Chaomg VIII DAN XUAT HALOGEN A-TY LUAN VIEL. C,HyCl 6 4, C5H, Br c6 8 va C,H, *, 66 9 déng phan. VUOL2. a) 1,1,2,3-Tetrabrompropan ©) 1-Clo-3-metylbut-2-en >) 2-Clometyl-1,1-dimetylxiclohexan _f) 7,7—Diclobixiclo[2.2. 1Jhept-2-en ©) (@)-2-Brombut-2~cn (hay trans-2-brombut-2-en) 4) (R)-2-Clobutan 8) frans-1,2—Dibroixiclopentan h) trans-1,4—Dicloxiclohexan VIN.3. a) CH;Br, Dibrommetan b) CHCI, Triclometan c) CH,=CH-CH,Br 3-Bromprop-I-en 4) CH;CH,CHBrCH, 2~Brombutan ®) (CH;),CHCH,G] 1~Clo“2“metylpropan 1) (CH3),Cl 2-Tot-2-metylpropan 2) CsHsCH,CI Clometylbenzen h) (CH),CCH,C1 1-Clo-2,2-dimetylpropan. YIIL4. a) CH;CHCICCI(CH,)C,H,-n b)h) % & a” NaI EVILS. C,H,Cl cé ca thay 19 déng phan nh sau: BCICH=CH-CH-CH, H,C=CHCICH,CH; H,C=CHCHCICH; CH,=CHCH,CHCICH, ‘cis va trans~ 2 d6i quang 2 doi quang F CICH,CH=CHCH, — HjCCHCI-CHCH, CICH=C(CH;), —_-H,C=C(CH,)CH,CI © cis— va trans— cis va trans~ Ch Cl Cl P= be cl CH 4 déng phan, vita hinh hhge, vita quang hoc THL.6. CH] > CHjBr>CH,Cl > CH,F > CH, (phan tir khoi gidm) CCl, > CHCI, > CHCl, > CH,C1 > CH, (phan tir khoi giém). E n-CyHyCl > n-C;HyCl > CHCl > CHCl (phan tit khdi gid). VIIL7.. CHsF < CHsCl < C)HsBr < CyHg] (tang phan tit khéi). CH, < CHCl < CH, Cl, < CHCI < CCl, VIIL8. C4c din xuat halogen tan t6t trong cdc dung moi it phan cuc (n-hexan, toluen, benzen...), khong tan trong cdc dung méi phan cut (nude, axit, bazd...). VIIL9. Phan tir c6 2 nhém proton khong twong duong, Br;_,CH,-CH,Br,.,. Vi tin higu cita CH, 1a van doi vay y=1, tin higu cia CH, 1A van bon vay x=3. Hop chat dé 6 cOng thife edu tgo Ik CH;CHBr,. VILL10*. C,HBr; 06 3 déng phan: 1,2,3-tribrombenzen cho 4 pic, 1,2,4~ tribrombenzen cho 6 pic, chi c6 déng phan 1,3,5-tribrombenzen cho 2 pic cacbon trén phé 46 251VUL11. VIIL12. VIM1.13*. VIIL.14. VIIL15. 252 '8C NMR: 6 = 133ppm tuong tng véi 3 nhém C-Br tuong duong, 8 = 122 ppm Mar twong ting v6i 3 nhém C- H tong duong. Syl: 1 tigu phan trung gian (cacbocation), 2 trang thai chuyén tiép, Sy2: khong 6 tiéu phan trung gian, 1 trang thai chuyén tiép A. n-Butyl clorua > Isobutyl clorua > sec—Butyl clorua > tert—Butyl clorua. B.I>Br>Cl>F~ D, H,C=CH-CHBrCH, > CH,CHBrCH,> CH,CH,Br > H,C=CHBr E. (CH,);CI > (CH,),CBr > (CH,),CCI > (CH,),CF VILL F. F2> Fl a) CsHSCN (Sy2) b) (CH;);COH (Sy1) * vu. ¢) CH;CH,CH,NH, (Sy2) d) CHjCHCH,I (Sy2) ©) p-CHy-CgH,-CH,OH (Sy1> Sy2) Phan tg theo co ché Sy1 c6 tgo ra ion bromoni (vong) trung gian, téc nhan Br in cong tir phia sau (tan cong kigu anti). Tir (28,3R)-3—brombutan-2-01 cho sin phdém & (2R,38)-2,3-dibrombutan (déng_— phan | miezo). Tir (2R,3R)-3-bromobutan-2-ol cho sin phdm [& hén hop, raxemic (2R3R)- va (28,3S)-2,3-dibrombutan. a) A. B. & Ll pie OH b) D. E. F. Ch by ay . bi c) trans-But-2-en d) trans—4—Etylxiclohexanol ¢) Etyl (S)-2~xianopropionat. X: CgHs-CHBr-CH,~CH,~CHBr-C,H, : CgHs~CH=CH-CH=CH-C,H, 2: CgH;-CH=OVIIL16*, Theo quy téc téch anti-, a) CHI > CH,Br. a) CH;CH,CH=CH, ©) (CHy),C=CH, ©) Pent-2~en wong ting la: a) b) A. CH=CNa* C. Na C=CG,H, BE. CHsC=CCH,CH,OH ©) A. Ph-CyHy C. PhCH=CH, E. PhC=CH ¢) CH,=CHCH,Br > CH)=CHBr + a) A2> Al do nang lung lién két C-Cl > C-Br (327 vi 214 kI/mol). b) Bl>B2 do dung moi trong phan img BI phan cuc hon trong B2, + 6 trang théi chuyén tigp, Br va H phai & vj tri 1,2-diaxial. Dang bén cita déng phan cis dam bao du nhanh hon), cdn dang bén ciia dén; chuyén sang dang kém bén nén phan (Hy0)0 Jer trans kém bén ie diéu kién nay (nén téch ig phan trans khong dép img duce, phii ting cham hon. (CH) Br wore LF cis b) CHCl > (CH,),CC. b) CH,CH=CH-CH, 4) Xiclopenten £) 4Propylhept~3-en. C8 3 déng phan quang hoe la CHsCHCICH;CH,CH, (1), (CH,),CHCHCICH, (2) va CICH,CH(CH,)CyHs, Cho hap chat'(1) phan img ta duge eée sin phim Pent-2-en, pentan—2-ol, 2~aminopentan, pent-2-ylamoni clorua, A. B. c ; Br ani cr D. E. F, fis CH CH B.CH=C-GH, D. GH;C=CCH,CH;O"Na* B. PhCHCICH, D. PhCHBrCH,Br 253HON, CH=CH, —92A82 , Brilen oxit F ' ‘VII.22. a) CHBr 1)C)HsMeBr = H)SO4d —I-en __CeHsCO,0H é ‘ — tno Butan-1-ol —*-#—> But-I-en io » £ H [ He eae ei 1) 2CHsBr —N*_ Butan —¥2_, CH,CHBrCH,CH, 8 KOH/C)HsOH_, Byt-2-en —CsttsCO20H_, HyC— é_tay, h fe NigCOy : 0 7) c) Benzen ae PhCH,CH; —#2_, PhCHBrCH ii —NaOH/HZ0 , phCHOHCH, fF ai VIL.23. cis-1,1-Diclo-2,3~dimetyIxiclopropan. ae VIN1.24*. Sin phém chinh: (R)-trans—hex—4-en—2-ol San phim phu: (R)-hex-S—en-2-ol va (R)-cis-hex-4-en-2-ol. VINI.25. a) i. Crezol (p-HOC,H,CH, va m-HOC,H,CH,). ii, o- m- va p-Metoxianilin: iii, o~ va m-Metoxianilin. iv. 0- vik m-Metoxiphenyl liti. b) Coché arint. ViNL.26. a) nButylamin, Sy2 d) But-1~en, E2 by n—Butyl iodua, Sy2 ¢) Hex-1-in, Sy2 : ) n—Butyl xianua, Sy2 f) Butan. E VIIL.30. VIII.27, a) CH,CH,D (S\2). b) (cH) ;P=CHCH, : c) 3~Metoxi-3—metylhexan (raxemic, Syl). VIHIL28. a) cH,cH,cuel aoe CHsCHCH—ONat z CH; CHis Bul don gp 1,0 254CH 1.29. a) hote 2CH,CH,OH - a) CH,CI-CH=CH,, Sp b) Br ws c) CgHsCHCICH, Sg E>) (CH,),CBr—MHS/H29 CH), CSH—MOH 5 (CH, )CSNa—CHsCHAC_, gp ©) CH;CH,CH(CH,)CH,Br —MOH/TRO |, CH,CH,CH(CH,)CH,OH —St; CHjCH,CH(CH,)CH,ONa —CH:CL, gp_ > d) PhCl NRL PhONa —Ghl_, sp. p ©) phcH,cl —N_, pacH,cn 8) (R)-2-Brompentan—N#OH/H20 _, (g) —Pentan-2-ol. (S) -2-Brom~ 4~ metylpentan —!—} sn phém. i) (CH,),CCH,-CH,Br —ROHICGHSOH san pham. \) trans -1— Clo- 4—isopropylxiclohexan —N#OH/#20 , sn phim. n) (S)—CH,CHCIC,Hs__NaCN/H,0 san phdm. H2SO4, 18000 O2/Ag CHsCH,OH = — pe" CH)=CH, ——— y Her Melete khan DY 2)H,0" CHyCH,OH —“=—» CHSCH;Br = CHyCH,MgBr Os ——> | CH,CH,CH,CH,OH ioe ctucticHecH, Hol gp 203 Os, CH)=CH-CH=CH, Het, But-1-en aH \ Hp va but-2-en —HCL , sp, b) Toluen —22 5 PhCH,Cl, toluen —C2 5 p-CI-C,H,CH, + 0~C-C,H.CH, d) (R) - CH,CHDCI ($2) ©) CHyCH,CH)Br (Ap, higu ting Kharat) 8) p~ CHCsH,F (+ BF; + Ny + KCI) 255 ahVIIL3I. a) (CH,),C ~ C(CH), b) 2,2,3,3+tetrametylbutan oO a ae g VIIT33. Xiclohexan —!2+Y_, xiclohexyl clorua —N&C=CNa_, pixiclohexylaxetilen °) Hz/PAPbOO3_, | 2_pixiclohexyleten =o 1,2—-Dibrom-1 ,2—dixiclohexyletan. VITL.34*. ’ HyC., OH H:80« Hy E+HBr—> A. E+ HBi/peoxit —> B. eB, Hi /THE saud8 4 2j0,-—>Choace Sale THE_, _HZO2/OW E+ BryCCl, —> D. VINL38. KoHICH,OH O On 7 oO Nas Q KOHIC3HsOH oO Br eg ot cl Crty AK an NA OO clay se > > sp Ch Cl Tanck yf Chef cl ca 256OCH,COONa “aot cee No cr e H,0° wee z 0. xc | . ; OCH,COOH cr ‘Oo cl cr cl — TRAC NGHIEM vunL37.D VINL42.C VUIL38.D VIIL43.D VIIL39.A VIN.44.B ViNL.40.B VIILASB VILLA VIIL46.A 257Cheong IX HOP CHAT CO NGUYEN T6 A-TU LUAN IX.2. CsHy MgCl cé 8 déng phan cau tao. Céch goi ten: ankyl magie clorua. 