BÀI TẬP HÓA HỮU CƠ ĐẠI HỌC

CHUOWN: TNG HP HU C Bi 1: Cho s chuyn húa: OH (H3C)2C= CH2 H2SO4 H3C A H2 / Ni (áp suất) B CrO3 C OH 1) CH3MgBr H+, t0 2) H2O H2O D 1) O3 2) H2O/Zn E a) Hóy vit cu to cỏc cht t A n E b) Hóy vit c ch phn ng t phenol to thnh A Bi 2: Khi cho isobutilen vo dung dch H2SO4 60%, un núng ti 800C thu c mt hn hp gi tt l i - isobutilen gm hai cht ng phõn ca A v B Hiro hoỏ hn hp ny c hp cht C (quen gi l isooctan) C l cht c dựng ỏnh giỏ cht lng nhiờn liu lng C cng cú th c iu ch bng phn ng trc tip ca isobutilen vi isobutan cú mt axit vụ c lm xỳc tỏc Hóy gi tờn C theo IUPAC v vit cỏc phng trỡnh phn ng gii thớch s to thnh A, B, C Bi 3: Tin hnh phn ng ime hoỏ trimetyletilen cú H + xỳc tỏc thu c hn hp sn phm l cỏc ng phõn cú cụng thc phõn t C10H20 Cho bit cỏc sn phm to thnh da vo c ch phn ng Khi ozon hoỏ hn hp thu c sau phn ng ime hoỏ trờn , ngoi cỏc anehit v xeton ca sn phm d kin cũn thu c mt lng ỏng k butan -2-on, gii thớch c ch hỡnh thnh butan-2-on cỏc phn ng trờn Bi 4: un núng Stiren vi axit H2SO4 ta thu c hp cht: Hóy gii thớch quỏ trỡnh hỡnh thnh sn phm trờn Bi 5: T isopren hóy vit cỏc phng trỡnh phn ng iu ch trans - - metylxiclohexanol Bi 6: Vit cỏc phng trỡnh phn ng( dng cu to) to thnh A, B, C, D, M, N theo s sau: CH3OH,HCl khan dd NaOH, t a) BrCH2CH2CH2CH=O A B b) BrCH2 CH2CH2COOH 1) ddNaOH ,t H ,t C D 2) ddHCl + + Br2 ,H O H ,t c) HOCH2(CHOH)4CH=O N M Bi 7: Cho s chuyn húa: OH H COOC2H5 (COOC2H5)2 PBr3 A KCN B H+ C C2H5OH C2H5ONa + H HCOOC2H5 (D) OCH3 OCH3 (C2H5O)2CO E F G a) Cho bit cu to ca cỏc cht t A n G b) Gii thớch s hỡnh thnh cỏc cht E, F, G Bi 8: T propilen v cỏc cht vụ c cn thit, vit s phn ng iu ch: a) Axit 2,5-imetyladipic b) Axit hept-2-inoic Bi 9: T xiclopentanol iu ch axit 2-oxoxiclopentancacboxylic Bi 10: T benzen v cỏc hp cht C, hóy tng hp: O CH CH2 CH2 NH CH3 a) b) CH CH3 OH NHCH3 C2 H5 O NH C CH3 c) Cl C4H9 NH SO 2NH2 H2N d) COO CH2CH2N(CH3)2 e) HO CH HO CH2 NH2 HO CH2 CH2 NH2 h) HO CH3 OH NH2 OH HO f) g) Bi 11: T benzen v cỏc cht C, tng hp: CH CH HO O H3C HO O CH3 OH C(CH3)2 a) b) c) Bi 12: T CH3CH2CH2CH2OH v cỏc cht vụ c, tng hp O O H3C CH3 CONH2 Bi 13: OH H3CO H3C H3C T H3CO H3CO COOH v cỏc cht vụ c, iu ch H3C N O CH3 CH3 H3CO O Bi 14: T H2N-CH3 v CH2=CH-COOC2H5, tng hp Bi 15: Khi cho isobutanal tỏc dng vi axit malonic cú