CU TRC PHN T V TNH CHT HP CHT HU C

GS TS Nguyn Hu nh Khoa Ha hc Trng i hc S phm H Ni

Di y chng ti nu ra mt s cu hi lin quan ti vn Cu trc phn t v tnh cht hp cht hu c v tham gia tho lun cng cc bn.
1. Lin kt ha hc, cng thc Liuyt, cng thc cng hng A. Cu hi 1.0. a) thi tuyn sinh H nm 2009 c hi rng: Phn t no sau y c lin kt ion: HCl, NH4Cl, CH3COOH, CH3CH2OH. b) Nhiu GV thc mc v p n cho thi tuyn sinh H nm 2011 rng: Dng ion lng cc v dng phn t ca aminoaxit c phi l 2 ng phn ? 1.1. Da vo gi tr nng lng lin kt trong cc bng tra cu hy tnh a) Ho ca phn ng monoflo ho metan. b) Ho ca phn ng monoclo ho metan. Nhn xt kt qu tnh c. 1.2. Fomon l dung dch khong 40% fomanehit, trong n tn ti ch yu dng metaniol. a) S dng cc gi tr nng lng lin kt di y, hy gii thch v sao metaniol l dng ch yu trong dung dich, v sao khng th tch c n ra khi dung dch ? Lin kt E (kJ/mol) C-H 410 =C-H 435 C-O 359 C=O 736 O-H 431 HO ~30

b) V sao fomon thng to thnh lp bt trng y bnh ? c) V sao bo qun xc ng vt, ngi ta ngm chng vo fomon? d) Mc tiu ca mt s ngi dng fomom trong ch bin bnh ph l lm cho bnh ph ngt hn, hay trng hn, hay dai hn ? Gii thch? V sao ngi ta khng pht hin c hm lng fomandehit ng k trong bnh ph dng fomon? Tuy vy n vn c hi cho sc khe ngi tiu dng, v sao ? 1.3. Hp cht A c cng thc phn t CHON, th kh, di lin kt CN bng 121 pm, CO bng 117 pm. Ngay 0 oC cht A t bin i thnh cht rn X tng i bn, khng tan trong cc dung mi thng thng, di lin kt CN bng 140 pm. A tan trong nc to dung dch axit vi Ka = 1,2.10-4. Trong dung dch c A t bin i thnh Y c vng 6 cnh vi di lin kt CN bng 135 pm. Cho bit di lin kt trung bnh cc hp cht nh sau: Lin kt C-C C-N C-O C=N C=O CN Cacbon oxit di, pm 154 147 143 130 123 116 112 a) Xc nh cng thc cu to ca A th kh. b) Dng cng thc cu to vit phng trnh phn ng in li ca A trong dung dch nc v gii thc v sao lc axit ca n ln hn ca axit axetic. c) Vit phng trnh phn ng to thnh v cng thc cu to ca X v Y.

1.4. Khi cho cis-but-2-en hoc trans-but-2-en vo axit sunfuric th sau mt thi gian u thu c hn hp gm 85% ng phn trans v 15% ng phn cis. a) Hy gii thch hin tng . b) Hy tnh s chnh lch nng lng gia 2 ng phn 25oC. c) Nu nguyn nhn lm cho ng phn trans bn hn ng phn cis. d) S chnh lch nng lng gia cu dng syn v cu dng anti butan l 3,7kJ/mol. Chng t chuyn i ln nhau ngay nhit thng qua cu dng khut vi nng lng ln hn cu dng anti l 15 kJ/mol. V sao nhit thng trans- v cis-but-2-en khng t chuyn i ln nhau c ?
1.5. Hy vit cng thc Liuyt v ghi r in tch qui c (nu c) ca cc ng phn ng vi cng thc phn t CHNO. 1.6. Hy ch r v sao cc tiu phn sau y mang in tch +, - hoc trung ha:
H H N H H + H N H H H H C H H H C H H + H C H H H C H H

B. Tho lun 1.0. a) Cn xem li lin kt trong cc hp cht ion v trong cc hp cht cng ha tr. b) Cn xem li nh ngha ng phn. 1.1. a) Hp = nng lng ph v lin kt (du +) + nng lng hnh thnh lin kt (du -). H3C-H + F-F H3C-F + H-F E (kJ) : 410 b) 155 425 564 H = [410+155] + [(-425) + (-564)] = - 424 kJ. H3C- H + Cl - Cl H3C- Cl + H Cl E (kJ) : 410 239 325 425 H = (410+239) + [(-325) + (425)] = -101 kJ. Phn ng flo ho trc tip to nhit gp 4 ln phn ng clo ho, dn ti phn hu hirocacbon nn ch thu c HF v C. 1.2. a) Cha tnh lin kt hidro: CH2(OH)2 H hnh thnh: -2400

CH2=O - 1606

H2O -862 (kJ/mol)