1X.3. a) CsHsMgCl i) BH, b) CH)=CH — MgCl D (CHP c) HC=CMgBr k) SiH,OH. d) BrMgC=CMgBr ) (CH,),CHLi ) H,C-S-CH;C(CH,), m)(C)H,),AL ) p-Br-C,H,-SO,-OCH, n) CsH,CdBr 8) p-O,N-C,H,-SO,*CI- 0) C,H,HgBr 1X4, IX.5. 258 h) (CH,),CH-SH a) Dietylsilan i) Btyl natri b) Axit metylarsonic j) Trimetylstiban c) Triphenylboran k) Tetraanlylgecman ¢) Metyl triphenyl photphoni clorua 1) Thiéc tetrahidrua (stanan) ©) Triphenylphotphan m) Tetraphenylplumban (Triphenylphotphin) (chi tetraphenyl) f) Btyl liti n) Triphenylbismutan 8) Diphenylcadman (Diphenyleadimi) _ 0) Axit etylphotphonic “h) Metyl thuy ngan bromua p) Dimety! liti déng. a) CoHs fe HsComb py o oo Hs CoHs mat phang guong 1) BTHHHC +8b) Gis y l py H CoH Cols c) Kha nang phan tg: CH,Na > CHjMgBr > CHHgBr (Mite do phan cuc cia cua lién két cacbon-kim loai cang 16n, tinh ion ciia lién két tang- kha nang phan ting tang). CH,Na chéy trong khong khi; CH,Na, CH;MgBr chi bén trong dung moi tro, tfc dung nhanh véi kiém, CO, trong khi CHjHgBr tuong déi bén (ae dung cham), a) Nang lugng lién két Si-Si nhd hon C-C (7,2 kJ/mol), do d6 dai lién két Si-Si 16n hon. b) Xen phi 3p—2p kém hiéu qua do's chénh Iéch kich thudc céc obitan c) Do tong tac cita obitan d ciia Si va p cia O. a) Nhiét d6 s6i tang do phan tit khéi tang. b) Nhi¢t do soi tang khi phan tit kh6i tang va gidm khi khong con lien ket hidro. GH, 8) (H,),COHC Hs b) C,H,COOH h) C,HsCOH(CH,)C)H, c) Butanol i) CH,CH,C=CMgBr + C,H, d) Etyl clorua k) Xiclopentadieny! magie bromua va etan e) CHyCHOHC,H, n) (CH,),CHOH £) (C,H;),COHCH, m) (CjH,),CHOH. © IX.10. a) Kha nang phan ting: RCOCI, (RCO),0 > RCHO > RR'’C = 0 > RCOOR’ 259IX.11. 1X12. 260 Hop chat co magie + este thoat dau tao ra.xeton, kha nang phan ting cia xeton cao hon ciia este nén n6 phan ting tiép thanh ancol. b) Trong hén hop-e6 cdc phan ting sau: n-CyHoMgBr + CO, >» 120", n_C,H,COOH n—C,HoMgBr + H,O — CyHjq + Mg(OH)Br n-CjHpBr + n-C,HyMgBr -> C,H + C,Ho + MgBr, nC4HgBr + n-C,HoMgBr -> n- CyHy-CyHy -n + MgBry a) (CH,), CHCHOHC,H, ©) CH,CH,C=CH b) (CH;)sCHCOH(CH,)CH, —_f) Propylxiclopentan ©) GH,C=CLi g) CH,CH,CH,D. d) n-Pentan. a) cl on 0 O = Or 7 oy Cas CaM oni 2 140" b) Ph sscooe sn: Cts MeBe cHCOOG Hs my ou ¢) O oCF ==CNat > 2) 4,0 o : cH 2 cr rae CHC==cri A a 2)H,0° 1) Naki > 2 2) CH;CH,-O8—cH, °cia I)NaBHy/mesyl clorua Her CHyCHyCOCH, one CHyCH:CHCHy —" cH cuscricn, 220 OH a CH3COO'Na’ ee ata CH;COOCHC)H, CH; 1X14. IF a HO cigar —METHP Mee Hat cHcin , CcHsCHOHCH(CH,), P21, cH, COCH(CH,), 1)C,H,MgBi C)H;CoocH, 2CsH>MgBy (CsHy),.C—CyH, 2) H30* OH 4 0 ‘MgBr | (CH1s),CHCH=0 ———$5™" (cH), cH 2) HO" | On CoHeBr —MB/THF , @ “HsMebr Let CHsCH,CH,OH 00 AN I M (CHy),CHMgpr ——2_ (CH3),CHCH,CH,OH a (CH3),CHCH,COOH 2) Hy0* oll, CH; CyHyMgBr ———— ii 2) Hot 4 1)C3H;CH=O0 | cro; (CHs),CHCH MgB 5, — —CHCH(CH); ——> 2) Hy OH — ue Teena CoHsMgBr —'CCH=O , CcHsCHOHCH,CH, C's, CH.COCH, ESRC Mabe, CsHsCOH(CH,), UB, CoHsCBr(C,Hs), 2.H30* 261i) Xem much, DCH sMgBr IGE + C.H,CH,OH O03, CH,CHO 1X.15. a) Oxiran, oxetan Ia nhiing vong 3, 4 canh, site cang cita vong 16n, chting c6 xu hudng cong — mé vong, vi thé chting phan img dé dang véi thudc thir Grinha. THF la vong 5 canh, site cng vong nhd, khé bi pha vo. b) Cac dung m6i thudng ding: THF, dictyl cte, disopropyl ete ... Dung moi THF thudng duge sir dung khi C trong lién ket Ckim loai 6 trang thai lai héa sp’. 1X.16. al CoHsLi I(CH),C: Doge — essen ee cay ecu DOES cr yore 2) HjO* on >) cyHycocn, —N2BHs_, c,H,CHOHCH, °) HyfPd, PbCO3 1) BH, \ CgHs-——C==CH ——— CH CH=CH, ———_CgHHgC HCHO 2) H,07/H1,0 Na CHI > CHsCHCH,0°'Nat —— > G,HsCH,CH,OMe 1X.17. a L op omen 140" oc oT ob a b) CH; CHCl CHyMgCl _Megletekngn_ _CaHYCHICL —TMgch > CpHsCHCH2CcHs 262 1X1c) cl ch C KOWC,H,0H NBS, hy cc, Be (Chia = cincati Ht —_—> “cu CH= Ci + LiBr Noa \ HBr Me/ete khan (CHy),CHCH,OH > (CH;),CHCH;Br ———t (CH),CHCH,Mgbr cr 2» (CHy),CHCH,CH,CH,OMgBr HOS (CH) ,CHICH,],0H oxiran NaNH; C)HsBr HC2CH—NaNth_, HO=CNa FS HcsC-CH,_NaNH, NaC=C-C,H; —°8 _, NaOCH,CH,C=C-C,H,_H20_, HOCH,CH,C=C-C,H, — 12> HOCH,CH,CH=CHC)H, Bi cu Ste BS crc c—Mepr Se CHC: CHy —C(CH3)> NH,CI 1,0 Omger 1)CH;CH,CH=0 2) H,0* CIMgCH,COOCH, ‘CHyCH,CHCH,COOCH, OH 7 LCD MgBr ayo H,C=CHCHO —a > H,C=CHCHOHCD, HaC=CHCH)Br + H,C-CHCH)MgBr —yit—> (CHy=CHCH,), P )2CD.MeBr | cucoocn, Y2E2M8Bt j1.e—c—on 2) Ho" | cp; 1) axcton 180, cimgctt,coocn, a (CH,),c—cu,coocn, 2S H;0* on — cH, ‘CHCOOCH; 2631X.19. a) b) 1X.20. b) IX.21. 264 HBr CuHoLi (CoHs)P— 3 (Cyl) 3P’—CHsBr ee (CelHs)sP=CH(CH3), ~ CoH (CH3):CHBr ih -_CoHsLi® al (Catt PEAS (cots?! -CH(CHS) Br SE On (CattnP=CICHy) cre Libr es (CH), Se CHyp=0 + CH! (CH,0),;P-. ——— CH,OCH; + Pl; 200°C CoHsMgBr CHOCHH)s cH,C=cH > cHy;C=cMgBr————_ CH;C=C—CH(OCH;), A) = C)HsOMgBr (B) ,0° os Se cHyc=ccHo © HBr Mp/eté khan (Ch)gC=CHCH; ——S= (CH2)CBrCH,CHs, \——— (CH,),CCaHs MgBr nD Dos Cryjcontig\ PO CHyc—Caly 2) HO" (CH,CH;0H CH,CH,CI soch, My/ete khan 1)CH,COOGHs CH,CHC,H, ——™ CHjCHCyHs —— mune sae ba a MgCl eS eee ct, OF BrMgCH,CH,CH,CH,MgBr4) CH, =CH, + BrMgSCH, — ne CH,CH,CH = CH, + Mg(OCH,)Br 3C.HsMgBr + PC; > P(C,H,) + 3MgBrCl b) CgHsMgBr + HgCl, — C,HsHgCl + MgBrCl C,HsMgBr + CdCl, > CoH,CdCl + MgBrCl d) CgHyMgBr + ZnCl, > C,H,ZnCl + MgBrCl CcHsMgBr + SnCl, -> CoH,SnCl + MgBrCl 4CgHsMgBr + SiCl, > (CgH,),Si + 4MgBrCl. CH;MgCl + HgCl, > CH;HgC] Me, (cH,),Hg CHMgCl + SiCl, > (CH,),Si + MgCl, (CH,),CHMgCl + SiCl, — [(CH,);CH],Si + MgCl, (CHs),CCH,CH,Mg€l + CdCl, ~ [(CH;);CCH,CH,],Cd hy CH, + Cl, —“s CHCl cH,ci Meee kha cH mec 22% HD ZnCl CH;MgC1——» (CH),Zn 1)€0, CH;OH 1)2CH;Mgcl CH;MgCl ———» CH;COOH err CH;COOCH, 21,0" : 2 Ho" —® (CH;);COH eee (CH3);CBr —— (CH)),CLi CH,CH,CH,Br hoo, CH,CH,CH,OH S95 cH,CH,CHO ae CHsMgBr 1,0" Sein >? 2 CH.cH),cHon HBL, Li, (cH,0H,),081L =| i 1.25. [(CgH,):PCH'Cr' Sets, (CHy,P=CH, 1X.26*, a) b) ©) 1X.27. CoH LiCl PC + 3 et ocr cH:08 SP + 3HCI cr PCI; + C4HySH ——# P(C\HoS); + 3HCI 9 (CH,OH Ht PCh ——POCH), pq H—PCOCHS (Dimetyl photphonit) on &Y ten [01 (bay PH; —— Ron HOt ) FF o cccH=0 > CCCH—PLOCH) (Clorophot) I B- TRAC NGHIEM 266 1X.28. 1X.29, 1X.30. IX.31. 1X.32. B D B c Cc on 0 f on cleo olor, UsAsOy ine HNOYH SQ. a (Gucody hed asin, SneaNe ~ ity NHCOCHS on 1X.33. B 1X34, B 1X.35. A 1X.36. C 1X.37. DChung X ANCOL — PHENOL - ETE X.2. X.3. a) Ancol: nhém OH dinh vio op ; Enol: nhém OH dinh vao Coe khéng thom. b) Ancol thom: phan tir cé nhan thom nhung OH dinh vao C khéng thom; Phenol: OH dinh vao C thom. c) Diol: ancol cé hai nhhém OH; Gemdiol: ancol ma 2.nhém OH cing dinh v6i 1 C- d) Diol: ancol 6 hai nhém OH; Ancol bac hai: ancol ma nhém OH dinh véi C bac hai. pera “ye oe a “Butan—1-ol 2-Metylpropan-l-ol_~ Butan-2-ol 2-Metylpropan—2-ol E Ancol butylic AncoLisobutylic Ancol sec—butylic Ancol tert-butylic (Butyl ancol) (isobutyl ancol) (sec—Butyl ancol) —_(tert-Butyl ancol) Ancol bac T Ancol bac I Ancol bac II Ancol bac III a) Pentan—1-ol; Ancol amylic. b) 3-Metylbutan—1-ol: Ancol isoamylic. ¢) Prop-2-en—1-ol; Ancol anlylic. 