BI TP CHN LC V DANH PHP V LP TH
BI TP CHN LC V DANH PHP V LP TH
CA HIROCACBON VNG NO
ng Cng Anh Tun
Trng THPT Chuyn L Qu n
I. M U
1. L do chn ti
Chng ti chn ti Bi tp chn lc v danh php v lp th ca hirocacbon vng no vi nhng l do v mc ch sau y:
Mt l cn c gio trnh dy hc sinh chuyn ha, ng thi thc hin nhim v nghin cu cc chuyn bi dng hc sinh gii m nh trng ra trong nm hc ny.
Hai l, mng kin thc ny va l trng tm va l c s nghin cu nhng chuyn khc, nh hp cht t nhin, polime
Ba l, thi hc sinh gii quc gia hin nay c nhiu bi ton lin n cu dng v danh php ca cc hp cht hu c.
2. Nhim v nghin cu
Thit k, chn lc cc bi tp c h thng v danh php, cu hnh v cu dng ca hirocacbon vng no.
3. Phng php tin hnh
Tp hp cc ti liu tham kho c lin quan n i tng nghin cu:
Nghin cu c s l thuyt c lin quan.
Lp s nghin cu:
Thit lp, chn lc cc bi tp ph hp vi mc tiu ra.II. NI DUNG
Bi 1. Xicloankan l g? Th no l monoxicloankan? Th no l polixicloankan ? Cng thc chung ca monoxicloankan l g ?
( Bi gii
Xicloankan l hirocacbon no mch vng.
Xicloankan c mt vng (vng n) gi l monoxicloankan.
V d:
Xicloankan c nhiu vng (a vng) gi l polixicloankan.
V d: nobonan l mt bixicloankan.
Monoxicloankan c cng thc chung l CnH2n (n ( 3).
Lu : Trong chng trnh ha hc ph thng, xicloankan c hiu l monoxicloankan.
Bi 2. Vit cng thc phn t v c tn theo IUPAC cho cc xicloankan sau:
( Bi gii Qui tc c tn: Xiclo + tn mch chnh + an
Bi 3. Vit cng thc phn t v c tn theo IUPAC cho cc xicloankan sau:
( Bi gii
Qui tc c tn: s ch v tr + tn nhnh + xiclo + tn mch chnh + an
Bi 4. Cho bit cng thc chung ca hirocacbon c hai vng no, phn loi. Cho bit nguyn tc c tn ca cc loi ny.
( Bi gii
Cng thc chung ca hirocacbon hai vng no l CnH2n-2 n ( 4. N c 3 loi, l:
Hai vng ri
Ly vng ln lm mch chnh, cn vng nh lm nhm th.
V d:
Hai vng c chung mt nguyn t mt vng, kiu spiro.
Mch cacbon c nh s ht vng nh n vng ln, bt u t mt nguyn t k nguyn t chung.
Tn ca hiro kiu spiro gm cc b phn hp thnh theo trnh t sau y:
spiro + [cc s nguyn t cacbon ring (t s ln n s nh)] + tn hirocacbon mch h tng ng.
V d:
Hai vng c chung cu ni, kiu bixiclo
Mch cacbon c nh s bt u t mt nguyn t chung ( mt nh), n cc nguyn t ca cu ni di nht, tip n cc cu ni ngn hn.
Tn ca hirocacbon kiu gm cc b phn hp thnh theo th t sau:
bixiclo + [s nguyn t C cc cu ni (ghi t s ln n s nh)] + tn ca hirocacbon mch h tng ng.
V d:
Bi 5. Hy gi tn cho cc hp cht sau.
( Bi gii
Bi 6. Hy gi tn cc cht sau:
( Bi gii
Bi 7. Gi tn cc hp cht sau:
( Bi gii:
Bi 8. Cho bit cng thc cu to ca cc cht c tn sau:
(a) spiro[2,3]hexan
(b) 1-metylspiro[2.3]hexan
(c) spiro[3.4]octan
(d) 5-etylspiro[3.4]octan
(e) spiro[4.5]decan
(f) 8-ipropylspiro[4.5]decan
( Bi gii
(a) spiro[2,3]hexan
(b) 1-metylspiro[2.3]hexan
(c) spiro[3.4]octan
(d) 5-etylspiro[3.4]octan
(e) spiro[4.5]decan
(f) 8-ipropylspiro[4.5]decanBi 9.
