PHƯƠNG PHÁP GIẢI BÀI TẬP HÓA HỌC 11 TỰ LUẬN VÀ TRẮC NGHIỆM - CAO CỰ GIÁC

8/10/2019 PHNG PHP GII BI TP HA HC 11 T LUN V TRC NGHIM - CAO C GIC

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TS. CAO C GIC

I

PHNG PHP GII BI TP

HA HC 11T LUN V TRC NGHIM

( d d t tg H g l m m k ^ i i t M . i l d V i k t ) ' :

CP 2 ' ' -

f

l i .

NH XUT BN I HC QUC GIA H NI

WWW.FACEBOOK.COM/DAYKEM.QU

WWW.FACEBOOK.COM/BOIDUONGHOAHOCQU

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W.DAYKEMQUYNHON.UCOZ.COM

ng gp PDF bi GV. Nguyn Thanh T


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Vu n s A a /

p ng nhu cu nng cao cht lng dy v hc ha hc trng THPTtheo chng trnh mi (thc hin t nm hc 2006 - 2007), chng ti binson b sch PHNG PHP GI BI TP HA HC - T LUN VTRC NGHIM ln lt cho cc lp 10, 1 1 v 12 theo chng trnh c bnv nng cao. B sch c bit c ch cho cc lp bi dng hc sinh gii

Ha.hcv cc em hc sinh ang chun b thi vo i hc cao ngtheophng php trc nghim khch quan.

Ni dung ca b sch c bin son theo th t cc chong trongchng trnh mi, mi chng bao gm 4 phn:

A. PHNG PHP GII BI TP Phn nv gii thiu nhiu phrmgphp gii ngn gn, sng to vi cc bi tp c s ng cc php tnh.

Ngoi ra cn gii thiu nhiu kin thc ha hc b ch cng cp thmthng tn cho bn c, lm c s tr li cc bi tp trc nghim khchquan mt cch chnh xc v nhanh gn.

B. BI TP T LUN - Nhm kim tra kh nng p lun, vn dngkin thc trong qu trinh gii bi tp t d n kh- S lp lun sc

bn cng l tin c ch cho vic a chn phng n ng trongbi tp trc nghim khch quan (gi tt l trc righim).

c . BI TP TRAC n g h i m - Mi chng c bin Sn 50 bi tp trcnghim dng nhiu la chn (s dng ch yu trong thi i hc v

Olympic h hc) trong chi c mt phng n ng.Cc phng ncn li u sai di dng c v ng, hp/, phn nh cc phng phpugi nhm,g Ucu nhiu

D. P S V HNG DN Gll - Tt c cc bi tp u c p s v hng dn chi tit ivi nhng bi kh.

Nhn dp ny, tc gi xi c by t s cm. n chn thnh ti nhiu cgi l nhng nh gio, cc bn sinh vin v cc em hc sinh trn mi min tnc gi th ng vin, khch l, tip sc cho tc gi hon thnh b sch

trong nhiu nm qua. Tc gi s ht sc bit n v mong mun tip tc phnc n liu kin ng gp, xy dng t pha bn c cht lng b schngy cng c nng cao.

Tc g

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Ch n g HTOROCaCBON KHNG

A. ph n g ph p g i iBi TP

I. nh ngha v phn loi1. nh ngha

Hirocacbon khng no nhng hirocacbon c cha lin kt bi (linkt i hoc ba hoc c hai) trong phn t.

2. Phn oi

a) Hirocacbon kln no mch h

Mt iin kt c = c >anken CnI2u (n > 2 )

9 Ia lin kt i 0 - c ankaien Cnn(n > 3) Mt in kt ba c = c - ankin CnH2n2(n 52 ) Va c in kt i va c Hn kt ba -> ankenin.

b) Hirocacbon khng no mch vng Mt vng cha mt-ni i c = c - xicloanken Mt vng cha hi ni i c = c -> xicloankaien. Mt vng cha n ba c = c -> xicloankin

II. Cu trc phn t v ng phn

. Anken

Trong phn t c mt ni i c = c vi nguyn t cacbon lai ha sp2,to gc phng 12 0. trong c mt lin kt bn v mt in kt Xkm bn (trung tm ca cc phn iig).

Anken t C tr i c cc ng phn cu to:- ng phn mch cacbon, v d:

but-l-en

(butilen)

2 -metylpropen

(isbutilen)

- ng phn v tr i n kt i (nhm chc), v d:

CH2=CH-CH2-CH3 v CH3-CH=CH-CH3but--en but-2 -en

- ng phn nhm chc (lin kt i v mch vng), v d:

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.2

xiclopropan Hai nguyn t Cs 2 khng th quay t do c xung quanh lin kt

c = c, do cc anken t C4tr i c th xut hin ng phn hnh

hc (cs-trans hoc z - E) nu mi nguyn t C 2 ni vi hai

cis-ch hai nhm anky cng pha ni i c = c v trans-ch 2nhmankyl khc pha.z- ch hai nhm ln cng pha i vi c = c v E- ch 2 nhm lnkhc pha. Nhm ln c quy nh nh sau:

Vi anken t c6tr i cn c th c ng phn quang hc nu trong phnt c nguyn t cacbon bt i, k hiu c*. l nguyn t lin kt vi 4nguyn t hoc nhm nguyn t khc nhau c* abed (a * b *c * dX

* Cc s liu the nghim cho thy ng phn trans bn hn ng phncisdo gim lc y Van er Walls gia cc nhm ankyl. Thc nghimcng cho thy rng cng nhiu nhm ankyl nh vo lin kt i c .= cth anken cng bn. iu ny c gii thch l do hiu ng siu linhp ca cc lin kt C -H cch lin kt i mt lin kt n, tngdn theo s nhm ankyl.

ngyn t hoc nhm nguyn t khc nhau. V d:c h CH,CHs CHaCHa H

cis-pent-2 -enCH* CH2CH3

trans-peni-2 ~enC CH2CH3

v

(E) -2~copent~2~en (Z) -2~copent-2-en

I > Br > Cl > F > o > N > c > H(CH3) 0 > (CHsfeCH- > CH3CH2- > CHs~c = c > c = C > C - C > c - H)c= o > )cHOK > )c H ^ > )cH2

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bn nhit ng ca cc anken ni chung tng theo trt t sau:R R

CH2-CH2< R-CH=CH2< R - CH=CH-R < C=CH2< C=CH-RR R

R R R R R H\ / \ / \ /c = c < c = p < c = C/ \ / \ / \R R H H H R

V d: Entnpi hnh thnh (sinh nhit) ca cc ng phn hexen,butennhsau .

Hexen: CH2= CH(CH2)3CH3 CH2= C(C2H5)2-44,1 -51,6c h 3 c h 3 c h 3 c h 3V J \ G = c c = G

H C2H5 h3 \

AHt (kJ/mo): -58,7 -59,2

Buten: CH2= CH - CH2CH3CH, CH3 c h 3 h 3 / 3 \ 3 /c = c c = c/ \ / \

H H H CH. 7,0 11,2AHt(U/mol}: -0,8

.Ankaien

Hai lin kt i c = c c th lin nhau, hoc cch nhau mt lin ktn (ankain lin hp), hoc cch nhau nhiu lin kt n (ankaenkhng lin hp). V d:

CH2=C=CH2 c h 2= c h - c h = c h2propaien buta-l,3-cn(anlen) (butaicn)

CH2 = c - CH = CH, CH2=CH~CH2-CH=CH2Q ' penta-l,4-en

2r-metylbuta~l,3-ien

(isoprn)Trong phn t buta-l,3-ien tt c 10 nguyn t (4C v 6H) v 9 lin

kt (3 lin kt c - c v 6 lin kt c - H) u nm trn mt mtphng v to nn nhng gc ~ 120. Cc obitan p khng nhng xenph bn vi nhau to thnh Hn kt 71gia Ci vi c 2v C3 vi C4 mcn xen ph gia c 2vi C3do xut hin obitan 71gii ta trn tt c4 nguyn t cacbon (lin kt 71lin hp).

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Ankaien lin hp cng Gcc cu dng khc nha v cng c phn hnh hc, nu nguyn t Cs 8 u mch ni vi hai nguyn

hoc nhm nguyn t khc nhau. V d CH3CH = CH - CH = CHv cng phn hnh hc, CH3CH = CH - CH = CHC2H5 c 4 ng phhnh hc.

3. AlikinTrong phn t c lin kt b c=c V. nguyn t C lai ha sp nn ph

t axetilen c cu to thng, gc ha tr 180a. Lin kt ba CaC bao gm 1 lin kt bn v 2 lin kt 71km bn. T

nhin lin kt 7 trong c=c hi bn hn so vi lin kt 71 troc=c nn phn ng cng vo lin kt ba xy r kh hn cng vo lkt i.

di lin kt ba rt ngn (1,19 ) nn electron gn nhn v b h

nhn ht mnh nguyn t c ni ba c m in ln nht trocc loi nguyn t ccbon (xcac - 3,29) ->cc ankin c ni ba u m(ank-l-in) s c nguyn t H linh ng v lin kt H-C-C- phn crt mnh, d b ct t ng vai tr tc nhn trong phn ng choc phn ng th vi ion kim loi.

n. Tnh cht vt l

Hirocacbon khng no c nhiu tnh cht vt l nh nhit si, nh nng chy,:khi lng ring, tnh ta n ,.... tng t hirocacbon no

cung s nguyn t cacbon v cng b khung cacbon. Mt s quy lut v nhit si v nhit nng chy:- Ank-l-en v an k-l-in c nhit si thp hn ankan lng ng.- S chuyn dch ni i v ni ba t u mch vo pha trong l

tng nhit si v nhit nng chy.- ng phn cis c nhit si cao hn v nhit nng (hy th

hn ng phn trans. .- S lin hp m tng nhit si.

Hng s vt lc a mt s hirocacbon khng no

Tn C6ng ttic cu io c (C) c (C) (g/cra3)

eten (etilen)propenbt-1-en2-metylpropenc/s-b ut-2-en

ch2.= ch2ch2=chch3ch2=chch2ch3

CH2=C(CH3)2ci$-ch3ch=chch3

'169-186-185-141-139

-104-47-6-74

0.57 (-110C0,61 (-50C)0,63 (-6C)0,63 (-7C)0,64 (20C)

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1un*'*- pent-2-en trans-CH3CH=CHCH3 -106 1 0,66 (20C)PC.. i-en CH2=CHCH2CH2CH3 -165 30 0,64 {20C)CIS-pent-2-en cs-CH3CH=CHCH2CH3 -151 . 37 0,66 (20C)trans-pen-2-en rans-CH3CH=CHCH2CH3 -MO 36 0,65 (20C)buta-1,3-ien ch2=chch=gh2 -109 -4.5 0,65 (20C)

isopren CH2=C(CH3)-CH=CH2 -120 34 0,68 (20C)etin (axetilen) HChCH -82 -75 0.62 (-80C)

propin HCs C-CH3 -104 -23 0,68 (-27C)but-1-in HC-CCH2CH3 -130 8 0,67 (0C)but2n CH3CkCCH3 -28 27 0 70 (20C) .pent-t-in HC,CCHjCH2GH3 -106 40 0,70 (20C)pent-2-in QH3Q^CH2CH3 -101 55 0 71 (20C)

H. Thng tn v ph

. Ankon

Ph hng ngoi ca anken c c trng bi dao ng ha tr cac = c -vng - 1600 cm' 1 v dao ng bin dng ca =C-H trans ~ 980 cm 1v cs ~ 690 cm l.