4) Phenylmetanol (phenyleacbinol); Ancol benzylic ¢) 2-isopropyl-S~metylxiclohexanol; Mentol. g) 3,7-Dimetyloct-6-en-1-ol; Xitronelol. a. ) va (Z)~ 3,7-Dimetylocta-2,6-dien—1-ol. b. (R) va (8) 3,7-Dimetyloct-6-en-1-ol. c. (R) va (8)- 3,7-Dimetylocta~1,6-dien-3-ol. 267X.5. bén hon R-CH-CH; bén hon R-CH)- CH, oS ae R-CH- Ci +, AcOHg) AcOHg AcOHg X.6. enna (CHy))CH - CH, - CH) - OH Xl a ; a. (CH3)CH - CH= CH,;—J L He(OAc)H, i Ne : ETE ES (CHy)xCH - CH(OH) - CH, b) Tirmetylenxiclopentan, twong ty ctu a. c) TW CH, = CH - CH(CH,)C,Hs hidrat hod xtie tac axit (¢6 chuyén'vi) va hidroxi thuy ngan hod réi khit bing NaBH,/HO™. X.7. a) Phin ting (1) va (3) tao ra khé nhigu sin phim khong mong mudn Ia cdc dan xudt di-, wi-, tetracloro virthai HCI ra moi trugng, Phin img (2) va (4)'tieu tn NaOH 1a hod chat dat.'So'd6 diéu ché d6 khong sir dung dugc. b) CH, + H,0 —¥ ; co +2H, —"_, CHO > CO +3H, CH, = CH, H,0,H;P04,300°C,80atm CH,CH,OH (Btilen lay tir khi crackinh) X.8. a) Butan—1-ol, butan-2-ol va este (axetat, propionat, butyrat) cla chiing ding Jam dung m6i pha son t6ng hop. Butan~2-ol ding dé diéu ché ety! metyl xeton; ancol tert-butylic ding dé sn xuat tert—butylphenol lam chat chong oxi hod, b) —> (CH;)CH-cHo = HN. (CH), CH-CH,OH CH; - CH=CH, —€Oth _| 2 Ep. [Co(COnl L_» cn,-cHj-cH,-cHo 2 Ns cH, - cH) “CH, - CH,OH 268 SSCH3 - CH, -CH=CH, — pee Oly CH, CH- chs CH3;-CH=CH-cH, —J , OH @ 9. HL/Ni (Pt, Pd): khir cd nhbm C=C,C=C va NO, E COOH va COOR. Thutng ding trong cong nghiép dé k 1 Va xeton thanh ancol bac 2. khong khit duoc nhém — hit andehit thanh ancol bac LiAIH,: khong khir nhém C=C nhung khir ca nhém — COOH va COOR dén ancol bac 1, nhém NO, dén NH. NaBHj: khong khit hm C= C, - COOH, COOR va NO). LiAIH, va NaBH, thug ding trong phong thi nghiem, NaBH, rétién hon, dé bio quan hom, khong ddi héi moi truémg khan nhu LiAIH,. X.10. a) (i): CHyCH,CH,CH,OH; (i) va (iii): CH,CH = CH CH,OH. b) (®: p-HQN-CoHly-CH,OH; (i): p-O,N-CoH,~-CH,OH; (iii): p-HN-C,H,-CH,OH. ©) © va ii: CH,CH(OH)CH,COOK; (ii): CHyCH(OH)CH,CH,OHL. 4) (i): xiclohexanol; (ii) va (ii iclohex-2-en~1~0l, ®) CoHsMgBr + CHjCOCH, hoae CH, MgBr + C3H,COCH,, b) CH, = CH - CH,MgCl + HCHO hoac CH, = CHMgBr + etilen oxit, Chi: ¥: CHy=CHC) kém ‘hoat dong nén khon, CH,=CHMgcl. ©) CHsMgBr + CH3C = C~CHO hoae CHyC= CMgBr + CH,CHO, Chit ¥: CHyC = CH + CHsMgBr ~> CHyC= CMgBr + CH,. 4) 2CH,MgBr + CH;COCH,CH,COCH, hoac tan on 8 phan ting véi Mg dé tao ra Ho" i BrMg-C = C-Mgbr —2H:Coci, #0" yi. am Chui §: BrCH,CHBr + Mg —°©> CH, = CH, + MgB, col X.12. @) 2Cly = CH CH,MgCICICHSCHCy CH2 = CH (CH3),CH = ch Sa BrCH,(CH,),CH,Br gM EBS OH ,CHCaC(CH,),CHsBr Tecan > CHsCH;C=C(CH),CH,OH = 3.H,0° e1y,c00n. = CHSCHSC=C(CH),CHOCOCH, Hae = cis-CHyCH2CH=CH(CH,),CH,0COCH, 269b. CHyCH,C=C(CH,))CH;OH -NeNHi Io trans-CHyCHyCH=CH(CH2)yCHjONa CH,COC! TCOCN, frans-CHsCH,CH=CH(CH;)gCH,OCOCHs X.13. a) Cay CaHg C4Ho C4Hy Ht OH HO: H HO: H "HoH H CHy gC H CH3 Hy3C—-—H CyH; CgHy C3H7 CoHy, (42,35) (48.52 (ARSRY (48,5S)-4-metylnonan-5-ol a b. CHjCH,CH,CH-CH, Gra CH,CHyCH,CH,CH,OH —> 28 CHyCH;CHyCHyCH=O CH;CH,CHyCH=CH) swe CH,CH,CH,CH(CH,)MgBr CH,CH,CH,CH,CH=O + CHyCH,CH,CH(CH,)MgBr —> 49) CH,CH,CH,CH(CH;)CH(OH)CH2CH,CH2CHs X14. a)C>A>D>B b)G>K>E>L. X15. Nhan xét hexan-1-6l c6 khoi lugng phan tir 1én hon glixerol nhung Pres ty, 40 tan trong nude va th kh6i déu nhd hon so véi glixerol. Gi8i thich: Dya vao s6 Iuong lién két hidro lién phan tit va hinh dang phan wh. X16. a) Khoi luong ri¢ng cia dung dich gidm Khi néng d6 etanol tang, vi guuag) = 057893 g/ml nhd hein $0 VEi dyy,q = 1,000 (6 20°C). b) Thi du, tinh v6i 1! (1000ml) dung dich etanol 50%: Khi lugng 1 Lit dung dich etanol 50% la: 1000 x 0,9138 = 9138 g. Kh6i lugng etanol da ding = khéi lung nude = 913,8: 2 = 456,9 g ThE tich etanol di ding: Ve,1,o11 = 456.9: 0,7893 = 578,9 ml. Thé tich nuée da ding: Vy, = 456,9: 1,00 = 456.9 ml. Vo,non + Vu,0= 578,9 + 456,9 = 1035,8 ml > 1000 ml. ‘Tinh véi 1 lit dung dich etanol 90%: 270Tuong tu tren tinh duoc Vo,y,0% + Vujo = 932,7 + 81,8 = 1014,5 ml. Nhu vay thé tich dung dich etanol thu duge lun nhé hom téng thé tich cita etanol va nuée 4% ding. Nguyen nhan: lién ket hidro lien phan tit gitta HjO va C,H,OH manh hon. Dung dich etanol 50% c6 do rugu la: (578,9: 1035,8) x 100 = 56°, Dung dich etanol 90% 06 do rugu Ia: (932,7; 1014,5) x 100 = 92°, d) Néng d6 % etanol trong rugu 96° la: ((96 x 0,7893); (96 x 0,7893 + 4)] x 100 = 95%. a) Van hap thy héng ngoai voy: 3200 — 3600em™, manh, 1a, Van cong huténg tir proton elia nhém OH c6 49 chuyén dich hos hoc bién déi: 0,5 ~ 4,5 ppm, d6i khi bi Han vaio van HO dm hoac bj "nho’" di do lien két hidro, vi vay thutng khé nhan biet. Ion phan tit ancol thudng bj phan cét c tao ra ion oxoni b) Ding phuong phdp phd IR thuan Igi va chudn xdc hon ca vi tin higu cong hudng proton ciia OH thuéng bien déi, doi khi bj lin vio van H,O dm hode bi nho’ dido hen két H, khd nhan biét, con ion phan tik ancol thi c6 tung hgp thy dude, c6 trudng hop khong thiy duoc va sy phan cat a 1A dac trung cho ca ete, ami a) Rugu tuyét d6i vé nguyen tic 1A 100% etanol, Ruom tuyét doi bén trén thi truéng vin chita mot luong nhé nude do Ki thuat tinh ché va do né wy hat dm trong qué trinh bio quan. Tir rugu loding ngudi ta chung cit phan doan (thap chung cat) dé thu "rugu dang phi"'(96"). Tigp theo them mot it benzen (hoae mot cau tit kh ©6 kha nang tao hén-hop dang phi véi nude) réi chung cat phan doan thi loai di dutge én hop. dng phi 3 cau tir (CHJOH, CcH, vii HO). Khi rugu da vugt qua ‘anh phén ding phi (>96°) thi chung cat phan dogn sé loai di dugc hén hop ding Phi (C,HsOH va H,0) con lai rou gan véi sugu tuy@t di trong binh chung cat @) Su phan cut lién két O-H, d0i electron ty do 6 oxi b) Ancol [a axit yéu: khong lim 46i miu quy tim, ancol hau nhu khong tée dung v6i kiém. Chang han pentanol, xiclohexanol khéng hoa tan duoc trong dung dich NaOH trong khi.dé CgH;OH thi tan. Ancol chi tc dung duge véi cée kim loa kigm va kiém thd, ancolat bj thu phan hodn ton trong nude (tc ancol IA axit yéu hon nuée). Ancol 1a bazo yéu: ancol khong lam déi mau quy tim, ancol hdu nhu khong: phan ting voi dung dich axit loang, ce ancol khong tan trong nuéc thi cing khong tan trong dung dich axit long ma chi tan duge trong axit sunfuric dic ROH +H,SO, = ROH,* + HSO, ROSO,H + H,0 271X.20. X21, X.22. X.23. 