H phn ng: -1606 862 (-2400) = -68 (kJ/mol) Thm lin kt hidro: [CH2(OH)2...6H2O]; [CH2=O...2H2O] H hnh thnh: - 2400 + 8 x (-30 ) = 2580; -1606 + 2 x (-30 ) = 1666 (kJ/mol). H phn ng: -2580 (-1666) = 914 (kJ/mol). b) n CH2=O -(-CH2-O-)-n c) CH2=O khng nhng c tc dng dit vi sinh vt m cn c tc dng khu mch cc protein v cc hp cht hu c khc khin chng tr nn bn vng kh b phn hy. d) CH2=O phn ng khu mch vi cc nhm OH ca tinh bt lm cho n dai hn. Khi n khng cn trng thi t do d pht hin. Vo c th n c th c gii phng ra v phn ng ba vo cc nhm OH, NH cc hp cht c trong t bo. 1.3. a) Da vo di lin kt (trung gian gia lin kt i v ba, khng phi lin kt n) xc nh c A th kh l H-N=C=O (xem thm bi 1.5). b) A th kh l axit N nhng trong dung dch nc th chuyn thnh axit O, v vy c lc axit ln hn axit axetic:

c) Da vo di lin kt xc nh c cng thc cu to t c phng trnh phn ng:

1.4. a)
H C H3C C CH3 H + H+ - H+ H H C H3C H C
+

- H+ + H+

H3C C H 85% C

H CH3

15%

CH3

b)
o

K = [trans-but-2-en] : [cis-but-2-en] = 85 : 15 = 5,67 ng

G = - 2,303.RT.lgK = - 2,303.8,314.298.lg5,67 = - 4,3 kJ/mol. B qua i lng TS (v nhit thp), c th coi s chnh lch nng lng gia 2 phn l 4,3 kJ/mol.

c) ng phn cis-but-2-en km bn hn ng phn trans-but-2-en l do lc y Van de Van gia 2 nhm CH3 d) Nng lng hot ho ca s chuyn t cu dng anti sang cu dnh syn bng chnh 15kJ/mol. Nng lng hot ho ca s chuyn t cis- sang trans-but-2-en rt

ln, ti thiu phi ph v lin kt (~263 kJ/mol) nn nhit thng khng th chuyn i ln nhau c.
1.5

1.6. Bc 1: Tnh tng s electron ha tr ca cc nguyn t to thnh . Bc 2: m tng s electron ha tr c mi cng thc . Bc 3: So snh tng s electron m c vi tng s electron ha tr tnh c bc 1. Nu bng nhau th tiu phn l trung ha in, nu thiu th tiu phn mang in tch dng, nu tha th tiu phn mang in tch m. Bc 1 NH3 Tnh s e 5 + 3 = 8 ha tr H Bc 2
H N H

NH4+ 5+4=9
H + H N H H

CH4 CH3+ 4+4=8 4+3=7

H H C H H

CH3. 4+3=7
+ H C H H

CH34+3=7
H C H H

m s e Bc 3: So snh

H C H H

(3x2)+2=8 8-8=0

4x2=8 9 - 8 = +1

4x2=8 8-8=0

3x2=6 7 - 6 = +1

(3x2)+1=7 (3x2)+2=8 7-7=0 7 - 8 = -1

2. Hnh hc phn t

A. Cu hi 2.0. a) mt cun sch i hc c vit rng metan c tm i xng, trc i xng bc ba v mt phng i xng. Hy l gii ng sai. b) mt cun sch i hc ngi ta phn chia ng phn thnh ng phn phng, ng phn khng gian v vit Nu cc cht ng phn khc nhau v cu trc phng gi l ng phn phng (cc sch khc gi l ng phn cu to). Hy phn tch ng sai.
c) Hai cu dng c phi l 2 ng phn ? 2.1. Da vo du hiu no trong cng thc cu to phn t nhn ra C, O, N trng thi lai ha sp 3, sp2 hay sp ? Ly v d minh ha. 2.2. Hy cho bit dng hnh hc ca cc phn t sau (khng xt chi tit nhm CH3): a) CH4 b) CH3OH c) NH3 d) CH2Cl2 e) CS2 g) H2O h) CH2O i) CH3-CO-CH3 2.3. a. phn t metyl clorua c ti a my nguyn t cng nm trn 1 mt phng, c my mt phng nh th ? b. Phn t metyl clorua c tm i xng khng, c mt phng i xng khng ? Nu c hy ch ra.

: :
O

.. .. H-O C N ..

.. H-N=C=O ..

..

.. +1 H-O .. - N

-1 C

+1 -1 .. H - C N O ..

H-C=N

..

c. phn t 1,2-ddicloetan c ti a my nguyn t cng nm trn 1 mt phng, c my mt phng nh th ? d) Dng anti ca 1,2-icloetan c tm i xng khng, c mt phng i xng khng ? Nu c hy ch ra. e. dng anti ca etan, c nhm H-C-C-H no to thnh 1 ng thng khng, c ti a my nguyn t cng nm trn 1 mt phng, c my mt phng nh th ? Nu c hy ch ra.