mt piriin thu c hp cht A un núng A mụi trng axit thc hin phn ng ecacboxyl hoỏ thu c hai sn phm A v A2 l ng phõn ca A1 LiAlH4 A1 HCl A3 H3PO4 A5, A6 (A5 bền hơn) A4 (hợp chất no) Bit rng A2 b oxi hoỏ to thnh axit oxalic A1 l lacton Xỏc nh cu to ca A1, ,A6 v vit cỏc phng trỡnh phn ng Bi 16: Cú mt s dn xut gc CH3 ca axit axetic biu hin hot tớnh tng trng cõy trng CH2COOH OCH2COOH OCH2COOH Cl OCH2COOH Cl Cl (A) (B) Cl Cl (C) (D) Gi tờn A, B, C A c iu ch t naphtalen v axit cloaxetic cú mt cht xỳc tỏc 180 - 215 0C Vit phng trỡnh phn ng v gi tờn c ch ca phn ng B cng c iu ch t nguyờn liu trờn qua cht trung gian l - naphtol Vit s cỏc phn ng v nờu c ch C cng c iu ch t phenol v axit axetic Vit s phn ng Khỏc vi C, D c iu ch t mt dn xut tetraclobenzen(X) theo s : NaOH ClCH2COOH D X metanol H+ a) Hon thnh s trờn b) Trong quỏ trỡnh sn xut D ó sinh mt lng nh ioxin l cht cc kỡ c cú cụng thc: Cl O Cl Cl O Cl Gii thớch s to thnh ioxin C BI GII: Bi 1: a) (A) (B) OH (C) (D) O OH (E) CH3 CH3 O O H3C CH3 CH3 H3C CH3 CH3 H3C CH3 CH3 H3C CH3 CH3 H3C CH3 CH3 b) H + OH + C H -H OH + + OH Bi 2: CH3 CH2 + H C CH3 CH3 CH3 C (1) CH3 CH3 C CH3 + + CH3 C CH3 CH3 CH2 C CH3 (2) CH3 CH3 CH3 CH3 CH2 C CH3 CH3 CH3 CH3 C CH2 C CH3 CH3 C CH3 CH3 CH3 CH3 C CH3 CH (A) C CH3 CH3 H2/Ni CH C CH3 CH3 CH3 (> 80%) (A) CH3 -H CH3 CH3 Zaixep C CH3 C CH3 CH2 CH2 C CH2 CH3 (B) (< 20%) CH CH3 CH3 Isooctan(C) 2,2,4 - trimetylpentan (Qui ớc có số octan 100) * Isobutilen vi isobutan cú mt axit vụ c lm xỳc tỏc cng to C: C ch ca quỏ trỡnh tng t phn ng trờn giai on (1) v (2), sau ú: CH3 CH3 CH3 CH2 C C CH3 + CH3 CH3 CH3 CH3 CH3 CH CH2 C CH3 CH3 CH3 (C) CH3 H3C CH CH3 CH3 + CH3 C C CH3 sinh lại lặp lại (2) Cứ nh CH3 Bi 3: * Sn phm to thnh ime húa trimetyletilen: CH3 C H+ CH3 CH CH3 CH2 C CH3 CH3 CH3 CH3 CH3 CH2 CH3 + CH3 C C CH CH3 CH3 CH2 CH CH3 C CH3 CH3 CH3 CH3 CH3 C CH3 CH3 CH3 CH3 CH2 C CH C C CH3 C CH3 CH3 CH3 CH3 C CH2 -H+ CH3 CH3 CH3 CH3 CH3 CH2 C CH CH2 C CH3 CH3 CH3 * Ozon phõn hn hp trờn thu c: CH3 CH3 CH2 C CH3 C CH3 CH2 C CH3 CH3 CH3 C O CH3 ozon phân CH2 CH2 C C CH3 CH3 CH3 CH CH2 CH3 C CH3 CH3 CH3 CH3 CH3 C CH C O CH3 CH3 CH3 O C CH3 HCHO CH3 * S to thnh mt lng ỏng k butanon - l cú s ng phõn húa trimetyletilen, to thnh sn phm ph: H+ CH3 C CH CH3 CH3 C CH2 CH3 - + CH2 C CH2 CH3 H CH3 CH3 CH3 CH CH3 C CH3 CH2 