272 a) Tao duge phtic vong cang (5 canh) bén, tan trong nude. b) Hai nhém OH vixinal am cho H cita nhém OH 6 gidta linh dong hon va téch ra cing véi OH cita Cu(OH), tao thanh nude (tuong téc axit-bazo) va hinh thinh lien két C-O-Cu; nhém OH 6 cacbon diu mach tao véi Cu** lién két phéi tri, cau hin trans dé tao thanh hon cu hinh cis. Cin ctr vao nhiing nhan xét dé ma Iya chon cong thite ding. 4 HOH:C-HE—OW >o— CH, HOH:S-HE—OW 0G, Su Ww He—0f OCH. CH,0H Hee—o% “So—cH-cHoH oO a) H H z HOH,C - Heo _-0—CH, HOHC-He—0&_-0—cH.CHOH v C Heo S0—CH-cH,0H He—0~ S0—CH an 4 avy oH ©) A VAC Wi chting ¢6 cdc nhém OH vixinal. a) Luc bazo: ancol bac TIT > ancol bac TI > ancol bac I. b) Khong, vi sy solvat ho4 ROH," sinh ra trong nuéc va trong ancoll [a khée nhau nhiéu. a) ROH + CHyMgBr > CH,? + ROMgBr b) ROH + LiC,Hy > CyHj9 + ROLI c) 4ROH + LiAIH, > LiAWOR), + 4H, 4) ROH +KOH = RO K* +H,0 e) ROH +NaNH, > NH;1 +.RO”Na* ) ROH + NaC=CH > C,H)? + RO™Na’ Co ché phan ting: ()H;OH + H* ‘ C)HsOH) bt ‘OH, + GH;OH) + Br = HBr + H,0 CH; A. Luong HO nhiéu, phan img khé xay ra. B. La cach thich hgp nhat, C. 6 nhiet do phong téc do phan ting rat cham. fi tao duoc HBr khan va H)SO, c6 tac dung hiit nude.20H .24. a) ZnCl khan hod tan trong axit clohidrie bo khéi. b) R3C-OH + thuéc thir Lukas: tod nhiét, tao thanh R3C-Cl dang dau tach ra, R,CH-OH + thudc thit Lukas: khong thay tod nhigt nhumg sau 5 phuit thay c6 lép dau tach ra. RCH,-OH + thuse thir Lukas: & nhigt do phing khong c6 hién tuong gi xay ra. Vai trd ciia HC] va cla ZnCl, 1a tao phic véi ancol via hod tan ancol vita lam cho OH dé tach ra duéi dang H,O phéi tri véi Zn?*- ROH + ZnCl, + HC — RTZn(H,0)C,) —2 ROI + [Zn(H,0)CL) a) A: (CH),CHCH,CH(OH)CH;; B: (CH,),CHCH(OH)CH,CH,. \C) Ht ) (CH),CHCH, - CH - CH Sy (HCH C: * ae’ Ss, CH: i oe ay (H3C) HC. CH; PP Sesen (CH,),CHCH,CH=CHy 4” (a2) (A3)_. (phu) (CHs)xCHEHCH,CHs 77 (Ch),CHCHCHGCH, +> (CH)),C=CHCH;CH, + Al-+ a2 @ (B1) (chink) (CH;),CCH,CH,CH, TiP™ BI + CH, = C(CH5)CH,CHCH, (chinh) (B2) phu c) Téng hgp A tir ancol isoamylic va ancol metylic: (CH,),CHCH,CH,OH —S2""_ (CH,),CHCH,CH=0 —CUsMaBr_, _ HO", ‘Téng hop B tit ancol isobutylic va ancol etylic, tuong tu nhu trén, Al: CH,CH=CH,; —A2: CH; A3: CH,=CH,; A4: CH;CH;; A. BL: CH;CH,OH; —_B2: CH;CH(OH)CH,; BS: CH,CH,CH,OH; Cl: CH,COCH;; C2: CH,CH,CH=0; C3: CH,CH=0 a) Chit ¥: ancol khong no va andehit déu Lam mat mau nude brom. >) Chit ¥: phenol hoa tan trong dung dich NaOH hoac Na,CO,; Ancol benzylic cing nhu ancol anlylic phiin tmg v6i thude thir Lukas wong tw nhw ancol bac Ill (xem bai X.24), 273X.28. a) OH HO. OH Ho’ OH 1, 2,3, 4, 5, 6-hexahidroxixiclohexan. OH b) Réin, tan nhiéu trong nude. c) Tao ra hdn hop cc este chita t6i da 6 nhém axetyl. X.29. a) Tach H,0 ri lai cong H,0. b) Cong véi HCHO ri hidro hod. ©) CH,=CH, ABO, HeQ~CH, es HO - CH,CH, - 0- CH,CH, - OH y qi 4) CHs[CH,],CH, —Refomin_, xiclohexan —22*" 5 xictohexanon HN 5 xiclohexanol. e) CHy-CH=CH) Ag CH = CH - CH,CI 22428 cic, - CH(OH)~.CH;C! ES Hoc, - cH(OH)-CH,OH X.30. a) CyHpq420 + 3n/20, > nCO, + (n+1)H;O qd) CyHom4g0 + 3m/20, > mCO, + (m+1)H,0 (2) Goi s6 mol cia A va B la x way, theo (1) va'(2) c6: Noo, = NX + my = 3,584: 22,4 = 0,16 mol (a) Dyo= (n+ Dx + (m+ Dy = 3,96: 18 = 0,22 mol (b) (b) ~ (a) = 0,22 0,16 = 0,06=x+y © Ma + Mg = x(14n + 18) + y(14m + 18) = 14(nx + my) + 18(x + y) @) Thay (a) va (c) vao (d) ta duge m = 3,32g. Mg y= 3,32: 0,06 = 55,3 CyHoq420 < 55,3 < CyHm420 Voi m = n+ 1 suy ran =2;m=3. A: CH,CH,OH; B: CH,CH,CH,OH b) Thay n = 2, m = 3 vao (a) két hop véi (c) ta c6 hé phuong trinh: 2x + 3y = 0,16 > x =0,02 x+y=006 —>y=0,04 CyH;OH: 27,7%; CyH,OH: 72,3%. 274 18 BTHHHG -Ba) (CH,);CCH,OH + H* > (CH,);CCH, * “15 (CH,),C'CH,CH, —_, (CH),C(CDCH,CH,. V6i B cing xay ra sur chuyén vi tuong tu. b) (CH,);CCH,OH + PBr; > (CH;);CCH,Br + HPO . Véi B tuong tu. ©) (CH,),CCH,OH + C1SO,C,H,CH,-p —>(CHs);CCH,-OSO,C,H,CH,-p. Voi Btwong tu. 2, ,OH OH 1H ‘OH I es o-pinen a-tecpineol B-tecpineol y-tecpineol ; 33%. CH=CH, CH=CH, CH=CH, nye He e" opty CH,CH, -¢= CH - cH, he CH;CH, - C = CH - CH,OH dns Guy (Khong quang host) ak i+ ) CH, = CH - CH CH, i> [cH, “cH CH - cH; as Gy-cH=ch-cHy] : “Hy F OH BEe Chhy=CH-GH-CHy + BrCl -CH=CH-CHy Br pc) CH, = CH - CH-CH =CH- CH, ao cH, =cH-CH-CH=CH-CH, <> OH + CH, = CH-CH=CH-CH-CH, <> CH,-CH=CH-CH=CH-CH; +H,0, Typ” CHa = CH-CH=CH-GH-Cly + CH-CH=CH-CH=CH-CHy OH OH 275+H + @) CHp=CH- CH=CH -CH{CHjOH—Jpg™ CH, = CH - CH = CH-CHyCH Sey, ct; =CH-CH=CH-CH-CH; —»cH,=cH -¢H-CH=CH-CH; <> Gtiy-CH=CH-CH=CH- CH] +12, Cl= CH “CH =CH-CH-CH, + OH Ciy“CH-CH-CH=CH-CH + Cty-CH=CH-CH=CH-CHy OH OH KhA ming tg0 ving 6 canh eiia srans~CHj=CH-CH=CH-CH,C’H, rét nhd vi ctu hinh trans cia n6, x.34, ») \ C=C—OH =——~ H-C—c=0 7 I enol xeto Ta so sénh nang long hinh thanh dang enol va dang xeto bing cach tinh téng nang lung céc lién két khéc nhau gitta 2 dang: Al, (enol) = Beg + Ee-g + Egy ~ 614 + 359 + 431 = 1404 kJ/mol AH, (Xet0) = Be.¢ + Eo. + Eg-y ~ 736 + 351.4410 = 1497 ki/mol Dang xeto bén hon dang enol 93 kJ/mol: Oe © Mot céch gan diing, tuy dang xeto bén hon dang enol 93 ki/mol (nhu da tinh & ren) nhung chuyén tiy nhan benzen sang dang xiclohexa-1,3—dien phdi ton 150 kJ/mol dé pha vé sy lien hop thom (nang luong céng huéng cia benzen, so véi xiclohexatrien) va khoang 17,5 kJ/mol dé pha v6 sy lien hop cia lign két doi thi 3 (cla xiclohexatrien so v6i xiclohexa-1,3~dien). Vi vay dang phenol bén hon dang xeto tuong img khang: (150 + 17,5) - 93 = 74,5 kl/mol. (Xem ning lung cong hung cia benzen, nang lugng li¢n hop 6 dien lién hop). ise. intone, X.38. b) Chite phenol: CH3CgH,OH; o-, m-, p-crezol (2-, 3-, 4~metylphenol). hitc ancol: CsHsCH,OH; ancol benzylic, phenyl cacbinol, phenyl metanol. cH. Chife ete: CH,OC.H,; metyl phenyl ete, anizol, metoxibenzen. Fy 39, Ba) HO 276au ng 16 50 161 3 ng ng K:36. b) Phuong phap chuyén amin thanh mudi diazoni 16i the: dung trong phong thi nghi¢m vi né tign hanh diéu kign t khong ddi héi nhiét d6 cao va Ap suat cao. 'Y phan thutmg duoc 4p huan tign, nhanh chéng, Phuong phép oxi hod cumen hign nay duoc ding trong cong nghi¢p dé sin xuat phan I6n phenol vi nguyén li¢u ban du 1a benzen va propilen tir khi crackin, digu kign phin img ém dju hon phuomg phép thuy phan clobenzen, lai khong tao-nhiéy phé thai va sin xudi duge déng thdi cd axeton, vi vay gid thanh ha hon, 37. Bang dudi day cho niet do néng chay, nhiét do soi va do tan trong nude eita cfc : chat c6 lien quan Nhiét d6 néng chdy | Nhiét d6 sai Dé tan ec) Cc) (g/100g H1;0) Phenol al 181 6.8 (16°C) Xielohexanol 25 161 4.2.