2.4. a) Hy m t chi tit dng gh ca xiclohexan, c minh ha bng hnh v. b) Hy nu nguyn nhn dn n s chuyn i gia hai dng gh ca xiclohexan. 2.5. a) Hy ch r s lng tm i xng, mt phng i xng (nu c) dng gh ca xiclohexan. b) dng gh ca xiclohexan c ti a my nguyn t C cng nm trn mt mt phng, c my mt phng nh vy?
2.6. Hy gii thch v sao : a) CO2 = 0 trong khi SO2 = 1,6D b) CH 2Cl2 > CHCl3

2.7. Phn t hp cht hu c A cng thc C12H4Cl4O2 c tm i xng v c 3 mt phng i xng. A bn vi nhit, khng lm mt mu dung dch brom v dung dch kali pemanganat. a) Hy lp lun xc nh cc cng thc cu trc c th ca A. b) Hy d on trng thi ca A nhit thng v tnh tan ca n. c) Hy da vo cu to suy ra bn ca A i vi nh sng, kim v axit. B. Tho lun 2.0. a) Tm ca t din u khng phi l tm i xng ca n. b) Theo quan im ca tc gi Nu cc cht ng phn khc nhau v cu trc phng gi l ng phn phng th trans-1,2-dicloeten v cis-1,2-dicloeten l 2 ng phn phng tc l chng khng thuc loi ng phn khng gian! 2.1. xc nh trng thi lai ha ca C, O, N v dng hnh hc ca phn t hu c n gin cn lm nh sau: Bc 1. Vit cng thc cu to khai trin ca phn t. Bc 2. a) Nguyn t (C, N, O) no ch c lin kt n th trng thi lai ha sp3. b) Nguyn t (C, N, O) no c 1 lin kt i th trng thi lai ha sp2. c) Nguyn t (C, N, O) no c 1 lin kt ba hoc 2 lin kt i th trng thi lai ha sp. Bc 3. a) Nguyn t (C, N, O) trng thi lai ha sp 3 khi lin kt vi 4 nguyn t khc th s l tm ca t din m 4 nguyn t kia l 4 nh; khi lin kt vi 3 nguyn t khc th s l 1 nh ca chp tam gic m 3 nguyn t kia l 3 nh khc; khi lin kt vi 2 nguyn t khc th s l nh ca 1 gc m 2 nguyn t kia nm trn 2 cnh ca gc.

b) Nguyn t (C, N, O) trng thi lai ha sp 2 khi lin kt vi 3 nguyn t khc th s l tm ca 1 tam gic m 3 nguyn t kia l 3 nh; khi lin kt vi 2 nguyn t khc th s l nh ca 1 gc m 2 nguyn t kia nm trn 2 cnh ca gc.. c) Nguyn t (C, N, O) trng thi lai ha sp khi lin kt vi 2 nguyn t khc th s gia 2 nguyn t kia trn mt ng thng. 2.2. a) CH4 Bc 1
H H C H H

b) CH3OH
H3C O H

c) NH3
H N H H

d) CH2Cl2
H H C Cl Cl

Bc 2 Bc 3

Theo bc 2a: C lai ha sp3 Theo bc 3a:

H H H

Theo bc 2a: O lai ha sp3 Theo bc 3a:

O

Theo bc 2a: C lai ha sp3 Theo bc 3a: Chp tam gic

H N H H H

Theo 2a: C lai ha sp3 Theo bc 3a:

Cl H Cl

T din Bc 1 Bc 2 Bc 3

Gc

H3C

T din

e) CS2
S C S

g) H2O
H O H

h) CH2O
H C O H

i) CH3-CO-CH3
H3C C CH3 O

Theo bc 2c: C lai ha sp Theo bc 3c:

S C S

Theo bc 2a: O lai ha sp3 Theo bc 3a: Gc

H O H

Theo bc 2b: C lai ha sp2 Theo bc 3b: Tam gic

H H C O

Theo 2b: C lai ha sp2 Theo bc 3b: Tam gic

H3C H3C C O

Thng hng

2.3. Da vo trng thi li ha v bi 2.1,hy v cng thc phi cnh ri gia.

2.4. b) S quay ca cc nhm nguyn t xung quanh lin kt C C. 2.5. a) Tm i xng: 1 ; mt phng i xng: 3. b) C ti a 4 C trn 1 mt phng, c 3 mt phng nh vy.
2.6. . a)

..
O C O O S O

b)
Cl H H Cl H Cl Cl Cl

2.7. a) A l hp cht thm v khng lm mt mu dung dch brom v dung dch kali pemanganat. khng no ca A bng 9, l hp cht thm, bn nhit, nn n cha 2 vng benzen ni vi nhau bng 2 nguyn t O ete 2 v tr ortho (0,5). A c tm i xng v 3 mt phng i xng nn c cng thc l:

b) A c phn t khi ln, c nhiu lin kt phn cc nn l cht rn. A phn a nc (2 nguyn t O) rt nh so vi phn k nc (phn cn li tr 2O) nn n tan trong dung mi hu c, khng tan trong nc. c) - A tng i bn vi nh sng v l hp cht thm khng c lin kt no d b phn ct bi nh sng. - A bn vi kim v cc nguyn t Cl nh vi vng benzen nn A thuc loi dn xut halogen kh nng phn ng thp; - A bn vi axit v mt electron 2 nguyn t O di chuyn vo nhn benzen nn kh tc dng vi axit (0,5). 3. Cu trc v tnh cht vt l A. Cu hi

3.1. Hy gii thch s bin i nhit nng chy v nhit si ca cc pentan ng phn:
t nc ( C) tos (oC)
o o

n-pentan -130 36

isopentan -160 28

neopentan -16,5 9,5

3.2. a) Dng cng thc cu to, hy hon chnh s phn ng sau:

b) Hy so snh nhit nng chy, tan trong nc v lc axit ca cc cht A, B, C v D. Gii thch. 3.3. Trong mt cun sch c vit: So vi cc axit ng phn hoc ancol c cng khi lng mol phn t hoc phn t c cng s nguyn t cacbon th este c nhit si v tan trong nc thp hn hn. Th d: CH3CH2CH2COOH (M=88), si 163,5 C Tan nhiu trong nc
o