Trn ph t ngoi ca nken c cci 180 - 200 nm. Tn hiu v proton ni i th hin trong vng 4,5 - 6,5 ppm trnph cng hdng t ht nhn.

2, Poien Ph electron ca cc poien lin hp rt c ch trong vic xc nh cto ca cc polien thin nhin cng nh tng hp. Khi mch lin hpko di th Xjnax v max u tng mnh. Cc nhm th gn vo lin hplm tng Xmax theo nhng s gia ring c tnh cht cng tnh. V d,mi nhm ankyl lm tng Xtaax thm 5 nm, mi nhm RO- lm tng6nm v nhm RS- lm tng ti 30 nm.

Gi tr vc=cca cc polien lin hp nh hn vc=c polien thng cngnh anken, tt c chng u nm vng 1600- 165 cm-1. vc=c ca ca

anlen th ln ti 1950 cm' 1 tc lm nm trung gian gia vc=c anken vVc-C ankin (2100 - 2300 cm-1). Dao ng ha tr ca lin kt c -H

polien thng v polien lin hp ging nh ankn (3000 - 3100 era'1). . chuyn ch ha hc ca protn gn vi c . poien thng v

.poien iii" hp khng khc my so vi anken (~ 4,5 - 6,0 ppm) cn caproton anlen th thp hn hn (~ 4,0 - 5,0 ppm).

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H2C = CH2+ Br2 CH2- CHZ + CHy - CHZ

Br Br B r Cl(54%) (467i)

r* CHXH- CH.. m v/ CH;(CH-CH, (15%)

CH3CH=CH2+ Br2 LCTrong

Br OH

-> CHhCH - CH.,:7 -.*Br Br

CH.,CH CH, 1

1 Br

-CH5CH -C H 2

a%)

(16%)

(14%)

Br fa Khi sc kh etilcn vo H2SO4 m c (> 95%), ung ch b nng

ln v khng thy bt kh thot ra, Axit sunfijric , cng vo etien:CH2=CH2+ H2S04f) -> CHs-CHir-OSOsH ety hidrosunfat)

Cc anken lng khng tan trong cc ung, ch axit nhiig tan etrong 2SO4 m c (> 95%) cng l do phn ng tng t. Ccankyl hidrosufat to thnh d b th phn khi un nng vi ncto thnh ancol.

R-CH=CH, + H2S04() -> R - CH - CH, A--+ R - CH - CH,i . ' I-OSO.jH OH

Cc hirohalogenua (HX) cng vo anken to thnh aiikyl halogenuavi hiu sut tng i cao:

CH3)2C=CH2+HC (kh)


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I. CI2= CH2+.10H S fe g fr * CH3CH2OH(95%)

chuyn anken thnh ancol, trong phng th nghim ngi ta tdngphn ng hirat ha xc tc axit v n thng dn ti sn phmgm hn hp cc anco ng phn kh tch bit(ng phn do nhmOH cacbon bc cao hn, bc thp hn v ng phn do phn hg

I chuyn v).

I Mun thu c ancol m nhm OH nh vo cacbon bc cao hn, ngi ta thc hin phn ng cng nh tnh cht electrophin ca Hg2* trong thy ngn axetat Hg(OCOCH3)2trong dung dch tetra hirouran,

- Q < T H F ): .

R-CH=CH2 R - CH - CH , R - CH - CH,_ / \ / L* I ' _____

CH3CQO^Hg-OCOCH3 HgOCOCH, OHHgOCOCH,

(phn ng hiroxi thy ngn ha)Sau kh hp cht thy ngn bng ntri bohirua, NaBKj:4R CH CH., +NaBH4+ 40H

I TOH HgOCOCH,

4R - CH - r u 3 + NaB(OH)4+ 4Hg i+ 4CH3COO!OH

V hnh thc y cng l phn ng cng H20 vo anken nhng u

im l ch sn phm ancol bc II c th t ti 99,5% (anco bc ch chim-0,5%) v khng c sn phm chyn v.

Ngc li, mun thu dc nncol m nhm OH nh vo cacbon bcthp hn,ngi ta thng dng phn ng hiro-bo ha:

6RCH = GH2 + B?H,i 2(RCH2CH2)3Bitoran triankyl bo

(RCH2CH-Al + 3 IA 3RCH2CH2OH + H3BO3

u im cua phng php .ny l hiu sut cao v phn ng c tnh

chn lc cao, khng c sn phm ohuvn v. Qy tc Mccopnhicop: Trong phn ng cng ax hoc mcc (ki hiuchung l HA) vo lin ht c = c ca anken, nguyn t H (hay phnmang in dng) ch xi cng nguyn t cacbon bc thp (cnhiu H hn), cn A (phn nuing in m cng vo nguyn t ( .

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10/224

CH3- CH - CH3 (sn phm chnh t

CH3-CH=CH2+ HC1 -----< C1

CH3-CH?-CH2-C 1(sn phm ph)OH

rCHg - c - CH3 {sn phm chnh)CH, = c - CH3+ HOH CH

CH3 1 1CH2- CH - CH3 (sn phm ph)I OH CH3

Gii thich quy tc:Phn ng xy ra theo c ch cng Ae do giaion chm tin to ra cacbocation bn viig hn (.in tch dngca cacboation. dc gii ta khp phn t). bn ca cacbocationtng theo th t bc I < bc II < bc III. V d;

* CHy- C H-CHS CH3 - CH - CH3

U . C 'CH3-CH=CH2 (

\ (bn hn) (sn phm chnh)

CH3-CH - C H2-S U CH3-CH2-CH2-CI(km bn) (sn phm ph)

Cng c th gii thch quy tc Maccopnhicop theo hiu ng electron:Do gc ankyl y electron (hiu ng +1) lm cho lin kt 71b phn cc

theo chiu mi tn cong, nn in dng d gn vo cacbon mang, inm v ngc li: s\'

CHs Cp=CH2 + C - CH3- c h - CHg (1)

CI

(sn phm chnh)Theo quylut ny ta c:

CH2i"cH 2 c f + HB r->CH 2 CH2-COOH (2)^ ___ O -H . Br

Axit acrylic (sn phm chnh)

Nh vy phn ng (2) chy ngic ,qy tc Mccopnhicop. Thc ra c(1 ) v (2) u xy ra qua bc to cacbocation trung gian bn vng



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tng ng vi sn phm chnh. khng mt tnh tng qut, c thhiu quy tc Maccopnhicop nh sau:

Phn ng cng mt tc nhn khng i xng (nh HC, HBr, H2SO4,HoO, IC, ) vo mt anken khng i xng (nh CH3CH~CH2,CH3CH-CHC25, ...) s u tin xy ra theo hng to cacbocaton

trung gian bn hn.CHs-CH-CHa 2 4 CHgCHBrCHs

(bn hn) (95%)

CH3-C H2-CH* -2U CH2CH2CH2Br

(km bn) (5%)

R-CH=CHo+ - > RCH-CH2I + RCH-CH2C1I . . . 1

G1 I

(sn phm chnh) (sn phm ph)

E-CH=CH2 + H O - Cl RCH - CH2C1 + RCR - CH2OHI IOH C1

(sn phm chnh) (sn phm ph) Kh nng phn ng ca nken: Khi thay th nguyn t H trong

etilen bng nhm y electron (CH3, C2H5,-..), mt electron nii s tng ln v cacbocation sinh ra cng bn hn do phn ng

cng xy ra dng hn. Ngc li, nhm th ht electron s lmgim mt electron v cacbocation sinh ra cng km bn, do phn ng cng xy ra kh khn hn. Th t kh nng phn ngcng Ae ca mt s cht nh sau:

CH?=CHCOOH < CH2=CHC1 < CH2 = CH2< CH2= CHCHs < CH2= C(CH3)2

Kh nng phn ng ca hiro halogenna: Phi); ng cng HX voanken s dng nu HX c tnh axit mnh v x c tnh

nucleophin cao. V vy kh nng phn ng cng Ae ca HX gimtheo trnh tHI > HBr > HC1 >> HF

Trong trng hp cng HBr c mt O2, H2O2, peoxit, phn ag xy ratheo c ch gc Ar theo hng to tinhgctrung gian tng i bnhn, cho sn phm ngc quy tc Maccopnhicop (qy tc Kharat).

CH3- CH = CH2+ HBr CH3- CH2- CH2Br(sn phm chnh)

CH3CH=CH2 + HBr



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12/224

b) Aitkin

Phan ng cng halogen (X2) v HA vo ankin cung tng t phn nca anken v c ch phn ng, hng ca phn ng v nh hng cnhm th n kh nng phn ng. So vi anken, th ankin c khnng phn ng thp hn cng anken tng ng:

CH3C - CH > HC = CH > GH = CCOOH

H2C = CH2> HC EECH Phn ng clo ha hay brom ha ankin cho sn phm cng traniclo hay i brom anken vi xc tc l FeCl3, SbCI5nhit thp

Br Br Br1 I I

RC = CH R - c = CH R - c - CH

Br Br Br

Phn ng cng hiro halogenua v cng nc (hirat ha) cng tutheo guv tc Maccopnhicop:

Br

RC = CH R -C = CH,

Br

-> R - c - CH ,IBr

RC^CH + H20

HC CH + H20Km bnCH2=CH

ol

r - c - c h 3

xeon-> c h 3- c h = o

Km bn andehit

Ch : Phn ng cng HBr vo ankin kh c mt peoxit cng tuntheo quy tc Kharat:

R sC I > RCH = CHBr

Phn ng cng cia axetien vi axit / ancol:HC = CH + CI;;COOH c h 3c o o c i i = CH,

vinyl axctatn c , CI + CisII.v/COO -^g*-> ClflH,7GOOCIl = CH,

vinyl stcart



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13/224

KC 3 Gil + C2H5OH C2H5 - o - CH = I,II,

etyl vinyl ete

Phn ng cng bohirua BH3v oxi ha xy ra theo hai bc v chohai sn phm khc nhau, trong mi trng kim cho anehit, trongmi trng axit cho anken:

HO,

\ H / RCHCHORC = CH + BH3 T!IK-> c - C (

H XBH2 - Y* RCH = CH2

c) Ankaie

Cc halogen (X2) hidrohalpgenua (HX) v mt s tac nhn khc cngvo ien theo Cch cng electrophin (Ae) to ra hn hp cc snphm cng lv2v cng - 1 , 1 . T l gia cc sn phm ph thuc

ch yu v nhit .Nhit cng co,sn phm -1,4 cng chimu th. V d : 11

CH2=CH-CH=CH2 c h , - CH - CH = CH, + CH, - CH = CH - CH,z OCL I I I I

+ Br2 Br Br Br Br

(sn phm cng -1,2) (sn phmcng- 1,4)