(10°C) Flobenzen 45 85 # Anizol 315 154 0 7 o-Crezol 31 191 3,1. 40°C) m-Crezol 12 203 20,8 erro) Benzen-1,2~diol 105 + 246 45 (20°C) | Benzen-1,3-diol M0 a7 229 (30°C) Giai thich: a) Phan tit phenol gon hon va phan cuc hon xiclohexanol. b) O phenol e6 lign két H lign phan tit con flobenzen thi khong ©) 6 ede crezol e6 lién két H lien phan tir cdn anizol thi khong. 4) O benzen-1,2-diol c6 lin két H ndi phan tit, cdn & benzen- hidro lien phan tit. diol c6 lién két CH,OH = CH,OAc. CH,OAc —CHOAc CH,OAc Hy-OAc HOH = -HO-TH H+-OH H+-OAc CH,OH —-CH,OH CHZOH CH,OAc CH,OH CH,OAG CH,OAc AcO--H ‘OAc CH,OH — CH,OAc E HySO. > 8) HOCH,CH(OH)CH,OH + 3HNO, —*—45 0,NOCH,CH(ONO,)CH,ONO, + 1,0 i 277X42 ) nCeHyC203 + nHOCH,CH(OH)CH,OH > | COCsH{COOCH,CH(OH)CH,0 f, ¢) HOCH,CH(OH)CH,OH —PuOAS _ HOCH,CH=O + H,C=0 + Pb(OAc), + 2AcOH HOCH,CH(OH)CH,OH + 2HIO, > HCOOH + 2H,C=0 + 2HIO; + 2H,0 x44 8) , - «) HOCH,CH(OH)CH,OH —S#82"_, HOCH,CH,CH=O —HtiS04.1" (CH,=CH-CH=0 g) HOCH,CH(OH)CH,OH Bat, HOCH,CH(OH)CH=0 + HOCH,COCH,OH .40. ©) pK,(CsHjOH) < pK,(H0), trong nue phenol dng vai trd axit, nude d6ng vai trd bazo, vi vay 06 thé xée dinh duge pKa(C,H,OH) tir can bang: [catts0"] [0 [CsHs0H] CH,OH + H,0 = CgH,O" + H,0* K,(PhOH) = Luc axit ciia etanol nhé hon ciia nuée, trong nuéic né déng vai trd bazo: H,0 + C,H,OH = HO” + GH,0"H, ‘Trong NH; long (m6t bazo manh) etanol déng vai trd axit: GH,OH + NH; = C,H;07 + NH,* xl. a) O nhigt do phdng phenol it tan trong nuéc, khi Khudly thi tao huyén phi. voi nuéc. O nhiét d6 > 66°C phenol tan vo han trong nuéc. Phenol hoa tan trong dung dich Na,CO, nbd phan ting: (CgHsOH + Na,CO, — CyH,ONa + NaHCO, Phenol bj ket tia béi phan ting: CgHsONa + CO, + H,0 -> CsHsOH + NaHCO; b) Lurong phenol chua tan & hén hop A la: 18,8 — 6,3 = 12,5g. Bo qua sy thay d6i thé tich khi thém dung dich Na,CO,, ta tinh duge lung dung dich NayCO, 4M cfin hod tan 12,5g phenol [a 33 ml. x42. a) Nhan biét axit axetic bang qui tim; nhan biét phenol nhd phan img tao két tha véi nuée brom (viét phuong trinh phan tng). Etanol tan vd han cdn toluen khong tan trong nuéc. b) Nhan biét benzyl clorua bang dung dich AgNO, trong etanol; p-crezol tan duoc trong dung dich NaOH cdn ancol benzylic rat it tan (4g/100g nude & 17°C); p-crezol tgo phitc mau véi Fe™* 218 ners SEES aT ETAT Qa) Khudy v6i dung dich NaOH 20% (d = 1,22), chigt ly I6p ancol benzylic (d = 1,045). Axit hod 16p nude, téch lay phenol. b) vac) tong ty. a) PhOH + Ca(OH), -> (PhO),Ca + HO b) PhOH + HC! > khong phan ting (vi lye bazo qua yu khong bi proton hod). c) PhOH + MeONa -> PhONa + MeOH (PhOH axit manh hon MeOH). d) PhOH —"°_, pho” MeL, phomMe+ 1 PhO”, nucleophin manh), ¢) PhOH #2 pho” 2824, PhoMe + MeSO,- (PhO”, nucleophin manh). 8) PhOH + Mel —> khong phan tng (PhOH, nucleophin rat yéu). h) PhOH —#°_y pho~ —®°.5 khong phiin ting (PRCI thude loai kha nang, phan tng thap). i) PhoH HO > Pho. —¥s phoph +I” (dé phan cute hod, dé bi thé). k) PhOoH —#2—5 pho” —SL=GHC! , khong phin img (CHy=CHC! thude loai kha nang phan ting thdp). HO PhCHCt 1) PhOH > PhO” —FICHC™S PhOCH,Ph (PRCH,CI thude logi kha nang phan ting cao). m) PhOH | AcOH —122"_, hong phin tng (Lye nucleophin cia PhOH qua yeu). n) PhOH + Ac,O ~ PhOAc + AgOH (Lue electrophin ctia Ac,O manh). p) PhOH + PhCOCI + CsHsN -> PhOCOPh + C;H;N.HCI 4) PhOH + PhSO,Cl ~» PhOSO,Ph + HCI (Lye electrophin ciia PhSO,C! cao), 1) PhOH + CH,N, -> PhOCH, +N, s) PhOH + p-O,NC,H,N=C-O + Ph-O-CO-NH-C,H,-NO,~p ON NO, 279b)NO,* wf H3C HO3S, c) S03 d) $0; po ) Br BF ‘Br g) Br’, 2 h) Me;Ct y “fo i) PhCH,* fe + k) CH3CO [AIC], re) HC 1) HCs0*, re O)-oe 280Hc Hy OHC. ®) CLC: , Ho ro{7)-o10 Hy H3C p) [H-C=N'MesiCr, wo OPOCI, Hid HOH2C. ® *CH,-OH Hof) ens wt) H3C Hac Oo _ gh + ° oe Cueto ‘COOH oO Axyl hod xy ra & nh6m OH phenol: HO, OH ° ss HySO, 2 OH + oe ‘0 + H,0 ° ° H,SO, dic proton hod anhidrit phtalic thanh tic nhan electrophin manh nén d tan Ong vio vi trf para & nhiin benzen cia phenol (phan ting thé electrophin vao nhan phenol). NaxCry07 2 Cow eae. o prbencouinon 281NagCr,0, pe poet eee ae OH 0 Na,Cr,0; Cr ae CL o-benzoquinon ‘OH Te ‘Oo b) 6 o-quinon, 2 Iuéng cyc dién manh 6 sét nhau day nhau Kim cho né kém bén, X.48,Khi bj chieu séng AgBr chuyén thanh dang nhay cim [AgBr]* n6 dé bi khit béi hidroquinon thanh Ag tao ra nhiing ving den trén phim, con AgBr khong bi chiéu sang thi tao phtic tan voi NayS,O, va bj rita di dé lai ving tring trén phim. woC)-on + 2[AgBr]*, ——> o_o + 2Ag) + 2HBr b) Phenol hit dm tgo ra dang hidrat tan duge trong nuéc déng th’i phenol bi oxi hod béi oxi khong khf tgo ra quinon va c4c chat c6 chita nhém quinon [a nhing hop chat 6 mau. X49. a) Me3C, Ht WoC) me + 2Me,C=CH, 77 \ HO Me (BHT) Mec b) Oxi khong Khf tgo ra ee géc tw do (nhat 1a khi c6 énh sng). Géc tt do xdc tién qué trinh oxi hos thuc phdm theo kiéu phan ting day chuyén. BHT phan ting véi cde g6e-tu do dé tao ra géc ty do bén kém hoat dong hon do dé ma lam ait doan phan ting day chuyén ngan chin duge qua trinh oxi hod: OH 6 Mesc, Mey Me,C. Mey + Rt ——» RH + (g6c ty do bén) Me Me a) ote as ‘ CH,COCH, a 400 w0C)-¢ OF _Ca.on, 2C)-2-O-o, 10 Hi CHy W CH Ca hai giai doan déu thudc phan itng thé electrophin vio nhan benzen. X.50. 282+ GH b) w0—(C)—-{O)00 snag os oO CH CH CH; oO n Phan tg nay thudc loai phan tmg axyl hod nhém OH bing clorua axit, nd duge xiic tign béi kiém (lao ra Ar— Ova trung hoa HC! sinh ra). a) Ete chi céc hop chat 06 cong thtic chung R - O — R’; véi R va R’ Ia cde géc hidrocacbon giéng nhau, khéc nhau hodc tao thanh mot vong chung. Bte vong li ete ma nguyén tirO la thinh vien cita vong, Ete crao [a poliete vong, chita ti 4 nguyén ti O ete tré Ién. "Ete dau hoa" 1a tén thong mai chi phan doan hidrocacbon séi 6 khoang 30 = 60°C chung cat tir ddu md. b) Epoxit 18 tién 16 chi nguyen tir O lien két truc tip véi 2 nguyén’tit C ta mach dé tao thanh vong. Thi du: H,C—CH - CHCl HO * 1 ,3-epoxi-2-metylpentan 0 1-Clo-2,3-epoxipropan’. H,C - Ho—CH - CH, - CH, Oxiran 18 tén dj vong 3dinh ma 1 dinh la nguyén tir oxi, thi du: HCH, Hx - HE—CH - CH,CHs hae ; “Anken oxit" dugc ding déi véi cdc anken don gian: 2-Etyl-3-metyloxiran H,C-——CH, Ha - HE—CH \f—etilen oxit \f_propilen oxit a) 2C,Hyq4) OH > CyyHyya20 + HO a) 2CgHoms}OH > ComHyns2O + HzO Q CH! OH + CygHp4}OH > CyHyq¢)~O~ CyyHamper + HO 3) ‘Téng s6 mol ete = téng s6 mol H,0 = =0,3 mol. S6 mol ete khong d6i xting = 0,25 mol; so mol méi ete doi xing bing 0,025mol. 0,025(28n + 18) + 0,025(28m + 18) + 0,25(14n + 14m + 18) = 26,4 0,3(14n + 14m) + 5,4= 26,4 14(m +n) = 70 > n+m=5. 