cacboxyl ( -COOH) lin kt trc tip

vi nguyn t cacbon hoc nguyn t hiro. * Tnh axit: Axit cacboxylic in li khng hon ton trong nc theo cn bng:

R COOH +H2O H3O+ + R COO- ; 3

[ ][ ]

[ ]a

H O RCOOK

RCOOH

(Ka l mc o lc axit, Ka cng ln th axit cng mnh v ngc li) Axit cacboxylic l mt axit yu. Tuy vy, chng c tnh cht ca 1 axit: lm qu tm ha , tc dng

c vi kim loi gii phng hiro, vi oxit kim loi, vi baz, vi mui v ru. HCOOH +Na HCOONa +1/2 H2 2CH3COOH +MgO (CH3COO)2Mg +H2O 2CH2=CH COOH +Na2CO3 2CH2CH COONa +CO2+H2O

HOOC COOH +Ca(OH)2 22

\ / Ca

OOC COO H O

-Trong cc axit no n chc, axit fomic (HCOOH) mnh hn c. Cc nhm ankyl y electron v pha nhm cacboxyl nn lm gim lc axit. Cc nguyn t c m in ln gc R ht electron ca nhm cacboxyl .

*Phn ng vi ancol ( phn ng este ha )

* Tng qut: phn ng gia axit a chc v ancol a chc. R (COOH)n + R(OH)m Rm (COO)n.mRn + n.m H2O *Phn ng tch nc lin phn t: Khi cho tc dng vi P2O5. hai phn t axit tch i mt phn t nc to thnh phn t anhirit axit:


19

*Phn ng th gc no. Khi dng photpho xc tc, Cl ch th cho H cacbon bn cnh nhm cacboxyl

CH3CH2 CH2COOH +Cl2 3 2 | Cl

CH CH CHCOOH HCl

*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.

*Phn ng cng vo gc khng no. Axit khng no tham gia phn ng cng H2, Br2, Cl2 nh hirocacbon khng no. *Mt s phn ng c bit. +HCOOH cn cho phn ng trng gng (ch c axit fomic mi tham gia phn ng trng gng): HCOOH + 2AgNO3+4NH3+H2O (NH4)2CO3+2NH4NO3+2Ag +Axit cha no cn cho phn ng cng, trng hp. CH2=CH COOH +H2O HO CH2 CH2 COOH

nCH2=CH COOH 2 | COOH

nCH CH

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:

(C6H10O5)n +nH2O nC6H12O6

C6H12O6 2C2H5OH + 2CO2 *Hirat ha anken xc tc axit

CnH2n +H2O CnH2n+1OH

CH2=CH2 + H2O CH3CH2OH * T andehit v xeton.

R CHO +H2 R CH2OH ( ru bc I ) Ni

H2SO4, 3000C

H+

enzim

enzim

xt, t0, P

P


20

R CO R R CHOH R ( Ru bc II) *Thy phn dn xut halogen trong mi trng kim:

R Cl +NaOH R OH +NaCl

C2H5Cl + NaOH C2H5 OH +NaCl

2 2 2 23 3 | | | | | |

Cl Cl OH OH OH

CH CH CH NaOH CH CH CH NaCl

Cl

*Thy phn este ( x phng ha):

R COO R + NaOH R COONa + ROH *Metanol c th sn xut t 2 cch sau:

+CH4 +H2O CO + 3H2

CO +2H2 CH3OH

+ 2CH4 +O2 2CH3 OH 6.5.2 Phenol: *T C6H6:

C6H6 C6H5CH(CH3)2 C6H5OH + CH3COCH3 Benzen Cumen (isopropyl benzen) axeton

C6H6 +Cl2 C6H5Cl +HCl

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):

R CH2 OH +CuO R CHO +Cu +H2O

CH3OH +CuO HCHO +Cu +H2O

to,

to,

to, p

Fe

1)O2(kk); 2)H2SO4 CH2=CHCH3 , H+

to,xt,p

to,xt,p

to,xt

to

to

to

Ni,to


21

Fomandehit cn c iu ch bng cch oxi ha metanol nh oxi khng kh 600-7000C vi xc tc l Cu hoc Ag.

2CH3 OH + O2 , oCu t 2HCHO + 2H2O

*Oxy ho ankan iu kin thch hp.

CH4 + O2 HCHO + H2O

*Thy phn dn xut 1,1 ihalogen.

3

Cl |

2 | Cl

CH CH NaOH CH3CHO +2NaCl +H2O

*Oxi ha cumen ri ch ha vi axit sunfuric thu c axeton vi phenol:

(CH3)2CH C6H5 tiu phn trung gian CH3 CO CH3 +C6H5 OH

*2CH CH +O2 2 2, ,80oPdCl CuCl C 2CH3CH=O

*C2H2 +H2O CH3CHO *RCOOH=CH2 +NaOH RCOONa + CH3CHO 6.5.4 Xeton: *Oxi ha ru bc (II):

' | OH

R CH R +CuO 2' || O

R C R Cu H O

*T Canxi axetat

(CH3COO)2Ca CH3 CO CH3 +CaCO3 Hoc t CH3COONa:

2CH3COONa CH3 CO CH3 +Na2CO3 6.5.5 Axit cacboxylic. *Oxi ha hirocacbon, ancol

C6H5 CH3 C6H5COOK C6H5 COOH +Oxi ha ru bc I tng ng: 5CH2 CH2OH + 4KMnO4 + 6H2SO4 5CH3COOH + 2K2SO4+4MnSO4+11H2O +Oxi ha hirocacbon cha no: 5CH3 CH = CH CH3 +8KMnO4+12H2SO4 10CH3COOH + 4K2SO4+8MnSO4 +12H2O +Oxi ha ankan thch hp:

R CH3 RCOOH +H2O

[O], xt. t0

H3O+ KMnO4, H2O,t

0

to,

to,

2)H2SO4, 20% 1)O2

HgSO4,to

to,

to,xt


22

*T dn xut halogen:

R X R C N R COOH +Thy phn dn xut 1,1,1 trihalogen.