-80C: 80tf 20%-15C: 5-1'* 46% +40C: 2 0 % 80%+60C: 10% 90%

CH2=CH-CI=CH2 c h , - CH. - CH =CH.2+CH, - CH = CH - CH,

+ HBr -> Br Br

-80C: 80% 20% C: 70% 30% +40C: 2 0 r/r 80%

Cc ankain c th cng ti a theo t l s mol 1 : 2 to thnhsn phm no hon ton. V d:

CH2= c h - CH = CH2+ 2Br2-CH,- CH - GH - CH,i l l LBr Br Br Br

Theo quail nim hin nay, trong phn ling cng lectrophin vankaien, tc nhn electrophin IF , Br' , ...) tn cng vo u

17



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

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T

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N

H

N

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14/224

mang in m ca mch lin hp b phn cc ha v to ra mtcacbocation lin hp:

5 5* S '* T \___ __ *L S -r-lr + CH2=CH-CH = CH2 -> B r - CH2-H-CH~H2

1 2 2 3 4 2 1 2 3 4

ccbocation ny, in tch dng khng tp trung mt nguyn t

c 2m c gii ta ra c mch cho ti nguyn t C4 theo s :Br - CH- - CH2= : CH = H2

: 2 2 2 3 4

V vy, giai on th hai, anion Bre c th tn cng vo nguyn tC2hoc c 4, to ra cc sn phm cng -1,2 v cng - 1,4: ,

Br-CH2-H = CI te :H 2 + Br0Br-CH2-CHBr-CH=CH2

* BrCI2-GH=CHCHg-Br Phn ng cng mt tc nhn khng i xng (HC, HBr, ...) vo

ankaen khng i xng xy ra theo hdng ph-hp vi quy tcMaccopnhicop, ngha l phn mang in ng (H) s tn cngvo cacbon no c mt electron cao hn trong mch lin hp caphn t. V d:

HCH,

C H p b -C H -C H , - S ^ c n - C = c h = = c h 2isopren (1.2) cP (3,4)

GH, CH,

CH3 - c - c h = CH2 CH3 - c = CH - CH2

Cl C1

HH { p CH =CH-CH=CH2 - CH3- CH = CH = CH - GH3

H (1 ,2)

Cl (3,4)

penta-l,3-^ienCHa - CH = CH - CH - GH3 CH3- CH - CH = CH - CH,

3Cl C1 ^

18



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

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N

H

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15/224

Trong khi cc ankaien lin hp c th to ra hai sn phm cng(-1,2 v -1,4) th cc ankenin nh vinylaxetilen CH2-CH-C=CH cth to ra ba loi sn phm cng khc nhau (cng -1,2, cng -1,4 vcng -3,4). V d Br2 tc ng vi vinyl axetilen cho ba sn phm(I), (II), (III) trong sn phm cng -1,4 (I) c cu to anlen tngi t bn hn chim u th:

y r B r - CH2 - CH = c = CHBr (I)CH2= CH - c = CH CHCI3 1 ^ * CH2 = CH - CBr = CHBr (II)

Viny axeten ^ BrCH - CHBr - c = CH (in)Cc ng ng ca vinyl axetilen kiu CH2 = CH - c = c - R b o

ha v brom ha ch yu vo ni i.3. Phn ng cng - ng vng [4+ 2/ (phn ng Dies-Ader)

y l phn ng cng -1,4 ca mt lin kt i (thng l c = C) vomt ien lin hp to ra hp cht vng 6 cnh. V d, phn ng

cng etilen vo buta-l,3-ien:.CH,

//_H CH, 120 cCH " CH2

CH.

' O

2ien ienophin xiclohexen

Trong phn ng Diels-Alder (c - Noben 1950), ien lin hp c

gi n gin l ien, cnanken phn ng vi n c gi l ienophin.S cng ien vi ienophn xy r mt cch ng thi (phn ng mtgiai on) vi s tham gia ca 4 electron 7t thuc ien v 2 electron 71thuc ienophn nh l mt vng electron:

Y c%ien ienophin sn phm

V phn ng xy ra ng thi nn ien phi c cu dng Scis (S vittt ca single bond). Nhng ien khng chyn thnh dng s -cis cth khng tham gia phn iig Dils-Aider:- Mt s S-cis-ientham gia phn ng (hot ng)

c o Q O c c- Mt s S-rares-ien khng tham gia phn ng (khng hot ng):

19



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

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N

H

N

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N

H

N




16/224

Nhng ien kh chuyn v cu dng s -cisth phn ng xy r rt khkhn. V d: cs-penta-l,3-ien phn ng vi tetraxian etien(NO2C = C(CN)2chr hn ng phn transkhong 12.600 ln do lcy Vn der Walls lm n kh chyn v dng s -cs.

I I v C I : ,

II ' ' Hci.s-penta-,3-ien

c h 3v / H

S-cs

S--CStrans~penta-',3-ien

Phn ng Diels-Alder tr nn thun li hn nu a vo phn t iennhm th y electron (-CH3, -CH2CH3, -OCH3, ...) m khng cn trs chuyn dng S-trans sang dng S-eis, hoc a vo phn tienophin nhm th ht electron (-COOH, -CHO, -C sN ,...).Phn ng Dies-Aider c tnh c th hp th: phn ng xy ra theo

kiu cng syn, v th cu hnh, ca ienophin c bo ton khi toihnh sn phm.V7d: JL

+'.C .

COOCH3150-160"c

H ' " C O O C H s

cs-enophin

-COOCH-i

(68f.)

' COOCH3

ng phn cis

CH3OOC HC

+ Ii r COOCH3

trans-inophin

150-I(r;c

' C O O C I ,

ng phn trans



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

R

N

H

N

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17/224

i vi


18/224

HCsCH ^ HC= G9 + H Ka = 10"26(pk3= 26)

R-C^C - H + Na R = O C 0Na- +'I Ha

natri ankinuaR-D=c - H + [Ag(NH3)2]OH R-C^C-Agi + 4NH3+ 2HsO

bc ankina(mu vng nht)

HOCH + 2[AgNH3)2]H - ^ 5 ^ Ag-O C - Ag + 4NH3+ 2H20

bc axetienua

Phn ng ny dng nhn bit cc ank1-iii.

Lc axit ca ank -l- in ln hn anken v ankan nn ankin y canken. v ankan khi hp cht c kim ca chng. V d:

R-CsG-H + CzHsMgBr R-OC-MgBr + C2H6R-C^C-H + 11-C 4H9L Pv-OCe Li0 + 11-C 4H10

Lc axt ca ankin yu hn nc, nn cc anknua kim loi kim vkim th b thy phn hon ton trong nc. Cc ankinua kim loinng (Ag, Cu) khng tan trong nc th khng b th phn binc l o lin kt cacbon - kim loi chuyn tip khng phi linkt ion m l lin kt cng ha tr bn vng. V d:

R-C=CeNa* + HOH RC=CH + Na++ o i r

R-C=C - Ag + H+-> R-CsCH + Ag+.

Phn tigny dng ti to cc ank-l-in khi tch n ra khi hn hp.

5. Phn ng trung hp

Trng hp l qu trnh cng hp lin tip nhiu phn t nh ging nhauhay tng t nhau thnh phn t c phn t khi ln (cao phn t).

Cht u tham gia trng hp c gi 1kmonome, trong phn tmonome thng phi c lin, kt bi. Sn phm cao phn t thu c

gi lp9liiecha n mt xch c bnto ra t n phn t monome.Nu n - 2- 10 th polime c gi l oligomebagm ime(n = 2), trime(n = 3), tetrame(11= 4), ... (n l h s trng hphay trng hp).

a) Ahketi

Cc anken v dn xut c cng thc chung CH2= CH - R tng i trng hp iu kin rihit v p sut nht nh c mt xc tc,to ra cc polime tng ng. V d:

22



B

I

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N

GT

O

N

-

L

-

H

A

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P

2

3

1

0

0

0

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19/224

nCH2= CH2 T,c!2.fj| f - > fCH2 -CH ^

polietilen (PE)

nCH = CHo K?H-CH24i p c h 3 c h 3

polipropilen (PP)b) Ankadien

Trng hp kiu 1,4 cho polime n hi (cao su)

nCH2- CH - CH = CH2 -^2- CH2- CH - CH - CH24n

cao s buna

nCHg = C-CH = CH2 CH2- c = CH - CH24n

c h 3 c h 3cao su isopren

nCH2 = c - CH = CH2 {CH2 - c = CH - CH2 -n

Cl C1

cao su cloropren (neopren)

Mt phn e th trng hp theo kiu (1,2) to thnh polimekhng n hi. iu ny gii thch tnh n hi km ca mt s

loi cao su tng hp:nCH2= CH - CH = CH2 CH2- CH4n

CH = CH2

c) Ankin

Axetien tham gia phn ng oligome ha klc nhau ty theo iu kinphn ng. V d:

ime ha: 2CH EECH > CH2 =s CH - c =CH

but-l-en-3-in

(vinyl axetilen)

Trime ha: 3CH CH cjpiggh > CfiHfi (benzen)

Polime ha: nCH = CH t (CH>2n (Cupren)

23



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

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N

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N

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20/224

6.Phn ng chy (oxi ha hon ton)

a) Aken

1

c + 3- 02 --* nC0 2 + 11H2O; < 0 f2 t

' Phn ng ta nhiu nhit.

S mol CO2= s mol H20.b) Ankaien v ankin

CH2i,_2+ ?V ^ 2 nC2 +


21/224

5CH3- c h = c C, + 6KMn4+ 9H2S04I

C,

5CH3COOH + 5CH3-C - CH.. + 6MnS04+ 3K2S04+ 9H20

I3CH3-CH=CH2+ 5K2Cr207+ 20H2S04

-> 3CH;5COOH + 3C02t + 5Cr2(S04)s + 5K2SO4+ 23H20HC=CH + 2KMn4+ 3H2S04-> 2C02T + 2MnS04+ K2SO4+ 4H20

c) Phn ng ozon phn

Vi anken:

R\

Xp.

HR

\Zn/n,o c = o + o = c

* 1 \R' Hxeton anehitR R"

\ /C = 0 + 0 - C

> / \R' OHxeton axit

oznt / 'R Ur!xeton axit

C hai giai on, cng ozon (ozon ha) v phn ct ozonit, c gichung l ozon phn. C hai kiu ozon phn: ozon phn kh v ozon

phn oxi ha. Sau khi ozon phn, nhm yC =C^ca anken chuyn

thnh 2 nhm ^0 = 0 . Ty thuc vo cu to ca anken v vo ech

phn ct kh hay 0X1 ha m thu c anehit, xeton hay axitcaboxylic. Da vo cu to cc sn phm , ta xc nh c cu toc cc anken. V d:

Cu tao ankenSn phm zonphn

kh oxi ha

VH

HxV 0

I7(anehit fomici

H x' c = o

HO(axit fomici

25



B

I

D

N

GT

O

N

-

L

-

H

A

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2

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1

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0

0

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22/224

a

*

VII R \^ C = 0

H(anehit)

R \ > = 0H

(axit cacboxylic)

R \R

R \^ C = 0R

(xeton)

J )c = 0R

(xeton)

Phng php ozon phn c nhc im l i hi phi c thit bchuyn dng iu ch ozon v trnh xy r phn ng n. Bt ut nm 1955 - 1956, R.Lmer v Johnson da ra phng phpdng KM11O4chuyn anken thnh glicol (mc a) ri phn ct glicol

bng NaI04.V NaI04oxi ha c ion manganat v c M11O2thnh in pemanganat,nn ch cn s dung mt lng rt nh KMn04ng thi vi lng d

NaI0 4m khng phi tin hnh hai phn ig ring bit.V d: I

' KMnQ/NalO*

CH,OH k , CHOI + CH3'j 003* c Oil il

II

xitronelol o (10 0%)Khi dng OSO4 v NaiO th phi tin hnh hai phn ng k tipnhau nhng sn phm thu c khng b oxi ha thnh axit. vi d:

0 ^ c < Css** Vi akin: Khi ozn phn lun to ra axit cacboxylic.