283Vi ancol b§e 3 don gidm nhat Li (CH,);COH (C,HyOH) nén ancol bac 1 phai 1A CH,OH. Suy ra 3 ete li CH;OCH,, (CH;),C-O-C(CH,); va CH;-O-C(CH,),. b) Do dé bén cia cacbocation: (CHs),C-OH + H* ——> (CH)sC" wu tien hon CH,OH + H* aw? CHS Do yéu t6 khong gian: (CH;),C* + CH;0H ——— MTBE wu tien hon (CH3),C* + (CH,),COH — ete d6i xing. ©) CH3-O-C(CHg)s +H" > CHy-G-C(CHy)s —-» CH,OH + (CHy),C-1 H Co ché Sy Jon cacboni bac ba rat dé hinh thanh, phan tng xay ra theo co ché Syl nén khong tao ra metyl iodua. X53. a) CH, +H,O —"4 cO+3H, CO + 2H, —?_, CH,OH (CH)),C-CH, + H,0 —"5 (cH,),COH Phutong phip A: CHjOH + (CH,),COH =!" CHOC(CH,), Can ding CH,OH du nhiéu én (lim dung moi) dé wu tien tao ra MTBE trénb tao thanh ete 46i xing (xem bai X.31). Chung cat tich duge ete ra khdi hén hgp sau phan ting: Phuong phép B: CH,OH + (CH;),C=cH, —!“" 5 cH,oc(cH,), (Can ding CH,OH Tam dung mdi tao diéu kién dé ding cho sy hinh thinh cation tert-butyl. Tach sin phdm biing chung cat phan doan. b) Phuong phap A di tir 2 ancol va cin nhigt do cao hon dé téch nuée, Phuong phap B di tir | ancol (khong céin diéu che (CH,),C-OH) thuc hién 6 nhiét 46 thap hon, vi thé sé kinh té hon. X.54, HOH ZHL cH,On, HO CaHs-O 9-Cills a Cas O-C3Hs (Sy?) HOH tH, cyt Bie Saenon (Spar) -Ht 284X.55, a) B: PhCH,OCH,; C: PhCHgI; D: CH,0H la BYP: 24-(ON)CoHsCl;—G: 2.4-(O,N),CHOC gH ) H: Me,C-O-Me; I: Me,Cl; K: MeOH 7 4) L: THF; M: HOCH,CH,CH,CH,OH 3 /\ ©) N: CICH,CH(OH)CH,Cl; P; He —CH- CH, 8) Q: BrCH,CH,-O-CH,CH,: T: CH,=CH-O-CH,CH, X.56. A: HOCH,CH,OH; B: HOCH,CH,OCH,CH,OH C: HOCH,CH,OC,H,; D: HOCH,CH,OCH,CH,OC)H, E: HOCH,CH,NH,; F: HOCH, CH,NHCH,CH,OH X57, a) HeC——CH - CH +H HC: CHs CH,OH. FyCO™H,C—cH- cH. 3 9 2 ls fa NG a , (HY OH H Co ché Sy2 (CH3OH tin cong vao ché ft bi én ngir khong gian) b)H,C—cH - cH, CH;O" H;CO-H,C—CH - CH, H3CO - H.C—CH - CH, \/ he. ft HOH, e au os ee) o = CHO by CHg AMC SECH HY Hc—dicu I 7 SHEL Hec—cicttse CH.OH Ho -Hemb cH oH -H bet, Co ché Sy1 do cacbocation bac III bén. CHs d) HG —C(CHs)2 CHO (CH3OCH,C(CH. I aa . yi de CHLOH, HsCO -H.C~C - CH, 0 (Sy2) ° ~ CH30 | oH a) CéHsOCH; + HI —> CHO + CH! (Sy2) b) CoHsCHOCH, + HI —» CeHsCH,I + CHJOH (Sy1), c) Me3C-O-Me tdi ig Me;C-I + MeOH (Sy1) do HO phan cue a) Me;C-O-Me Hilti, MesC-OH + Mel (Sy2) do ete khong phan cue. 285X.59. meC Lames oC Doan @CLoaercas CI 97 OCHS = CH 97 OCH:C = Cli 7 TOCHEC = CCH 0 Q X.60. B-TRAC NGHIEM X61. X.62. X.63, X.64. X65. X.66. X.67. X.68. X.69. X.70. 286 HI axit manh hon HCl, I dé phan cue hod hon CI” nén cfing 1a téc nan nucleophin manh hon. a) A: CH, = CH ~ C(CH), ~ OCHC,Hs: B: BrCH,CH,C(CH,),0CH,C,H, CgHsCH)Br/Ag,0 dé hinh thanh CsHsCH,* B dé bi hidro hod thanh toluen + ancol. f EOP Oe Oba OgO BP ar =n S07 On 07 0° TRO No TH Yo : 4 a) Dietyl ete (hau nhur khong tan trong nuéc): dung moi cho ahiing chit ft phan cuc; chat gay mé... 7 b) Tetrahidrofuran (THF, tan v6 han trong nuéc); dung moi cho nhiing chét it phan x cuc va phan cuc, nguyén ligu cho téng hgp hitu co. c) Diphenyl ete (chat ran): dung méi cho nhiing phan tmg dai hdi nhiét d6 cao. d) Ete crao: dung moi cho mot s6 mudi vo co "gitt chat" cation lam, ting mic 46 hoat dong cia anion; xtic tac chuyén pha,.. aA; wc ODA OB S&B ga. a) E; vB. je. a)A; \ BAS >” c) B: dC eG BA GS 4 ad wD OD WS oD; g)D. a) Ly by L; e)N. a)D; b) B; c) B dc. ¢ D. a) D; b) Ss c)D; d)D.Cheong XT ANDEHIT - XETON PA-TYLUAN TJ. a) 2-Metylpentan-3~ on b) 3+ Phenylpropanal c) Octan-2,6—dion d) trans-3—metylxiclohexancacbandehit e) Pentandial f) cis-2,5~ dimetylxiclohexanon 8) 4~ Metyl-3-propylhexan-2-on hh) Hex—4-enal. ©) CH-C-CH,-CHO 5) CHyCH-GH-CHCH,CH-CHO CCH 1C(CHa)3 CH; CHy CHCI-CH, PCC” 8) CHsCH,CH,CH,CH,OH 7G» CHsCth;CH,CH;CHO 2 fk no b) CH)=CH ~(CHy)3 -CHy Danie CH,(CH,);CHO ©) CH;(CH,);COOCH, ao CH3(CH);CHO 3 287XL4. XL a) CH;CH,C=CCH,CH, HESS. CHCH,CH,COCH;CH, éiicon COCH: py Br COCHs a) b) er AIC, Pep, Cel Br ~ 6 4 Cr Me Cc CHO oh [0] ci. ts oe. oH ete khan 2) Hj0* by ‘ .CHy CHy ae "1 BH [0] eet 2) H;O,/ OH" Nu O OH XLS. Mr? i-Pr),AIH, a) CH,CH,OH ——~ CH,COOH (cucooyca "5 cxycocrly THO, HySO, KOHAwou CHyCHOHCH;——~CH CH=CH, CH CHBrCH;Br. ‘CH;G=CH 4s Hi b) CH;COOH ——=(CHCOoy,Ca ——* ‘chycoch, —“. crycHoncH; Tho, CuO e)CH;CHOH YC. cHyCHO MOH CH;CH=CHCHO tH) " d) CHsCH;COCH; ———» CH;CH,CHOHCH; 1801 dBc cHeCHCH, KOH/rugu CHjCHBrCHBrCHy CH,G=CCH; LiAIH, é +H. e) CH,CH,CHO——+. CH,CH,CH,OH HaSda ste CH,CH=CH, — XL6. Ht CH;CHOHCH; CH;CH,CH,CH,OH PCC. CHyCHLCH;COOC,H, DIA, CH,CH,CH,COCI —LiAIHy CH;CHjCH,CN DA 288| XL7. CO+HCI a) CoH ——> CgHsCHO AICI; Ch, H,0/KOH i C6HsCHy ———> CgHsCHCl, ————> C,HsCHO . as HNO,/Ht KMn0,/H* B0h macy Sate a ( ' N- ach —<_\-0) COCH,CHs [H ° C + CHyCHCOCI On eth A $a -CH2CH3 4 X18. CH;CH,CH,OH oo CH CH;CH,CI CHsCH,CH:MBBr. (A) CH\CH,CH,OH CHCH,CH=0, (8) Bp Ee. CH,CH,CH:CH,CHCH; = CH;CH,COCH,CH,CH,, on yf ONAN i CHACH,CHCL 1. BH, b) HC*CH aie HC#CNa SECHCIRCL icec. CHEN, Tryon: CHCHzCH,CHO 10 Hay C+ 1,0 H8% cHcoch,cu,cH, BL 2 a OL pentanal soct M ©) (CH;),CHOH = (CH,),CHC] SE (CHy),CHMgct +8 (CHy),CH-CH-CH,CHs on —K2£00r_, (CHy),CH— C-CHCHls B 0 . ao Me Come! noe anon 22 a0 Oh a < eae oe “Eni OHC-CHACHACHY CHO 19 BTHHHG - 4 289 mmeqne mere ceyrren =~e KOH [01 1. CHyMyBr CH Daa. Oa Cee OS 9 { — Coos ES cry co-cn,crcH- co 2 © Deonon 2 pane Ye -cnmuc $B -cronenon rf XL10. - ac 1/KOH KOH a) CH;CHO—— CI,CHO ——> CHI; i (H] HCI b) CH;CHO ———» CH;CH,OH —> CH,CH,CI XL12 KOH Bry KOH ¢) CH;CH,C| ———> CH,=CH, ———» CH)Br -CH,Br ——» CH=CH C,HsOH C)H;OH 4) CH,Br chp CH,OH -CH,OH NaOH Zn/ CHyCOOH e) CH;CHO ———> CH;CH=CHCHO. ———* \CH;CH,CH,CHO tH) 1eSOt HCl XL 2) CHjCH,CH,CHO —» CH,CH,CH3CH,OH—® CH,CH,CH=CH, ——» CH;CH;CHCICH; ae de or CHyCHSCHCH; mcmenchecr, KOH 5 ) CCH CH=CH, mse “Store CHACH,C=CH XIE CH; 11,0 . Oh asd eCHsCHCOCH, XL [0] a) cu,cu-o' “2. cr,coon “8+ (cH,C00),Me “3: XLL¢ POs. “CH;COC! (A) NaNHy Nils ling’ b) CHyCOOH CH;CH,C#CNa —M. cu,cH,c= CH3CH,C=CH -COCH; 290 \ BTHHHC «8OH oH ° d i kM, | Os Oe on be eps HBr Mg =e ae Mabe e (8) + a —- ~ 2 CFC) yHCH ret (CH)_CHM CHER SHO(CH),CH-CH,OH FS (CH),CHCH,CIME_. (CH,)yCH-CH,Mgci -SHsCH0(CH),CHCH,-CHOH-CH, 6 4) cx,coch; . (cny,ch.on nae —> (CH), CHCH, -CO-CH, DXi. : a) CHscocH; = 4H Cg .CHOH-CH, b) — CgHsCOCH, eee Colts a —e ou?" 1. CGH; sr CH ©) CsHsCOCH; saat (CoHs)2 CL XL13. Cloruaaxetic > axetandehit > axeton > dietylxeton >diisopropylxeton. ~Dién tich duong nhém > C*=0 gidm din. 4 = Higu img khong gian loai hai ting din, qe XLS. Xtc téc H* hoat héa nhém > C=0: CH,CH-O + Ht === CH;-Clon SHO CH-CH-OCHy CH-CH-OCHs on oH hemiaxetal SE cu-cH-ocn, 22 | cH CH-OCH; —~ CH-CH=0cH, Sten CHCH(OCH;), = *OH, axetal ; XLI6. E