Bi 10. V cng thc cu to ca cc hirocacbon hai vng no sau:
(a) Bixiclo[2.2.1]heptan
(b) Bixiclo[5.2.0]nonan
(c) Bixiclo[3.1.1]heptan
(d) Bixiclo[3.3.0]octan
( Bi gii
Bi 11. Cho bit cng thc cu to ca cc cht c cng thc sau:
(a) bixiclobutan
(b) 2-metylbixiclobutan
(c) bixiclo[3.2.1]octan
(d) 8-metylbixiclo[3.2.1]octan
( Bi gii
(a) Bixiclobutan
(b) 2-metylbixiclobutan
(c) bixiclo[3.2.1]octan
(d) 8-metylbixiclo[3.2.1]octan
Bi 12. c tn cc cht sau:
( Bi gii
Ch : Hai nhm th cng pha l ng phn cis, cn khc pha l ng phn trans.
Bi 13. Xicloankan no c ng phn cis trans ? Nu c v c hai ng phn .
(a) 1,3-dimetylxiclopantan
(b) Etylxiclopantan
(c) 1-etyl-2-metylxiclobutan
( Bi gii
(a) 1,3-dimetylxiclopantan. C ng phn cis trans
(b) Etylxiclopantan. Khng c ng phn cis-trans.
Hai cht trn l mt.
(c) 1-etyl-2-metylxiclobutan: C ng phn cis-trans
Bi 14. Hai hp cht hu c A v B u c cng thc phn t C5H10. C hai u khng phn ng vi Cl2 trong ti v lnh. A phn ng vi Cl2 c nh sng, nhng cho mt sn phm duy nht l C5H9Cl. Cn hp cht B cng tc dng vi Cl2 trong cng iu kin nhng cho 6 ng phn C5H9Cl khc nhau, c th phn bit bng phng php vt l. Hy xc nh cu trc ca A, B v cc sn phm monoclo .
( Bi gii:
A v B c cng thc C5H10 nn chng c th l anken hoc xicloankan. Theo u bi, cc cht ny khng tc dng vi Cl2 ti v lnh nn A v B l cc xicloankan.
A tc dng vi Cl2 cho mt monoclo duy nht nn A l xiclopentan
B tc dng vi Cl2 (nh sng) tao ra 6 dn xut monoclo, nn B phi l metylxiclobutan.
Bi 15. Sc cng Baeyer l g?
( Bi gii
Xut pht t hai tin l cc vng no c cu trc phng v gc bnh thng ca hirocacbon no l 109028, nm 1885, Baeyer cho rng s o nh hay trng rng cc gc ca vng no u dn n mt sc cng l cho tnh bn ca vng gim i. Ngi ta gi l sc cng Baeyer. Sc cng cng ln, vng tng ng cng t bn. mnh ca sc cng c nh gi bng (. ( c tnh theo cng thc
v d:
n3456789
(2404490440044-5044903312046-15006
Bi 16. V sao ni lin kt C-C trong xilopropan c gi l lin kt qu chui ?( Bi gii Xiclopropan l hp cht vng no duy nht c cu to phng. Theo quan nim hin i, phn xen ph cc i ca cc m my electron khng nm trn ng thng ni lin hai nguyn t cacbon m c s un cong. S un cong ny lm cho phn xen ph m my electron c gim i, nhng sp xp nh th c li v mt nng lng. Cc lin kt C-C ny c gi l lin kt qu chui, n mang tnh cht trung gian gia lin kt ( v ( bnh thng. Do s un cong nh vy, thc t gc lin kt ca vng ch bng 1060 ch khng phi 109028 v ln hn nhiu so vi gc cu to phng ca tam gic u (600). Xiclopropan rt d b m vng di tc dng ca hirohalogenua, Br2 v b hiro ho c cht xc tc.
Bi 17. Th no l lc y Pitze?