0-0

R ~C =C -R '-^ R c C R' -^> RCOOH + R'COOH + H20 2

VH-ChCH RCOOH + HCOOH

) Oxi ha nh bng oxi khng kh trn h xc tc P d2- CU2CI2

Phn hg ny c dng trong cng nghip sn xut CH3CH0 t etilen:

2CH2= CH2+ 0 2 c; ^ c - > 2CH3CHO



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

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N

H

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N




23/224

V. iu ch

1.Ankeit

ehiro ha ankan tng ng:

GJ0w - ^ U C A + H2

ehirat ha ankanol tng ng:CHaiOH > CaHa, + H 20

Kh ha mt phn ankin

c v'nAX2n A*2V-/

dn

\ / R'm / S o q , -> ) c = c \ (cis-anken)

W XH

R-C=C-R'

Na/NH3> (trans-anken)\ /HW X R' ehirohalogenua ha dn xut monohalogen ankan

CnH 2n+1X + KOH 22 U CJIj fc + KX + H 20

V d: CH2- CH2 + KOH - ?* > CH2= CH2+ KC1 + H20

H C1

ehalogea ha dn xut 1,2'ihalogen

R - CH - CH - R' + Zn (hoc Mg) R-CH=CH-R' + ZnX2I IX X

Vi d: CH2 - CH2 + Zn CH2= CH2+ ZnBr2

Br Br

Crackinhankan:C TT arackinh . p t l _ . p I In- 2n+2 '-'X-I12X+2 + L/yXl2y ,(ankan)n - x + y (nkan) (anken)

2. Ankaiena) iu ch hta-,3-ien (vinyl)

ehiro ha butan hoc buten nhit cao (600C) c mt chtxc tc (Cr203/Al203):

C4H10 -~ H > C4Hs+ 2H2

C4Hs C4H6 + H2

27



B

I

D

N

GT

O

N

-

L

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H

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P

2

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0

0

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24/224

ehiro ha v ehirat ha etanol nh xc tc (ZnO hoc MgO vA2O3)'.

2CH3CH2OH CH 2= C H -CH =C H 2 + H 2 + 2H 20

i t axetilen:2CH=CH CH2=CH-C^CH CH2=CH-CH=CH2

irae ha anehit buta-l,3-ien H H

C H ,- C o + H -C H 2 - C ^ - = * . C H ,-C H -C H 2 - C ^^ 0 Ho

anolH2Ni/t

CH2= CH - CH = CH2 but-2-in-1,4iol> butari-l,4-iol 7r-> buta-l,3-ien

- r / \ /nT" _/ C-: + - > C s C - H + 0 = c f -> CEL.-C^C-CH,

II \ h I iOH OH

bu t-2-in -l, 4-ol2H2|Ni/t0

CH2=CH-CH=CH2 < - r - CH2 - C R ; - C H 2 -CH 2

OH OH

butan~,4-ol

b) Diu ch 2-metlbut-,3-ien (isopren) -

ehiro ha isopentan hoc isopenten (sh phm ca crackinh du m):

CH3 - CH - CH., - CH, CH3 -C = CH-CH, +H2CH;l CH.J

-H 2xt/t

c h 2 = c - c h = c h 2ICH.,

28



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

R

N

H

N

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25/224

Cng hp axetilen vi axetonCH.

----- H2Pd/t

CH,i20 + CH, = c - CH - CH2 CH2= CI - e - CH,

OH

t propen:2CH2= c h ^ CH3-CH-CH, - c - c h , - 4 ^ CH* = CH - c =

CH, CH., CH.J

. Ankin

T than , vi -> CaC2(t n) -> C22

CaC2+2H2O 4 HC = CH + Ca(OH)2Axetilen iu ch theo cch ny thng ln nhiu tp cht nh H-2S,NH3, PH, ... Sn phm ph ca kh l cc v nha than .

* T metan:

2CH* - i d g j b r * CHS GH + 3H2 T c v 2

Than ' 1c > than cc (C)CaCOs CO + C02tCaO + 3C CaC2+ COT

2C + H2 C2H2 ehiro ha ankan tng ng;.

1 CJA.2i\+' CuH-2iv2+ 2H2

ehiro ha dn xut dihalogon (geminal v vixinal) H X I T> h n T' NaNii. v 0 n - n D'R - C - - R'

J XH X

> R c = c ~ R'

H XI _

R - - - R' II X

gemnal NaNHoH

- * u R - C = C - R JX

vixina

29



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

R

N

H

N

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H

N




26/224

Phng php tng mnh cacbn:

H - . C a c - H ^ > H - c ^ CNa ?^ HC G R-- Nila*''-' XTCT

NaNH2 . T

N = C-RR'-XNH j

R-C = c - Ag + ' - X -> R - c = c - R' + gX T mui axetien: 5

A g C s C - A g + .2HCl. r> HC = C + 2Agl iCu - c = c - Cu + 2HC1 HC = CH + 2CuCli

VL Tecpe h

1. Kh i nim chung v tecpen

Tecpen l loi hp cht hirocacbon khng no c cng thc tgqut (CsHgVvi n > 2, thng gp trong gii thc vt. Tcpen c nhiu trntnh du tho mc nh tinh du thngi s, qu, chani, cam,:..

Phn t ca cc hp cht ny c cc mch nhnh l cc nhm CHxu t hin mt cch u n trong rch cacbon. Quri trng hn ctecpen l cc dn xut cha oxi ca n (iecpenit) nih ancol, aneht vxetn. Chng thng c; mi thcmi hp dan han l cc tcpen.

Ng ta coi cc (icocacbon teq)en iih l. ghp cc phn tisopren vrihau tho ku "u noi .ui": *- tc isprEi cu tecpen

Ruacka (1921).CH2=C -CH = GH2

V d:

CH3

ispren

Prn v"spren ximn (iRi6)



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

R

N

H

N

G

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H

N




27/224

I I j % J . I Squalen(C30H50)

khng theo kiu u ni vi ui Mt cch tng qut: Tecpen l nhng hp cht cha c, H v o m b. khung cacbon gm nhiu mt xch ging v khung cacbon ca isopren,

tc l c th biu din bi cng thc (iso-C5>u vi n > 2. Mt mt xchisopren cn c gi l mt n v isopren. xc nh s lng cccfn v ispren trong tecpen ngi ta thng dng cc gch nt t ()

phn ct cc n (SO-C5).

khung conbon isopren (SO-C5)isopren

Phn o i tecpn

Tecpen c phn loi theo s lng Q v S0-C 5nh sau:

Loi tecpen Khung cacbon; S lng c V dMonotecpen (iso-C5)2 ' 10 C10H16, CioHisQ, CxoHigOSecquitecpen (SO-C5)3 15 C15H24, C15H24O, C15H22itecpen (SO-C5)4 20 C2oI32>C20H32O, C20H30OTritecpen (SO(C5)6 30 C3050, C30H50OTetratecpen (SO-C5)8 40 C40H56

Mts' tecpnTn gi

oximen

y ngun gc thin nhin c h

Cng thc Cng thc cu to Ngun gcphn t

C i o H e du L hng qu

mrxen g 10h 16: du ngyt qu, c roinga



B

I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

R

N

H

N

G

O

T

P

.

Q

U

Y

N

H

N




28/224

limonen CjoHie

apinen CioHie

s a b i n e n C 10 I 16

du chanh, bi, cam,bc h, ht tiu

du thng

u tng

camphen CioHie

zingiberen C15H24

3-salinen C15H224

caryophylen

Squa]f>n

Licopen

du gng, s

u gng

du cn ty

4. Mt s tecpenoit

) Tch t tinh du hoa hng, tinh dus , . . .

32



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I

D

N

GT

O

N

-

L

-

H

A

C

P

2

3

1

0

0

0

B

T

R

N

H

N

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.

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H

N




29/224

c h 2o h

c h 2o h OH

c h 2o hX

xitroneol geranio nero inal

b) Tck t tinh du chnh, tnh du s,.,.

CHO

geranial nera(xitra-a) (xitral~b)

c) Tch t tinh du bc h

CH20H

OH

mentol menton

d) Vitamin A (retinol) c trong long trng, du gan ca,...

;OH?OHG20H29OH

e) Pho (C2H.39OH) dng ste to thnh

mt nhnh ca clrophin c trong chtdip lc cy xanh

5. Th cht v ng dng Tinh d.l loi sn phm khng tan trong nc, d bay hi, khc vi

u m, khi ta nh ln t giy thi khi bay hi khng li du vt g. Dng lm hng liu cho thc phm ch bin nh bia, ru, bnh ko,

nc gii kht;,... Dng lm hng liu cho du thm, nc hoa, u gi u, x phng

thm, kem nh rng,...

Dng lm hng liu cho dc phm nh xitro ho, ko ngm bc h,ko cao su,...

6.PhMg ph p tch tinh du t thc viC th dng mt trong ba phu'ong php sau: Ct li cun h-Ji nc cc thc vt nghin nh (tch tnh du bc h,

tinh du s, tinh du hanh, tinh'daii hi, tinh du qu, tinh du x X...).S chng ct Oin li nuc trong phong th nghim lh hnh 6.1 .

33



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30/224

Chit bng .cc ung mi hu cnh ete du ha, hoc ete, hoc ancol(tch tinh u t hoa nh tinh du hoa hng).

p cc thc vt (nh p v chanh, du thc vt,...) .

1. Bnh cp hi nc

2 . Bnh cha nguyn liu chng ct3. Lp tinh du4. Lp nc.

7.Phng php nghi n cu tnh du

Tinh du l hn hp cc cht cha ti hng trm cu t, vic nghin cutinh u l rt phc tp, ngy nay ngi ta s dng phi hp gia cc

phng php: sc k, 'sc k phi hp vi khi ph k, ph hng ngo(IR), ph t ngoi (V), ph cng hng t ht nhin (NMR),...

vn. Lu khi gii bi tp. Nu bi cho bi ton c ng:

hirocacbonHn hp kh X khng no

_v Hj

Ni/r- Hn hp kh Yhirocacbon nohirocacbon khng no ()

H2(d) Phng trnh ha hc ca phn ng tng qut;

CnH2n+2-2a + 3^2 C nI2a+2

Ty vo hiu sut phn ng m hn hp Y c hirocacbon no v cth c hirocacbon khng no d hoe 2d hoc c hai cn d.