BryNaOlt 1,0 a) CH;CH,CH;COCH; CHyCH,CH;COOH + CHBr3} b) (CH,),C=CCH-COCH, —N20BL. (CH,),C=CH-COOH + CHBRy NaOBr ©) CHyCOCH; CHBr + CH;COOH 291 erent neseXL17. XI.18. XL19. ‘X1.20. X1.21. Cac chat 6 nhém metylxeton CH;-CO~; CH,CHO; hoac CH;CHOH- Trong moi trutmg kiém sé thé di, tri-halogen nhanb, sau dé thity phn ct dit lien két C-C.dé to axit theo so d6 Hon! 70H es R-cocx, 1} R-CQ ——= R-C-OH_ + CX; EPOX & CX; + HO = = CHX; + OH™ CH,COOH khong c6 phan tng nay vi khong tgo dang enol trong moi tung kiém. a)CjHsCH=CHCH,OH b) C,H,CH,CH,CH,OH ¢) CsHCH,CH,CH,OH 4) C,HsCH=CHCOOH ) (prc 5b) Cg) CHy-CH OH ° 17 G=N- NH 4) _CgH,,COOH + CH;COOH CH; Phan ting tgo hemiaxetal va axetal v6i ancol etyli¢ va thioancol. a) CyHsCOCHCICHs b) Oo CHy Br ©) CgHsCOONa + CoHsCH OH d) HCOONa + CH,OH @) p-O2N-CgHy -COONa + p - ON -CgHyCHjOH g) _p-CH;O -CcHyCH,0H + HCOONa CICH,COOC;Hs + NH ——» CICH-COOC,H; + NH; 292 VSS 98: oy fl CHL. CH. *SE—CH - COOCHs —> ‘CH - COOC)HS cHs chy XL2 X12 = a) b) °) d) X12[22. Trong HCl: 4 a \CH,CHCH;CHO + Ht —+ HO-CH,CH)CH,-CH*-OH—> ‘OH H O 2 eae OH, —— on tH Cyn sp cron C yo HW a) CHjCOOH + CH;CH,COOH —&)_ CgHs- CH= CH-CO- CH b) CHjCHOHCH,CH; 8) CH;-CH,CH,-CH; CH; qT = ~y ©) C1yCty-G-CHC-CH hy CH,-C = CH-CHy-CHy CH; ONa @) CHy-C- CHy- CH NoH a) m-O,N-CgH4-COCH; d) CoHs-CH -\CH3 f Ou b)CgHls-C=N - NHGgHs o) \Cais).¢ -CH, cH; OH ©) CéHs-C= CH CH, 1.25. ) OI ha Voi KyCryO7/Hy80, —~ CoH1sCOOH MH Cocoon —Y+ Celie b) CcHsCOOH PCS. CH.CocI 1. NH fe) CsHsCOCI CyHsC=N 1, LiIATHy ———" CsHsCHO ) CcHCOCI + CHJOH —> clcoocH, == FX1.26. a) CglsCH = CHNO, 2 ACN H= Hs cauciee 2 ©) CoHsCt cut NO» CoHs d) C6HsCHOH-C=CH 293Co ché Ay etia benzandehit véi cdc téc nhan: GHNO, , CHCN)C gH , CHC H(NO2)24 Sau d6 croton héa. x27. a) A: CH,CH,CHOHCH B:; CHxCH,CHBrCH ©: CH,CH -CH -MeBr CH; Ds CHjCH, -CH -CH,OMgBr_E: CHCl: CH -CH,OH F: CHsCH -PH -CH,CI CH, CH, Hy : . = x1.28 b) A: CHjCH,CH=CH B: CHyCH,CHCICH3 ©: CHyCH CH -CHy OH D: CH;CH -C -CHs E: CHsCH - (=N -NHCsHs 6 CH 1H c) A: CHy a -CH3 B: (CH3)9C -COOH CCE -COOH, oS on Hs xi2 D: (CHy-CH-CH),B E: CH -FH -COOH 1 cooH CH,OH Hol 4) As CaHsCH “CH -CH,CHyB: CgHsCHy FH -CoHs C2 CgHsCH -CH -CoHs Br OMgBr oo Da QyHsCh FH Calls E: CgHsCHyCH)CH,CHs sa MgBr @) A: CsHjCO -CH -COOC}Hs B: CoHsCO "i -COOC;Hs C: CeO - -COOCAHs H3 GHs GHs D: CyHs -CO -C -COOC,Hs - E: CoHs CO i -CyHs GHs CH; 8) A: CH)=CH -CHO B: CH,OH -CHBr -COOH c i om D: CH,OH -CHBr -COOH oO HO, HY = h) CH;CH,COCH, + Br, ————> CH3C0O + CHBr; 294Vai trd cia OH thity phan cét lien két CHjCH,CO ~ CBr. Vai trd cita H* tang cudng dign tich duong ctia: CH; -CH < -CBr, OH sBr k) A: CH;=CH-CHO B: CH,CICH,CH(OCH,), uct C: CH)=CH -CH(OCH), D: CH,OHCHOH -CH(OCH,), X128, e 8) Clip -CH CH, -CO-CH, oH b) HCOOH + (CH);C -CH,OH 0) (CH)96 -CHLOH CHO - XL29, HCHO. + CH;CHO CHa CHe CHO HCHO, cH, -cH-cHO HHO oH OH CH,OH Hs apa i HERE ; HA oH Ge cron HBS CHy+ C-CH,Br 2 DX] OH CH,OH Br CH2Br X130. 8) CH;CO-CH,Cooc,H, He-Ne CHC -CH,COOCH, EAGT CH N-NH), b) CHjCHOH-CH,CHOH ©) CHy-CH-CH,COOCHs NH-CHy, LOOC Hs NF, t? /CONH, d) HAC a a ay “COOCHs ‘CONH, ©) CH3CO-CHBr-COOC,Hs hog CHyCO-CBry-COOC,Hs 295XI.31. Om A : dA CoH PACH) COGHB |B [cay + 2 a) A: (CoHs)3P(CHs)Br, BB: (Cols)sP=CHp ,C. ho. 0) Az (CoHs)3P-(CH)3P(CoHs).2Br a) Az (Ceg)sPCHCH,CH;BF ;B: (Cel1s):P=CH-CH)CH C: CHy- C= CH-CH)CH; CHCH; XI.32. a) Cong nucleophin: AyCO CH(COOC;Hs). + CrHsONa CH(COOC;H), + a +Nat 2 + OH CH(COOG Hs» + HCHO —= GH(COOGHs» = eH{COOCH9a “CHO T CHO" CH,OH Tiép tuc tuong tu nur trén. ¢) Benzoin héa: onrO)-o) Stale on O)-g cro GHOH. cnO)-or-0 + CN" —= oOo =N —= =| cuC)-é-en — cH (O)-c-c-8 CeHsCH=CH-COCHs OH ~ Vai tr OH” lay Ha cia CH;COCH,CH, 296phan ting Ay (Cong Ax va tich). ) HySO, trong CH;COOH hoat héa nhém > C=O: ie + = CgHsCH=O ——+ C,H,CH -OH Phan ting Ay (cong ri téch H,0). 2) Ay, téch— mé vong A: cHy{_ eNO : oR car Fo ‘OH NH c: NHy-CH,CH,-CH-CH,CH,COOH CH; OH ¥ » C)-on NaHSO;, CK khong tan trong ete $03Na | | Phan nuéc them NaOH, H,SO, loang dé ha tan ket tia, chigt bing ete Idy xiclohexanon. yy — Na,SO, khan lam kho nut6e. — Cat & 150°C lay xiclohexandn, © Vai tr eta Ht: 4 OH 2H OH 3 : ou > ESD OR To Oxgan samp Ort ae Ovo = — Vai trd cla OH: On. = O& . 4 —. ‘0 + S-ONa e ae E ‘SO;Na ‘ Kew 8 x34. a — Oxi héa tao C;H;COOH. ee — Két tha véi semicacbazit va 2,4~ dinitrophenylhidrazin chiing t ¢6 nhém >C=O s 3 c6 nhan benzen (46 khéng no 4), 3 lign két x & vong benzen va 1 lién két x 8 nhém >C=0. — Phan biét xeton, andehit bing KMnO, lanh hoic Ag,O/NH3. 297~ Phan biét I va IT bing I,/KOH (II tao két téia CHI,). — Phan biét III va IV bang do op, IV c6 C. — Phan biét bing 'H-NMR. XL35. A: CHjCH,CH,CH,CH,C = C - Na; B: CH, (CH ),C = C(CH,),Cl; C: CH; (CHa), C = C(CH,); MgCl; D: CH, (CH) )4C = C(CH); CHOHC Cl; E: CH3(CH), ), CH = CH(CH, )3 ~ CH ~ CH oH. wens ou Chat dy din CH, (CH,),CH = CH(CH,),CO- CoH. X1.36. OH 7 » Ons Ofte One OH D: OHC(CH)(COCH; — ;_ E: HOOC(CH3),COCH; X137. K: CHj;CHOHCH,COOC3Hs L: CHyCH=CHCOOCH, 1 2g 47? c-NMR CHy—E—C-¢. ae H ‘OCH,CHs Cy: 166.7ppm; Cy: 144.Sppm; Cy: 122.8ppm; Cs: 60.2ppm; Ce: 17-9ppm; Cy: 14.3ppm. X1L38. / CH,BrCH,CH,CHO ; A: cecal | oO Bi CHy—CHy—CHy— of) MgBr 298C: CoHli:0x: CH3CH(OH)CH,CH,CH,CHO Dz CyHy4Op: CHyCH=CHCH,CHy -CH -OCH OH a) CH3I/NaOH b) Cu, 1°; nwo \- CHO ce) CH; TT -COOEt Br 4d) LiAIH, A: CHy=CHCHO Br CHy=CH-CH-OCH, OCH, ©: OH -CH-CHOCH): : OH OH EXLAL. n-CH,CHOHCH-n © X42. (CH,);CH-CHO © x143. CH,CHOH)CHICH,), Cee -CHO (CH)sCH3 ~ X1.45. OH ; OH OH OCH; OCH; OCH; CHCl; 120 NaOH CHCh, CHO vanilin 299 Pensa reSin phim phu: OH OH OHC: OCH; OCH; OH o-vanilin iso-vanilin X46. oH A: CH - CH= CHO Bi CH -CH-CH -Clg CH=CH, CH=CH, OH 0 C: CH - CH - CH -CgHs D: CHy- CH-C- Cols CH,CH,OH CH,COOH CH, E: CgHs - CH oH -CH,COOH F: CH; ° ° XL47.__a) A: CgH,COCH,CH3; b) A’: CoHsCH,COCH, B- TRAC NGHIEM XL48, _D XLS3. B X1.58. A X163. A XL49. B X54, D XL59. D XL64. A XL50. D X155. B XL60. B XL65. CE XLS1. A XL56. C XL61. B X1.66. A X1L52. C X57. C X1.62. C X67. B 300 X168. X1.69. X1.70. XL71. X172. X173. DAAY D>Cheeng XIT AXIT CACBOXYLIC VA DAN XUAT — TU LUAN II.1. 1C (mot nguyén tit cacbon): Axit fomic, axit metanoic 2.C: Axit axetic, axit etanoic 3 C: Axit propionic, axit propanoic 4.C: Axit n=butitic, axit butanoic 5.C: Axit n-valeric, axit pentanoic 6 C: Axit n-caproic, axit hexanoic 8 C: Axit n-caprilic, axit octanoic 10 C: Axit capric, axit decanoic 12 C: Axit laurie, axit dodecanoic ; 16 C: Axit panmitic, axit hexadecanioie . 