CH3[CH2]3CH2OH (M=88), si 132 C Tan t trong nc

o

CH3COOC2H5 (M=88), si 77 oC Khng tan trong nc

Hy tra cu ti liu xem s khi qut ha nh trn ng sai nh th no? 3.4. Cho bng s liu sau : Axit bo : tnc, C :
0

axit stearic 69,6

axit panmitic 63,1

axit oleic 13,4

axit linoleic 5,2

a) Bit cng thc phn t ca axit oleic l C 18H34O2 c cha 1 lin kt i dng cis C9-C10 (C cacboxyl l C1), cng thc phn t ca axit linoleic l C 18H32O2 c cha 2 lin kt i u dng cis C9-C10 v C12-C13 (C cacboxyl l C1). Hy vit cng thc cu trc ca axit oleic v axit linoleic. b) Hy nu nguyn nhn dn ti s gim dn nhit nng chy ca 4 axit cho. c) Hy gii tch v sao cht bo thc vt thng c nhit ng c thp hn cht bo ng vt? 3.5. Triglixerit c phn t khi ln gp khong 3 ln nhng nhit nng chy thng ch xp x nh axit bo to ra n, Hy gii thch. 3.6. V sao lipit khng tan trong nc m tan trong xng du? 3.7. V sao nhit phng glucoz, fructoz (M = 180 au) u th rn, trong khi axit oleic c phn t khi ln hn nhiu (M = 282 au) li th lng. 3.8. V sao cc isaccarit c nhit nng chy cao hn cc monosaccarit hp thnh. 3.9. V sao tinh bt v xenluloz khng nng chy. 3.10. V sao cc ancol, anehit, axit cacboxylic, este c cha 6-12 C u hu nh khng tan trong nc, trong khi cc monosaccarit (C6H12O6) v isaccarit (C12H22O11) u tan tt trong nc. 3.11. Hy th gii thch cc hin tng sau: a) Tinh bt v xenluloz u khng tan trong nc mc d mi gc glucoz to ra chng u c 3 nhm OH l nhm a nc. b) un nng tinh bt vi nc th to thnh h tinh bt, un nng xenluloz vi nc th chng c g. 3.12. Hy nu nguyn nhn dn ti s khc nhau v nhit nng chy ca cc cht trong bng sau : Hp cht M, au to nc, oC CH3COOH 60,05 17 HSCH2COOH 92,11 - 16,5 HOCH2COOH 76,05 97 H2NCH2COOH 75,07 262

3.13. Hy sp xp cc cht sau theo chiu tng dn nhit nng chy v gi thch: CH3CH2CH2CH2NH2 (a), CH3CH2CH2CH2OH (b), CH3CH2OCH2CH3 (c), CH3CH2COOH (d), H2NCH2COOH (e), 3.14. Hy gii thch cc hin tng sau: a) Khi un nng, cc amino axit thin nhin khng si m b phn hy. b) Cc amino axit thin nhin hu nh khng tan trong benzen nhng tan tt trong nc. c) Cc axit cacboxylic c trn 5C rt t tan trong nc, trong khi cc amino axit thin nhin c trn 5C vn tan tt trong nc. 3.15. Hy gii thch cc hin tng sau :

a) Polime l nhng cht khng bay hi v khng c nhit nng chy xc nh. b) Nhng polime thng thng u l nhng cht cch in. c) Polime thng kh ha tan trong cc dung mi thng thng, khi tan th to thnh dung dch keo nht. d) Vt liu polime dng trong nh th bn hn so vi dng ngoi tri. 3.16. Khi ha tan mt loi PVC trong etanol ri cho tc dng vi bt km th thy tch ra ZnCl2 v thu c mt polime cha 20,82% Cl, khng cha lin kt i, khng tan trong etanol. Da vo kt qu hy cho bit s phn b cc nguyn t Cl trong mch PVC (iu ha hay khng iu ha) v cu to ca polime thu c. B. Tho lun Quy lut chi phi nhit nng chy v nhit si: - Hp cht ion thng c nhit nng chy v nhit si cao hn hp cht cng ha tr. - Trong cng dy ng ng, hoc trong mt dy cht m mc phn cc khng khc nhau nhiu th nhit nng chy v nhit si thng tng theo phn t khi. - Trong dy cht ng phn th cht no c cha nhm phn cc hn, to c nhiu lin kt hidro lin phn t hn th thng c nhit nng chy v nhit si cao hn. i vi cc ng phn khng to c lin kt hidro th ng phn no c cu to gn gng hn (cu to i xng hn) thng c nhit nng chy cao hn nhng nhit si th thng thp hn. Quy lut chi phi tnh tan: Ging nhau th tan vo nhau Khi xt tan trong nc ca cht hu c cn ch ti tng quan v s lng v lc tng tc ca hp phn a nc so vi hp phn k nc. 3.1. Khng nhng cn ch ti khong cch gia cc phn t m cn cn ch ti din tch b mt tip xc gia chng. 3.2. Nhit nng chy: D > C > B > A (D c cu to ion lng cc). tan trong nc: D > C > B A. Lc axit: B > A > C > D. 3.3. Theo ti liu tra cu th tan khng theo nhn nh m tc gi a ra: CH3CH2CH2COOH CH3[CH2]3CH2OH CH3COOC2H5