Trong phn ng cng H2, s mol kh gim sau phn ng:nHs phn** = nx - nY(n>: > nY)



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31/224

Nu hirocacbon khng no trong hn hp X l anken -> rij phan ng -

naakec phn ng - Hx - ny. Do khi bi ton cho s mol u rix v s molcui nYta s dng kt qu ny tnh iWen phn ng = pbn .

S mol ca hn hp gim nhng hm lng c v H khng thay i nntheo LBTKL - mx - my = me + mg, mt khc Hx > n do

Mx < My v d % = = = (gi s X, Y o cung iu kin vMy nx Pj

th tch v nh ). * V hai hn hp X, Y cha cng s mol c v H nn t chy X hay Y

u cho cng kt qu: .n0i(t A) - nQ (t Y)

nCO CfiH2. 2(n l s nguyn t cacbon trang bnh) ^

phn ng phnttg 2 + b)h

Ankin cng H2thng cho 2sn phmCuI2n-2 + H2 CnI2n (1)

CH2q + H2 CnI2n+2 (2)Nu phn ng khng: hon ton, hn hp thu c gm 4 cht: anken,

ankan, ankin d v H2. Khi ta gi:nkjji ~ k } nankenp.x + ynank> = X, nankim- y nH2p = X+ 2y

-> nankin - [a (x + y), nH?d = [b - (x + 2y)]

S mo -hn hp ban u: nx = a + bS mol hn hp sau phn ng:

Hy = + HanJcan + nanjnn


32/224

=*-x + + C - (x + )3+ [b (x+ 2y)]= (a + b) - (x + 2y) = nx - (x + 2y)

Ch : iiH,*-=: X + 2y = nx - riY * nankmpi

V d 1 :Cho 19,04 lt hn hp kh X (ktc) gm H2 v 2 anken k tipi qua bt'Ni un nng thu c hn hp kh. Y (H =100%), gi s tc phn ngca 2 anken l nh nhau. Mt khc t, chy 1/2 hn hp Y thu

c 43,56gC02v 20,43 g H20. Cng thc phn t ca 2 'anken lA. C2K4v C36c. cs v CgHio

19,04. - oc ,nx = - - - = 0,85 mol

22,4

B. C3H6v C4HsD. C5Hi0v CeHi2.

B i g i iC5H2g : X moH2 : y mol

Thay v t chy hn hp Y ta xt t chy X:

CaH25 + y l Q j - HC02 + n,0

H2

y

nx = 2 .

2 2

nx nx

H20

y43,56

44= 1,98

. 0 20 .43 4>r7^nx + y - 2. - = 2,27

X f y - 0 ,8 5

18

y =0,29v i 0 ,5 6

I- __19.8n = a 3,5 56

- > n = 3,5 \_c,Ha

Phng n B.

V d 2 :Mt hn hp kh X gm C3Hg, C3H8v H2. Cho 22,4 lt X i quaNi un nng thu c hn hp kh Y c t khi hi ca X so vi Ybng 0,70. Tnh th tch hn hp kh Y? Bit cc th tch o ktc.A. 31,99 lt B. 6,72 lit c. 15,68 lit

B i g ii

D. 13,44 lit.

Nx = 22.422.4

= 1 moi

C3H6: a molC3Hg : b molHa : c mol

dy -Mv nx

Phng n c.

= 0,70 -nY= 0,7 V = 0.7.22,4 = 15,68 lit

36



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33/224

V d 3:.Mt hn hp kh X o 82c, 1 atm gm anken A v H2 c t. l s mol l : 1 . Cho X i qua Ni/t thu c hn hp Y (Hiu sut h%).

Bit t khi ca Y so vi H2bng 23,2. Gng thc phn t no ca Asau y l khngng?

A . C48 B . C36 c. C(jH 2 D. C5T0.

Bi g i i

t Hr; H = nR, = a molttr2o

CqH2d +' H2 ^ CttHto

bb- a anp; ah ah ah

n$: (a - ah) (a - ah) ah

- ns (2a - ah) mol = ny

-> d% = i i = = g t o n j j a =

7 i 2 2 .nY 2-nY 2(2a -ah )

14 n + 2 =23;2 ^ h , 454 - 7n2(2 - h) 23,2

Vi 0< h < 1 - < < 1 -> 3,2 < n < 6,523,2

-> n = 4 (C4HsX .11= 5 (C5H10), n = 6(CeHi2) -> Phng n B.

2.Nu bi ton c ng:

rTs T , , , ,, hirocacbon. khng no1 ~ h ,Hn hp kh X H vmx > ra

Khi lng bnh Br2tng = khi lng ca hirocacbon khng no =mx - my.

V d 4:Mt hp hp X gm 1 ankan v 1 anken c t l s mol 1 : 1- Snguyn t cacbon ca ankan gp hai ln s nguyn t cacbon caanken. Ly a gam X thi lm mt mu va dung dch cha 0,1 moiBr2. t chy hon ton a gam X thu c 0,6 mol C2. Cng thcphn t ca chng l

A. C2H4v C4H10 B. C36v CeHuc. C4H8v CgHig - D. C5H10v C10H22-

37



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34/224

Ilanken = Hankan = nBl, = 0,1 mol nx = 0,2 mol

CSHV xCOz

V d 5 :Cho hon hp 2 anken li .qua bh ng nc brom d th y khlng bnh dng nc brm tng 8 gam. Tng s mol ca 2 ankan lA. 0,50 B. 0,05 C. 0,25 D. Khng xc nh

' Bi gii S mc sai lm nu lp un:

' ; CnI2a + Br2 -> CnH2nBr2.1 moi -> Am=160g

X m o < Am = 8 g

Q .__-> X = = 0,05 ml -* Phng ri B.

160 .

Thc t khi lng bnh brom tng khc khi lng anken tngphng n D l ng.

V d 6:un nng 5,8 gam hn hp X gm C2H2 v H2 trong bnh kvi xc tc thch hp th c hn p k Y: Dn kh Y qua bng dung dc Br2d thy khi lng blial tng; 1,2 giii v cn. hn hp kh z. Khi lng hn hp kh z l

A. 4,6 gam B: 7, O-gam

c. 2,3gam D. Kt qu khc.

Hn hp X | ^ 2 2| hp ti a

V iix = m = 5,8 gamjv ~ 1>2 gam -

->mz = my V ( ) = 5,8 TT1,2 = 4,6 gam

- ^ T ^ h n g ^ ^ t i r : ^ ^

c 2h 6 - ;

C2H 4 : . Brg dtf- 2 1^ 2 6C ^ H 2 d v [ K d Ha d

0,2 > 0,2 X = 0,6

[C2H4 ^ AX = 3 -> < ->Phng n A.lC4H10



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35/224

B. BI TP T LUN

c inh sn phm cng hp chn lc (sn phm chnh) ca cc cht saupi brom trong ccu theo t l mol 1 : 1 ?

-C H 2 = C H - C H 2 - C = CH|>) CH3 - CH = CH - CH2- CH = CHBr

(CH3)2C = CH - CH2 - CH = CH2f i CH2= CH G = CH) CH2 = CH - c - o - CH = CH2

S'V' II*.-.. : - .. Ip ho bit c eh phn ng cng Br2 ca:

c's-bt-2-ea / b) rans-but-2-en3 i: Vit sn phm v gii thch c ch phn ng ca etilen vi:1' ) Br2trong CCLt . b) Br2trong H2Oll lf c) Br2trong, H20 c pha NaClpkPropen phn ng vi nc brom c ha tan mt lng nh Nai c th to

t V t n h h a n n V i i t c n rv h m *? V t n V i i r n f r i n f i n V i n l i f n n i tV iifV *

II cp 4ng phn quang hc (enantiomer, diastereoisomer).| |k cho isobtilen vo duiig dch HBr c h tn aCI, CH3OH c th to

ra nhng hp cht g? Gii thch.

Cho bit sn phm phn ng. ca isobutilen vi H2S trong H2SO4 .c. Ti'P sao phn ng khng xy ra nu khng c H2SO4c?^Gii thch s ng phn ha c xc tc axt gia cs-but-2-en v

tr n s b t^ e n .Ijssi.v V.. / ' ->. Tyong dung dch H2S4 60% xy ra s ime h isobutlen thnh 2 ankenl l . l X (chim 20%) v Y (chim 80%). Hiro. ha 2 anken trn u cho

p ankan z (CgHis). c th iu ch z bng cch cho isobutilen tc dng viv isBta c !HF lm xc tc.

^S^ Lir tH il vx^- pL^aa^ ncL 'Ki ic. Gi tn X; Y, z. tho ;daiih php IUPAC. .

b) T r i^ by c di" S c phn utog.

39



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36/224

10. Cho CyHisBr tc dng vi kim mnh thu c hn hp gm 3 anken X,Y, z c cng cng thc C7 14. Hiro ha mi anken u ch.2-metylhexan. Phn ng ca X vi B2H6trong ete ri tc dng tip viH20 2v OH" cho ancol Q. Phn ng tng t ca Y hay z cho mt lng

bng nhau ca Q v ng phn ca n l G. Xc nh cng thc cu toca X v G.

1 1 . a) Tin hnh phn ng ime ha 2-metylbut-2-en c xc tc H+. Hyd on cc sn phm to thnh da theo c ch phn ng. '

b) Khi ozon phn kh hn hp thu c sau phn ng dime ha trnngoi cc anehit v xeton ca sn phm thi cn thu c mt lngng k butan2on. Gii thch.

12. ime ha isobutilen (hp cht X) trong ung ch H2SO460% thu chn hp cht A l sn phm chnh c cng thc phn t CgHie- Hiroha A thu c B l 2 , 2 , 4-trimetylpentan. Nu dng Y l isobutan tc

dng vi X khi c xc tc HF cng thu c B. a) Hy vit cc phng trnh phn ng nu trn?b) Trnh by c ch phn ng: X -> A v Y ->B. c)Thnh phn ca B trong xng gi l g? ng dng ca B trong xng.

13. C hai hirocacbon A v B u c cng cng thc phn t C7H14. Xc nh cng thc c to ca , B bit: Oxi ha A bng dung dch KMn04/H2.S04 to ra hai cht l

CH3CH2COCH3v CH3CH2COOH

Phn t B c cu to mnh thng v khi b oxi ha bi dung dchK2Cr207/HCl to ra CO2.Hon thnh phng trnh ha hc ca cc phn ng oxi ha - kh trnv ch ra cht oxi ha, cht kh v cht m trng.

14. Anken (A) c cng thc phn t l CeHi2 c ng phn hnh hc, tcdng vi dung dch brom cho hp cht ibrom (B). Cho (B) tc dng viKOH trong ancol un nng thu c ankaien (C) v mt ankin (D)Khi (C) b oxi h bi dung dch KM11O4/H2SO4 v un nng thu c axit axetic v kh CO2.

a) Xc nh cng thc cu to ca (A), gi tn v vit phng trnh ha hc. b) Vit cng thc cu to cc ng phn hnh hc ca (C).