( Bi gii
Thc t, cc vng no (tr xiclopropan) khng phi l nhng vng phng. Trong mt vng ngoi sc cng gc Baeyer c c mt lc y na l lc y gia cc nguyn t hiro trng thi che khut mt phn hay ton phn gy nn, o mt vi nguyn cacbon ca vng b lch ra khi mt phng vng. Lc y gi l lc y Pitze
Bi 18. Nguyn nhn no xiclobutan tn ti dng khng phng?
( Bi gii
Theo quan nim hin nay, xiclobutan c cu to khng phng gc gp c gi tr khong 20-250. Tnh khng phng ca xiclobutan c chng t t cc d kin thc nghim ca gin Rnghen, gin electron, momen lng cc, ph cng hng t ht nhn v mt s phng php khc. Nguyn nhn ch yu xiclobutan tn ti dng khng phng l gim sc cng Pitz.
Bi 19. Xiclopentan tn ti hai cu dng khng phng: dng phong b v dng na gh. Hy v hai cu dng ny v cho bit dng no c tm i xng, dng no c trc i xng.
( Bi gii
Nu gi s phn t xiclopentan nm trn mt mt phng th gc lch 0044, do coi nh khng c sc cng Baeyer. Nhng y 5 lin kt C-C dng che khut nn li xut hin sc cng Pitz. Thc t xiclopentan tn ti hai cu dng khng phng l cu dng phong b c mt phng i xng nn cn gi l cu dng Cs. Cu dng na gh c trc i xng bc hai nn cn gi l cu dng C2.
Lu : Khi thc hin php quay phn t xung quanh trc i xng Cn mt gc sao cho phn t trng vi chnh n. Trc quay Cn gi l trc i xng cp n.
Bi 20. Da vo gin th nng sau, cho bit cu dng no ca xiclohexan bn nht ? Gii thch ?
( Bi gii
Cu dng gh bn hn cu dng thuyn, v n c th nng thp nht. Nguyn nhn dn n s khc nhau v bn gia hai dng gh v thuyn l lc y tng tc gia cc nguyn t hiro ca vng. dng gh tt c u c phn b theo hnh th xen k. Trong khi dng thuyn ch c 4 h thng (C1-C2, C3-C4, C4-C5 v C6-C1) l phn b xen k, cn hai h thng cn li C2-C3 v C5-C6) th phn b che khut. Hn na nguyn t H C1 v C4 ch cch nhau 1,84 nn n c mt lc y khong 3 kcal/mol. Tng cng th nng ca dng thuyn ln hn dng gh 6,8 kcal/mol.
Cng thc Newman dng ghCng thc Newman dng thuyn
Bi 21. Trong xiclohexan, xc inh lin kt trc (axial) v lin kt bin (equatorial). So snh tnh bn ca a-metylxiclohexan v e-metylxiclohexan. Gii thch.
( Bi gii
Trong xiclohexan, sau nguyn t cacbon dng gh c phn b trn hai mt phng song song. Mt phng th nht cha C1, C3 v C5 ; mt phng th hai cha C2, C4 v C6. Trc i xng bc ba ca phn t thng gc vi hai mt phng. 12 lin kt C-H c chia lm hai nhm: nhm th nht gm 6 nguyn t H song song vi trc i xng bc ba ( 3 lin kt hng ln v 3 lin kt hng xung). Ta gi l lin kt trc, k hiu l a (axial). Nhm th hai gm 6 lin kt cn li, chng hng ra ngoi bin phn t (to vi trc i xng mt gc 1090 c gi l lin kt bin, k hiu l e (equatorial).
Kt qu kho st l thuyt cng nh thc nghim e-metylxiclohexan bn hn a-metylxiclohexan. nhit thng e-metylxiclohexan chim 95% cn a-metylxiclohexan chim 5%.
a-metylxiclohexan km bn v c n hai tng tc syn, trong kho e-metylxiclohexan khng c tng tc syn no c.
e-metylxiclohexana-metylxiclohexan
Bi 22. Xt cu dng sau:
(a) Nhm metyl gn pha di C-6 l lin kt trc (axial) hay lin kt bin (equatorial) ?
(b) So snh bn khi nhm metyl gn pha di C-1 v C-4.
(c) Khi nhm metyl gn vo C3 th to ra cu dng bn, vy n gn vo di hay trn?