Tan c trong nc Tan 2,7g/100g nc 22 oC Tan 7,66g/100g nc 15 oC Cn ch rng tan trong nc ph thuc vo tng quan gia hp phn a nc v hp phn k nc trong phn t. 3.4. th rn cc phn t axit stearic c cu trc thng, gn gng, d sp xp cht kht nn lc ht gia chng mnh hn, trong khi cc phn t axit oleic c cu trc un gp ( ch cu hnh cis), cng knh, kh sp xp cht kht nn lc ht gia chng yu hn. Hnh di y cho thy cng mt th tch s cha c nhiu phn t c cu trc thng hn l phn t c cu trc un gp:

3.5. Gia cc phn t axit bo c lin kt hidro lin phn t, cn gia cc phn t triglixerit th khng c lin kt hidro lin phn t. 3.6. Phn t cc cht lipit cu to ch yu t cc nhm khng phn cc (nhm k nc) v t phn cc nn chng tan trong dung mi khng phn cc m khng tan trong nc. 3.7. Phn t glucoz, fructoz (C6H12O6) u c cu trc gn gng (vng 6 hoc 5 cnh) c 4 nhm OH v 1 nhm C=O u l nhng nhm phn cc v to c nhiu lin kt hiddro lin phn t. Phn t axit oleic (C18H34O2) c cu hnh cis cng knh m ch c 1 nhm OH v 1 nhm C=O to c t lin kt hiro lin phn t. 3.8. isaccarit c nhiu nhm phn cc v to nhiu lin kt hiro lin phn t hn so vi monosaccarit hp thnh nn c nhit nng chy cao hn. 3.9. Tinh bt v xenluloz l nhng hp cht cao phn t, li c v vn lin kt hiro lin phn t lm cho lc ht gia cc phn t rt ln, n nhit cao vn khng ri nhau ra (khng nng chy) m b chy nu c oxi hoc b phn hy nu khng c mt oxi. 3.10. Mi phn t ancol, anehit, axit cacboxylic, este (cha t 6-12 C) u ch c 1-2 nhm a nc cn li l k nc v vy hu nh khng tan trong nc, trong khi cc monosaccarit (C6H12O6) c 5-6 nhm a nc, isaccarit (C12H22O11) c 10-11 nhm a nc nn u tan tt trong nc. 3.11. a) Tinh bt v xenluloz l nhng hp cht cao phn t kch thc phn t qu ln so vi cc phn t nc, li c v vn lin kt hiro lin phn t lm cho lc ht gia cc phn t rt ln, nn cc phn t nc khng th ko tng phn t ra khi b cao phn t ha tan c. b) Do phn t amiloz c cu trc xon, phn t amilopectin c cu trc phn nhnh, tinh bt s lng nhm OH to c lin kt hiro ni phn t ln hn nhiu so vi xenluloz nn lc ht gia cc phn t tinh bt nh hn gia cac phn t xenluloz. Do khi un nng vi nc, gia cc phn t trong tinh bt c th to ra cc khong trng cho cc phn t nc thm nhp vo thc hin s hyrt ha to ra th keo t gi l h tinh bt. Cc phn t xenluloz to ra cc b cao phn t ht nhau rt cht, ung nng cng khng ri nhau khin cho cc phn t nc ch tip xc mt ngoi ca b cao phn t lm t chng m khng to ra th keo t c.

3.12. HSCH2COOH tuy c phn t khi ln hn CH 3COOH nhng do nhm SH hu nh khng to lin kt hiro m li c kch thc ln lm cho phn t cng knh sp xp km kht khao, nn c nhit nng chy thp nht. HOCH2COOH c thm nhm OH phn cc v to c lin kt H lin phn t nn t o nc cao hn HSCH2COOH v CH3COOH. Amino axit H2NCH2COOH tn ti dng ion lng cc, H3N+CH2COO-, lc ht gia cc phn t tng mnh ng thi vn to c lin kt H lin phn t, v vy to nc cao nht. 3.13. Cc hp cht cho c khi lng phn t hn km nhau khng nhiu. Amino axit H2NCH2COOH (e) dng ion lng cc, H3N+CH2COO-, nn c to nc cao nht. CH3CH2OCH2CH3 (c) cha cc lin kt t phn cc v khng to c lin kt H lin phn t, nn c t o nc thp nht. Nhm -OH phn cc hn v to lin kt H mnh hn nhm -NH 2 nn CH3CH2CH2CH2OH (b) nng chy cao hn CH3CH2CH2CH2NH2 (a). CH3CH2COOH (d) c nhm -COOH va phn cc mnh va to lin kt H mnh nn nng chy cao hn CH3CH2CH2CH2OH (b). Nh vy to nc tng theo trt t sau: (c) < (a) < (b) < (d) < (e) 3.14. a) Khi un nng, cc amino axit thin nhin khng si m b phn hy v chng dng ion lng cc, CH3CH(NH3)+COO-, lc ht gia cc phn t mnh, nhit nng chy cao ti mlm cho chng va nng chy va b phn hy. b) Cc amino axit thin nhin hu nh khng tan trong benzen nhng tan tt trong nc v chng dng ion lng cc, CH3CH(NH3)+COO-, nn tnh tan ging vi cc hp cht ion. c) Cc axit cacboxylic c trn 5C rt t tan trong nc, trong khi cc amino axit thin nhin c trn 5C vn tan tt trong nc v chng dng ion lng cc, CH3CH(NH3)+COO-, c cha 2 nhm rt a nc l (-NH3)+ v -COO- trong khi cc axit cacboxylic ch cha 1 nhm a nc -COOH. 3.15. a) Polime l nhng hp cht cao phn t, lc tng tc gia cc phn t rt ln gi cho chng khng bay hi. Mi polime l mt hn hp cc phn t vi h s polime ha khc nhau v vy chng khng c nhit nng chy xc nh m thng nng chy hoc chy do mt khong nhit kh rng no . b) Nhng polime thng thng l nhng cht khng cha cc in tch linh ng c th chuyn dch thnh dng di tc dng ca hiu in th nn chng l nhng cht cch in. c) Lc tng tc gia cc phn t polime rt ln gi cho chng khng b cc phn t dung mi solvat ha. Phn t polime c kch thc rt ln nn khi ha tan ra vn khng chuyn ng linh ng nh cc phn t nh m thng kt cu vi dung mi nhau to thnh dung dch keo nht. d) Vt liu polime dng lu thng b gin, bin mu ri h hi. Nguyn nhn ca s lo ha ch yu l do tc dng ng thi ca nh sng v oxi khng kh lm gy mch polime. ngoi tri cng nh sng cao hn trong nh, nhit cng cao hn nn polime chng b lo ha hn. 3.16. Trong PVC clo chim 56,8 %, sau phn ng vi Zn cn 20,82% cho thy clo b tch i kh nhiu m li khng to thnh lin kt i C=C tc l trong mch phn t polime 2 nguyn t Cl khng nh vo