15. ime ha buta1,3ien thu c cht X. Tetra ha axetilen thu cht Y. Khi hiro ha X cng nh Y u thu c xiclooetan. Xc nhcng thc cu to ca X, Y v gi tn chng theo nh php IUPC.

16. Cho mt hirocacbon A c cha 88.89' cacbon v klii lng. a) Xc nh cng thc n gian nht ca.



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37/224

b) t 0,01mol A, sn phm chy tc dng khng ht 150 m! ruug HichBa(OH)2IM. Xc nh cng thc phn t ca A.

c) Khi ozon phn A thu c sn phm:

G = CH - (CH2)4- c - c - (CH2)4 - CH = ol 0 0

Xc nh cng thc cu to ca A. Bit A c th tc dng vi tc nhnienophin.

17. Hp cht X c cng thc phn t Csio tc dng vi hiro theo t l mol1 : 1 khi c cht xc tc. Thc hin phn ng ozon phn X thu c0 = CH - (CH2)4 - c h = o

a) Xc inh cng thc cu to ca X v vit phng trnh phn ng.

b) Vit phng trnh phn ng oxi a X bng dung dch KMn4trong nc.

18. Hirocacbon A c cng thc phn t CsKg. Bit 1 mol A tc dng vi

dung ch KM11O4/H2SO4thu c 2mo CO2v 2mol HOOC - COOH.a) Xc nh cng thc cu to ca A.

b) A c ng phn hnh hc khng? Nu c hy vit cu to cc ngphn hnh hc ca A v gi tn chng.

19. Khi un nng hn hp buta-l,3-ien v etilen xy ra phn ng cngng vng Diels - Aider to thnh xiciohexen. Phn ng ny s trnn d dng hn nu thay H trong etilen bng nhm ht electron nh-COOH, -CGR, -CHO, ... v thay H trong butaien bng nhm y

electron nh-CH 3, - C 2H5,...a) Hy cho bit khi phn ng, butaien c cu trc khng gian nh th

no? Vit phng trhh phn ng xy ra gia bta-l,3-en v etlen.

b) un nng ra/ispenta1,3ien vi aciylic CH2 = CH CQOH v isoprenvi este CH2=CH-C0 0 C3. Xc nh sn phm chnh v gii thch.

c) So snh tc phn ng khi un mi ien sau y vi axit acrylic.

Gii thch

a) 2-metyIbuta-l,3-ien v 2-clobuta-1 ,3-ien(3) Cs-penta-l,3-ien v rans-peata-1,3-ien

20. a) Vit c ch ankyl ha anken bng ankan sau:

(CH3)2C = c h 2+ HC(CH3)3 ^

b) Gii thch ti sao ankyl ha etilen bng (CH3)3CH thu c(CH3)2CHCH(CH3)2m khng cho (CH3)3CCH2CHS?

41



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38/224

21. Phn ng no sau y c th xy ra? Gii thch,a ) H C = C N a + C H 3 H b ) H C - G I + C H 3L i -

c) HG = CH + NH -> d) HC = CH + NaCN-*e) HC = CNa + CH3GOOH

22. Cho tc ng mi hirocacbon l tan, etilen v axeten -vi amid

natri trong amnic ri co tc dng tip vi metyl iua th s thc sn ph m g. Vi t phrig trnh phn ng v. gii thch: . T snh tnh axit ca cc cht ., ^

c . BI TP TRC NGHIM

Hy nh du vophng n ng ch mi cu. sau y:1. Trong cc cch iu ch etiln sau y, cch no khngc dng?

A. Tci H2khi etan.B. Tch H2O tancol etylic.

c. Cho cacbon tc dng vi hir

D. Tch HX khi h xut halogen.

2. iu kiri no thc hin chuyn ha:

CH2= C H - = CH ^ CH2= GH - C-CH3 ' II

,

A .H 20/H+ b HzO/Oir C. H20/KMn04 D. H20/Hg2+. 3. Cho hn hp X gm 0,02 mol C2H2 v 0,03 mol H2 vo mt bnh kn

mt xc tc Ni ri 'n nngth c hn hp kh Y Ch Y li t t vbnh nc brom d tha c 448 m kh Z (ktc) bay r? Bit ti khi hi cz so vi hir biig 4,5!: Tinh kh i lng bnh brom tng sau phn ng?

A. 0,40 g B. 0,58 g G-. 0,62 g D. 0,80 g:

4* Khi t chy th ;tich hiroccbbn X ;67th tich sih r 4 th' ticixIsKr CO2.' Tm'mtTmu ung dch iic brom- y cng h

- ~ iudro to t h a ^ ioft^ndn^pbpn^:n'mci ifnhl; Cng thc ca t. ' c X l: . V -

A. (C H )2C _= C H 2 B. C H 3CH = C(CH3)2' G.iCHs^CB G H ~ _ D CH s C CH(CH3)2. '

5., Hn hp X gin 1 ankn v 1 ankan. t chy X thu c a mol H2O

' : b mrOgTTrgoT - co gi;ar , b * -



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39/224

I J a ! o , 5 < T < 2

a 1,5 3 B . 3 > 2 > 1 C. 1 > 3 > 2 . 2 > 1 > 3.

| c


40/224

11. Cho etilen tc dng vi img dch H2SO4 long un nng, sn phmchnh l

A . C H 3CH 2O H B . CH 3CH 2O SO 3H

c. CH3CH2SO3H D. CH2= CHSO4H.

1 2 . Cho hn hp 2anken c s moi bng nhau i qua dung dch nc bromthy lm mt mu va 200g dung dchBrnng 16%. S mol mianken lA. 0,05 mol B. 0,10 mol c. 0,20 mol . 0,15 mol.

13. phn bit but-l-n v but-2-in c th dng thuc kh n sau y?

A. Dung dch AgN03/NH3 B. Dung dch KM11O4/H2SO4 -a Dung dch CuCiyNHa. D. C A, B, c.

14. Dn 17,4 g hn hp kh X gm propin v but-2-in li tht chm quabnh ng dng dch AgN03/NH3 d thy c 44,1 g kt ta xut hin.

Xc nh %th tch mi kh trong X?A. C3H4 8 0 % v C4I6 20% B. C3H4 7 5 % v C4I6 2 5 %c. C3H425% v C4H675% D. C3H420% v C4H680%.

15. t chy hon ton hn hp A gm 2hirocacbon cng dy ng ng.Hp th hon ton sn phm vo 100 mi dung dch Ba(OH)2 0,5M thuc kt ta v khi lng dngdch tng 1,02 g. Cho Ba(OH)2d vdung dch thu c kt ta vtng khi lng kt ta hailn15,76 g. hn hp A thuc dy ng ng no?

A. Ankan B. Anken c. Xicloanken D. Ankin.16. Phn ng cng Br2(dung mi CCI4) xy ra nhaiih nht vi cht no sau y?

A. CH2 = CH2 B. CH2 = CH - CHOc. CH2 = CH - COOH D. CH2 = CH - CH3-

7. Phn ng cng Br2(ung mi CCI4) xy ra chm nht vi cht no sau y?

A. CH3 - CH = CH2 B. CH3 ~ CH = CH - CH3c. c h 3- c = g h 2 d . c h 2 = c h 2.

c h 318. bn ca cc ng phn ca buten thay i nh th no?

c h 2= CHCH2CH3 c h 3 c h 37: \ /(a) c = c

/ \H H

(b)

44



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41/224

CH, H CH,\ /c = c

V VH CH,

G = CH,

CH3(c) (d)

-: A .a < b < c < B. d < c < b < a

c. a < c < b < D. a <


42/224

- Hiro ha hon ton ph n 2 sau t chy hon ton sn phth tch C2(ktc) thu c l:

A. 22,4 lit B. 11,2 l i t . c . 44,8 lit D. 33,6 lit.24. t chy hon ton 8,96 lt (ktc) hn hp hai anken l ng ng lin

tip thu c m(g) H2O v (m + 39) g CO2- Hai aiken d l:A. C3H6 v C2H4 B. C4Hsv C5H10c. C^g v CH p. C5H1Qv CgHi2*

25. Anken no sau y phn, ng vi HI chm nht?A: CH3CH2CH = CH2 B. CH3CH = CHCH3

C.CH3 -C = CH2 d. c h 3 - c = c h - c h 3.

c h 3 c h 3

26. Anken no sau y phn ng vi HI nhanh nht?

A C U f H C H C H C H . C H , B .C H .C H C H .C H .C H C ra ,

CH3 h 3

c. CH3CHCH = c h c h ' c h , . CH3C = c h c h 2c h 2c h 3 .

h 3 c h 3

27. Trng hp elen thu c poetien (PE). Nu t chy ton b lngetilen s thu dc 8800 g CO2. H s trng hp n ca qu trnhpolime ha l

A. 100 B. 200 a -100 D. 500,28. Polime -(CH2~CH-)-n l sn phm ca phn ng trng .hp mnome

CH = CH2no sau dy?

A. CH2 = c h CH2 CH3 B. CH2 = CH C H = CH2c. CH2 = C H -C = CH2 D. HC = c - CH = CH2.

CH3

29; Mt ankin X khi t chy hon ton thu c khi lng nc bngkhi lng ca X ban u. Cng thc phn, t ca X l

A.C2H2 B. CaH* c. C A D. C5H8:

30. CMa lin hp hai ankin thnh hai phn bng nhau. Phn 1 n quadng ch brom d thy c m(g) brom phn ng. Phn 2 em t

.chy hon ton thu c 6,18 g C02v i;80gH2O. Gi tr mlA.9,6 B.6,4 c. 12,8 D. 19 ,2 .

46



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43/224

31. t chy hon ton V lit (ktc) mt ankin th kh thu c 25,2 g snphm gm H2O v Cg. Nu cho sn phm chy i qua nc vi d thuc 45 g kt ta. Gi tr V l

A. 6,72 lit B. 2,24 lit c . 4,48 lit D. 3,36 it.

32. Cng thc phn t ca ankin bi 32 l:

A. CgH2 B . C3H 4 c . C4 6 D. CsHg.33 . Mt hn hp A gm 2 ankin c th tch Va - 17,92 Ht (ktc). Thm H2

vo chn hp X c th.tch Vx = 62,72 lit (ktc). Nung X vi xc

tc Ni thu c hn hp Y c th tch gm i so vi th tch ca X.

Phn ng cng hiro xy ra vi hiu sut

A. 100% B .75% c . 80% D. Kt qu khc.

34. t chy hon tn mi hn hp gm 2 an kin thu c 13,2 g CO2v

3,6 g H2O. Khi ngBr2 ti a c thcng hp vo 2 ankin trn lgi tr no sau y?A- 8g B. 16 g c. 32g D. 64g.

35. Hiro ha hon ton int anken cn dng 448 ml H2. Cng lng anken em tc dng vi brom thi to thnh 4,04 g n xut ibrom. Ccth tch ktc, hiu sut cc phn tig t 100%. Aken dng lA. Etilen B. Propen G. Buten D. Penten.

