HA HC HU C PHN HYDROCACBON.

. GV L VN PH THPT LONG KHNH CH 1 CU TRC PHN T V NG PHN CA CHT HU C ---oOo--PHN TH NHT CC DNG LIN KT THNG GP TRONG HA HU C I) LIN KT CNG HA TR: 1)S lai ha obitan : Ng.t C to ra 3 dng lai ha + Lai ha sp3 : 1 AOs v 3 AOp t hp vi nhau to ra 4 AO lai ha hng ra 4 nh ca t din u c trc cc AO to ra gc 109028. + Lai ha sp2: 1 AOs v 2 AOp t hp vi nhau to ra 3 AO lai ha hng ra 3 nh ca tam gic u c trc cc AO to ra gc 1200. + Lai hoa 1sp : 1 AOs v 1 AOp t hp vi nhau to ra 2 AO lai ha hng ra 2 u ca 1 on thng. T l % AOs trong AO lai ha cng cao th m in ca ng.t C cng ln m in Csp > Csp2 > Csp3. 2) Nng lng lin kt (NLLK): bn ca lin kt c nh gi bng nng lng lin kt. LK cng bn th NLLK cng ln v ngc li. NL cn thit phn ct ng li mt mol LK l NL phn li LK. NL phn li LK ph thuc vo bn cht hai nguyn t tham gia LK v bi LK gia chng. NLPLLK CC < C=C < C C. Ngoi ra NLPLLK cn ph thuc cu trc hai phn phn t c chung LK b phn ct. NLPLLK C-H th 2 khc vi LK th nht, th 3 khc th 2v th thng ly gi tr TB cho c phn t. Vd: CH4 C + 4H c H = 1659KJ/mol th NLPLLK trung bnh = 415KJ/mol. NLPLLK trung bnh C-H ca ankan l 410KJ/mol. Tuy nhin gi tr NLLK TB khng ng i vi 1 s hp cht thm ch 1 LK c th no c tuy vy n vn dng so snh bn LK, bn nhit ng ca cc tiu phn hoc tnh gn ng hiu ng nhit ca phn ng Vd: Cho NLLK C=C; =C-H; C-O; O-H; C-C; C=O; C-H ln lt l 614; 435; 359; 431; 351; 736; 410 (KJ/mol). Xt xem khi cng H2O vo axetylen s to ra cht no sau y: CH CH + HOH CH2=CHOH CH3-CH=O Nhit to thnh H = -2709 -2752 Vy axetandehit bn hn etenol v NL hnh thnh ca n m hn 43KJ/mol. 3) di lin kt: di LK l khong cch cn bng gia 2 hat nhn ca nhng ng.t LK vi nhau. di lin kt C-C ca Csp = 1,2A0, Csp2 = 1,34A0, Csp3 = 1,54A0. di lin kt C-H tng ng ca cc ng.t C l : 1,05A0; 1,07A0 v 1,09A0. Trong nhiu trng hp thng dng di LK trung bnh ca 1 LK nht nh nhiu hp cht khc nhau. di LK v NLLK c mi lin h cht ch. di LK cng nh th NLLK cng ln chng LK vi nhau cng bn vng. 4) Gc lin kt: Gc gia 2 LKCHT ca 1 ng.t gi l gc LK hoc l gc ha tr. Gc ha tr thc t thng sai khc vi so vi gc lai ha. Da vo gc ha tr c th suy ra trng thi lai ha. 5) S phn cc lin kt: + Lin kt sigma: Hai ng.t c m in khc nhau lin kt vi nhau th lin kt s phn cc v pha ng.t c m in ln hn ( 1 u m v 1 u dng) v c biu din bng mi tn thng. Mc phn cc c nh gi bng mo men lng cc in (n v l Debai. 1D = 0,333.10-30 C.m). cng ln th s phn cc cng mnh. = q.l (q l gi tr in tch; l l di lng cc in). + Lin kt pi: S phn cc lin kt pi v pha ng.t c m in ln hn c biu th bng mi tn cong. II) CC LIN KT YU: II. 1) LIN KT VANDEVAN (lc ht VanDeVan): L LK yu gia cc phn t cng c bn cht tnh in gy ra do lc ht gia cc lng cc v gim nhanh theo khong cch gia cc phn t. a) Lc tng tc lng cc lng cc: Trong p.t do c nhiu ng.t c m in khc nhau nn to ra cc LK phn cc lm cho p.t tr thnh lng cc (tr cc lin kt phn cc to momen lng cc trit tiu 1

nhau). Cc lng cc co xu hng sp xp sao cho cc cc tri du li gn nhau v th gi l tng tc nh hng (lc nh hng). Lc ny t l thun vi ln ca 2 lng cc v vy cc p.t phn cc mnh s tng tc vi nhau mnh lm tng nhit nng chy v nhit si. b) Lc tng tc lng cc lng cc cm ng: Di tc dng ca 1 ion hay 1 lng cc mt p.t khng phn cc s tr thnh phn cc tm thi l lng cc cm ng; lng cc ny tng tc vi lng cc c nh bi 1 lc nht nh gi l tng tc cm ng (lc cm ng). c) Lc tng tc lng cc cm ng lng cc cm ng: Cc p.t khng phn cc trong mt thi im no vn c th sinh ra mt lng cc nht thi do s chuyn ng ca cc electron gy ra. Lng cc ny tc ng n cc electron ca p.t bn cnh gy ra lng cc cm ng khc v th cc p.t vn c tng tc vi nhau. Tng tc ny gi l tng tc khuch tn (lc khuch tn). 2) HNH DNG PHN T: Phn t c cu trc v kch thc xc nh nn c hnh dng xc nh. Nhiu tnh cht l, ha...cc cht ph thuc vo hnh dng phn t. + Cht c KLPT cng ln th nhit nng chy v nhit si cng cao. + P.t c hnh dng i xng cng cao cng sp xp cht kht hn cc p.t km i xng lm tng lc ht VandeVan s tng nhit nng chy. th lng p.t c kch thc cng gn vi hnh cu s c din tch b mt nh hn dn ti s tip xc gia cc p.t nh hn, lc VandeVan b hn nn nhit si thp hn. 3) S Y VANDEVAN V HIU NG KHNG GIAN: Khi 2 p.t hoc 2 nhm ng.t trong p.t li gn nhau hn khong cch to bi lc ht VandeVan gia chng s xut hin lc y chng ra xa nhau l s y VandeVan. a) Hiu ng khng gian loi I: L hiu ng ca cc nhm th c kch thc ln lm cn tr s tip cn ca cc trung tm phn ng phn t cc cht tham gia phn ng. Ng.nhn l do lc y VandeVan. b) Hiu ng khng gian loi II: Hiu ng ca cc nhm th lm vi phm tnh ng phng ca h lin hp dn n gim kh nng lin hp ca nhm th vi cc nhm khc trong phn t. II. 2) LIN KT HIDRO: 1) Bn cht : Lin kt hidro hnh thnh khi ng.t H LKCHT vi 1 ng.t c m in mnh nn tch in dng ln ( X-H vi X l O, F, N) tng tc tnh in yu vi ng.t Y c cp electron t do ( Y l F,O hay N). in tch ca ng.t H v ng.t Y cng ln th lin kt hidro cng bn. 2) bn ca LK hidro: bn LK hidro ph thuc nhiu yu t: + LK hidro mnh nht khi 3 ng.t X-HY thng hng. + m in X v Y cng ln th LK hidro cng mnh v th LK hidro yu dn theo chiu F>O>N. Ngoi ra LKH cn chu nh hng bi phn cn li ca phn t. 3) Phn loi: LK hidro lin phn t v lin kt hidro ni phn t. LK hidro m hp phn cho v hp phn nhn 2 p.t khc nhau hoc ging nhau gi l LK hidro lin phn t. Nu hp phn cho v hp phn nhn u cng 1 p.t gi l LK hidro ni phn t. Trong trng hp ny hp phn cho v nhn phi 2 v tr sao cho H c th tip cn vi AO cha i e cha lin kt ca Y. Vd: o-dihidroxylbenzen to c LK hidro ni p.t cn ng phn m, p th khng. LKH ni p.t thng bn hn LK hidro lin p.t nn nu ng.t H to LK hidro ni p.t th chng khng tham gia LK hidro lin p.t na. 4) nh hng ca LK Hidro n tnh cht vt l: + Nhng cht c p.t khi, momen lng cc, hnh dng p.t khng khc nhau nhiu th cht no to c LK hidro lin p.t cht c nhit nng chy v nhit si cao hn. + Nhng cht to c LK hidro vi nhau th tan tt vo nhau. + Cht to LK hidro ni phn t th tnc, ts thp hn ; tan trong dung mi phn cc thp hn; tan trong dung mi khng phn cc cao hn so vi cht to LKH lin phn t c cu to tng t.

PHN TH HAI 2

NG PHN CA HP CHT HU C I) NG PHN CU TO: 1. Khi nim: L nhng cht c cng CTPT nhng khc nhau v cu to ha hc. a) ng phn mch cacbon. b) ng phn v tr nhm chc. c) ng phn nhm chc. d) ng phn h bin: Hnh thnh do s thay i v tr 1 nguyn t hidro dn ti s thay i v tr 1 ni i. Vd: CH3-CO-CH3 CH2=C(OH)-CH3. Trong chng trnh ph thng ch xt 3 loi ng phn u. 2. Cch vit ng phn cu to: a) Tnh bt bo ha: Tng s lin kt pi v vng trong phn t. (2.n + 2 + m x) a= . Vi n l s nguyn t cacbon; m l s nguyn t ha tr 3 (N); x l s nguyn t 2 ha tr 1 (H; Cl; Br; Na) V d: C3H6BrCl th a = 0; C5H8N2O2Cl2 th a = 2 ( vi N ha tr 3). b) Xc nh nhm chc (loi cht) c th c. c) Xc nh kiu mch cacbon. d) Vit ng phn v tr nhm chc cho mi loi mch cacbon. e) in nguyn t hidro vo mch cacbon cacbon ha tr 4. II) NG PHN LP TH Ha hc lp th nghin cu cu trc khng gian ca phn t trong khng gian ba chiu. 1) Hnh dng phn t: M t dng hnh hc ca phn t. 2) Cu hnh: Cho bit s phn b cc nguyn t hoc nhm nguyn t trong khng gian xung quanh mt nguyn t trung tm hay h trung tm nht nh no . S khc nhau v cu hnh dn n hin tng ng phn hnh hc v ng phn quanh hc. 3) Cu dng: L cu trc khng gian sinh ra do s quay ca mt nhm nguyn t ny i vi mt nhm nguyn t khc xung quanh lin kt n gia chng m khng lm t lin kt . Mt phn t c v vn cu dng khc nhau song c rt t cu dng bn vng. Nhng cu dng bn ca 1 cht gi l ng phn cu dng tuy rng khng tch c chng ra v chng chuyn ha ln nhau theo mt cn bng. 4) Cc loi cng thc biu din cu trc khng gian trn mt phng giy: + Cng thc phi cnh: Nguyn t C no lin kt vi 4 nguyn t hoc nhm nguyn t. Cc nguyn t hoc nhm nguyn t ny trn nh ca hnh t din m tm l nguyn t C . Da vo thc t l mt vt cng xa mt th cm thy nh i v ngc li ngi ta qui c: Nt gch thng biu din lin kt trn mt phng giy, nt gch gin on biu din lin kt hng v pha sau t giy (xa ngi quan st), nt gch m ch nhng lin kt hng v pha trc t giy (gn ngi quan st). V d: Phn t CH2ClBr
H

C
Br Cl H

+ Cng thc chiu Niumen: Nhn dc phn t theo mt lin kt no (thng l lin kt C-C c la chn c ch ) ri chiu tt c cc nguyn t ln mt giy. Nguyn t C u lin kt gn mt (C 1) c th hin bng 1 vng trn v che khut nguyn t C u bn kia (C 2). Cc LK vi C1 c nhn thy ton b chng xut pht t tm hnh trn C1. Cc LK vi nguyn t C2 ch nhn thy phn l ra t chu vi hnh trn C1. V d: Propen CH3-CH=CH2.

+ Cng thc chiu Fis: t cng thc phi cnh ca phn t sao cho nguyn t C c chn nm trong mt phng giy, 1 ng.t hoc nhm ng.t bn phi v bn tri ng.t C nm trn trang giy ; 2 ng.t (nhm ng.t) cn li nm di trang giy. Chiu CT phi cnh ln mt giy th c CT chiu Fis. Cc nhm 2 u nt ngang gn ngi quan st (a v b), 2 nhm 2 u nt gch ng xa ngi quan st (c v d), giao im ca chng l ng.t C no. c a b d Nhm ng.t c mc oxi ha cao hn c t pha trn (v tr c); nhm ln nht thng nm v tr d; cc nhm chun nh OH; NH2; Halogen v tr a hay b. Ch : T CT chiu Fis c th suy ra CT phi cnh hoc CT Niumen. CT phi cnh v CT Niumen c th xoay theo nhng gc bt k m khng chuyn thnh phn t khc. Nhng khng ty tin xoay CT Fis v c th chuyn thnh phn t khc. CT Fis ch c th quay 1800 hay 3600 mi gi nguyn cu hnh. T CT Niumen mun a v CT Fis ta chuyn CT Niumen v CT phi cnh dng che khut ri chuyn thnh CT Fis. III) CC DNG NG PHN LP TH: A. NG PHN HNH HC 1) ng phn hnh hc: L loi ng phn khng gian do c s phn b khc nhau ca cc ng.t hoc nhm ng.t hai bn mt b phn cng nhc (vng no; ni i). 2) iu kin c ng phn hnh hc: + Phn t phi c b phn cng nhc (khng cho ng.t hay nhm ng.t LK vi n xoay t do) nh vng no; ni i. + mi ng.t C ca LK i (hoc nhiu ni i lin tip) v t nht 2 ng.t C ca vng no phi c 2 ng.t hoc nhm ng.t khc nhau. V d: abC=Cab hay ab ab Trng hp c 1 ni i : + H abC=Cab. Vd Stinben C6H5-CH=CH-C6H5 + H abC=Nc . Vd : axetandioxim CH3C=NOH. + H aN=Nb c th a =b. Vd : azobenzen C6H5N=NC6H5 b) H c nhiu ni i: + H gm s l ni i lin tip xem nh 1 ni i. V d: i phenyl-i-m-nitrophenylbutatrien m- NO2C6H4(C6H5)C=C=C=C(C6H5)C6H4NO2-m c 2 dng cis v trans + H c nhiu ni i ring l th xt ln lt tng ni i: Vd : Cao su thien nhien ( cau hnh cis) CH3-CH=CH-CH=CH-CH3 c cc ng phn cis-cis; cis-trans; trans-trans. c) Trng hp c vng no : V d: 1,2- imetyl propan c p cis v trans 3) Danh php ng phn hnh hc. a) Danh php cis trans. Mch chnh ca anken cng pha vi ni i l cis, nu mch chnh khc pha gi l trans. i vi hp cht vng, hai nhm th cng pha so vi mp vng l cis khc pha l trans. b) Danh php syn- anti: (t s dng) Thng dng cho hp cht c lin kt N=N- v C=N Vd: C6H5-N=N-C6H5 c dng syn (tng t nh cis) v anti (tng t nh trans) c) Danh phap Z-E: Bao trm c 2 h danh php trn. + So snh hn cp ca cc ng.t hoc nhm ng.t ni i. - Ng.t LK trc tip vi ng.t C ni i c s hiu ng.t Z cng ln th hn cp cng cao. Vd: Cp ca cc nhm lin kt vi Csp2 l: Cl > F> O>C>H. - Nu 2 ng.t LK vi Csp2 l nh nhau th xt n ng.t tip theo ngha l ng.t Lk trc tip vi ng.t th 1. Vd: Nhm CH3 s l C(H,H,H); nhm etyl s l C(C,H,H) v nhm CH2OH s l C(O,H,H). V Z ca O > C> H nn cp ca cc nhm l: CH2OH > C2H5> CH3. - Ng.t nhm th mang ni i hay ni 3 xem nh tng ng 2 ni n hoc 3 ni n. Vd: C=O tng ng 2 ni C-O. Nhm COOH s l C(O,O,O). 4 a)

C CH se la C1(C,C,C) va C2(C,C,H) + Danh php Z E: abC=Cab. Nu hn cp a>b va a>b. Nu a va a cng pha gi l Z ( ting c Zusammen : cng). Nu chng khc pha gi la E (Engegen: i. 4) S khc nhau v tnh cht ca cc ng phn hnh hc: Hai p hnh hc c bn ging nhau v tnh cht ha hc nhng khc nhau v mt s tnh cht vt l. a) Nhit nng chy: p trans c tnh i xng cao hn d sp xp cht kht hn nn thng c nhit nng chy cao hn p cis . b) o ben nhiet ong: p trans bn hn cis, G0 nh hn. c) Momen lng cc va nhiet o soi: Ty tng cu tao c th. Thng cht c mo men lng cc ln hn th c nhit si cao hn. Cht c 2 nhm th ging nhau kiu aCH=CHa mmen lng cc ca ng phn trans =0 trong khi ng phn cis c mmen lng cc 0. Trng hp c 2 nhm th khc nhau aCH=CHb mmen lng cc lun khc khng. Nu a v b cng y hoc cng ht electron th cis > trans; nu a v b c tnh cht electron ngc nhau th cho kt qu ngc li. d) Tnh axit ca axit khng no : p cis c tnh ax mnh hn p trans. e) Phn ng tch nc ca ax 1,2 icacboxylic : Dng cis b tch nc thnh anhydritaxit (ni phn t) cn dng trans th khng. IV) S LC V NG PHN QUANG HC : 1) nh sng phn cc phng v tnh quanh hot: nh sng thng gm cc sng in t m vect dao ng ca chng hng theo tt c cc hng trong khng gian min l vung gc vi phng truyn ca tia sng. Khi cho as qua lng knh Nicon s c as m vect dao ng ca chng nm trong cng 1 mt phng gi l mp phn cc l as phn cc hay as phn cc phng. Nhng cht khi t trn ng truyn ca as phn cc phng m lm quay mp phn cc theo mt gc no gi l cht quang hot. Tnh cht l tnh quang hot. 2) Phn t c ng.t C bt i v vn quang hot : Khi trong phn t c ng.t C nh vi 4 ng.t hay nhm ng.t khc nhau Cabcd s sinh ra pt bt i xng v c tnh quang hot. Vd : CH3-CH(OH)-COOH ; Cl-CHI-SO3H; CFClBrI. Trong 1 pt c th c 1 hay nhiu ng.t C bt i. Vd: Glucozo : CH2OH-CHOH-CHOH-CHOH-CHOH-CH=O c 4 ng.t C bt i. Cc phn t bt i c tnh quang hot. 3) ng phn quang hc : + Cht i quang : Khi phn t bt i xng th bao gi cng c cp cht i xng vi nhau nh vt v nh qua gng. Hai phn t i xng qua gng khng bao gi chng kht ln nhau ngha l chng l 2 cht ring bit. Hai cht gi l hai cht i quang cn gi l p quang hc. + Tnh chat: Cc p quang hc c cu to ging nhau nhng khc nhau v cu hnh dn ti s bt i xng trong p.t. Cc p quang hc c cc tnh cht vt l v ha hc thng thng ging nhau ch khc nhau tnh cht vi nh sng phn cc. Vd: ax lactic CH3-CH(OH)-COOH c ng.t C s 2 bt i nn c 2 p quang hc. Mt p lm quay mp as phn cc sang bn phi gi l ax L-(+)-lactic; mt cht lm quay mp as phn cc sang tri gi l ax D(-) lactic. Hai p ny c gc quay mt phng as phn cc nh nhau nhng i nhau gi l hai cht i quang. Nu phn t c n ng.t C bt i th chng c th c 2 n ng phn quang hc trong c 2n/2 cp i quang (ng phn enan). Cc ng phn quang hc khng i quang gi l ng phn dia. V d: 2 brom- 3- clobutan c 2 nguyn t cacbon bt i: CH3 C*HBr- C*HCl-CH3 c 4 ng phn quang hc trong c 2 cp i quang. CH3 H H Cl Cl CH3 H Cl CH3 H H CH3 Cl H

Br Br H H Br Br A B C D Trong CH3 B; C vi D l cc p enan. A vi C hay D; CH3 C hay D l cc p dia. A vi B vi CH3 CH3 4) Danh php cu hnh : Gm h danh php D,L v danh php R,S.

a) Danh php D,L : Xt phn t glixerandehit CH2OH-CH(OH)-CHO Dng cng thc chiu fis biu din cu hnh trn mt phng giy sao cho: + Ng.t C bt i nm trn mp giy. + Cnh nm ngang pha ngi quan st, cc nhm a,b nm trn cnh ny pha trn mp giy. + Cnh thng ng c cc nhm th c,d nm sau mp giy. Ch nhm ln nht nm v tr d(CH 2OH), nhm nh hn hoc c bc oxh cao nht chim v tr c (CHO), cc nhm chun (OH,NH2,Halogen X ) v tr a hay b. Cht c nhm chun nm bn phi gi l cu hnh D, nhm chun nm bn tri l cu hnh L. Vd : CHO CHO H OH DGlixerandehit (R) L-Glixerandehit (S) HO H CH2OH CH2OH Nhng cht c cu hnh nh trn gi l cu hnh tng i v phi so snh vi cu hnh glixerandehit. b) Danh php R,S: Bn nhm ng.t C* c sp xp theo trnh t hn cp a>b>c>d. Nhn theo hng C* - d nu th t a>b>c i theo chiu kim ng h ta ni pt c cu hnh R (phi), tri li trnh t ngc chiu kim ng h pt c cu hnh S (tri). Ch : Nu nhn vo ct chiu Fiso m d cnh ngang th p R trnh t a>b>c li tri chiu kim ng h cn p S li c th t a>b>c thun chiu kim ng h. Cu hnh xc nh theo qui tc trn gi l cu hnh tuyt i v khng phi so snh vi cht no khc. 5) Bin th Raxemic: L tp hp 2 cht i quang c s mol bng nhau nn chng b tr nhau v nng sut quay cc. Bin th raxemic khng c tnh quang hot. 6) ng phn meso: Khi phn t c 2 trung tm bt i hon ton i xng vi nhau th khng c ng phn i quang v c gi l ng phn meso. Vd: Ax tactric HOOC-CHOH-CHOH-COOH c 2 p i quang l S,S v R,R v 1 p meso R,S. BI TP MINH HA 1) Vit cc ng phn cu to ca cc cht sau: a. C5H10 (cha mt vng). b. C5H11OH. c. C6H14. d. C4H9Cl. 2) Vit CTCT khng gian cc ng phn cis-trans ca axit sobic: CH3-CH=CH-CH=CH-COOH. 3) HSGQG-94: Nhng cht no trong cc cht sau c ng phn cis-trans: 2-brom-3-clobut2-en; 1-brom- 1-clo-2-metylprop-1-en; 3-in-pent-1-en. Vit CTCT khng gian cc ng phn . 4) Ch r p no (A hay B) l Z, p no l E: a) FCH=CHF c A = 0,0D v B = 2,4D. b) C6H5CH=CHCOOH c tnc (A) = 680C, tnc (B) = 1340C. 5) HSGQG-98: Vit CTCT cc ng phn cu to v p hnh hc ca :C3H5Cl v ClCH=C=CHCl. 6) Vit CTCT ca ax trans-butenioic ( axfumaric); cis-1,4-imetylbutatrien; Z-4-etyl-3metylhept- 3-en. 7) Mt xeton trong tinh du bc h c tn l Menton v Adrenalin l mt hocmon ca tuyn thng thn. Chng c CTCT nh sau:
H3C H

H HO C

OH CH2NHCH3

O H CH(CH3)2

HO

8)

Xc nh cu hnh mi cht l R hay S? Xc nh cu hnh tuyt i ca cc ng phn c cu to sau

Cht no sau y c ng phn h.nh hc, gi tn cc ng phn theo danh php Z, E. a. (CH3)2CHCH=CH2 b. CH3CH=CHCH3 c. CH3CH=CHF d. C2H5C(CH3)=CHCH3 e. CH3CH=C=CHCH3 f. Cao su thin nhin g. CH3CH=C=C=C=CHCH3 h. 1,2dimethylcyclopropan. 10) Nhng cht sau y c th tn ti bao nhiu ng phn lp th. a. 1phenylethanol. b. 2clo but2en. c. 1,2dibromopentan. 11) C bao nhiu p lp th trong mi trng hp sau, vit CTCT ca chng km theo cc k hiu E,Z,R,S vo nhng ch thch hp : a) 1-brom-1-clo-2-metylbut-1-en. b) 3-metylpenta-1,4-ien. c) 4-metylhepta-2,5-ien. d) 2,5-dibromhex-3-en 12) Hp cht no c ng phn quang hc i quang : Cis-1,2-imetylxyclohexan; Trans-1,2-imetylxyclohexan. Gii thch . 13) Vit cng thc tt c cc ng phn hnh hc ca hp cht C 3H4BrCl v dng danh php Z;E gi tn. 14) Vit CTCT cc ng phn cis-trans ca ax linoleic (octadeca-9,12-dienoic); octa-2,4,6trien. Hng dn 1) a) vng no c 5 p. b) ancol c 8 p. c) ankan c 5 p d) c 4 p. 2) cis-cis; cis-trans; trans-cis; trans-trans. 3) 2-brom-3-clobut-2-en c 2 p hnh hc; 1-brom- 1-clo-2-metylprop-1-en c 2 p hnh hc; 3-in-pent-1-en khng c p hnh hc. 4) a) Cht A l p E; B l p Z b) Cht A l p Z; B l p E. 5) C3H5Cl c a= 1 nn c mch C=C c 2 p hnh hc; vng no khng c p hnh hc. ClCH=C=CHCl khng c p hnh hc. 7) hn cp nh sau: C lin kt nhm C=O > C lin kt nhm CH2 > nhm CH3 > H nhn theo trc C H s thy cht ny s c cu hnh R. hn cp LK vi C bt i l: OH> CH2NHCH3> C=C>H. Nhn theo trc C-H ta c cu hnh pt Adrenalin l R. 8) Ba cht c tn gi ln lt l : 2(S),3(S)-2,3-iclobutan axit 2(R),3(S)-2,3-ihydroxyl-2,3-imetyl-butan-4-al-oic 2(R),3(S)-2-brom-3-clo butan 10) a. (A) c 1 C* nn c 21 = 2 ng phn quang hc, (A) khng c ng phn hnh hc. Vy (A) c 2 ng phn lp th. b. (B) c 2 ng phn lp th l 2 ng phn hnh hc. c. (C) c 2 ng phn lp th l 2 ng phn quang hc. 11)a) ClBrC=C(CH3)-CH2-CH3 c 2 p Z;E. b) CH2=CH-CH(CH3)-CH=CH2 c 2 p R,S. c) CH3-CH=CH-CH(CH3)- CH=CH-CH3 c 1 C* nn c 2 p quang hc R,S v 2 ni i u c p hnh hc l Z,Z; Z,E; E,Z; E,E. d) CH3CHBr-CH=CH-CHBr-CH3 c 2 p hnh hc Z,E v 2 ng.t C* nhng c s i xng ring trong phn t nn c 3 p quang hc gm 1 cp i quang v mt p meso. 12) p Cis c mp i xng nn khng c p i quang; p trans c 2 p i quang. 13) a= 1 nn c 1 ni C=C hay 1 vng. Trng hp vng c 1 cht to p hnh hc Z,E. Trng hp ni C=C c 5 cht to c p hnh hc. 14) ax linoleic (octadeca-9,12-dienoic) c 4 p ; octa-2,4,6-trien c 7p. 7

9)

CH 2 QUAN H GIA CU TRC PHN T VI TNH CHT VT L CA CHT HU C ----oOo--S CHUYN DCH MT ELECTRON PHN T CHT HU C I) HIU NG CM NG : 1) Bn cht v c im: S dch chuyn mt electron dc theo mch lin kt trong phn t gy ra bi s chnh lch v m in gi l hiu ng cm ng. K hiu bng ch I v c bng mi tn thng hng v pha ng.t c m in ln hn. 2) Phn loi: + LK C-H khng phn cc, nu thay H bng Cl th Cl s gy hiu ng cm ng bng cch ko e lectron lin kt v pha n gi l hiu ng cm ng m, k hiu I. Nu nhm y e gi l hiu ng cm ng dng +I nh nhm ankyl CH3 + Hiu ng I tng nu m in ca ng.t cng ln. Vd : Br< Cl < F ; NH2 < OH < F ; CH=CH < C6H5 < C C. + Hiu ng +I ca nhm ankyl tng theo bc ca nhm ankyl. CH3 < C2H5 < CH(CH3)2 < C(CH3)3. + Hiu ng cm ng gim nhanh khi mch C tng dn. Vd : Tnh ax CH3CH2CH2COOH < CH2ClCH2CH2COOH< CH3CH ClCH2COOH < CH3CH2CH ClCOOH. II) HIU NG LIN HP : 1) Bn cht v phn loi: + Lin hp - xy ra khi 2 lin kt pi cch nhau bng 1 lin kt n trong cc electron LK bi ny xen ph vi cc electron LK bi khc v c biu din bng mi tn cong. + Lin hp p - : Ng.t c cp electron p cha lin kt ni vi ng.t mang lin kt pi to ra s lin hp p - c biu din bng mi tn cong theo hng t cp e lectron p n lin kt pi. 2) Hiu ng lin hp: Khi cc nhm ng.t lin hp vi nhau th mt electron hoc p ca chng b thay i, b chuyn dch. l hiu ng lin hp, k hiu bng ch C. Nhm ht electron hoc p v pha mnh l hiu ng lin hp m (-C). Nhm lin hp m l cc nhm c LK bi vi ng.t c m in ln nh nhm NO2; C=O; Nhm ng.t khi tham gia lin hp m y electron ti nhm khc gi l hiu ng lin hp dng (+C). Nhm +C thng l nhm c 1 hoc 1 cp electron p cha chia (t do) d ng.t mang chng c m in ln th chng cng dch chuyn n ch c electron hoc obitan trng nh ng.t Cl; O; F c cp electron t do. Mt nhm th hin +C hay C cn ph thuc tng quan vi nhm lin hp vi n. Vd: Trong C6H5NH2 th gc phenyl c hiu ng C nhng trong C6H5NO2 th li c hiu ng +C. Cc ng.t tham gia vo h lin hp phi ng phng m bo cho trc cc obitan p tham gia lin hp song song vi nhau c im ca hiu ng lin hp : Hiu ng lin hp t bin i khi mch C ko di. V d:

III) HIU NG SIU LIN HP: Xy ra khi c lin kt C-H v tr i vi ng.t C khng no k hiu l H biu din bng mi tn cong, s lin hp ny lm dch chuyn electron vo h lin hp. S lin kt C-H cng nhiu th hiu ng siu lin hp cng mnh. Ngc vi LK C-H cc LK C-F v tr lin hp gy hiu ng siu lin hp m. 8

QUAN H GIA CU TRC PHN T V MT S TNH CHT VT L I) NHIT NNG CHY V NHIT SI. - KLPT cng ln Lc ht VandeVan cng ln nhit si cng cao. - phn nhnh cng cao , nhit si cht cng gim v gim s tip xc gia cc phn t Vd : isobutan c nhit si thp hn n-butan. - Anken v ankin c lin kt kp u mch c nhit si thp hn ankan tng ng v thp hn ng phn c lin kt kp pha trong mch . - Nu gia cc phn t khng c lin kt hidro th phn t no phn cc mnh hn (mo men lng cc ln hn) s c nhit si cao hn. Vd : nhit si C6H14 < C4H9Cl < C4H9CH=O < C3H7NO2. - S c mt ca lin kt hidro lin phn t lm tng mnh nhit si, LK hidro cng bn th nhit si cng cao. - Phn t c lin kt hidro ni phn t th nhit si thp hn ng phn khng c lin kt hidro ni phn t. - ng phn cis c nhit si cao hn ng phn trans nhng c nhit nng chy thp hn. - Dn xut halogen ca anken si v nng chy thp hn dn xut ca ankan tng ng. II) TNH TAN TRONG DUNG MI: - Nhng cht c cu to tng t nhau d tan vo nhau hn, nhng cht phn cc km d tan trong dung mi km phn cc : benzen , CCl4 Cht phn cc mnh d tan trong dung mi phn cc nh nc , axit - Phn ln nhng cht d nng chy v d si th cng d tan trong nhiu dung mi. - Hidrocacbon tan trong cc dung mi khng phn cc hoc phn cc yu nh ancol,chng khng tan trong nc. - Dn xut ca hidrocacbon khng c kh nng to lin kt hidro vi nc th tan km trong nc. - Dn xut ca hidrocacbon c kh nng to lin kt hidro vi nc th c th tan t nhiu trong nc. Gc hidrocacbon cng nh th cng d tan. - Nhng dn xut c nhiu nhm th nu to Lk hidro ni phn t th gim kh nng tan vo nc v tng kh nng tan trong dung mi km phn cc. BI TP MINH HA: 1) Xc nh hiu ng ca cc nhm th sau khi lin kt vi gc phenyl: Cl, C(CH3)3, -CHO, NO2, CN, CH2CH3, N+(CH3)3. 2) So snh bn ca cc ion sau: a. (1) CH2CH3, (2) CH(CH3)2, (3) C(CH3)3. b. (1) CH2CH3, (2) CH2OCH3, (3) CH2NHCH3. c. (1) C(CH3)3, (2) CH2C6H5, (3) CH(C6H5)2. 3) Gii thch ti sao nhng v tr o- hay p- ca hp cht C6H5CH2Cl tng i giu electron trong khi ti cc v tr o- hay p- ca C6H5CCl3 li thiu electron. 4) So snh di lin kt CCl trong CH3CH2Cl v CH2=CHCl. Gii thch. 5) HSGQG 98. Hy gi tn v sp xp cc hp cht sau theo th t tng dn nhit si. Gii thch. (CH3)4C(1) ; CH3(CH2)4CH3(2) ; (CH3)2CHCH(CH3)2(3); CH3(CH2)3CH2OH(4) ; (CH3)2COHCH2CH3(5). 6) in cc gi tr nhit si sau: 2400C; 2370C; 2850C cho 3 p ca benzendiol v gii thch. 7) Sp xp nhit nng chy cc cht trong mi dy sau. Gii thch? a) benzene, etylbenzen, toluene. b) m-xilen v p-xilen. c) trans-stiben v cis-sitiben ( 1,2-diphenyleten). 8) So snh kh nng tan trong nc ca cc cht sau a. (1) HO(CH2)4OH, (2) HO(CH2)3CHO, (3) C3H7CHO. b. (1) C6H5NH3Cl, (2) C6H5NH2, (3) C2H5NH2. 9) So snh nhit nng chy v momen lng cc ca 2 acid sau:

10)

(1) acid iso-Crotonic (2) acid Crotonic HSGQG 2005: Sp xp c gii thch theo th t tng dn nhit nng chy cc cht: 9

COOH S

COOH

COOH N

A B C HSGN-03.Cho cac cht sau : CCl4, NH4Cl, NH3 , SO2, CO2. Hy cho bit : a. Cht no tan tt trong nc? Cht no tan km trong nc. b. Cht no tan tt trong benzen? Cht no tan km trong benzen. Sp xp theo th t tng dn tnh tan ca cc cht. Gii thch? 12) HSGQG. Cho cc hp cht sau : etanol, C10H21OH ; glixerol ; phenol ; ancol benzylic ; anilin ; axit axetic ; glucoz ; etan v hexan. a. Cho bit nhng cht tan tt , tan km trong nc. b.Vit CT cc dng LK hidro gia cc phn t phenol v etanol. Dng LK no bn nht v km bn nht? 13) HSGQG 2000: C 5 l ng ring bit cc cht: cumen(A), ancol benzylic(B), metylphenylete(C), benzandehit(D) v ax benzoic(E). Bit A,B,C,D l cc cht lng. Hy sp xp chng theo th t tng dn nhit si. Gii thch. Hng dn 1) Khi lin kt vi gc phenyl th: CHO, NO2, CN gy hiu ng I, C; Cl gy hiu ng I, +C N+(CH3)3 gy hiu ng I ; C(CH3)3 gy hiu ng +I; CH2CH3 gy hiu ng +I,+H 2) So snh bn: a. (3) > (2) > (1). b. (3) > (2) > (1). c. (3) > (2) > (1). 3) Do nh hng ca hiu ng siu lin hp +H ca nhm CH2Cl v H ca nhm CCl3 i vi gc phenyl. 4) di lin kt CCl trong CH2=CHCl ngn hn trong CH3CH2Cl v: 11) - CH3CH2Cl c hiu ng I. Ngoi hiu ng I cn c thm hiu ng +C lm gim di lin kt CCl (lm di lin kt CCl ngn hn lin kt CCl bnh thng ng thi lm lin kt C=C di hn di lin kt C=C bnh thng). 5) Ancol c nhit si cao hn hidrocacbon v c LK hidro lin phn t. Pt (4) mch cacbon khng nhnh nn kch thc pt nh hn (5) vy nhit si (4)>(5). (2) v (3) l ng phn nhng (2) c mch cacbon khng nhnh nn nhit si (2) >(3). (1) c nhit si thp nht v KLPT b v mch cacbon phn nhnh. 6)

(1) 240oC (2) 273oC (3) 285oC (1) c lin kt hydro ni phn t nn nhit si l b nht. (2), (3) u c lin kt hydro lin phn t nhng lin kt hydro ca (3) bn hn ca (2) do t b cn tr v mt khng gian. 7) Gii thch: a) Nhit nng chy tng khi KLPT tng. b) p-xilen c nhit nng chy cao hn so kch thc phn t nh hn nn sp xp cht kht hn so vi m-xilen. c) ng phn trans c nhit nng chy cao hn (gii thch tng t cu b). 8) a. (1) > (2) > (3). b. (1) > (3) > (2). 9) So snh - Nhit nng chy ca (2) > (1) . - momen lng cc ca (2) > (1). 10) Nhit nng chy C < A < B. Do MC < MA cn B c thm LK hidro lin phn t gia ng.t N ca p.t ny vi H trong nhm COOH ca pt khc. 11) Nc l dung mi phn cc, benzen l dung mi khng phn cc. Nhng cht phn cc cng mnh cng d tan trong nc v kh tan trong benzen, ngc li nhng cht phn cc km li d tan trong benzen v kh tan trong nc. phn cc ca cc phn t gim nh sau: 10

NH4Cl(hp cht ion) > NH3(p.t hnh thp nh N tch in m y l 3 ng.t H tch in dng) >SO 2 (p.t dng gp khc O=S=O; S tch in dng, 2 ng.t O tch in m )> CO 2 (cu trc thng hng O=C=O, khng phn cc) > CCl4 (LKCHT khng cc). Khi vo nc p.t CO2 s c lc tng tc cm ng vi lng cc nc mnh hn lc cm ng gia nc v v CCl 4 do lin kt C=O l lin kt phn cc. Vy: a) Tnh tan trong nc tng theo th t: CCl4 < CO2 < SO2 < NH3 < NH4Cl b) Tnh tan trong benzen tng dn: CCl4 > CO2 > SO2 > NH3 > NH4Cl 12) a) Cht c nhiu nhm OH s to nhiu lin kt hidro vi nc, gc hidrocacbon cng nh th cng d tan vo nc v vy cht tan tt trong nc l: etanol; glixerol; axit axetic; glucozo. Cht tan km trong nc l cc cht C 10H21OH, phenol, ancol benzylic, anilin mc d c to LK hidro vi nc nhng phn t c gc hidrocacbon ln v th kh tan vo nc. Etan, hexan khng tan trong nc. b) C 4 dng LK hidro gia etanol v phenol gm: C2H5-OHOH-C2H5(1); C6H5-OHOHC6H5 (2); C2H5-OHOH-C6H5(3)v C6H5-OHOH-C2H5(4). Do hiu ng C ca gc phenyl trong phenol v hiu ng +I ca gc etyl trong ancol m ng.t H trong nhm OH ca phenol tch in dng ln hn ng.t H trong OH ca ancol, ng.t O ca ancol tch in m ln hn ng.t O ca phenol nn dng lin kt (4) l bn nht. Dng km bn nht s l dng (3). 13) Ancol B v Ax E u c Lk hidro lin phn t nhng E va c LK Hidro lin phn t bn va c KLPT ln nn nhit si cao hn B. Pt D phn cc hn so vi C nn nhit si D cao hn C. A c nhit si thp nht v kch thc pt ln v km phn cc nht.

CH 03 PHN NG HU C Phn ng hu c l s bin i cc LK trong p.t lm ph v LK c hnh thnh LK mi di tc dng ca cc iu kin v tc nhn phn ng dn n s to thnh p.t mi. I) PHN NG PHN CC (PHN NG D LI) 1) Cacbocation v Cacbanion: + Trong nhng iu kin nht nh nhng LK phn cc trong p.t c th b phn ct khng ng u: ng.t c m in ln chim lun c cp electron chung tr thnh tiu phn tch in m ng.t (nhm ng.t) cn li mang in tch dng. l s phn ct d li p c gi l p d li (phn ng phn cc). Vd: (CH3)3C-Br (CH3)3C+ + Br- (1) (C2H5OOC)2CH-H + NaOC2H5 (C2H5OOC)2CH- Na+ + C2H5OH (2) (CH3)2C=CH2 + H+ (CH3)2C+-CH3 (CH3)2C-Cl (3) Cation (CH3)3C+ mang in tch 1(+) gi l cacbocation k hiu R+. Anion (C2H5OOC)2CH- mang in tch 1(-) gi l cacbanion , k hiu R-. Chng l nhng tiu phn rt khng bn ch sinh ra tc thi ri b bin i ngay thnh cc hp cht bn hn nn gi l tiu phn trung gian. bn ca tiu phn trung gian ph thuc cu trc ca chng: hiu ng electron no lm gii ta (gim bt) in tch ca ng.t Cacbon s lm cho ion bn hn. Vd: C6 H 5CH 2 > CH 2 = CH CH2 > CH3 CH2 CH2 > (C2 H5 OOC )2 CH > C2 H5 OOCCH2 C6 H 5CH 2 > CH 2 = CH CH2 > CH3 CH2 CH2 ;(C2 H5 OOC )2 CH > C2 H5 OOCCH2 Tiu phn trung gian c thi gian sng cng ngn cng t c xc sut chuyn ha theo hng to sn phm mong i ngc li nu cng bn cng c xc sut ln chuyn thnh sn phm. V vy p hu c u tin xy ra theo hng to tiu phn trung gian bn hn. Vd: CH2=CH-CH3 + HCl sn phm chnh l CH3-CHCl-CH3. 2) Tc nhn electronphin v tc nhn nucleophin: + Cht hu c tc dng cht v c th cht hu c gi l cht phn ng cn cht v c gi l tc nhn p. Nu 2 cht hu c tc dng vi nhau th cht hu c n gin hn gi l tc nhn p. Vd: Propen tc dng HCl th propen l cht p. giai on 1 tc nhn p l ion H + cn giai on 2 tc nhn p l ion Cl-; cht p l cacbocation CH3CH+CH3. + Cc ion dng nh cacbocation v cc p.t nh SO 3 (S mang in tch dng ln) hoc cc p.t c ng.t thiu ht electron so vi qui tc bt t nh BF3 c khuynh hng nhn electron ngha l chng c i lc vi electron. Cc cation v nhng p.t nh trn gi l cht electronphin (a electron). Khi cht electronphin ng vai tr tc nhn p th n gi l tc nhn electronphin. Cht electronphin, tc nhn electronphin k hiu l E+. 11

+ Cc anion nh cacbanionv nhng p.t c cc electron nh anken, arenhoc c cp e t do nh NH3, H2O, aminc i lc cao vi in tch dng nn gi l cc cht nucleophin (a ht nhn). Khi cht nucleophin ng vai tr tc nhn p th n c gi l tc nhn nucleophin. Cht nucleophin, tc nhn nucleophin k hiu l Nu-. II) PHN NG KHNG PHN CC (PHN NG NG LI): 1) Phn ng vi s tham gia ca gc t do: S phn ct ng u cp electron LK gia 2 ng.t trong p.t gi l s phn ct ng li s sinh ra cc gc t do. K hiu R. Vd: Cl2 2Cl. (gc clo) ; CH3 H + Cl. CH3. (gc metyl) + HCl Gc t do l tiu phn trung gian bn hn nu electron c thn c gii ta nh hiu ng lin hp hoc siu lin hp. bn mt s gc nh sau: (C6H5)3C. > (C6H5)2CH. > C6H5CH2. > (CH3)3C. > (CH3)2CH. > CH3CH2. > CH3. > CH2=CH. I. > Br. > Cl. > F. 2) Phn ng ng li khng hnh thnh gc t do: Mt s p khng c s tham gia ca gc t do nhng c s phn ct ng li nh p hidro ha anken xc tc Pt; p ng vng inx-An III) PHN LOI PHN NG HU C THEO S BIN I PHN T CHT PHN NG: Da vo s bin i phn t hp cht hu c trc v sau phn ng c th chia thnh cc loi sau: 1) Phn ng th. K hiu bng ch S (vit tt ca Substitution); Nu tc nhn tn cng l gc t do gi l c ch p th gc t do k hiu l SR ; Tc nhn tn cng thuc loi electrophin gi l c ch th electrophin SE ; tc nhn tn cng l cht nucleophin gi l p th nucleophin SN. 2) Phn ng cng. K hiu bng ch A (vit tt ca Addition). Ty theo bn cht ca tc nhn tn cng g quyt nh tc p chia ra p cng gc AR; cng electronphin AE; cng nucleophin AN. 3) Phn ng tch. K hiu bng ch E (vit tt ca Elimination). 4) Phn ng phn hy. P xy ra lm mch p.t b ph hy n mc khng th nhn ra l s th hay s tch. V d: p nhit phn metan; p t chy cht hu c 5) Phn ng ng phn ha: Thay i v tr ni i; thay i v tr khng gian; chuyn v. IV) PHN NG OXIHOA- KH TRONG HA HU C: Qui tc xc nh s oxi ha; cht kh - cht oxi ha; s kh - s oxi ha v phng php cn bng phn ng tng t nh phn ng gia cc cht v c. V) C CH PHN NG: Con ng chi tit m h cc cht u i qua to sp p gi l c ch phn ng. C ch p cho bit cc giai on c bn ca p , cch thc phn ct LK c v hnh thnh LK mi, qu trnh thay i cu trc cc cht u dn ti sp. 1) Phn ng 1 giai on: Xt p th CH3-CH2-Br bng NaI: CH3CH2-Br + NaI (trong axeton-nc) CH3CH2I + NaBr (1) Biu thc tc p l: v = k[C2H5Br].[I-] Bc ca p l bc hai suy ra giai on quyt nh vn tc p hai cht u p phi tng tc trc tip vi nhau. S p.t tng tc trc tip l 2 nn phn t s ca p l hai ngha l p lng p.t. Khi obitan giu e ca I- tip xc c vi obitan ngho e ca ng.t C lin kt vi brom s xy ra tng tc xen ph thng lc y VandeVan. I- + CH2(CH3)-Br to ra trng thi chuyn tip I -...CH2(CH3)...Br - dn n s to ra sp (1). C ch th trn gi l c ch th nucleophin lng p.t vit tt l SN2 (ch S l vit tt ca p th, ch N ch tc nhn tn cng giai on quyt nh l nucleophin, s 2 ch p.t s ca p). 2) Phn ng nhiu giai on: Xt p thy phn tert-butylbromua bng ddNaOH: (CH3)3C-Br + NaOH (trong nc) (CH3)3C-OH + NaBr (2) Tc p ch ph thuc vo nng tert-butylbromua: v= k[(CH3)3CBr] nn bc ca p l mt. S d p l bc mt v p ny i qua 2 giai on: (CH3)3C-Br (CH3)3C+ + Br- (3); (CH3)3C+ + OH- (CH3)3C-OH (4) P (3) l n p.t; p (4) l lng p.t nhng p (3) xy ra chm hn nn quyt nh tc p ny v th p ny l bc mt. P ny l p th nucleophin n p.t vit tt l SN1. P (2) qua 2 giai on, mi g u tri qua 1 trng thi chuyn tip. Nh vy p nhiu g th g chm nht quyt nh tc p. 12

VI) CHIU V HNG CA PHN NG HU C: 1) Chiu din bin ca p hu c: Tiu chun xt chiu din bin ca 1 p hh nhit v p sut cho l bin thin nng lng t do G (nng lng Gip): G = H -TS. H l entanpi ca p; S l bin thin entropi; T l nhit tuyt i. H th hin ch yu xu hng tng tc gia cc nguyn t cc p.t hng ti sp mi c nng lng (th nng) thp hn. H gi l hiu ng nhit ca phn ng. Cch tnh H : + Ly tng entanpi hnh thnh cc cht sp tr tng entanpi hnh thnh cc cht u. + Hoc ly tng i s nng lng cn ph hy ng li tt c cc lin kt (nng lng ng.t ha) ca cc cht u v nng lng hnh thnh tt c cc LK cc sn phm. Ch l nng lng phn li lin kt ghi du cng (thu nhit); nng lng to thnh lin kt ly du tr (ta nhit). Nu H <0 l p ta nhit, H > 0 l p thu nhit. i lng S (bin thin entropi) th hin mt qui lut ca t nhin l mi vt lun c xu hng tin ti phn b hn lon. Entropi(S) l thc o mc hn lon ca h. Khi chuyn t h trt t sang h km trt t (hn lon) hn th S >0. Nh vy p lm tng th tch nh p tch, hy... th S > 0 cn p cng, kt hp th S < 0. Trong cng 1 cht Srn < Slng < Skh. Cch tnh S : Ly tng S ca cc sp tr i tng S ca cc cht u. 250C gi tr H v S ca mi cht gi l gi tr chun. H0 ; S0. Chiu p ph thuc du ca G. Nu G < 0 th p t xy ra n cng m khng cn cung cp nng lng cho n. Nu G > 0 th p xy ra theo chiu ngc li, G = 0 th p trng thi cn bng. nhit thp gi tr T nh nn i lng TS t c ngha chiu p c quyt nh bi du v gi tr ca H. Vd: nhit thng nhng p ta nhit th xy ra t pht cn p thu nhit th khng xy ra. nhit cao gi tr (-TS) c ngha. Khi S > 0 th - TS cng m nn G cng nh, kh nng xy ra p cng ln. Nu S<0 th cho kt qu ngc li, kh nng xy ra cng gim khi nhit tng. nhit rt cao th du v gi tr ca G c quyt nh bi i lng -TS v th d p thu nhit H >0 nhng nu S >0 v nhit cao th G <0 v p xy ra c. Vd: CH4 + H2O CO + 3H2 c xy ra khng? nhit 25 0C p khng th xy ra v H0= 207KJ v gi tr chun G0 tnh c l 143,4KJ. Nh th ch c th xy ra p ngc li. V S ca p trn >0 nn cho G <0 th cn nng nhit ln 9690K. Cho nn trong cng nghip p trn c thc hin 12000C iu ch hn hp CO; H2. 2) Hng ca phn ng: c im ca p hu c l trong cng iu kin thng to ra nhiu sp hu c ng phn ngha l p xy ra theo nhiu hng khc nhau. Vy hng no l u tin? Sp no l chnh? bit iu ny phi bit c ch phn ng v s bin i nng lng trong qu trnh p. Vd: Khi cng brom vo buta-1,3-dien nhit -80 0C th sp chnh l CH2Br-CHBr-CH=CH2 (cng 1,2) nhng 400C th sp chnh li l CH2Br-CH=CH-CH2 (cng 1,4). C ch: + Giai on 1 (quyt nh tc p): ion Br tn cng to 2 cation trung gian: CH2Br-CH(+)-CH=CH2 (1) v CH2Br-CH=CH2-CH2(+) (2). Giai on 2: To ra 2 sp nu trn. Do nng lng hot ha trng thi chuyn tip (1) < nng lng hot ha ca trng thi chuyn tip (2) nn nhit thp sp chnh l cng 1,2 do hng ny c tc p ln hn. Vy hng no c nng lng hot ha thp hn s l hng u tin hn, ngi ta gi l s khng ch ng hc. Nhng nhit cao sp chnh l cng 1,4 do sp sinh ra bn hn kh b tch ion Br- hn ( gio vin v gin nng lng gii thch). Lc ny hng ca p khng chu s chi phi ca tc p m c quyt nh bi bn nhit ng ca sp phn ng. Ngi ta ni p b khng ch nhit ng hc. Vy hng ca p c th chu s khng ch ng hc hoc s khng ch nhit ng hc y l c s gii thch hng ca p. BI TP MINH HA 1) So snh kh nng phn ng ca cc cp cht sau vi dd NaOH: 13

a. Theo SN1: CH3CH2CH2Cl (1) ; CH2=CH2CH2Cl (2). b. Theo SN2: CH2=CHCl (1) ; CH3CH2Cl (2). c. Theo SN1: p-NO2C6H4CH2Cl(1) ; p-CH3OC6H4CH2Cl(2) ;CH3CH2CH2Cl(3). 2) So snh v gii thch bn tng i ca cc ion v gc t do sau: a. CH2=CH-CH2+ (1) v CH3CH2CH2+ (2) b. CH2=CH-CH2. (1) v CH3CH2CH2. (2) c. CH2=CH-CH2- (1) v CH3CH2CH2-(2) 3) Cho bit sn phm to thnh trong cc phn ng sau, ghi k hiu ca loi phn ng a. CH3CH=CH2 + Cl2 (1:1) nhit b. CH2=CH2 + Br2 trong CCl4 c. H2C=CHCH=CH2 + Br2 trong CCl4 d. C6H5CH3 + Cl2 (1:1; Fe) 4) Hon thnh chui p sau v ghi k hiu ca loi phn ng: Propan isopropylbromua propen propan Ancol isopropilic propen 5) Cho bit cc phn ng sau xy ra thuc loi phn ng g: Th; cng; tch; hy? Ghi sn phm. a. CH3MgCl + C2H5COCH3 b. CH3CH2Cl + KCN c. CH3CH2Cl + H2O OH- d. 2C2H5OH xt Hng dn 1) a. (2) > (1) do cation trung gian (2) c hiu ng +C nn bn hn (1) b. (2) > (1) do Cl (1) c hiu ng I v hiu ng +C ca cp e t do trn ng.t Cl lm gim in tch dng ng.t C lin kt clo (1) so vi (2) ch c hiu ng -I. c. (2) > (3) > (1) do nhm CH3O v vng benzen c hiu ng lin hp +C ln ion p-CH 3OC6H4CH2+ nn cation trung gian sinh ra t (2) bn hn (1) ch c hiu ng +I ca gc C 2H5. Nhm NO2 gy hiu ng C lm gim bn cation trung gian p-O2NC6H4CH2+ sinh ra (1). 2) a. (1) bn hn (2) do hiu ng lin hp ca ni C=C mnh hn hiu ng cm ng ca gc C2H5. b. tng t cu a. c. (1) bn hn nh s lin hp p- 3) a. CH3CH=CH2 + Cl2 Cl CH2 CH = CH2 + HCl (phn ng th SR). b. CH2=CH2 + Br2 BrCH2CH2Br (phn ng cng AE) c. H2C=CHCH=CH2+Br2 (1) BrCH2CH(Br)CH=CH2 ; (2) BrCH2CH=CHCH2Br (phn ng cng AE) d. C6H5CH3 + Cl2 (o v p) CH3C6H4Cl + HCl (phn ng th SE). 5) a. CH3MgCl + C2H5COCH3 (CH3)2C(C2H5)OMgCl (phn ng cng AN) b. CH3CH2Cl + KCN CH3CH2CN + KCl (phn ng th SN2). c. CH3CH2Cl + H2O CH3CH2OH + HCl (phn ng th SN2) d. 2C2H5OH C2H5OC2H5 + H2O (phn ng th SN2) CH 4 PHN NG CA HYDROCACBON Cc phn ng ca Hidrocacbon thng gp l phn ng th, phn ng cng, phn ng tch, phn ng phn hy, phn ng oxi ha hidrocacbon. Trong phn ng th, phn ng cng v phn ng oxi ha hidrocacbon c ngha quan trng lin h mt thit n cu trc phn t. A) PHN NG TH I) PHN NG TH HIDRO CA NGUYN T CACBON NO. Phn ng c trng ca hidrocacbon no l phn ng th ng li ( clo hoa , brom hoa , nitro hoa). 1) C ch th : Phn ng halogen ha tiu biu theo c ch th gc t do (S R) thuc loi phn ng dy chuyn: Khi mo pht trin mch tt mch. Flo p ankan ch yu xy ra p hy. Iot p khng thun li ch c Clo v brom tham gia p th nhng clo xy ra d hn. Kh nng p th ca ng.t H ph thuc vo bc ca ng.t C cha ng.t H . Ng.t H ng.t C c bc cng cao th ng.t H cng d th. Nguyn nhn l do gc ankyl sinh ra trong qu trnh phn ng c bn khc nhau. Gc ankyl bc III c siu lin hp vi nhiu lin kt C-H hn nn bn hn gc 14

ankyl bc II, tng t gc ankyl bc II bn hn gc ankyl bc I. Tuy nhin lng sn phm th sinh ra cn ph thuc vo s lng ng.t H cc bc khc nhau. Vd: CH3CH2CH3 p Clo to 57% CH3CHClCH3 v 43% CH3CH2CH2Cl CH3-CH(CH3)-CH3 p clo to 64% CH3CH(CH3)CH2Cl v 36% CH3CCl(CH3)CH3. + nhit cng cao th tc p nhanh hn nhng tnh chn la gim i t c s chnh lch v sp th. 6000C th kh nng p ca cc ng.t H cc bc khng cn chnh lch na. t l % mi sn phm ch ph thuc vo s lng nguyn t hidro cng bc. + Nu p brom ha th p xy ra chm hn nhng tnh chn la cao hn, ch yu xy ra ng.t C bc cao. 2) nh hng ca vng thm trong ankyl benzen Hiu ng lin hp: Nh hiu ng +C ca gc phenyl lm tng bn ca gc t do nn ng.t H v tr cu ankyl benzen c kh nng p cao. CH3-H < C6H5 CH2-H < C6H5-C(CH3)2 H. 3) nh hng ca nhm th rt electron. Hiu ng I : Ng.t H cng gn nhm th rt e th kh nng p th H cng gim. Th d : CH2-CH-CH-CH2 CH2-CH-CH-CH-Cl H H H H H H H H (1) (3,6) (3,6) (1) (1) (3,7) (2,1) (0,8) Kh nng p ca ng.t H c ghi trong du ngoc.V vy khi clo ha ax butanoic c chiu sng sp chnh l ax 3-clobutanoic. Ch : nu clo ha c xt l P th sp chnh l ax 2-clobutanoic. 4) Phn ng sunfoclo ha v phn ng nitro ha: R-H + SO2 + Cl2 (as) R-SO2-Cl + HCl R-H + HONO2 (c 420 n 4500C) R-NO2 + H2O Hai p trn cng xy ra theo c ch gc. II. PHN NG TH HIDRO CA NG.T CACBON THM: Phn ng th electron phin l p c trng ca vng benzen(SEAr). C ch p th H ca ng.t C thm theo hng to phc , tc nhn p l Br+ hay NO2+, CH3CO+, SO3. C ch chung: C6H6 + E+ Ion Benzoni C6H6E+ (1) C6H6E+ C6H5-E + H+. (2). Giai on (1) xy ra chm to ion dng nu trn gi l phc . 1) Phn ng halogen ha : Phn ng xy ra ch yu vi clo v brom. Clo v brom khng tc dng benzen nhit thng, trong bng ti( nu ciu sng th xy ra p cng clo ). Nu c xt FeCl3 hay AlCl3 s xy ra p th. C ch p brom ha : FeBr3 + Br2 Br+[FeBr4]-. C6 H 6 + Br + C6 H6 Br + C6 H5 Br + H + H + +[ FeBr4 ] HBr + FeBr3 Nu dng HOBr hoc HOCl, HOI v mt axit manh th : HOBr + 2H+ H3O+ + Br+. Sau Br+ s tc dng benzen. Sp th c th xy ra nhiu ln th to: C6H5Cl ; 1,2 hay 1,4 C6H4Cl2; 1,2,4 C6H3Cl3 Khi trn vng thm c nhnh ankyl nh Toluen th p th xy ra d hn v u tin th vo v tr octo hay para. Nu khng c xt m chiu sng th xy ra p th nhnh. 2) Phn ng nitro ha : Khi c hh HNO3 v H2SO4 un nh vi benzen th to nitro bnezen. i vi toluen p trn xy ra ngay nhit thng to sp chnh l o v p nitrotoluen. H O NO2 + H 2 SO4 HSO4 + H2 O+ NO2 H 2O + NO2 + H 2 SO4 H3 O+ + HSO4 + NO2 + Sau NO2+ tc dng tng t Br+. 3) Phn ng sunfo ha : Phn ng gia benzen v H2SO4 un nng gi l p sunfo ha, to ra axit benzensunfonic. 2H 2 SO4 SO3 + HSO4 + H3 O + C6 H 6 + SO3 C6 H6 SO3 + C6 H5 SO3 H 4) Phn ng ankyl ha : Benzen tc dng vi mt vi tc nhn ankyl ha electrophin s to ankyl benzene. Tc nhn sinh ra t : R-X/AlCl3 (phn ng Friden-Crap); R-OH/H2SO4 ; Anken/H2SO4hoac AlCl3. 15

Vd: C6H6 + C2H5Cl ( AlCl3) C6H5C2H5 + HCl. C6H6 + CH2=CH-CH3 Cumen. Phn ng Friden-Crap c nhc im l ion cacboni sinh ra d b ng phn ha nn to hh sn phm, th hai l p thng khng dng li bc th 1 ln m c th tip tc xy ra cc ln th tip theo. Vd: C6H6 + C2H5Cl (AlCl3) C6H5C2H5 v c hai cht o,p- C6H4(C2H5)2. khng ch p th 1 ln thng dng d benzen. 5) Phn ng axyl ha : l p gn nhm axyl R-CO- vo vng thm nh clorua axit R-CO-Cl hoc anhydrite axit (RCO)2O c AlCl3 khan xt. Vd: C6H6 + CH3-CO-Cl (AlCl3) C6H5CO-CH3 ( axetophenon) +HCl. 6) Ni dung qui lut th dn xut mt ln th ca benzen: + Tt c cc nhm th mang in tch dng ng.t trc tip lin kt vi vng benzen nh NO 2 + ,-SO3H, -C +H=O , -COR, -C N, -CHO, -COOH, -COOR u l nhng nhm th nh hng meta ng thi l nhm phn hot ha. + Cc nhm th cn cp electron n ng.t lin kt trc tip vi vng benzen ( c hiu ng +C) v cc nhm ankyl, aryl nh OH- , -OR, -NHR, -NHCOR, -NH2 , -Cl , -CH3 , -C6H5 u l nhm nh hng th o p. Tr halogen thuc nhm phn hot ha , cc nhm khc u hot ha vng thm. 7) Quy lut th hp cht thm khc : a) Hp cht 2 ln th ca benzene : + Nu c nhiu nhm nh hng o p th nhm c nh hng mnh hn chim u th. + Nu mt nhm nh hng o-p mt nhm nh hng meta th nhm th nht chim u th. + S th hng n v tr gia 2 nhm th meta ch xy ra mc rt t. Vd: m-bromclobenzen khi nitro ha ch c 1% th v tr s 2; 62% th v tr 4 v 37% th v tr 6. b) Hp cht thm nhiu vng ngng t : V tr hot ng ca naptalen l v tr s 1, ca antraxen l 9 v 10, ca phenantren cng l 9 v 10. V tr 1 ca naptalen c kh nng p th cao hn v tr 2. Khi c nhm th hot ha v tr 1 th p th nh hng vo v tr 4. Nu nhm th v tr 2 th s nh hng cho nhm th mi vo v tr 1. Khi c nhm th phn hot ha v tr 1 hay 2 u nh hng cho nhm th mi vo v tr 5 v 8. III) PHN NG TH CA ANKEN: Di tc dng ca nhit cao, nh sng hoc peoxit th clo, brom c th th cho nguyn t H nguyn t C k cn lin kt C=C. Vd: CH2=CH-CH3 + Cl2 (400-5000C) th kh CH2=CH-CH2Cl + HCl. Phn ng ny xy ra theo c ch gc, phn ng u tin theo hng to gc t do bn hn. IV) PHN NG TH CA ANKIN: Ng.t H ankin (nh vi Csp) linh ng hn so vi H ca anken v ankan. N c th b th vi kim loi kim. R-CC-H + Na (1500C) R-CC-Na+ + H2. Ankin y c anken v ankan khi cc hp cht c kim ca chng. R-CC-H + C2H5MgBr (ete) R-CC-MgBr + C2H6. Ankin l ax yu hn nc nn cac ankinua kim loi kim, kim th b phn hy hon ton trong nc nhng mui ca kim loi nng khng tan trong nc th khng b phn hy trong nc. Ank -1- in tc dng vi phc kim loi trong dd amoniac nh ddAgNO3/NH3. BI TP MINH HA 1) Cc cht freon gy ra hin tng " l thng ozon ". C ch phn hy ozon bi freon (v d CF2Cl2) c vit nh sau: CF2Cl2 Cl + CF2Cl (a) O3 + Cl O2 + ClO (b) O3 + ClO O2 + Cl (c) Gii thch ti sao mt phn t CF2Cl2 c th phn hy hng chc ngn phn t ozon? Trong kh quyn c mt lng nh kh metan. Hin tng g xy ra ng thi vi hin tng " l thng ozon "? Gii thch.? 2) Cho isopentan tc dng vi Cl2 (nh sng) thu c 4 sn phm vi thnh phn t l nh sau: 1clo2 metylbutan (30%), 1clo3metylbutan (15%), 2clo3metylbutan (33%) v 2clo2metylbutan (22%). a. Cho bit sn phm no d hnh thnh hn, gii thch. b. Tnh kh nng phn ng tng i ca cc nguyn t hydro gn vi carbon bc I, II, III. 3) Kh nng phn ng tng i ca cc hydro bc I, II, III i vi phn ng clo ha ankan l 1: 3,8 :5 tng ng. a. Tnh phn trm ca cc sn phm khc nhau khi monoclo ha butan. b. Tnh phn trm cc sn phm monoclo (Cl ha mt ln) khi Clo ha 2metylbutan. 16

4) Phn ng th theo c ch gc t do gia isobutylbromua v tert-butylbromua vi Cl 2 u cho cng mt sn phm chnh l 1-brom-2-clo-2-metylpropan. Hy gii thch hin tng ny. 5) HSGQG. Hai xicloankan M v N u c t khi hi so vi metan bng5,25. Khi mono clo ha c chiu sng th M cho 4 hp cht, N ch cho mt cht duy nht. Xc nh CTCT M v N gi tn cc cht theo IUPAC. 6) HSGQG-98: Cho cht A c CTCT : Vit ptp. to thnh sp khi cho 1mol A tc dng vi : 1mol HNO3 ( c H2SO4xt); 1mol Br2( as); KMnO4 c nng d. 7) Dng mi tn ch hng th u tin nht trong cc trng hp sau:
CH3 CH3 CH3 CH3

CH3

NO2 N

CN NO2 OCH3 Cl

8) Ba hp cht trimethylbenzen sau, cht no c kh nng hot ha mnh nht trong phn ng th SE: (1) 1,2,3trimetylbenzen ; (2) 1,2,4trimetylbenzen ; (3) 1,3,5trimetylbezen. 9) Vit cc sn phm to thnh ca cc phn ng sau y: a. Phn ng sulfonic ha p-metylcumen. b. Phn ng sulfonic ha p-acetyltoluen. 10) Cht A c cng thc C8H6 v lm mt mu nc Br2, phn ng vi AgNO3/NH3 cho kt ta, oxygen ha thu c acid benzoic. Xc nh cng thc cu to ca cht A. 11) Cho s sau:

a. Vit cc phng trnh phn ng theo s chuyn ha trn. b. giai on chuyn B2 thnh B3, trong iu kin c rt t Br2, ngoi B3 ngi ta cn thu c mt lng nh ankan B4 khc. Hy xc nh B4 v gii thch s to thnh B4. 12) Gii thch cc d kin sau: a. Kh nng phn ng ca chlorobenzene km benzene trong phn ng th i in t, d rng nh hng vn u tin o-, p-. b. Ion phenolate tham gia phn ng th i in t cc v tr o-, p-. c. Phn ng th i in t ca acid benzoic u tin cho sn phm m. d. Phenol d b Br ha hn benzen. Hng dn 1) Phn ng phn hy ozon l phn ng dy chuyn theo c ch gc. Nguyn t Cl sinh ra phn ng (c) li tip tc tham gia phn ng (b), qu trnh c lp i lp li hng chc ngn ln. Do mi phn t CF2Cl2 c th phn hy hng chc ngn phn t ozon(O3). Trong kh quyn c mt lng nh metan. ng thi vi hin tng "l thng ozon" l hin tng " ma axit " do: CH4 (kh quyn )+ Cl HCl + CH3 2) a. 2clo2metylbutan d to thnh nht v trong phn ng th gc S R, gc t do cng bn th sn phm cng u tin, m gc ankyl c electron t do nm trn carbon bc III bn nht. V vy s kt hp ca gc Cl vi gc ankyl trn l d xy ra nht. 17

b. Kh nng phn ng tng i ca cc nguyn t hydro gn vi carbon bc I : bc II : bc III tng ng t l: 1 : 3,3 : 4,4. 3) a. C 6 nguyn t H hnh thnh 1clobutan (A) v 4 H hnh thnh 2 -clobutan (B). T l nguyn t ca H (I) : H (II) l 3 : 2. Lng tng i ca sn phm l: (A) = 3 1 = 3 v (B) = 2 3,8 = 7,6. Phn trm (A) v (B) l: % A = 3.100/10,6= 28% % B = 100% - 28% = 72% b. C 4 sn phm monochlorated khc nhau: 1clo2metylbutan (C) 2clo2metylbutan (D) 2clo3metylbutan (E) 1clo3metylbutan (F) Ta c lng tng i v % cc sn phm l: (C) 6.100/21,6= 28% ; (D) 5.100/21,6= 23% ; (E) 2 3,8.100/21,6= 35% (F) 3.100/21,6 = 14% 4) C ch gc to ra gc t do bn l gc bc III. C s chuyn v khi tert-butylbromua tc dng clo. 5) KLPT hai cht = 84 suy ra CTPT C6H12. M l metylxyclopentan; isopropylxyclopropan; N l xyclohexan. 6) Tc dng HNO3 to sp th v tr p vng thm do v tr o b khng ch bi hiu ng khng gian. Tc dng brom, as u tin th H ng.t C bc III ca vng no. Tc dng KMnO4 s oxh lm t vng no: 3C6H5-C6H11+14KMnO43C6H5COOK+3C3H6(COOK)2+14MnO2+ 5KOH+5H2O. 7) Hng th ln lt l: o (so vi CH3); o (so vi nhm OCH3); o (so vi nhm CH3); v tr s 4 so vi nhm CN; v tr 4 so vi nhm CH 3; v tr 5 so vi nhm NO 2; N gy hiu ng I phn hot ha nn th v tr 5 so vi ng.t N. 8) (3) > (2) > (1). 9) b)
COCH3

SO3H CH3

11) 12)

10) Cht A c a = 6. A l C6H5-CCH. B4 l butan do s kt hp gia 2 gc t do etyl to nn. a. Do nguyn t Cl c hiu ng +C. b. Do nh hng y in t ca O, cng hng lm cho cc v tr o-, p- tng in tch m. c. Do nh hng ht in t ca nhm CHO lm cho v tr o-, p- gim in tch m so vi v tr m . d. Do hiu ng +C ca nhm OH. B) PHN NG CNG CA HIDROCACBON

I) PHN NG CNG M VNG CA XYCLOANKAN: Vng 3 cnh ca xycloankan c th cng m vng vi Br 2; HX; H2 v c benzen. Vng 4 cnh ch tham gia phn ng cng vi hidro nhit cao. Vng 5 cnh tr nn khng tham gia phn ng cng nh trn. Do kh nng phn ng cc lin kt C-C gn nh nhau nn tc nhn c th tn cng vo cc lin kt C-C khc nhau to hn hp sn phm cng. Vd: metylxyclopropan cng Br2 cho 2 sn phm ng phn cu to. II) PHN NG CNG VO ANKEN: 1) Phn ng cng electronphin: Khi anken cng halogen, axit, nc l phn ng nhiu giai on. Tc nhn tn cng giai on chm quyt nh vn tc phn ng l E+ nn c gi l phn ng cng electron phin (AE). Hng ca phn ng cng electron phin xy ra theo hng u tin hnh thnh cacbocation trung gian bn (c s ca quy tc cng Macconhicop). Vd: R-CH=CH2 + I-Cl R-CH(Cl)-RCH2I l sn phm chnh. C ch phn ng cng xy ra theo kiu cng trans (anti): xy ra t 2 pha i nhau so vi mt phng ca lin kt pi trong ni C=C. 18

Vd: Xyclopenten + Br2 (CCl4) Trans-1,2-ibromxiclopentan): C5H10Br2. Ch : - Nu trong mi trng p c mt cc tc nhn nucleophin nh H2O , CH3OH, I- th cc tc nhn ny c th tham gia giai on hai ca p to hh nhiu sp. - Phn ng cng halogen ta dng clo, brom hay Br-Cl, I-Cl m khng dng Iot kh phn ng v Flo gy p hy. - Phn ng cng Hhal vo Lk kp kh nng p bin thin nh sau: HF<< HCL<HBr< HI. - Phn ng cng nc dng xc tc axit thng to hn hp cc ancol bc cao, bc thp v ng phn do phn ng chuyn v. - Mt e Csp2 cng cao th cacbocation hay ion H+ cng d cng hn. V vay neu thay the ng.t H trong etylen bang nhm y electron th toc o p tng ln. Kh nng phn ng ca Etilen < propilen < isobutilen. - Nu cc dn xut th ca etilen vi cc nhm th ht e li c kh nng p km hn : Kh nng phn ng ca CH2=CH2 > CH2=CHCl > CH2=CH-COOH 2) Phn ng cng theo c ch gc t do (cng ng ly AR) - Phn ng xy ra khi c chiu sng hoc cht khi mo nh oxi, peoxit - Tc nhn tham gia p thng l Cl2 , H-Br cn HF,H2SO4 khng tham gia p ny. - Tng t p th c ch gc, p cng c ch gc t do l p dy chuyn. Khi mo : RO-OR 2RO.. RO. + H-Br ROH + Br. . . Hay O2 + H-Br HOO + Br Pht trin mch : Br. + R-CH=CH2 R-CH.-CH2Br (bn) R-CH.-CH2Br + H-Br R-CH2-CH2Br + Br.. . Tt mch: 2Br Br2 ; R-CH.-CH2Br + Br. R-CHBr-CH2Br 2R-CH.-CH2Br R-CH(CH2Br)-CH(CH2Br)-R Nh vy sp cng HBr theo c ch gc xy ra theo hng to gc t do trung gian bn hn; sn phm sinh ra l ng phn ca sp cng HBr theo c ch cng electron phin ngha l theo hng tri quy tc cng Maccopnhicop. 3) Phn ng cng hidro trn b mt xc tc kim loi : Hidro ha thng dng xc tc l cc kim loi chuyn tip chng khc pha vi cc cht kh v th gi l xc tc d th. + Pd/C xc tc cho hidro ha anken thnh ankan trong dd etanol di p sut thng ngay 0 20 0C. Trong iu kin nhn benzen, nhm C=O; CN khng b kh. Vd: C6H5-CH=CH-COOCH3 + H2 (Pd/C; etanol) C6H5CH2CH2COOCH3. + Xc tc Pt thng dng trong etanol, trong etylaxetat di p sut thng. + Xc tc Ni r hn so vi kim loi qu nhng hot ng yu nn phi dng nhit cao hn: 50-1000C p sut t 5 10atm. + Phn ng cng hidro trn b mt cht xt kim loi l p cng ng thi kiu cis (syn), cng vo cng pha ca lin kt C=C. 4) Phn ng trng hp: a) Trng hp gc: V d phn ng trng hp to PE, PVC, PS l trng hp gc. Cc monome cng vi nhau theo kiu u uiv phn ng cng gc xy ra theo hng to ra gc t do trung gian bn hn. n CH2=CHR [-CH2-CHR-]n b) Trng hp ion: Anken khi gp axit mnh th trng hp theo c ch ging nh cng electrophin gi l trng hp cation. Xc tc thng l AlCl3, BF3 v mt lng nh nc. III) PHN NG CNG VO ANKIN: 1) Phn ng cng electrophin AE: Tng t anken y l phn ng in hnh v quan trng nht i vi ankin. + Cng halogen v hidro halogenua v c ch tng t anken, sn phm chnh u tin theo hng to cacbocation bn hn. Phn ng c th thc hin qua hai giai on to sn phm no. Vd: C6H5CC-H C6H5CCl=CH2 C6H5-CCl2-CH3. + Cng nc: Ankin cng nc to enol khng bn nn b ng phn ha thnh andehit hoc xeton, c 2 giai on cn xc tc l axit. Sn phm tun theo qui tc Maccopnhicop. 19

Tc cng brom, clo vo anken ln hn nhiu so vi cng vo ankin, cn tc cng HX th hn km nhau khng nhiu. 2) Phn ng hidro ha: a) Hidro ha khi dng xc tc kim loi: Khi dng xc tc nh Ni, Pt, Pd ankin cng hidro thnh anken nhng anken phn ng ngay thnh ankan. Mun dng giai on ton anken cn lm gim hot tnh ca xc tc v d Pd/CaCO 3 phn hot ha bng (CH3COO)2Pb (xc tc Lindlar) hoc Pd/C tm quinolin hay piridinsn phm ch to anken cu hnh cis. Vd: C6H5-CC-C6H5 + H2 (Pb/C, quinolin) Cis-Stilben: C6H5-CH=CH-C6H5. b) Kh bng Na/NH3 lng: Kh ankin bng Na/NH3 lng cho anken cu hnh trans. Vd: C3H7-CC-C3H7 + Na/NH3 lng Trans oct-4-en + NaNH2 Khc vi p cng electrophin, p cng hidro vo ankin d hn anken v nu thm nhm ankyl vo etylen th phn t kh tham gia p cng hn. Vd : Axetylen > etylen > propen > isobuten. Tuy nhin anken d cng hidro hn aren. IV) PHN NG CNG VO POLIEN LIN HP : Ankadien lin hp c kh nng phn ng cao c th cng theo c ch gc, cng electrophin. Ngoi kh nng cng v tr 1,2 cn cng v tr 1,4. 1) Phn ng cng electrophin vo dien lin hp: nhit thp thun li cho sp cng 1,2 nhng nhit cao sp 1,4 chim u th. Nguyn nhn l do trong qu trnh cng electrophin to ra 2 cacbocation trung gian. Vd: CH2=CH-CH=CH2+Br+CH2=CH-CH+-CH2Br v CH2Br-CH=CH-CH2+. Sau ion Br- tn cng vo 2 ion trn to ra sn phm. Sp cng 1,2 xy ra nhanh hn nhng km bn hn so vi sn phm cng 1,4. V th nhit thp phn ng xy ra theo hng u tin to sp cng 1,2 (khng ch ng hc). nhit cao sp cng 1,4 bn hn (do ni i gia mch hiu ng siu lin hp ln hn) nn cn bng dch sang pha to sp cng 1,4 (khng ch nhit ng hc). 2) Cng hidro vo dien lin hp: Khi dng d hidro dien b kh thnh ankan. Nu dng hidro kh dien t l mol 1:1 nhit thp to hn hp 2 sn phm cng 1,2 v 1,4. kh chn lc vo v tr 1,4 ngi ta dng tc nhn kh l Na dng hn hng (Na/Hg) hoc Na trong amoniac. 3) Phn ng cng ng vng (4+2) gi l phn ng inx-An. Nhiu dien lin hp tham gia cng ng vng vi anken hoc ankin. Vd: Buta-1,3-dien + etylen xyclohexen.
CH2 HC

+
HC CH2

CH2 CH2

H2 C

2000C 300 atm

HC HC C H2

CH2 CH2

phn ng inx-An, ien lin hp gi l dien; anken phn ng gi l ienophin. S cng dien vi anken cho sp tng t nh kiu cng 1,4 nhng xy ra ng thi (1 giai on) nn hp phn dien phi cu dng S-cis (gi cis) lc tham gia phn ng. Nhng dien khng chuyn thnh dng S-cis c th khng tham gia phn ng ix-An. Nhm y electron ien nu khng cn tr s to ra cu dng S-cis th lm tng tc phn ng, cn nhm ht electron th lm gim tc phn ng. ienophin nu c nhm ht electron th phn ng xy ra thun li. Phn ng inx-An c tnh c th lp th xy ra theo kiu cng syn. Phn ng ny ph bin v quan trng trong tng hp hu c hin i, phm vi p dng rt rng ri. BI TP MINH HA 1) HSGN: Hy vit cc sp chnh to thnh trong p clo ha propen trong dd etanol nc c mt KBr. 2) Khi cho isobuten vo dung dch c ha tan HBr, NaCl, CH 3OH c th to ra nhng cht g, gii thch v vit c ch phn ng. 3) HSG N: Vit CTCT sp chnh v gii thch: as a)CH3(CH2)2COOH+Cl2 C5 H 9ClO2 b) CH 2 = CH COO CH = CH2 + I Cl C5 H6 ClIO2 4) HSGN: Hp cht X c CTPT C9H16. X tc dng vi hidro d c Ni xc tc thu hh gm 3 cht X 1, X2, X3 l 1-etyl-3-metylxyclohexan; 1-etyl-4-metylxyclohexan v 1,4-imetylxycloheptan. Xc nh CTCT X? 5) Cho bit sn phm to thnh khi cho isobuten tc dng vi cc cht sau: 20

a. HI. b. HBr (Peroxide). c. Br2/H2O. d. Br2 + NaCl (H2O) 6) Hon thnh cc phng trnh phn ng di y v biu din ng phn lp th ca cc sn phm to thnh bng cng thc chiu Fischer. a. cisbut2ene + Br2 b. transbut2ene + Br2 7) Vit phn ng DielsAlder (inx-An ) ca Buta1,3diene vi cc hp cht sau y: a. Anhydride maleic. b. Methylvinylcetone. c. Acid maleic. d. Acid fumaric. e. H2C=CHCH=CH2. f. C6H5CH=CHNO2. 8) HSGN: Cho s phn ng: ddBr2 (1:1) ddNaOH ,t 0 (A) CH 3 CH = CH COO CH = CH CH3 B C + D a) Vit PTP dng CTCT cc cht trn v gi tn A,B,C,D. b) Cho bit s p lp th ca A,B,C,D (mi CT c bao nhiu p lp th). c) Cho A c cu hnh bn nht th cu trc B nh th no? 9) Khi trng hp Buta1,3dien to cao su Buna thng to ra sn phm ph l vng 6 cnh cha no (phn ng DielsAlder), khi phn ng vi H2 d xc tc Ni th to ra etylcyclohexan. Vit cc phng trnh phn ng v cho bit iu kin phn ng ng vng DielsAlder xy ra d dng. 10) HSG N: Vit CTCT cc sp c th c khi tin hnh trng hp buta-1,3-dien v isopren cho cc trng hp : a/ Hai pt vi nhau. b/ Hai loi polime to cao su. 11) Cho dn xut halogen CH3CH=CHCH2Cl (A) a. Cho (A) tc dng vi nc Cl2 trong bng ti. Vit cng thc cu to ca sn phm. b. Nu un nng (A) vi dung dch kim long thu c monoancol tng ng. Cho thm kim vo, tc phn ng khng thay i. Hy cho bit c ch phn ng v so snh kh nng phn ng ca (A) vi CH3CH2CH2CH2Cl v CH2=CHCH2Cl trong cng iu kin phn ng, gii thch. 12) C 6 chai ga (Cht kh t0 thng) l ng phn ca C4H8 u b mt nhn v c dn nhn t A n F. Hy xc nh ho cht mi chai bit rng : - A, C, B v D lm nht mu Br 2 nhanh chng (ngay c trong bng ti), trong khi E v F khng lm nht mu Br2. - Cc sn phm ca B v C vi Br2 l ng phn lp th ca nhau. - A, B, C u cho sn phm ging ht nhau khi phn ng vi H2 xc tc Pd . - E c im si cao hn F v C c im si cao hn B. Hng dn + 1) Clo trong nc s to tc nhn Cl cho cation trung gian bn CH3-CH+-CH2Cl. Trong dd c cc tc nhn nucleophin: Cl-; etanol; H2O, Br- nn s to hh 4 cht tng ng. 2)Sp phn ng l: (CH3)3CBr ; (CH3)3COH ; CH3[(HO-)C(-Cl)]CH3 ; (CH3)3COCH3 Trong dung dch c 4 tc nhn l Br, Cl, H2O v CH3OH c kh nng kt hp vi carbocation. Phn ng theo c ch cng electrophin (AE). - u tin, H+ tn cng vo C to carbocation (CH3)3C (giai on chm.) - Sau 4 tc nhn trong dung dch s kt hp carbocation to sn phm (giai on nhanh). 3) a) Nhm COOH gy hiu ng I nn sp th SR to sp chnh CH3CHClCH2COOH. b) Nhm vinyl giu in tch m hn, c ch cng AE nn I+ s cng vo nhm CH2. Sp chnh l CH2=CHCOO-CHCl-CH2I. 4) a = 2, sau p cn 1 vng no. Vy CTCT X:
CH3 H3C

5) a. tert-butyliodua. b. isobutylbromua. c. 1brom2methylpropanol. d. 1-brom-2-clo-2-methylpropan; 1,2-dibrom-2-methylpropan; 1-brom-2- metylpropan-2-ol. 6) a. To 2 p i quang 1,2-ibrom butan b. to p meso 2,3-ibrom butan 7) 21

8) HSGN: Cho s phn ng: ddBr2 (1:1) ddNaOH ,t 0 (A) CH 3 CH = CH COO CH = CH CH3 B C + D a) A l (1-propenyl)-2-butenoat; Do ni C=C th 1 b lin hp bi ni C=O nn brom cng vo ni C=C th 2 to B l CH3-CH=CH-COO-CHBr-CHBr-CH3(1,2-dibrompropyl)-2-butenoat; C l CH3-CH=CHCOONa Natri-butenoat; D l OHC-CHOH-CH3 2-hydroxylpropanal. b) A c 4 p hnh hc; B c 2 ng.t C bt i c 4 p quang hc v 2 dng hnh hc vy c 8 p; C c 2 p hnh hc; D c 2 p quang hc. c) A c cu hnh bn trans ni C=C th 2 th khi cng brom AE s cho cu hnh cng kiu trans (2 ng.t brom cng pha trong CT fis) . 9) To sp 1-vinylxyclohex-3-en. iu kin: Hp cht diene (A) phi c cu hnh S-cis. Phn ng ny tr nn d dng hn nu thay H trong dienophin bng nhm ht electron nh COOH, COOR, CHO, v thay H trong dien bng nhm y electron nh: CH3, C2H5, 10) a/ Vit cc sp cng khng ng vng v ng vng inxo-An gia 2 phn t vi nhau. b/ Vit hai loi polime to cao su (ng trng hp). 11) Thm kim m tc p khng i vy y l p th SN1. Giai on chm A to ion CH3-CH=CH-CH2+ sau kt hp ion OH- to sp. Kh nng p th SN1: A > CH2=CH-CH2Cl > CH3CH2CH2CH2Cl do hiu ng +C ca ni C=C v hiu ng +H ca nhm CH3 nn cation CH3-CH=CH-CH2+ bn nht. 12) 6 ng phn ca C4H8. But-1-en cis-but-2-en v tran- but-2-en Metyl propen xiclobutan v Metyl xiclopropan - C4H8 lm nht mu Br2 phi c lin kt kp, cn khng lm nht mu Br2 ch c lin kt n. Vy A, B, C, D l 4 Anken, cn E, F l 2 xyclo ankan - Hydro Cacbon c im si cao hn do c momen lng cc. Metylxiclo Propan c momen lng cc n l E. Cn Momen lng cc ca xiclobutan = 0 n l F. - Mun to cng sn phm khi Hidro ho th cht ban u phi c cu trc tng t nhau, ch khc nhau v tr lin kt i A, B, C l But-1-en v But-2-en . Suy ra D l Metylpropen. - 2 ng phn hnh hc th khi cng Br2 d to ra ng phn lp th ca nhau. cis-But-2-en to dng meso ca 2, 3- dibrom propan trans-But-2-en to ng phn i hnh R,R v S,S tng ng ca 2,3-ibrom propan Vy B v C l cis-but-2-en v tran- but-2-en Suy ra A l But-1-en v tran- but-2-en c momen lng cc trit tiu nn im si thp hn C l cisbut-2-en, B l tran- but-2-en. C)PHN NG OXI HA HIDROCACBON I) OXI HA MT S ANKAN : 1) CH4 b oxh bi oxi ty theo nhit c th sinh ra HCHO; CO hay C. 2) Butan b oxh bi oxi c Mn2+ xt sinh ra CH3COOH, sp ph l HCOOH c lng ng k. 3) Cc parafin b oxh bng oxi ct mch ankan sinh ra hh axit cacboxylic n chc dng iu ch x phng. II) OXI HA ANKEN: 1) Oxi ha lin kt gi li lin kt bng cch dng dd KMnO4 long lnh , Osmitetra oxit OsO4. y l p cng kiu cis vo ni i to diol. 22

Vd : etylen etylen glycol. Xiclohexen Cis- xiclohexan-1,2-diol + Nu dng peoxiaxit (peaxit) nh HCO-O-OH, C6H5COO-OH lm cht oxh thu c epoxit hay oxiran. Cho epoxit tc dng vi ax v c thu c trans-diol. Vd : propen + ax pebenzoic ( CHCl3) to metyloxiran v ax benzoic .
CH3
H C O CH2

CH2=CH-CH3 + C6H5COO-OH C6H5COOH

Xiclohexen + HCOO-OH epoxit trans-xyclohexan-1,2-diol.

OH H H OH

2) Oxi ha lm t ni i : + Oxh bng KMnO4: un nng anken vi KMnO4 hoc dd KMnO4 trong axit ni i b t to thnh axit cacboxylic hoc xeton. Da vo cu to ca sp ngi ta c th suy ra cu to ca anken b oxi ha. V d: CH3CH=C-CH3 KMnO4 CH3-C=O + O=C-CH3 CH3 OH CH3 + C th dng p ozon phn (cng ozon ri thy phn): Sau khi cng ozon vo lin kt C=C ( cng kiu syn) to ra hp cht vng ozonit khng bn sau chuyn thnh axit (andehit) hoc xeton . giai on thy phn ozonit, nu dng cht kh l Zn/axit hoc (CH3)2S th LK Csp2-H c bo ton ( to andehit; xeton), nu dng H2O thy phn s to H2O2 (i khi thm vo nc mt t H2O2) th Csp2-H chuyn thnh Csp2-OH ( axit), xeton c bo ton.
O H3C C H C CH3 CH3 H3C O CH3 C H O C CH3

+ O3

Ozonit
O H3C C H O C CH3 H2O2/H+ O CH3 H Zn/CH3COOH H3C C O

CH3

C CH3

Ozonit

CH3 H3C C OH O

C CH3

T sp ozon phn khi vit CTCT cc sp sao cho cc nhm C=O i din nhau ri xa nhng ng.t O v ni hai ng.t C vi nhau s to ra anken ban u. V d: sp ozon phn anken ban u CH3CH=O + O=C(CH3)2 CH3CH=C(CH3)2 3) Oxh lin kt Csp2-H: Oxh etylen thnh axetandehit dng oxi c PdCl2 xc tc.. III) OXI HA ANKIN: Ankin lm mt mu dd KMnO4 ging anken nhit thp v mi trng trung tnh phn ng dng li giai on to thnh i xeton (gi nguyn mch cacbon). Nu khng khng ch pH ca mi trng v khng lm lnh th mch cacbon b ct ti lin kt ba to axit cacboxylic. CH3CCCH2CH3 trong ddKMnO4 CH3-CO-CO-CH2CH3 00C; pH =7,5. Nu un nng th sp l CH3COOH + CH3CH2COOH. Phn ng ozon phn ankin lun dn n sp l axit cacboxylic. Phn ng oxh bng KMnO4 v ozon phn c dng xc nh v tr lin kt ba trong mch cacbon. IV) PHN NG OXI HA VNG BENZEN: Cc cht oxi ha thng dng oxi ha anken nh CrO3, H2O2, OsO4, KMnO4 thng khng tn cng vo benzen. Tuy nhin iu kin c bit vng benzen vn b oxi ha. 1) Benzen v naptalen: Dng oxi c V2O5 xt v nhit cao, benzen b oxh thnh anhydrite maleic ( +CO2 v H2O), cn naptalen thnh anhydrite phtalic.

23

c bit ozon tn cng vo vng benzen to 3 phn t OHC-CHO. 2) Antraxen v phenantren : V tr s 9 v 10 ca antraxen v phenantren c th p th, cng v b oxh. Dng K2Cr2O7 trong H2SO4 c th oxh antraxen thnh 9,10-antraquinon, cn phenantren thnh 9,10phenantroquinon.
O O O

V) PHN NG OXI HA NHNH CA VNG BENZEN: - Khi un nng vi KMnO4 cc ng ng ca benzen b oxi ha sinh ra C6H5COOK. - Oxh lin kt i nhnh (nh styren) trong iu kin m du to glycol, trong iu kin khc nghit to axit. - Trong CN c th oxi ha toluen to ra phenol C6H5CH3 + 2O2 C6H5OH + CO2 + H2O. Oxi ha cumen bng oxi sau thy phn trong dd axit thu c Phenol v axeton. BI TP MINH HA 1) Cho bit sn phm to thnh khi ozon ha cc hp cht sau y: a. CH3CH=CH2. b. CH2=CHCH(CH3)CH=CH2. c. 1metylxyclohexa1,4dien. 2) HSGN: Mt hidrocacbon A (C7H12) ha hp vi hidro cho hidrocacbon B(C7H16) va 2khi b ozon ha v phn gii A cho ra HCHO; CH3COCH2COCH3. Tm CTCT ca A? + H 2O 3) HSGN: Vit ptp : propen + O3 A1 A2 + A3 + H2 O2 4) C 2 hydrocarbon (A), (B) u c cng thc phn t l C7H14. Bit rng: - Oxi ha (A) bng dung dch KMnO4/H2SO4 to ra 2 cht CH3CH2COCH3 v CH3CH2COOH. - (B) c cu to mch thng v khi oxi ha bng dung dch K 2Cr2O7/HCl to ra CO2. Xc nh cng thc cu to ca (A), (B) v hon thnh cc phng trnh phn ng. 5) Mt anken sau khi ozon phn to ra sn phm hu c duy nht l CH3CHO. Khi cng hp vi Br2 trong bnh lm bng vt liu phn cc th ch to ra mt sn phm l mt ng phn khng quang hot. Hy cho bit cng thc phn t ca anken v vit cng thc cu to ca sn phm theo Fis, Niuman ri gi tn sn phm. 6) Anken (A) c cng thc phn t l C6H12 c ng phn hnh hc, tc dng vi dung dch Br 2 cho hp cht dibrom (B). Cho (B) tc dng vi KOH trong ancol un nng thu c ankadien (C) v mt ankin (D). Khi (C) b oxi ha bi dung dch KMnO4/H2SO4 v un nng thu c axit acetic v CO 2. Xc nh (A), (B), (C), (D) v vit cc phng trnh phn ng xy ra. 7) HSGN. Hp cht C6H14O un nng vi H2SO4 c 1700C to cht A c th lm mt mu dd KMnO4 v nc brom. un nng A trong dd hh gm K2Cr2O7 v H2SO4 thu axeton v axit propionic. Nu cho A hp nc khi c axit sunfuric th thu c cht C6H14O ban u. Xc nh CTCT cc cht, vit ptp.ng. 8) Cht A c ctpt l C9H14. Khi oxiha hon ton A bng K2Cr2O7 trong H2SO4 thu xeto iaxit X mch thng , pt X t hn A 1 ngt C. Khi A ha hp vi hidro to propylxyclohexan. Khi A tc dng dd KMnO4 long c cht Y c s ng.t C bng s ng.t C trong A. Bit M Y l 190vc. Y p vi CH3COOH c H2SO4 xt ch to ra Z c CTPT l C15H24O7. Vit ctct v gi tn A. 9) Cho cumen tc dng vi CH3Cl/AlCl3 thu c cc sn phm monometyl ha trong c A. Khi cho A tc dng vi KMnO4 un nng thu c cht B c cng thc C8H4O4K2. Cho A tc dng vi Br2 (xc tc bt Fe) thu c hai sn phm mono-Br C v D. Vit cng thc cu to, gi tn A, B, C, D v hon thnh cc phng trnh phn ng minh ha. 10) Cho s phn ng: + KOH + Cl2 + KMnO4 H 2 / Pd Ben zen A B C D (C6H10O4) H 2O as t0 24

Xc nh cng thc cu to ca A , B , C , D. 11) -Tecpinen l tinh du t nhin tch ra t nha thng c cng thc C 10H16. Khi hidro ha trn xc tc Pd n to ra C10H20, cn khi ozon phn ri kh ha bng Zn/H2O n to ra 2 cht c tn: Glyoxal v 6metylheptan-2,5-dion. Hy xc nh cu trc ca -Tecpinen. 12) Ozon phn mt tecpen A (C10H16) thu c B c cu to nh sau: .

CH3

C CH2 CH O H3C C

CH CH3

CH2 CH

Hidro ha A vi xc tc kim loi to ra hn hp sn phm X gm cc ng phn c cng thc phn t (C10H20) a) Xc nh cng thc cu to ca A. b) Vit cng thc cc ng phn cu to trong hn hp X. 13)Mt h mch vng X (cng thc tng qut C10H14) tc dng vi hiro, c bch kim lm cht xc tc, to thnh hp cht A (C10H18). Phn ng ozon phn vi X v sau l phn ng kh oxi (Zn/ H3O+) dn n hp cht:
O HC O O CH2 CH2 CH2 C C O CH2 CH2 CH2 CH

a) Hy cho bit X c th c cu trc nhng vng no? Vit s ca phn ng vi ozon. b) Bit rng X c th tc dng vi anhirit maleic thnh mt sn phm Diels alder. Hy nu cu trc ng ca X v gii thch. Trnh by phn ng Diels Alder 14) Cho ba hirocacbon u c cng cng thc phn t: C9H12. Khi un nng vi dung dch KMnO4 ( ly d) trong H2SO4 long th A v B u cho nhng sn phm c cng thc C 9H6O6 cn C cho hp cht C8H6O4. Khi un nng vi Brm c mt bt st, A ch cho mt sn phm monobrm, cn B v C mi cht cho 2 sn phm monobrm. Hy xc nh cng thc cu to ca 3 hircacbon trn. 15) T nha thng ngi ta tch c xabinen v chuyn ho theo s sau:
1) O3 ; 2) Zn/HCl

(1)
H2N

A
OH (4)

KMnO4 ,H+

(2)

B
P2O5

H2/ Ni , t0

(5)

(3)

C1 , C , C3 2

A c cng thc C9H14O. a) Vit cng thc cu to ca cc sn phm hu c: A , B , C1 , C2 , C3 , D , E . b) Sn phm no c to thnh ng phn v ch r s lng ng phn ca mi sn phm. Hng dn 1) a. CH3CHO + HCHO b. OHCCHCH3CHO + 2HCHO. c. OHCCH2COCH3 + OHCCH2CHOCH3CH=CH2. 2) A c a = 2 cng c 2 pt hidro. T sp ozon ha suy ra CTCTA: CH2=C(CH3)-CH2-C(CH3)=CH2 3) A1 l CH3-CHO3CH2; A2 l CH3COOH; A3 l HCOOH 4) A: CH3CH2C(CH3)=CH-CH2-CH3. B: CH3(CH2)5CH=CH2. 5) Anken l But2en. Phn ng cng Br2 vo But2en l cng trans nn to ng phn khng quang hot th anken phi dng trans. Cng thc Fis, Niumen ln lt l:

6) (A) l: CH3CH2CH=CHCH2CH3. (B) l: CH3CH2CHBrCHBrCH2CH3. (C) l: CH3CH=CHCH=CHCH3. (D) l: CH3CH2C CCH2CH3 . 7) A l anken: CH3CH2CH=C(CH3)-CH3. Ancol ban u l CH3CH2CH2CHOH(CH3)2. 25

8) A c a= 3. T gt suy ra A c cu to vng. M Y MA = 68 l 4 nhm OH. Khi p CH3COOH ch c 3 nhm OH to este. A l (3-propenyl)xyclohexen 9) A l p-metylcumen. Cc phn ng: A+8KMnO4p-KOOCC6H4COOK(B) + 2K2CO3 + 8MnO2 + 2KOH + 4H20. C l o-Brom-p-metylcumen. D l m-Brom-p-metylcumen. 10) A l C6H12; B l C6H11Cl; C l C6H11OH; D l HOOC-(CH2)4-COOH (10. 2)+2-16 11) bt bo ha ca C10H16 = = 3 v cng 2 mol hidro c 2 lin kt . bt bo ha ca 2 (10. 2) + 2 20 C10H20 = = 1 cn 1 vng 2 - T cu to ca glyoxal OHC CHO v CH3 CH C CH2 CH2 C CH3 CH3 O O Suy ra cu trc ca -Tecpinen
CH3 CH3 1) O3 2) Zn,H2O H3C CH3 H3C O O O H

+
O H

CH3

12)
b)

a)

+ 2 2H

13) C 2 vng tha mn X u cho cng mt sn phm khi b ozon phn: b) Ch c (X2) nh s quay (X1) c cu hnh dng cis tham gia phn ng Diels-Alder.
Quay quanh trc C-C

v (X2)

quanh lin kt n C C t cn thit (s-cis) th mi c th

Cu d ng s-trans

Cu d ng s-cis

Trong (X1) cc lin kt i b c tham gia phn ng Diels-Alder. CH 14) A l B l:

3

nh trong cu dng s-trans nn khng th

CH3 H3C CH3

C l

CH3

H3C

CH3

15)
O

CH2CH3

COOH COOH

COOH COOH

COOH COOH

COOH COOH

C1

C2

C3

HON

C1 c 2 ng phn quang hc;

O C O

C3 c 2 ng phn quang hc; C2 c 4 ng phn quang hc. 26

C1, C2, C3 l 3 ng phn cu to. D c ng phn E, Z.

27