( Bi gii
(a) Nhm CH3 l lin kt trc (a)
(b) C-1 km bn hn C-4, v lin kt trc km bn hn lin kt bin (e).
(c) Nhm CH3 gn vo C-3 to ra cu dng bn th phi l lin kt bin, tng ng vi v tr ny l gn vo pha di.
Bi 23. Xc nh cu trc bn trong mi cp cu dng cho di y?
( Bi gii:
Cc cu dng bn l:
Bi 24. t chy hon ton etylxiclopropan v metylxiclobutan, so snh nng lng gii phng ca mi ng phn.
( Bi gii
Etylxiclopropan v metylxiclobutan l ng phn (u c cng thc phn t C5H12). ng phn no bn gii phng nng lng thp. Etylxiclopropan c sc cng gc ln v km bn hn metylxiclobutan.
Bi 25. So snh tnh bn ca ng phn lp th 1,3,5-trimetylxiclohexan.
( Bi gii
Tt c nhm CH3 l equatorial trong cis-1,3,5-trimetylxiclohexan nn n bn hn trans-1,3,5-trimetylxiclohexan c cha mt nhm CH3 l axial.
Bi 26. Vit cu trc phn t c cu dng bn nht cho mi hp cht sau:
(a) trans-1-tert-butyl-3-metylxiclohexan
(b) cis-1-tert-butyl-3-metylxiclohexan
(c) trans-1-tert-butyl-4-metylxiclohexan
(d) cis-1-tert-butyl-4-metylxiclohexan
( Bi gii
(a) c ng phn cu dng bn nht th nhm tert-butyl l equatorial. Sau thm nhm CH3 (axial) vo C-3 ca vng xiclohexan.
( (b) Trc tin v xiclohexan dng gh vi mt nhm tert-butyl v tr equatorial. to ra cis-1-tert-butyl-3-metylxiclohexan th phi gn nhm metyl vo C-3 v tr equatorial.
( (c) trans-1-tert-butyl-4-metylxiclohexan c hai nhm tert-butyl v C-4 metyl u l equatorial.
( (d) Ln na, nhm tert-butyl v tr equatorial, tuy nhin, trong cis-1-tert-butyl-4-metylxiclohexan, C4-metyl phi v tr axial.
Bi 27. V cc ng phn v gi tn ca hirocacbon c hai vng nhng khng cha nhm th ankyl c cng thc phn t C5H8.
( Bi gii
Bi 28. Vit cc ng phn v gi tn ca hirocacbon c hai vng nhng khng cha nhm th ankyl c cng thc phn t C6H10( Bi gii
Bi 29. Hy v mt m hnh phn t cho nobonan (bixiclo[2,2,1]heptan). Vng 6 cnh dng thuyn hay gh? Hp cht monoclo nobonan c bao nhiu ng phn khc nhau?
( Bi gii nobonan
Vng 6 cnh ca nobonan dng thuyn.
monoclo nobonan c 4 ng phn:
ABCD
A v B c th c ng phn quang hc
Bi 30. Nhit t chy ca mt s xicloankan nh sau:
Xicloankan(H (kcal/mol)Xicloankan(H (kcal/mol)
Xiclopropan499,83Xiclonoan1429,50
Xiclobutan655,86Xicloecan1586,00
Xiclopentan793,52Xiclounecan1742,40
Xiclohexan944,48Xicloecan1892,40
Xicloheptan1108,20Xicltriecan2051,40
Xiclooctan1269,20Xiclotetraecan2203,60
Hy tnh nhit t chy ca nhm metylen trong mi xicloankan. Hy tnh sc cng gc trong cc xicloankan trn. Bit rng xiclohexan l tng trng cho h khng c sc cng gc (sc cng gc t do). Hy lit k cc loi sc cng gc trong cc vng c kch thc khc nhau.
(b) Hy gii thch ti sao nhng vng c kch thc trung bnh (C7-C11) c tng hp vi hiu sut thp hn so vi vng nh (C3-C6) hoc vng ln (C12-Cn)?
( Bi gii
(a) tnh nhit t chy ca mi nhm CH2 c trong cc xicloankan ta ly nhit t chy ca xicloankan chia cho s nguyn t C. Hexan c sc cng gc bng khng nn nhit t chy ca nhm CH2 khi khng c sc cng gc l 157,41 kcal/mol. T ta c th tnh c nhit t chy ca cc xicloankan tng ng khi khng c sc cng gc bng cch ly 157,41 nhn cho s nguyn t cacbon.
Kt qu th hin trong bng sau.
nNhit t chy kcal/molNhit t chy ca CH2 kcal/molNhit t chy khng c sc cng gc kcal/molSc cng gc
kcal/mol
3499.83166.61472.2427.59
4655.86163.97629.6526.21
5793.52158.7787.076.45
6944.48157.41944.480
71108.2158.311101.896.31
81269.2158.651259.319.89
91429.5158.831416.7212.78
101586158.61574.1311.87
111742.4158.41731.5510.85
121892.4157.71888.963.44
132051.4157.82046.375.03
142203.6157.42203.79-0.19
Nhn xt
Sc cng gc gim dn t xiclopropan n xiclohexan. V c s kt hp sc cng gc (sc cng Bayer) v s y tng h gia cc nhm th v tr che khut (sc cng Pitzer). Cc vng ln n ( 12 sc cng gc nh khng ng k. Cc vng trung bnh (C7-C11) c sc cng gc.
(b) Entropi nh hng n cu dng ca vng nh. Nhng vng ny c kh nng ng vng ln ngay c khi c sc cng. Nhng vng ln c th to ra vi hiu sut hp l v chng c sc cng gc b v yu t entropi c th vt qua bng s la chn iu kin phn ng ph hp. Cc vng trung bnh v mt entropi v sc cng u khng thun li nn hiu sut phn ng nh.
Bi 31. So snh bn ca hai cu dng sau, gii thch ?
( Bi gii
Cu dng B bn hn cu dng A v c 2 CH3 H 1,3-diaxial repulsions trong khi cu dng A c mt CH3-CH3 1,3-diaxial repulsion v hai CH3-H 1,3-diaxial repulsion.
Bi 32. V cc cu dng gh ca trans-1,2-dimetylxiclohexan v cis-1,2-dimetylxiclohexan. So snh bn ca cc cu dng .
( Bi gii
Bi 33. V cc cu dng gh ca trans-1,3-dimetylxiclohexan v cis-1,3-dimetylxiclohexan. So snh bn ca cc cu dng .
Bi 34. V cc cu dng gh ca trans-1,4-dimetylxiclohexan v cis-1,4-dimetylxiclohexan. So snh bn ca cc cu dng.
( Bi gii
Bi 35. (a) 2-Isopropyl-5-metylxiclohexanol c 4 ng phn cis trans, hy vit cc ng phn . (b) V cu dng ca cc ng phn . Trong s 4 ng phn ng phn no bn nht?
( Bi gii
(a) Cng thc ca 4 ng phn
(b) Biu din cc cu dng
(c) Cu dng bn nht l trans-2-Isopropyl-cis-5-metylxiclohexanol. V tt c cc nhm th u dng e.
Bi 36. Gii thch ti sau 1,2-dimetylxiclohexan c ng phn hnh hc trong khi 1,2-dimetylxiclododecan th khng ?
Di vng xiclododecan ln cc nhm nguyn t c th quay t do, v th n khng th tn ti ng phn cis-trans.
Bi 37. Vit cng thc cc ng phn lp th khng i quang(ng phn lp th i - a ) ca 2 - clo - 1,3 - imetylxiclohexan v cho bit cu trc sn phm to thnh khi cho cc ng phn tc dng vi CH3ONa.
( Bi gii
Bi 38. Su hirocacbon A, B, C, D, E, F u c cng thc phn t C4H8. Cho tng cht vo brom trong CCl4 khi khng chiu sng th thy A, B, C, D tc dng rt nhanh., E tc dng chm hn, cn F th hu nh khng phn ng. Cc sn phm thu c t B v C l nhng ng phn quang hc khng i quang(ng phn lp th i - a) ca nhau. Khi cho tc dng vi H2(Pd, t0) th A, B, C u cho cng mt sn phm G. B c nhit si cao hn C.
1. Xc nh cng thc ca 6 hirocacbon trn. Gii thch?
2. So snh nhit si ca E v F.
3. Nu c C, D, E, F. Hy nu phng php ho hc nhh bit chng.
( Bi gii.
1. Cc ng phn c th c ca C4H8:
- V F hu nh khng phn ng vi Br2/CCl4, nn F l:
- E tc dng chm vi Br2/CCl4, nn E l:
- V A, B, C c hiro ho u cho cng mt sn phm G chng t A, B, C c khung C nh nhau, nn cn li D:
V B, C tc dng vi Br2/CCl4 cho nhng ng phn quang hc khng i quang ca nhau(c t nht 2*C), nn B v C l ng phn cis - trans ca nhau.Do B c nhit si cao hn C nn B l ng phn cis (phn cc hn).
( A: CH3 - CH2 - CH = CH2
III. KT LUN
Nghin cu ti ny, chng ti thu c mt s kt qu sau:
1. Tng quan c l thuyt ca ti nghin cu.
2. Chng ti thit k v chn lc 37 bi tp v danh php v lp th ca hirocacbon vng no c li gii, trong :
Bi tp v khi nim: 9 bi
Bi tp v danh php:9 bi
Bi tp v cu hnh: 4 bi
Bi tp v cu dng: 11 bi
Bi tp tng hp:
4 bi
3. Xy dng c h thng bi tp t d n kh, t n gin n phc tp, gip cho cc em hc sinh d tip thu. ti ny l mt ti liu gip cc em hc sinh t hc, t nghin cu, l ti liu tham kho cho gio vin bi dng hc sinh gii cc cp.
Kin ngh:
Danh php v lp th ca cc hp cht khc, nh : hirocacbon khng no, hirocacbon thm v cc dn xut ca hirocacbon s tip tc nghin cu sau ny.
TI LIU THAM KHO
[1.] ng nh Bch(2001), Nhng vn ha hc hu c, NXB Khoa hc v K thut
[2.] Trnh nh Chnh (1995), C s l thuyt ha lp th, Ti liu BDTX.
[3.] Trn Quc Sn, (1977), C s l thuyt ha hu c, NXB Gio dc.
[4.] Trn Quc Sn Trn Th Tu (2003), Danh php hp cht hu c.
[5.] Thi Don Tnh (2002) Gio trnh c s l thuyt ha hc, NXB Khoa hc v K thut.
[6.] Nguyn Trng Th (2000), Olympic ha hc Vit Nam v Quc t, tp 3 Nhng bi tp chun b cho k thi Olympic quc t ln th 30, 31, 32, NXB Gio dc.
[7.] Ng Th Thun (1999), Ha hc hu c, phn bi tp, NXB Khoa hc v K Thut.
[8.] Nguyn nh Triu (2003), 2000 Cu hi v bi tp trc nghim ha hc hu c, Tp 1, NXB Khoa hc v K Thut.
[9.] Francis A. Carey (1996), Organic Chemistry, The McGraw-Hill
[10.] Robert Thormnton Morrison (1992), Organic Chemistry, Prentice Hall.
[11.] http://depts.washington.edu/chemcrs/bulkdisk/chem237B_aut06/handout_Chapter_3_CHEM237Baut06.pdf[12.] http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch03/ch3-0.html[13.] http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch03/ch3-0.html[14.] http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch03/ch3-0.html[15.] http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch03/ch3-0.html[16.] http://www.columbia.edu/itc/chemistry/chem-c3045/organic/text_chapters/ch3.html[17.] http://www.chem.uic.edu/web1/OCOL-II/WIN/ALKANE/F3.HTM[18.] http://stezlab1.unl.edu/Chem251-2005/PowerPoint/JJSChapter%203.ppt[19.] http://www.cem.msu.edu/~parrill/movies/conf.html[20.] http://www.chemistry.mcmaster.ca/courses/2oa3/lecture_two.pdf[21.] http://www.chemistry.mcmaster.ca/courses/2oa3/lecture_two.pdf[22.] http://chemistry.uca.edu/faculty/manion/2401/2401res/chap4.pdfMonoxicloankan
Polixicloankan
Cng thc cu to
Danh php
Cu hnh
Cu dng
Hirocacbon
vng no
C2
C5
_1264779194.unknown
_1264779210.unknown
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