CH3 + CH2 C CH3 CH2 CH3 CH3 CH2 C CH3 CH2 C CH2 CH3 CH3 CH3 CH3 CH3 CH2 C CH2 C CH2 CH3 CH3 H+ CH3 CH2 C CH C CH3 CH3 CH2 CH3 Khi ú: CH3 CH3 CH3 CH2 C CH2 CH C CH2 CH3 CH3 CH2 CH3 C CH3 CH3 ozon phân CH3CH2CCHO CH3 CH2 C O+ CH3 HCHO CH3 CH3 Bi 4: CH = CH CH = CH H + CH CH3 + CH3 C CH2 + HC Bi 5: CH2 H3C + CH2 t0,p H3C CH2 CH2 CH3 + - + H2B CH3 CH3 H B H H BH2 CH3 H2O2/OH H - H3BO3 Hiệu suất 75% OH Bi 6: a) Br-(CH2)3-CH=O NaOH HO-(CH2)3-CH=O t0 H O (A) OH CH3OH HCl khan H O OCH (B) b) Br-(CH2)3-COOH NaOH HO-(CH2)3-COONa H+ ddHCl HO-(CH2)3-COOH O (C) O (D) c) CH CH2 HOBr CH =O OH OH Bi 7: a) (A) B r OMe Br OMe CH2 CH OH OH (B) COOH + (M) H (C) Br O HO-CH2-CH O OH (N) (E) CN O COOH C2H5O2C C C OC2H5 O OMe OMe OMe OMe (F) (G) O C2H5O2C O C2H5O2C C C H OC2H5 OMe OMe b) Gii thớch s hỡnh thnh ca: OC2H5 COOC2H5 H C 2H5ONa - HC COOC2H5 + H C 2O C O H C 2O C O H5C2OOC - C O COOC2H5 H5C2OOC - C 2H 5O - O COOC2H5 OCH3 OCH3 OCH3 E: OCH3 Tng t, gii thớch c s hỡnh thnh F v G Bi 8: Cl2 HBr Na ,t CH2 = CH CH2Cl a) CH2 = CH CH3 CH2 = CH CH2 CH2 CH = CH2 4500 C Mg CH3 CH(Br) CH2 CH2 CH(Br) CH3 CH3 CH(MgBr) CH2 CH2 CH(MgBr) CH3 ete 1) CO2 HOOC CH(CH3) CH2 CH2 CH(CH3) COOH 2) H 3O + Cl2 Br2 Na ,t CH2 = CH CH2Cl b) CH2 = CH CH3 CH2 = CH CH2 CH2 CH = CH2 1:1 4500 C H / Pd CH2Br CH(Br) CH2 CH2 CH = CH2 CH2Br CH(Br) CH2 CH2 CH2 CH3 1) KOH / e tan ol CH MgCl HC C CH2 CH2 CH2 CH3 ClMgC C CH2 CH2 CH2 CH3 2) KNH 1) CO2 2) H O + HOOC - C C CH2 CH2 CH2 CH3 Bi 9: OH Br HBr MgBr Mg/ ete khan 2) H3O NaOH, t o COOH CuO, t o COOH 1) CO2 + COOH Cl 2/ P o t Cl COOH O OH Bi 10: a) CH 2=CH2 + H CH 3NH2 Pd, t C2 H5 o CH CH2 HBr, peoxit CH2CH2Br CH2CH2NHCH3 b) CO, HCl CHO AlCl3 CH 3NH2 CH CH CH3 HO OH CH C2H5 1) C2H5MgBr + 2) H3O KOH/etanol HOCl CH = CH - CH CH CH CH3 Cl HO NHCH3 c) HNO3 H 2SO4d Fe, HCl Fe, HCl NO2 NHCOCH3 H2N HNO3 H 2SO4 d NH2 NaNO2+HCl to NO + NH3HSO4 ClO 2S - C 2H 5Cl Fe, HCl Cl PCl5 NHCOCH3 NHCOCH3 HO Cl2 AlCl3 NO CH 3COCl NH2 HNO3 H 2SO4 C 2H O H 2SO4d + NH3 HSO H2NO 2S Cl NHCOCH3 d) + NH3 HSO4 HO 3S Cl Cl NH3 NHCOCH3 O2N - NaHCO3 Cl NH2 H2NO 2S Cl e) + + (CH3)2 - N - H + CH 3Cl CH3 AlCl3 HOOC (CH3) 2-N-CH 2-CH 2-OH O NH2 (CH 3)2-N-CH2-CH 2-OH C 4H 9Cl H9C4HN HNO3 H 2SO4d H3 C HOOC NO2 NHC4H9 KMnO 4, t PCl5 o HOOC ClOC NO2 Fe, HCl NHC4H9 COO-CH 2-CH 2-N(CH 3) f) o 1) NaOH,t ,p + 