3

Cl |

3 | Cl

CH C Cl NaOH CH3COOH +3NaCl + H2O

*Ln men gim:

CH3CH2OH +O2 CH3COOH +H2O *Oxi ha andehit tng ng:

CH3CH=O + O2 CH3COOH

OHC CHO + O2 HOOC COOH *T metanol

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.

Cacbohidrat l nhng hp cht hu c tp chc v thng c CTC : Cn(H2O)m

Cacbohidrat chia lm 3 nhm ch yu :

+Monosaccarit l nhm khng b thy phn . vd: glucoz , fuctoz

+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

I.L tnh .Trong mu ngi c nng glucoz khng i khong 0,1% .

II.Cu to .Glucoz c CTPT : C6H12O6

Glucoz c CTCT : CH2OH-CHOH-CHOH-CHOH-CHOH-CH=O hoc CH2OH[CHOH]4CHO .

Glucoz l hp cht tp chc

t0

to, xt

to, xt

to, Mn2+

Men gim, 20-300c

H3O+,t0 KCN


23

Trong thc t Glucoz tn ti ch yu dng mch vng: dng -glucoz v - glucoz

III. Ha tnh . Glucoz c tnh cht andehit v ancol a chc ( poliancol ) .

1/ Tnh cht ca ancol a chc:

a/ Tc dng vi Cu(OH)2: nhit thng to phc ng glucoz (dd mu xanh lam- nhn bit glucoz)

b/ Phn ng to este: to este cha 5 gc axit axetic

2/ Tnh cht ca andehit:

a/ Oxi ha glucoz:

+ Bng dd AgNO3 trong NH3:amoni gluconat v Ag (nhn bit glucoz)

C6H12O6 3 3/AgNO NH 2Ag

+ Bng Cu(OH)2 mi trng kim: natri gluconat v Cu2O gch (nhn bit glucoz)

+ Tc dng vi dung dch nc Brom(Br2)

C5H11O5CHO + Br2 + H2O C5H11O5COOH + 2HBr

b/ Kh glucoz bng H2 sobitol (poliancol)

3/ Phn ng ln men: C6H12O6 2C2H5OH + 2CO2 ( Khi gii bi tp ch n Hiu sut phn ng)

IV. 1/ iu ch: Trong cng nghip

+ Thy phn tinh bt

+ Thy phn xenluloz, xt HCl

2/ ng dng: lm thuc tng lc, trng gng, rut phch,

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)

Fructoz OH glucoz


24

+ Trong mi trng baz fructoz chuyn thnh glucoz fructoz b oxi ha bi AgNO3/NH3 v Cu(OH)2 trong mi trng kim.

* Glucozo v fuctozo u tc dng vi H2 tao ra cng mt sn phm l sobitol

7.1.3. SACCAROZ , MANTOZ

I. SACCAROZ (ng knh)

CTPT: C12H22O11

-Saccaroz l mt isaccarit c cu to t mt gc - glucoz v mt gc fructoz lin kt vi nhau qua nguyn t oxi.

-Khng c nhm chc CHO nn khng c phn ng trng bc v khng lm mt mu nc brom.

3. Tnh cht ha hc.

C tnh cht ca ancol a chc v c phn ng thy phn.

a) Phn ng vi Cu(OH)2

2C12H22O11+Cu(OH)2(C12H21O11)2Cu+2H2O

mu xanh lam(ng saccarat)

b) Phn ng thy phn.C12H22O11+H2O C6H12O6 + C6H12O6

( - glucoz) ( fructoz )

c, Phn ng vi sa:

C12H22O11+ (CaOH)2 + H2O C12H22O11CaO.2H2O (khng tan)

C12H22O11CaO.2H2O + CO2 C12H22O11 + CaCO3 + 2H2O ( phn ng ny dng tch ng Saccarozo)

4.ng dng: Dng trng gng, trng phch.

II. MANTOZ ( ng mch nha)

CTPT: C12H22O11 ( Gm 2 gc - glucoz Hoc 1 gc - glucoz v 1 gc - glucoz)

Trong phn t cn c nhm OH hemiaxetal nn c th m vng to nhm chc CHO nn c phn ng trng bc v lm mt mu nc brom

C12H22O11 3 3/AgNO NH 2 Ag

a) Phn ng vi Cu(OH)2


25

2C12H22O11+Cu(OH)2(C12H21O11)2Cu+2H2O

mu xanh lam

b) Phn ng thy phn.C12H22O11+H2O C6H12O6 + C6H12O6

( - 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 .

Cc mt xch -glucoz lin kt vi nhau to hai dng:

-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).

Tinh bt ( trong cc ht ng cc , cc loi c )

3. Tnh cht ha hc.

a) Phn ng thy phn: tinh bt b thy phn thnh glucoz.

(C6H10O5)n + nH2O n C6H12O6

b) Phn ng mu vi iot:To thnh hp cht c mu xanh tm (phn ng dng nhn bit Tinh bt)

II. XENLULOZ

1. Tnh cht vt l, trng thi t nhin.

-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

-CT : (C6H10O5)n hay [C6H7O2(OH)3]n

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