36. Phn ng cng no sau y xy ra tri vi quytc cng Maccopnhicop?

A. CH2 = CH - CH3 + HC1->B CH2= CH - CHs + HBr ->C; CH2C1 - CH =CH2 + HG1 >

D. CH3- CH2- CH = CHZ+ HBr 37. Phn ng oxi ha propen bng dung dch KM11O4 long, ngui cho sn

phm no sau y?

A. CH3CH0 B. CH3COOH c. CH, - CH - CH, D. CH, - CH2 - CI .

I 1 I 1OH OH OH OH

38. Cho phn ng: Axetlen + H20 - > A

A l cht no sau y?A . C H 2 = C H O H B . CH 3CH O

c. c h 3c o o h d. c 2h 5oh.

47



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44/224

39. Cho phn ng: Propin + H2O - H.02d thy khi ng bnh tng thm 6,2 g v to ra19,7gkt ta. Khng nh no sau y ng?A. Ankan v aokin c cng s nguyn t cacbonB. Ankan v ankin c cng s' nguyn t hiroc. Ankan v ankin c khi ng ban u bng nhaD. Ankan v ankin c s mol ban u nh nhau.

44. .sopren c th cng KBr theo t l moi 1 : 1 to ra s sn phm ti a(khng k ng phn hnh hc) l:A. 2 B. 3 c. 5 D. 6.

45. Isopren c th cng Br2 theo ti mol 1 : 1 to ra s sn'phm ti a(khng k ng phn hnh hc) lA. 2 B. 3 c. 4 D. 5.

48



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45/224

46. Cho s phn ng sau:

7-> Y (sn phm chnh)

B. CH = c CH2- CH2BrIBr

c. CH2 = C -C H = CH2 Br

47. Hiro ha hon ton X thu c isopentan, trng.hp X thu c mtloi cao su thng dng. Cng thc cu to ca X l:

48. Cho 4,96 g hn hp A gm Ca v CaC2 tc ng ht vi nc thu c2,24 lt hn hp kh R. un hn hp kh B c mt xc tc thch hp thuc hn hp kh X. Ly 1/2hn hp X trn vi 1,68 lit O2trong bnhkin dling tch 4 lit (khng c khng kh). Cc th tch kh o ktc. Bttia la in t -chv ri. gi nhit bnh 109,2c. Tnh p suttrong bnh nh ny?

A. 0,784 atm B. 0,384 atm c. 0,874 atm D. 2 atm.49. Khi cho etilen phn ng vi nc brom c ha tan NaGl ngi ta thuc hn hp sn phm: 1,2-ibrometan v l-brom-2-cloetan. iu

chng t:- A. Etilen v cc anken khc c th cng hp ng thi nhiu cht

B. Phn t brm tn cng ng thi vo 2nguyn t cacbon ca ni i.c. S cng hp din ra theo nhiu giai on.

D. Etilen tham gia c phn ng cng vi NaCl.

50. Hn hp A gm 3 hirocacbon X, Y, z. Khi hiro ha hon ton X, YI du thu c z. X c to ra khi nung cao su thin nhin trong bnh kn khng c oxi 250c. Y l ng phn ca X. Cho hn hp A phn ng vi dung dch AgNOa/NHs d thu c kt ta. X, Y, z ln lt l

A. CH3 - CH - c = CHIc h 3 o h 3

c h 3

a . ch 3 - g h 2 - g h - c h 3j CI2= c h - c = c h 2, h c ^ c - c h - c h 3

c h 3 c h 3 c h 3

49



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46/224

B. c h 2= c h - c = c h 2, h c = c - c h - g h 3, c h 3 - c h 2 - g h - c h

CH, CH, CH,

c. CH2= CH - CH = CH - CHs,HC = c - GH - CHg, CH3- CH2- CH - CH3

CH3 c h 3D. CH2 = CH - c = CH2, CH3-CH 2- CH - CH3 , HC s c - CH - CH

c k3 c h 3 c h 3

D. P S V HNG DAN GII

1. a) CH, - CH - CH2 - c = CHL I

Br Brb) CH, - c h - CH - CH2- CH = CHBr 7Br Br

c) (CH5)2C -C H -C ^ -C ^ C H * d) CH2 - C H - C = CH

Br Br

e) CH2 - CH - c - o - CH - CH2

. Br Br

Br Br

2 . a)

II .1 , 1o . Br Br

HV BrfiL :

^ C H s - Ib - > j ^ B r CHs CH3

cis-but-2 -en ion bromoniumBr

(SS)

raxemic (trit quang)

50



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47/224

trans-but-2 -en ion bromoniumBr

(RS)

meso

Phn ng xy ra theo c ch Aequa 2bc: Bc chm (quyt nh tc phn ng) to ra cacbocation bromonium:

CH2= CH2+ Br2

Br5

/I\c h ; CH2 +Br

lon bromonum

Bc nhanh c hnh thnh bdi phn ng ca ion bromonium vicc tc nhn nucleophin (Br, H2O, ci) to ra sn phm:

Br BrCHa - CH2Br

>Br-CHs-CHz-OH + Br-CHz-CHjr-Br + H+

Br

/ \ CHj c ,

CCL,

Br'

(NaCll ->Br-CHz-CHa-OH

+ Br-CH2-CHHBr+Br-CH2-CH2-Cl + Na* + H+C ch cng Ae tng t bi 3xy ra qua 2giai on:

Giai on chm to cacbocatin bromonium:

Br



B

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48/224

ai oan nhanh l s tn cng ca cc ion m vo ion bromonium to thnh sn phm, bao gm:

CHs - CH i CH2+ Bra -> CH3- CHBr - CH2Br (1)CH3-CHI-CH2Br + Br" (2 )

CHs-CH=CK2+ Br2+ r

CH3-CH=CH2+ Br2+ H20

5. C ch cng A :

CH3- CH = CH - CHa + BrOH CH3-CH

CH3- CHBr - CH2I + Br (3)

-* CHa - CHOH - CH2Br + HBr (4)

CH3- CHBr - CH2OH + HBr (5)

Br

,CH- CH3+ OH'

CH, - CH

Br

o , CH - CHs + OH - CHS- CH- CH - CHs!OH

a) Vi ci$but-2en

H H\ / -

c = c + BrOH/ \

H3 c h 3

Br(A */ V i V

H CH3 H CHj

OH~

b) Vi rans-bt-2-en

H..C H\ /c = c + BrOH

/ \H CH,

CH3 BrH. /

r10* C6 . (SS)I /

OH HBr CH3

I H\/ , ' C (HR)

H CH*

(2).

'enantiomer

Br

, < A *CH3 H H CH,

OHT

52



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49/224

h 3c

Mi quan h gia cc ng phn:

enantiomer(1)' *(2)

ia (diastereo isomer)

(4)

CH,Sn phm phn ng l hn hp gm:

CH3'I

CH3 CBr - CH3; CH3CCH3; CH3CCICH3 vCH 3- C -O -C H

CH3 OH CH3 h3

Gii thch da vo c ch phn ng: Trong dung dch c cc qu trnh phn li:HBr H++ Br"

NaCl - Na++ Cl ... ...Do trong dung dch c 4 tc nhn nucoplin l Br, Cl, H20 vCH3OH c kh nng kt hp vi cacbocation. Phn ng theo c chcng electrphin (e)

Trc ht tc nhn electrophin (H+) t cng vo c 5- to cacbocatioii(giai on chm):

CH3 G /=VCH2 + H+ CH3- C- CH3

CH,CH,l 3 ^ * 3

Sau l qu trnh kt hp cacbocation vi cc tc nhn nucleophinBr', cr, H20 v CH3OH to thnh sn phm (giai on nhanh):



B

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50/224

CH. CH.

CH3- c* + Br ?h3"h >CH3 - c - Br

CH3

CH3CHj

c h '

CH., - c* + cr - 2 * CH, - c - ClCH3

c h

CH.c h 3

CH3 -C * +HOH CEL - c - OH + H1 !CH, c h 3

c h 3 c h 3 I

CH3 C e + CH3OH > CH3 c o CHg + H*c h 3 c h 3

7. Phn ng:CH,[

CH3 - C = CH2 +H2S C H - - C - S - HT ICH., CHj

Gii thch: H2S xit yu v khng th bt u phn ng bng ccng H+vo c = c m phi nh H2SO4 m c cng H+ vo c = cto cacbocaton (C3)3c 0 ,sau lin kt vi s ca H2S to. ra lin hp ca(CH3)3(CH3)3CSH2 v trli H+ cho HSO to

phm cui nng V -

8. ngphn ha v tr:H3C H

\ /c = c

/ \

H CH3

H

CH2'H

'CHa(treats)

c h 3 c h ;V Jc = C

/. \H H

(cis)

54



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51/224

9a) Xc nh X, Y, z v tn gi:' CH 3 CH 3 C H 3 C H 3

c h 3 - c = c h 2+ c h s - c = c h 2 H ^ C H 3- C - C H = C - CH

C H ,3.

2,4,4 -trmetylpent-2 -en

(X)

CH, CHLL _ 1 \

+ c h 3 c c h 2 c = c h 2

c h 3

2,4,4-trmetylpent-l-en (Y )

c h 3 c h 3

y ~ r * . . . C O H , C H C H j

c h 3

2,4,4-trimetylpentan

I (Z)

I CH, CHo CH, CH3

I 1 1 I I*;CH, - C - H + CH2 = C-CH3 CH3- C -C H 2-CH -CH3p - V I

c h 3 c h 3

CH3-Cc h 3

c h 3 c h , c h , c h 3! , i . X -

C H , c + C K , = c CH3 CH 3 C C H 2 C C H 3I I

c h 3 c h ,

55



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52/224

CHa CH, 3

CH,1 3i

- C - CH = c - c h 3 c h 3 - C - CH2 *i

c h 3 c h 3

(X) (Y)

CH, 3 c h 3

c h 3j

- C - C H 2 -- c - c h 3 +(HVC - CHS1CH,

c h 3

c h 3 c h 31>c h 3 - e - C H 2 - CH - CH;

1c h 3

CEL!

CH3

ICBL

(Z)10 . Phn ng ca B26vi anken xy ra tri quy tc Maccopnhicop nn ch.0

mt hp cht ankyl bo khi hiro cacbn ni i iic nhan (anken bti) v cho hai lng bng nhau khi hiro cacbon n i gng nhau(anken i xng), sau oxi ha cho anco tng ng.

V th, hp cht X phi c cu trc -CH = , hp cht Y hay z c cu

trc -CK=CH-. Vy suy ra anken l metyl hexen.T c: X l GH3- CH2- CH2- CH = c - CH3

CHS

-> Q l CH3 - CH2 - CH2- CH - CH - CH3I IOH CH3

Y trans- CH3-CH^CHr,CH-CH(CH3)2z l cis- CH3-CH2-CH=CH-CH(CH3)2

u cho Q v G l CHCH2CHOHCH2CH(C3)2nn C7H15Br lCH3-CH2-CH2-CHBr-CH(CH3)2' ' -

56



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O

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-

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53/224

Nu Ci7H15Br l CH3CHBrCHrCH2CH(CH3)2 choCH2=CH-CH2-CH2-CH(CH3)2cho u tin mt ancol, v cis hay transCH3CH=CHCH2CH(CH3)2cho 2anc nhng khc vi ank-l -e n trn.