2 C cnh nhau nh cu trc khng iu ha A. Suy ra cc nguyn t Cl phi cch u nhau mt nhm -CH2- tc l c cu to iu ha B:

Polime thu c khng tan trong etanol nh polime bn u suy ra n b khu mch to thnh polime cu trc mng:

4. Cu trc v tnh cht ha hc A. Cu hi 4.0. a) Hai dng h bin c phi l 2 ng phn ? b) Trong mt cun sch i hc c vit: Xiclooctatetraen l hp cht phn thm. Khi no th mt annulen khng phng? 4.1. Cu 7.2. trong thi chn HS gi QG lp 12 THPT nm 2010 nh sau: So snh (c gii thch) tnh baz ca cc hp cht A v B di y:

Hng dn gii ca Cc kho th vit nh sau: A tm baz l nguyn t N-piridin chu nh hng I v +C ca nhm NH. Hiu ng khng gian ca mch nhnh lm kh cho s proton ha. B tm baz l nguyn t N-piridin chu nh hng I (yu hn v cch xa hn) v +C ca nhm NH. Mch nhnh khng gy hiu ng khng gian. Vy A < B. Hy cho nhn xt v vn nu trn. 4.2. Hiro ha hon ton naphtalen ngi ta thu c ecalin (C 10H18). Oxi ha ecalin th thu c hn hp cc ecalon (C10H16O). a. Trong hn hp ecalon ni trn c ti a bao nhiu ecalon ng phn ? Gii thch. b. Hy v cng thc cc ng phn lp th ca 1-ecalon, bit rng hai vng 6 cnh trong phn t ecalon u dng gh. c. Ha tan cis-1-ecalon vo dung dch baz th n b ng phn ha thnh trans-1-ecalon ti 95%. Hy gii thch s ng phn ha ca cis-1-ecalon v cho bit cis-2-ecalon c b ng phn ha thnh trans-2-ecalon trong iu kin cho hay khng, v sao? d. Trong dung dch baz, 1-ecalon phn ng vi benzanehit cho hp cht T, phn ng vi metyl vinyl xeton cho hp cht U. T lm mt mu nc brom cn U th khng. Hy vit cng thc cu to ca T v U. e. Vit s phn ng tng hp 2-(1-aminoetyl)ecalin t ecalin. 4.3. T du m ngi ta tch c mt s hirocacbon c cng thc phn t C 10H18. Chng u bn nhit v khng lm mt mu dung dch KMnO4. Chng u khng cha C bc I v C bc IV, t l gia s nguyn t C bc III trn s nguyn t C bc II l 1:4. a) Hy lp lun ngn gn vit ra cng thc cc ng phn cu to ph hp vi cc d kin nu trn. b) Hy v cng thc cc ng phn lp th ng vi 3 ng phn cu to tm c. c) Cho mt ng phn cu to tm c tc dng vi clo c chiu sng. Hy vit cng thc cu to cc dn xut monoclo thu c v cho bit dn xut monoclo bc no chim t l cao hn, v sao? 4.4. Canxi xianamit c iu ch t canxi cacbua v c mt s phn ng nh sau: CaC2 + N2 CaCN2 + C (1) CaCN2 + 3 H2O CaCO3 + 2 NH3 (2) CaCN2 + H2SO4 CaSO4 + CH2N2 (3)

a) Da v cc phn ng trn hy suy ra lin kt trong CaCN2 v CH2N2. b) CH2N2 tn ti di 2 dng h bin. Hy v cng thc cu trc ca chng. c) CH2N2 t chuyn ha thnh nhng hp cht bn hn: A cng thc phn t C2H4N4 v B cng thc phn t C3H6N6. Hy v cng thc cu trc ca A v B. d) D on tnh cht vt l v ha hc ca B. e) Cho B (1mol) phn ng vi fomandehit (3 mol) thu c hp cht trung gian C ri to ra polime D. Vit cng thc cu to ca C v D v d on tnh cht ca D. 4.5. Xicloocta-1,3,5,7-tetraen (COT) c tng hp u tin vo nm 1911 t hp cht thin nhin K qua 13 bc c tm tt nh sau:
O (K) NMe2
Na/EtOH