2) H Cl2 AlCl HNO3 OH Cl Fe, HCl OH OH NH2 NO NaNO2 + HCl o t OH CO + HCl HO AlCl3 OH HO HCN CHO HO HO CH CN H 2/ Pd HO HO CH CH2 NH2 HO HO g) HO KOH/ etanol CH CH2 NH2 HO HO HO CH CH NH2 H 2/ Pd HO HO CH2 CH2 NH2 HO h) HO CH 3CH 2NO2 OH CHO HO HO CH HO HO CH CH CH3 OH NH2 + HO NO HO Fe, HCl H 2O/H C CH3 CH HO HO CH CH3 NO Bi 11: a) CH2=CH-CH2Cl CH2-CH=CH AlCl3 HBr/ peoxit 1) (CH3)2CO CH2-CH 2-CH 2-MgBr 2) H3O CH2-CH 2-CH2-Br CH2 + CH3 C OH CH3 Mg/ ete H 2SO4 b) CH 3Cl AlCl3 CH3 Cl2, as CH2Cl Mg/ ete CH2MgCl 1) O 2) H3O CH2-CH 2-CH 2-OH COCl Cl CHCl-CH 2-CH 2-OH NaOH + CH(OH)-CH 2-CH 2-OH O O O c) o 1) NaOH,t ,p Cl + 2) H Cl2 AlCl3 H3C C CH3 H O HO + OH OH + H3C C CH3 HO OH CH3 OH CH3 + C CH3 CH3 OH HO CH3 C CH3 + H - H 2O OH Bi 12: CuO, t OH NH3, t H O + Br 2, H 2O Ag2O CONH2 Bi 13: CONH2 O CH3 O + H CH3 O OH + CH3 O CH3 H 2SO4,t o NH2 O CH3 CH3 COOH LiAlH O O O + CH3 + CH3 OH Bi 14: H + CH3 CH3 COOH CHO O O OC2H5 CH3 CH3 + NH CH2 CH2 COOC2H5 OC2H5 CH3 N CH2 CH2 COOC2H5 CH2 CH2 COOC2H5 C 2H 5ONa CH3 N + o H ,t O CH3 N O COOC2H5 (S dng phn ng cng Micheal v ngng t Claisen) Bi 15: CH3 CH CHO + CH2 COOH COOH CH3 CH3 CH3 CH CH COOH CH CH CH3 COOH CH CH3 Piriđin t0 COOH -CO2 OH CH COOH OH (A) CH3 CH CH CH3 CH2 COOH OH CH3 CH CH3 CH CH3 CH CH2 H+,t0 OH C CH3 CH CH3 CH3 CH3 COOH -H2O CH CH COOH [O] CH3 CH CH (A2) CH COOH CH2 COOH CH3 CH COOH + HOOC COOH CH3 CH3 CH3 C CH CH2 COOH H+ CH2 CH3 CH3 CH3 CH3 C CH2 O CH3 CH3 CH2 C LiAlH4 C CH3 CH2 C CH2 O H+ CH3 (HCl) C CH2 O C O (A1) CH3 CH3 O C C O OH + CH CH2 CH2 CH2 OH (A3) CH3 CH2 C Cl OH O - O C CH2 CH2 C CH3 Cl CH CH2 CH2 + H2O OH (A4) CH3 C CH3 C CH3 OH CH2 CH2 CH2 (A3) H3PO4 OH CH3 CH3 (A6) H2C CH2 C CH2 CH3 O + ClCH2COOH CH2COOH t0, xt SE + HCl OH OSO3H H2O ClCH2COOH -H2SO4 Kiềm, SN -HCl H2SO4 + H2 O (A5) Bi 16: A: Axit (1 - naphtyl)axetic B: Axit (1 - naphtoxi)axetic C: Axit (2,4 - iclophenoxi)axetic [2,4 - D] D: Axit (2,4,5 - triclophenoxi)axetic [2,4,5 - T] OH OCH2COONa OCH2COOH H+ -Na+ OH OH ONa Cl Cl2/CCl4 -HCl Cl NaOH -H2O Cl Cl 10 CH3COOH Cl2, P đỏ CH2COOH -HCl Cl NaOH -H2O CH2COONa Cl OCH2COONa ONa Cl Cl + CH2COONa Cl H+ -NaCl Cl Cl OCH2COOH Cl Cl Cl Cl Cl Cl ONa NaOH SN2Ar Cl Cl Cl (X) Cl OCH2COONa ClCH2COOH SN2 Cl Cl Cl OCH2COOH H+ Cl Cl S to ioxin: Cl Cl NaO Cl Cl Cl Cl Cl O + 2NaCl + Cl ONa Cl O Cl 11 12