Nu Ci7H15Br l CHa-CH2CHBr-CH2-CH(CH3)2 cho 4 anken v 4anco tng ng'.

1 1 . a) C ch phn ng: .

CH3-> c C c h - CH3 CH3- C- CH2- CH3TCH3 c h 3

-CH, + CH, - c c h - CH.CH, C- CH.

CH. CH;

CH.

CH, CH, c CH c CH

CHXH, c CH;

CH; CH,-CH2-C -C = C-CH,I L LCH3CH3CH3

CH, CH2 c CH CH,: . { -HCH3CH3 c h 3 Ic h , c h , CH c = CH.

CH3

CH,CH, CH;

Ozon phn kh hn hp trn thu c:

CH.

c h 31

CEL-CH, - c - c = o

CH, CH, c c = c CH, CH, CH.

CH.CH.CH,

CH;

CH3 ch 2 c CH c = eH2-r I rCH.CH, CI, ;

CH3CH3 c h 3

CH, c = oI v HCHOCH.,



B

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54/224

S to thnh mt lng ng k btan-2-on l do:

CHS- c = CH - CH3 CH3-C -C H 2 -CH3 -^p> CH2=C-CH2-CH3

CH, CH, CH,

CH3- C- CH2- CH3 + C = c - CH2- CH3

CH, CH,

c h 3_' I _ _ __ .

c , - c h 2- - CH2V - c h 2- CH3

c h 3 c h 3

c h 3 ' ch 3 @ __- -

CH3 - CH* - C - CH2 - C - CH2 - CH3 CH3 -CH g - C - C H = C - CEL, - CH.

CH, CH3 CH3 CH3

CH, = c - c h 2- c h 3Ic h 3

c h 3

c h 3- c h 2 - c - c h = c - c h 2- c h 3

CH, CH,

CH3 - CH2- G = o

c h 3

bu tan- 2- on

CH3I

CH3-CH2-C-CHO

CH,

HCHO

12. a) Phng trnh p h i ng

CH,chnh

2CH3- c = CH2

c h 3

(X)

HiSo,60:

>c h 3- c - c h 2 - c = c h 2 (A)1 2 2c h 3

CH,

CH,

-E^ C H 3- - CH = C - CH3

CH, CH,

sa



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55/224

CH,

A + H2 CH3- -C- CH2 - CH - CH3 (B)

CH, CH,*3 wiX32,2,4trimetylpen tan

CH,CH ^-CH-C H, + C H ^C -C H ; CH, - G- CHo - CH - CH,

I I ' ' ICH3 . CHg CH3 H3

(Y) (X) . (B)b) C ch phn ng (Ae)

H2SO4 - H++ HSO,CH,

CH3 - c = CH2 + H+- c h , - C3 I _c h 3 c h ,c h 3 c h

CH3 -C + cri^= C -C H 3 -* CH3- C -

c b ; c h 3 c h

CH3

CHg'-.C

CH,

CH, CH3 l

CHg - c - CH2 - crrI 2 ICH, CH,

CH3

- ^ 2 ^ CH, - C - CH2 - c = CH2 (A)I I c h 3 c h 3

(ngc quy tc ZcUxep)CH,

, ICH3- C - CH = c - CH3

i CH, CH3

(/Aeo quy tc Zaixep)

CH3 CH3 CHg

CH3 - c - CH2 - c* + CH3 - c h - CH3 CH3 - C - CH2 - CH - CH

CH3 CH3 CH, CH3 (B) CH3

+ CH, - -CH,CH,

59



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I

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O

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-

L

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56/224

c h 3 c h 3 c h 3I r I

CH, - c r + CH2 =C-CH 3 C H , - C - C H 2-C1 2 I 3c h 3 c h 3 c h 3 c h 3

c) Thnh phn %ca B trong xng gi l ch s octan.Isooctan c trngcho tnh n ca xng khi b nn. Ch s octan l mt trong nhtig tiu

chun nh gi cht lng ca xang.13. Da vo sn phm ca cc phn ng oxi ha khng hon ton ta xcnh c cng thc cu to ca A v B:

() CH3- CH2- CH = c - CH2- CH3 3-metylhex-3-en

CH3

(B) CH2=CH-CHr ^CH2-CH2-CH2-CH3hept-l-n,Cc phng trnh phn, ng:

5CH3- CH2 - c h = c - CH2 - CH3 + 6KMn04 + 9H2SO4

CH3-> 5CH3CH2COOH + CHsOHaCOCHs + 6M11SO4+ 3K2SO4+ 9H20

3CH2=CH(CH2)4CH3 + 5K2Cr207.+ 40HC-> 3C02t + 3CH3(CH2)4COOH + lOCrCs + 10KC1 + 23H2D.

14. Cng thc phn .t ca: (A) CeHi2; (B) C6Hi2Br2; (C) v () l CeHio-a) Kh oxi ha (C) bi KMn Cng thc cu to ca ien (C): CH3-CH=CH-CH=CH-CH3V ankin (D): CHs-CHz-CbC-CHii-CHs

=> (B) l: CH, - CH2 - CH - CH - CH2- CH3r LBr Br

=> (A) l : CH 3CH 2CH CH CH 2CH 3

Cc phng trnh ha hc ca'phn tig:C H 3-C H 2- C H = C H - C H2-C H 3+ Br2 -V CH 3 - C H 2 - C H - C H - C K 2 - C H 3

Br BrCH, - CH, - CH - CH - CH2- CH, + 2KOH

s 2 r r .Br Br

CH3-CH=CH~CH=CH-CH3 + 2KBr + 2H20CH3 - C H , - C H - C H - C H 2 -CH 3 + 2KOH

B r . B r

. CHs-CHa-GsC-CHr-CHa + 2KBr + 2H20

60



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57/224

5 CH3CH=CHCH=CHCH3+ I8KM11O4 + 2 7 H?S0 4-> IOCH3COOH + 10C02t + 18MnS04 + 9K2S04+ 32H20

b) Cc ng phn hnh hc ca (C):CH, H

H

H

CH

, H - H

p = ^ _ /C = C\/ \ = c/ uns-vns CH/ \ =Q/ cis~rars

/ \ x / ^CH3>

= 7"

H

CH,/ \ c = c/

/ YH H

cis-cis

15.c h 2 H2C

XCH1CH

CH1CH

c h 2 h 2c Vxicloocta-1,5~isn \-h 2H2

(X)

^ C H H C ^

CH CH+

CH CH-

CH HC

N r - f xiclooctan

xicoocta-1,3,5,7-tetraen(Y)

1 Xn XI _ 88,89 XU1 _ o o16. a) CXHV- > x : y = - : = 2 : 312 1

Cng thc n gin nht : C2H3

b) (C2H3)n + 1 ^ 0 2 > 2nC02 + - - H204 2

0,01 0,02n

61



B

I

D

N

GT

O

N

-

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-

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A

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2

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1

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0

0

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58/224

CO2 + Ba(OH)2 BaC03^ + H2O0,02n -> 0,02n=> 0,02n < 0,15 n < 7,5 (n l s chn)=> A l: C4H6, CgHi2, C12H18

c) T sn phm ca phn ng ozon phn -+A l C12H18v cng thc

to c th l:

(1) (2) (3)DoA tham gia phn ng vi tc nhn ienophin nn A phi c c

, hnh Scis ^ A l (1 ).9 - 1 * 9 - 1 0

17. Hp cht X l Cgio c = ----------- ---------= 2 v tc dng.2 '

1 : 1 >X l xicoanken v khi ozon phn thu c 0=CH-(CH2).r-CH- Cng thc cu to ca X l:

(xclohexen)

Cc phng trnh pthn ng:

I +IM

+ O3 >

3[ ] + 2KMn04+ 4H20 - 3 | . + 2Mn02 + 2KO

18. heo bi ra: 1 mol -+2 mol CO2+. 2 mol HOOCCO-> A phai c 2 nhm CI2= v 2nhm =CH-CH=

Cng thc A l CHs c a = 2.6 + 28 c 22

Cng thc cu to ca A l:

CH2=CH-CH=CH CH=CH2 hexa-1 ,3,5-trienA c ng phn hnh hc:

62



B

I

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N

GT

O

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-

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-

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2

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0

0

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59/224

/ H H H CH = CH2\ / ' V /

c = c v / c _ c \CK, = CH CH = CH2 CH2 = CH H

cis~hexa-l,3,5~trien trans-hexa-l,3,5 -trien.

9. a) Khi tham gia phn ng cng vng th buta-l,3-ien phi c cu trcS-cis(S vit tt Singbnd: ng lin kt dn). Phng trnh phn ng:

CH2

CH ) f CH V + ^ 1 A CH ^ CH

S-cis ^b) Phn t penta-l,3-ien o nhm -CH3 dy electron v phn t axit

acrylic c nhm -COOH ht electron nn c s phn cc cc lin kt71 theo chiu mi tn cong. Sn phm chnh c to thnh do ccnguyn t c mang din tch tri du kt hp vi nhau:

CHs

5+ c h 2 COOH

/ . COOH

CH > CH + V liCH CH,

c h 2

Trong phn t isopren, nhm -CH y electron v phn tCH2=CHCOOCH3 c nhm COOCH3 ht electron lm phn cc cclin kt 7 theo chiu mi tn cong nh sau:

c ? 3 C *V /c CH

+ H ^C HS-V

2

c h 2 COOCH3 COOCH3

c) a) 2-metylbuta-,3-ien c nhm CH3 y electron lm tog mt electron trn nguyn t Ci nn kh nng phn ng cao. Ngc li,trong phn t 2-clobuta-l,3-ien c nhm -C1 ht electron lm gim

63



B

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60/224

mt electron nguyn t Ci nn kh nng phn ng kh hnphn ng xy ra chm hn:

c h 3 c h 2

, ;tH ,I + c II^H

>c h 2 c o o h c o o h

C1 CHS

2C5+

COOH

c h 2r II

CH2 a c o o h5+p) cis-penta-1 ,3-ien c nhm -CH3gy n ng khng gian lm cntr phn ng nn tc ca phn ng rarcs-penta-1,3ien vi axitacrylic ln hn:

5+^ .CHr / \CH CHaICH

^ C H *

cis-penta-l,3~ien

v

CHaN 5+

LCH

trans~penta-l,3-ien20. a) Cho sn phm (CH3)2CHCH2C(CH3)3theo c ch phn ng:

(CH3)2C=CH2 ^ (CH3)2CCH3 (CH3)3CCHg(CH3)2

' * r I(CH3)3 + (CH3)3CCH2CH(eHs)2

Giai on (1), (2) phn ng to' cacbocation ime ha R, giai on (3 ;

l trao i H t ankan ti gc bc III:CH, CH3

(CH3)3CCH2C1 +ffyC(CH3)3> (CH3)3CCH2 H 4 C(CH3)3

c h 3 c h 3

b) Phn ng chuyn v: ^

H2OCH2 H3C C H 2 H3CCH3 + (CH^g

64



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0

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PHƯƠNG PHÁP GIẢI BÀI TẬP HÓA HỌC 11 TỰ LUẬN VÀ TRẮC NGHIỆM - CAO CỰ GIÁC