Me2N (Q) (R) NMe2 COT

H2SO 4

MeI

N (P)

Phng php nhiu x tia X cho thy COT c cu trc khng phng, khong cch gia cc nguyn t cacbon cnh nhau ln lt l 1,33 v 1,46 , trong khi ianion [ COT]2- ([C8H8]2-) c cu trc phng vi khong cch gia cc nguyn t cacbon cnh nhau u bng 1,41 . a) COT c cu trc G (dng gh) hay T (dng thuyn), v sao ? b) Hy biu din cu trc ca [COT]2- sao cho ph hp vi d kin nhiu x tia X. c) Vit cng thc cu to ca L, M, v N. d) Hy vit y cc tc nhn v iu kin phn ng dng cho cc bc tip theo thc hin s chuyn ha t N n COT. e) Hy a ra mt tng iu ch COT theo mt cch thc n gin hn s cho trn. 4.6. Cu 1.1.c trong thi chn HS gii QG 2011 : Vit cng thc cu to ca A, B, C v gii thch qu trnh chuyn ha to thnh C trong s phn ng i y:

4.7. Cu 3.2a trong thi chn HS gii QG 2011: Hy gii thch c ch ca phn ng sau:

4.8. Cu 3.2a trong thi chn HS gii QG 2011: Hy gi thch c ch ca phn ng sau:

 Khng cho bit iu kin phn ng th gii th no? 4.9. Axit shikimic, cng thc phn t C7H10O5 (K), tch c t qu hi, l nguyn liu c bn dng tng hp thuc tamiflu. Cu to ca n c xc nh da vo dy chuyn ho sau:

a) Trong dung dch, L c th tn ti nhng cu to nh th no ? Trong s cc cu to , cu to no chuyn ho thnh M, N ri P ? b) Hy xc nh cng thc cu to ca M, N v K. c) Hy dng cch v n gin nht biu din cu trc ca cc ng phn lp th ca K. d) Hy ngh s phn ng tng hp ra mt hp cht c cu to nh axit shikimic t nhng hp cht cha khng qu 6 nguyn t C. B. Tho lun 4.0. a) Cn nm vng nh ngha ng phn. b) Xiclooctatetraen l hp cht khng thm. 4.1. Cu Hiu ng khng gian ca mch nhnh lm kh cho s proton ha l sai. Mch nhnh A ko di ch che chn mt pha ca N-piridin cc pha khc vn thong, mt khc proton d di dng H 3O+ khi tham gia phn ng proton ha th hu nh khng i hi phi hon ton thong v mt khng gian v kch thc nh b ca n. Nguyn nhn ch thc l: Sau khi proton ha, nhm N +H cn c solvat ha khi kt hp vi OH-. S solvat ha i hi s tip cn ca nhiu phn t dung mi quanh nhm N +H nn s chu nh hng ca y t khng gian. AH+ nhm N+H kh b solvat ha hn BH+ do nh hng khng gian ca mch nhnh. 4.2. a) Trong hn hp c 12 decalon ng phn gm: trans-1-decalon: 2 i quang; cis-1-decalon: 2 cp i quang (xem hnh cu 2); trans-2-decalon: 2 i quang; cis-2-decalon: 2 cp i quang. b) 6 ng phn lp th ca 1-decalon:
O

c). Nguyn t C cu ni tr thnh C - v b nghch o khi kt hp vi H +. Cn bng chuyn dch v pha ng phn trans bn hn:

H -H

+ H+ - H+ O

+ H+ O O

Cng c th gii thch bng cch da vo dng enol c cu to phng . cis-2-decalon khng c s ng phn ha nh vy v C n khng phi l cu ni, ni quyt nh cu hnh cis hoc trans. d). T l sn phm ngng t, U l sn phm cng Michael ri ngng t tip theo: O
T: O CHC6H5 U:

e). Ngng t vi EtNO2 ri kh:

O
CH3CH2NO2 HO-

CH3 H2/Ni , t o NO2

CH CH3 NH2

4.3. a) A c 2 C bc III v 8 C bc II, khng cha vng 3 hoc 4 cnh. Loi 2 vng ring r ch c 1 cht gm 2 vng 5 cnh ni vi nhau bi 1 lin kt n. Loi 2 vng chung nhau 2 nh (2 C bc III) nh th cn sao cho tng s C bc 2 bng 8 (tng cc s trong du [ ] bng 8) v khng to ra vng 3 hoc 4 cnh, th d: Bixiclo [4,4,0] decan; Bixiclo [5,3,0] decan; Bixiclo [4,3,1] decan; Bixiclo [5,2,1] decan; Bixiclo [4,2,2] decan; Bixiclo [3,3,2] decan. 4.4. Canxi xianamit c iu ch t canxi cacbua v c mt s phn ng nh sau: CaC2 + N2 CaCN2 + C (1) CaCN2 + 3 H2O CaCO3 + 2 NH3 (2) CaCN2 + H2SO4 CaSO4 + CH2N2 (3) a) Cc phn ng 1, 2, 3 cho thy CN2 tng c th thay th bi cc anion C22-, CO32-, SO42-, Vy n l anion CN22-, cu tao : -N=C=N- . Phn ng 3 thc cht l axit mnh y axit yu ra khi mui, do suy ra CN22- c cu tao -N=C=N- v CH2N2 c cu to H-N=C=N-H. b) Cu trc ca 2 dng h bin ca CH2N2 l:

c)

d) B c cu trc gon gng, c nhiu lin kt phn cc, c nhiu nhm to c lin kt hidro lin phn t v vy B c nhit nng chy cao, tan c trong nc. B c 3N-piridin nn c lc baz tng t piridin, B c 3 nhm amino nn c tnh cht tng t amin. e)

Cc mt xch ca D c vng thm v cc lin kt n C-N bn, cu trc ca polime D thuc loi mng khng gian. V vy D l polime bn c v ha v c nhit. Hm lng % N trong D rt cao m li khng cha O nn khi b chy kh nit sinh ra s ngn cn khng cho s chy tip tc. 4.5. a) COT c cu trc dng thuyn m bo cu to phng cho tng lin kt i, COT khng th dng gh c v nguyn t C2 v C5 khng ng phng vi lin kt i C3-C4 v nguyn t C1 v C6 khng ng phng vi lin kt i C7-C8:
H
1 8 7

H
6

H
1 2 8

H
7 6

H H
3 4

H
5

H H

H
3 4

(T)

(G)

b)

...
c)
N OH (L) N (M) N
I

(N)

d)
N
I

(N)

1) [Ag(NH 3)2]OH o 2) t

(P)

1) MeI 2) [Ag(NH 3)2]OH o 3) t

(Q)

1) Br 2, 2) Me 2NH

Me2N (R) NMe2

1) MeI 2) [Ag(NH 3)2]OH o 3) t

e)

4.6. S tch nc ca A xy ra qua giai on to thnh cacbocation km theo s gii ta in tch dng nn to ra B. Khi B b un nng c th xy ra phn ng Diels-Alder ni phn t to thnh C nh c phn ienophin -C6=C7- v hp phn ien -C1=C2-C3=C4-.

Bi tp ny rt hay, n gip rn luyn t duy logic bit suy lun t phn ng lin phn t n phn ng ni phn t. Hiu sut ca phn ng Diels-Alder ni phn t k trn khng cao do hp phn ienophin (C 6=C7) v hp phn ien (C1=C2-C3=C4) ch cch nhau mi mt nguyn t C 5 nn kh sp xp ph hp vi yu cu lp th ca phn ng Diels-Alder v v phi to ra vng 3 cnh c sc cng ln. Trong trng hp un nng B, phn ng Diels-Alder bnh thng (lin phn t) to ra D1 v D2 c l s din ra thun li hn v tip theo c th to ra E1 v E2:

Nhng hp cht phc tp cha cc h a vng nh trn khng h xa l cht no v chng thng c trong cc loi thc vt quanh ta. 4.7. Cu dn ca u bi nn sa li nh sau: Hy ngh c ch phn ng gii thch s to thnh hp cht a vng sau. Vi u bi nh vy, phng php gii nn nh sau: thy c nhng lin kt mi no c hnh thnh, nhng lin kt c no b t trong s hnh thnh sn phm Z, hy vit li cng thc ca cht u K thnh K cho tng ng vi sn phm Z:

Khi chuyn t K sang Z ta thy: Hai vng 6 cnh A v B c chung nhau cnh a vn gi c s tng ng; Lin kt e b t, lin kt n d chuyn thnh lin kt i d Z; 2 lin kt pi vng A khng cn; lin kt f l lin kt mi c hnh thnh.

 Lin kt e b t l do s tn cng ca OH- (thy phn xc tc baz). Do hiu ng lin hp m H (H v tr gama so vi nhm cacbonyl vng A) xeton ,-khng no I tr thnh linh ng v s enol ha to ra enol II. Dienol II b xeto ha thnh dixeton III.

Xc tc OH- khng nhng lm thun li cho qu trnh enol-xeto ha to thnh II v III m cn chuyn III thnh cacbanion IV thc hin phn ng cng Michael vo nhm xeton ,-khng no vng A to thnh lin kt mi f, tc l to ra V,VI, cui cng khi axit ha th to thnh sn phm Z:

Dixeton III l hp cht bn, di tc dng ca xc tc axit cng c th chuyn ha thnh Z nhng hiu sut thp hn so vi xc tc baz nh trnh by trn. 4.8. Cu dn ca u bi nn sa li nh sau: Hy ngh c ch phn ng gii thch s to thnh hp cht a vng sau. Ta ch rng axit malonic mnh hn axit axetic nhiu (hy gii thch iu ) th ta c th tin rng n s cung cp proton xc tc cho phn ng ny, v c ch phn ng s nh sau:

Bi tp ny tuy kh nhng rt hay, n gip rn luyn k nng phn tch cu trc trong khng gian ba chiu v i hi mt s hiu bit su v c ch phn ng. 4.9. Cu to v cu trc ca axit shikinic: