NG CH CH NG II- HIDROCARBON Gm ni dung: A- ANKAN ( T C ) B- ANKEN C- ANKIN ( T C ) D- HIDROCARBON TH M Tờn qu quc t : Tờn ankan i AN th thnh EN ỏnh s cho liliờ ờn kt ụi cú s nh nh Cl CH 4-Metylciclohexen B - ANKEN 5-Clociclohexadien-1,3 II iu ch ch : Hidro húa ankin : I Gi tờn : C C + Tờn thụ thụng th thng : CH2 CH2 CH2 Etylen CH CH3 CH2 Propylen CH CH2 CH3 H2 Pd to C C H H Kh Kh nc ancol : -butylen R-CH2-CHOH-CH3 R-CH=CH-CH + H2O CH3 CH3 CH CH -butylen CH3 CH3 CH Isobutylen CH2 - iu ki kin : H 2SO4 (170oC) ho hoc Al2O3 (400-800oC) Kh ph n ng : ancol III > ancol II > ancol I Kh nng ph nh hng ph phn ng : tuõ tuõn theo quy tc Zaixep IV Tớnh ch ch t húa hc : Kh Kh HX ca RX (halogenua ( halogenua ankyl) ankyl) : - R-CH2-CHX-CH3 - Kh Kh nng ph phn ng : - nh hng ph tuõ õn theo quy tc Zaixep phn ng : tu KOH/ ru R-CH=CH-CH3 + HX R-I > R-Br > R-Cl R-Cl > R-F Bc > bc > bc Kh Kh X2 ca -dihalogenua (vic-dihalogenua (vic-dihalogenua)) : C C X X - + Zn to C C + ZnX N i ụi C = C c a anken g m n i b n v n i k ộm b n d b b g ó y Do v y ph n ng c tr nh t ca tr ng nh anken l cỏc ph phn ng cng ú ni b t ra Ngo Ngo i c ỏ c anken c ũ n c ú c ỏ c ph ph n ng oxi h ú a, ph n ng th th H ng dng : bo v ni ụi III- Tớnh ch ch t vt lý i ph n ng ca anken Cỏc lo lo ph anken:: T c Cng H2 P P. ng cng Cng ion P P. ng ca anken KMnO4 P P. ng oxi húa O3 IV.1- Ph Phn ng cng : Ph Ph n ng cng H2 : Xỳc tỏc Ni, Pt C ch ch hp ph ph R-CH=CH2 + H2 R-CH 2-CH3 Ph Ph n ng cng ion: ch ph ph n ng : Ph C ch Phn ng cng ỏi in t ( thõ thõn in t, electrophil ) Tỏc nh nhõ õn ỏi in t: l cation ( H+, Br+, Br+,) ho hoc phõ phõn t phõ phõn cc C ch ch: giai on: Ph Ph n ng s x y thu n l i n u anken c ú m t electron cao ni ụi C=C: R-CH=CH2 < R-CH=CH-R < R 2C=CH-R < R2C=CR2 Cỏc ph ph n ng cng ỏi in t c th th : a- Cng halogen: R-CH=CH2 + X R-CHX-CH 2X b- Cng HX ( HCl , HBr , HI ): HCl, HBr, R- CH=CH + HX R-CHX-CH Nu R- l nhú nhúm y electron: Ph Phn ng x y theo Qui t c Markownikov : H c ng v o C mang nhi nhiu hidro hn: H R - CH - CH3 X _ R - CH = CH2 + X Giai o n : T ỏ c nhõ nhõ n ỏ i i n t t n c ụ ng v o C t ch in õm ca liờ liờn kt ụi to carbocation ( bc ch chm ) + CH CH + + - X Y Bửụự c chaọm R CH CH2 + Giai on : Anion tn cụng vo carbocation C+ hỡnh th ph m ( bc nhanh ) thnh sn ph _ CH2 + X Y CH2 Y X _ CH CH _ R R R Cl CH CH3 Cl + Bửụực nhanh CH2 + H Y X + CH R - _ R i th Gi Gi thớớch Qui tc Markownikov : Nu R- bt k ( cú th th y ho hoc hỳt electron ): H cng vo C phõ phõn cc õm: + CH2 CH CH2Cl + H Cl CH2Cl CH2 CH2Cl Tr Trng hp c bi bit: Ph Phn ng vi HBr cú mt mt peroxit n ng hidro-bo húa: 3- Ph Ph ( ROOR ), s n ph m Kharash:: H c ng nh tu õ n theo qui t c Kharash vo C mang ớt hidro hn: P ca anken vi boran BH3 Phn ng xy theo c ch trung tõm: CH2 CH CH3 HBr Peroxit CH2 CH2 CH3 (sn ph chớớnh nh)) phm ch R + CH Br H CH2 R + BH2 Lu ý : Peroxit ch HBr,, khụ ch cú nh h ng vi HBr khụng cú tỏc dng vi cỏc tỏc nh nhõ õn bt i xng khỏ khỏc nh nh HCl, HCl, HI, H 2SO4, H2O CH = CH CH3 + HCl peroxit CH CHCl CH3 + CH CH2 H BH2 + R CH2 CH2 BH2 ankyl boran Ankyl boran cũn liờn kt B H nờn cú th p vi phõn t anken na: 2R CH CH2 R CH2 CH2 BH2 (R CH2 CH2 B triankyl boran H2O2/OH B R CH CH R CH2 CH2OH + H3BO3 ( 2 ) ) c- Ph Ph n ng cng H2SO4 v hidrat húa ( cng H2O ) : Ph Phn ng c vi vi t tng cng nh nh sau: sau: R CH2 + H2SO CH R CH (1) CH3 OSO 3H R CH CH3 + H2O R CH R CH3 + H2SO4 (2) OH OSO3H CH CH2 + H2O H2SO4 CH2 1- BH3 2- H2O2/OH- R CH2 CH2OH so sỏnh: Cng (1) v (2) ta c phn ng hidrat húa anken: R CH R CH OH 3) CH3 (3) H2O/H2S R CH = CH2 O R CHOH CH3 Ph Phn ng ụzon gi gii cho s n ph phm l andehit ho hoc xờton tựy thu thuc cu to anken: anken: IV.2- Ph Phn ng oxi húa : Ph Phn ng oxi húa vi KMnO4 : a Vi dung dch KMnO4 loó loóng, ng, nhi nhit th thp : 3R -1 -2 CH CH2 + 2KMnO4 + 4H2O +7 3R -1 CH CH2 + OH OH CH CH2 +4 2MnO2 + 2KOH R' 1- O3 CH R CH R R' R CH COOH + CO + H O R + O COOH C CH CH + HOOC-COOH + O R" CH CH3 O CH CH + O O C CH3 H CH3 C 1- O3 2- H2O/Zn O + C C CH R' O H CH3 CO2 C =O + C CH R" CH CH2 CH H C R" V D D CH CH H R' KMnO4 C = O + HCH = O R" 2- H2O/Zn : V D D KMnO4 CH CH R C b Vi dung dch KMnO4 c, nhi nhi t cao : R R 2- H2O/Zn = 1- O3 R ng dng: P ozon gii thng dựng xỏc nh cu to anken: Ph Phn ng Ozon gi gii : R 1- O3 X 2- H2O/Zn Gm ph phn ng: ng: (1)- ụxi húa bng O3 v (2)- th thy phõ phõn cú mt bt Zn R1 R3 C C R2 R4 O3 CH2Cl2 O R1 C ( ) R4 O O Ozonid O R1 C R3 C R2 R4 O O H2O,Zn hoaởc H3O+ R1 R3 C R2 O + O CH O + O C R' CTCT X l: R3 C R2 R C R4 (2 ) 1: V D D X 1- O3 CH CO CH ( sn phm nht ) CTCT X l: 2H2O/Zn (CH3)2C = C(CH 3)2: 2: V D D Y 1O3 2H2O/Zn 2,3-dimetilbut-2-en CHO (CH 2)4 CHO Y l: Ph Phn ng th th H H : CH3 CH CH2 + Cl2 450oC Cl CH2 CH CH2 + HCl