18 C: Axit stearic, axit octadecanoic. PXIL.2. a) (CH,),CHCH,CH,COOH b) CgHsCHj,COOH c) HOOC(CH,), COOH 4d) p-CH;-C,H,-COOH e)'0-C,H,(COOH), £) m~ CgH,(COOH), &) p~ CgH«(COOH), i) (CH,),CH-CN 1D) p-HO-C,H,-COOH k) (CH,),CCOOH 1)dd KMno, a) Toluen FP gaerr PhCOOH » b) Pape Me. PhMgBr 92, prcoomenr —H*. PhCOOH Ete khan dd KMnO,,H + ©) PhCH,OH ————1"_.- pacoon t 301PhCOOH 1) H,0./ HO" d) PhCCI; BOLE 2)Ht Hit ¢) PhCN + H,O0 ———> => PhCOOH XIL4. a) CH;CH;CH,CH,OH —-S2'259s , CH,(CH,),COOH b) n—PrOH "8 +n — Pr BrME->n — Pr MgBr 2» —H 4 n-PrCOOH hun 9 i i c) n-Pr-C-CH, yop H +nPrcoo” —! 5 n—PrCOOH a XILS. a) 2déng phan b) 4 déng phan ©) 4 déng phan ) 4 déng phan, XIL6. 8‘ aC \ ABE (cry) 2S Never) yen 449) Hooc(cu),cooH 1) 2H1, KMn0,.H+ b) . \ Dred HOCH OH, Aut Hooccr,»,coon XIL7. a) PhCOOK b) (PhCOO),AL ¢) axit m= nitrobenzoic d) Phcoci ©) Khong phan ting £) PhCH,OH 8) (PhCOO),Ca h) PhCOONa i) PhCOONH, j) Khong phan img k) m-HOOC-C,H,-SO,H 1) Khong phan ting. XIL8, ‘ ancol isobutylic 1) LiAIHy a) Axit isobutyric ae © iprcoon = SOC!2, i prcoci ; | i soci NH. aceon Se arco i-PrCONH,a iprcoon M8, (-Prc00)Mg Ht €)i-PrCOOH + EtOH i-PrCOORt +H,0 . XIL9. LiAll H,0 a) Pacoon Ate 120 PhCH, OH b) PhCOOH aS pacoct ?=C0! 5 Toy! benzoat ) PHCooH OS, pacocy nome ‘m—bromphenyl benzoat d) Pacoon-PCls phcoc. NU3,_ PRONE, e) PhCOOH NAOH, phcooNa + Ho PCI - -j ) PhCOOH ——S= prcoct "POH pacoo-npr + HCl > XI10. DE Sa -Mgpr _1)CO> a)PhCH; ————> CH, ae ee CH, COOH 2)Mg. 2)H30" 1) ddKMn0,,° b) Toluen. ——____, (M) Dw PhCOOH (M) o) Toluen, C2 “prc cS pac exe PRCHCOOH (N) oe 00H OM Cl Fe Cl Cl, Fe ¢) Toluen 2° ( KMn0. ™ Ch, - C1 _EM NOS cy, -COOH ) Toon 2 p-bromtoluen. CHC cN> <> a cs eof ome a) nN DP pact COOH 303 she ec imranrreneanaqceentermnntreenCH; COOH xl CHs COOH h) PhCH, —SH:CL, __cHic! DKMnO, O) 3 AICI, AICI, 2)H* CH; COOH XILI1. a) OOH COOH COOH CH) H. Br Br H xl H Br H Br + Hi ‘Br CHy CH CH; + pou COOH COOH CH, = =——_J Br H H Br eae B—}-H + -Br—}_H CH3 CH; CH. Erytho Threo (AIB) (B/A) b) Axit fumaric + HCOOOHL xay ta phin img hidroxyl hod theo anti cho san phém (©) I axit meso tactric: a COOH COOH Poe / HOH tion , HO-}—n ica “HCOOH = H—OH * HOW} —H FA ‘COOH ‘COOH COOH ©) Tit 1,4-xiclohexadien 6 cong thie phan tir la CsHy tée dung voi CHBry/ {-BuOK cho hgp chat D c6 cong thite phan tir 1A C;H,Brp, chtmg t8 hop chat du 4 cong nhém CBr, vao dien.Cau tric cis cha D, E va F nhu sau: Cee > (D) (e) CF) Meso Meso 3041.12. = Axetilen —&MB2"_, CH = CMgBr—S2 > HC = C- COOMgBr—82_, “Chi, HC = C~ COOH —H20#S0c+H880e_, OFC — CH, COOH KM! 5 CH, (COOH), : HC=CMgBr : HC = CCOOMgBr : HC=C-COOH : OHC-CH,COOH. aN a)CsH;COOK CooH NO2 CH; c) CH,CH,CHBrCOOH d)n~ CgH,,COOH + HOOC(CH); COOH e) Ce COOH f) Axit raxemic threo-9—10—dibromooctadecanoic 8) Axit raxemic threo—9—-10-dihidroxyoctadecanoic h) 0~CgHy(COOC; Hs), :Etyl phtalat ss i) CsHsCOOCH, CH, 00CC,H : Etylen glycol dibenzoat div By Gaon COOH OH OH va os - Br ‘XI1.14. a) CH,;CH(OH)CH,CH,OH 20 BTHHHG - A 3058) CHs—C—CH,COOC)Hs NNH, ©) CH;CHCH,COOC,Hs NHCH; XILIS. X: CH,~CH,CH(CH,)COOH XIL16. a) dd NaHCO, ©) AgNO, ©) dd NaHCO, XILL7. Axit benzoic a) Dé bay hoi ) Nhiét do néng chay thaip c) Khong tan trong nuée Tan trong ete etylic d) La axit hon XILI8. a) Thye hign phan ing brom hod véi Br, / Py, (Phin iimg Hell ~Volhard~Zelinsky) b) Este hod véi etanol co xtic t&e axit, c) Dun néng véi SOCl, 4) Tée dung v6i NH sau 46 dun néng dé loai nude ©) Nitro héa vio vong thom véi HNOs/ H,SO, ) CoHsCH,COOH ——» CoHlsCHCOOH —» CoHsCHCOO™ —Sy cgsco—coo” 12H, CgHscH—CooH 1 8) Thuy phan C5H; CH(B1)COOH -— C,H, CH(OH)COOH XILA9. Dua vio higu ting (£1, C, + H) va sip x€p tinh axit ting dfn theo thew sau: 8) CH;CH;CH(Br)COOH > CH;CH(Br)CH,COOH > CH,(B1)CH,CH,COOH > ————— CH), ae ose oe +C)H;OH \ Y: HCOOCH(CH,)CH,CH; b)dd NaHCO, d) dd NaHCO, Natri benzoat Khé bay hoi Nhi¢t 46 néng chiy cao hon Tan trong nuée Khong tan trong ete etylic LA bazo hon. Br Br H,0, Ht, &n COOH CH,CH,CH,COOH 20 BTHHHC -8b) HOOCCH,COOH > HOOCCH,CH,COOH > CH,COOH ¢) Axit 2,4,6-triclobenzoic > Axit 2,4-diclobenzoic > Axit p-clobenzoic > axit benzoic d) Axit p-nitrobenzoic > axit benzoic > axit p-toluic. e) HOOC-COOH > HOOCCH,COOH > HOOCCH,CH,COOH. £) Axit p-nitrobenzoic > Axit p-brombenzoic> Axit p-hidroxibenzoic > Axit benzoic> Axit p-metylbenzoic. 8) H.S0,>CH,COOH >H,0 >CH,CH,OH > CH = CH >NH; > C,H. : XI1.20. a) cH, COOH Br so, $0, “an aa NO, b) Toluen -> p~ icone p- aminotoluen GROG, p-CH,CONH-C,H,-CHy Bi. p-CH,CONH-m-Br-C,H,-CH, 2, m-brom—p-aminotoluen Waar m-brom~p-diazonitoluen EPS, m=bromtoluen —ME> m-BrMg-CcH,-CH, Sy in-BriMgOOC-CH,-CH, 22» sp ©) HNO. Toluen "3 i DEM 1280, p-Nitrotoluen ae Axit p-nitrobenzoic @d) 1,80, Fe ; Totwen 2. Ane p-metylbenzensunfonie—2°2"% Axit 4-metyl-3-brombenzensunfonic Hy0, Ht + HI o.tromtotuen 202 HY Axi o-brombenzoie e) Bro, Fe cro, , Ht Toluen —2’ > 2,4,6-tribromtotuen FO3 > Ba it 9.4 6-741 brombenzoie nhiét 1, 3, 5—Tribrombenzen. 307XIL21. Téng hop qua este malonat: CH,(COOG Hj» > “CH(COOG Hisy —P—> RCH(COOCH,). 22", RcH(COOH), —”-> RCH,COOH, ~©0, Chi can thay R = CH;CH, duge axit n—butiric, R = CH,;CH,CH, duge axit n-valeric, XIIL22. a) CH;\COOCH(CH,)CH,CH, b) AcB2 c) 26 déng phan XII.23. HCOOC;H, va CH;COOCH, XIL.24, - Téng hgp aspirin: 1) Bra Fe 2) NaOH,t9P_ 3) Ht (cH3COy30 heh HS0, 8% Sm 0c0cHs ~ Téng hop metyl salixylat: tir axit salixylic thuc hin phan ting este héa déi véi nhém cacboxyl bing metanol. X25. a) Benzen: 6 Phenol NIGH jatriphenolat 2 cons F Axit o-hidroxibenzoic CH3COOH\_S CHiyCOON SO Ch, jee CHCl + HCL B AICL in. emaen + CHCl AES rotuen 2 2.ctotuen KMS 5. so disbannnia NOR Fe He 1,80, 4 b) Bry KMno, Benzen- SRS Toluen 2 p-Bromtoluen, “Fa > Anit p-Brombenzoie 3 ©) Cols ~> CgHs CH -> CyHsCOOH —2-+ Axit m-brombenzoic. Fe 4) Lay sin phém (b) & ten tée dung véi hén hgp axit HNOs/ H,SO,.XII.26. ch. he (city980, ro =e sa C1 Heel Sa Ochs Ee coon cng He HI R ae GH cH, Och, on XIL.27. CH. . 2 eh aeeots Hy CH=CH, 1) Ho~ 2)G, H COC! Hi HE CsHs COO XIL28. a) CHsCOOC;H, + CHCOOC3H; EEE calsgcricoocst + CHOW iy Benarisetat OCHH. b) Cig ort + CoHSCH,COOCH, OHS CgHcHCCOOCHS)s + CoH;OH Dietylphenylmalonat XIL29, a) Digu ché Axit a~ propionic: CH;CH,COOH + Bry CH,CH(B)COOH —2™2_, CH,CH(NH,)COOH 2H b) Digu che axit lactic: CH,CH(Br)COOH — ae CH,CH(OH)COOH ) Digu ché axit metylmalonic: 130. a CH,CH(B)COOH —e CH,CH(CN)COOH ae CH, CH(COOH), abr 309XIL30. Xem gido trinh, XIIL31. Z: (CH,),CHCH (OH)CH, XIL32. A : CH)=C(C,H;)COOH B: CH;CH(C,Hs)COOH XII.33. a) X: CH;CH=CHCH,CN b) A: CH)=CHCN ; B: CH,=CH-COOH ©) T: CSHsCH=C(COOH), ; U: CH;CH=CHCOOH XII.34, a) X: CH;CO-CH,COOC;H; (Etyl axetoaxetat). b) CgHsCH(COOC,Hs), (Dietyl phenylmalonat). c) T¥Z: HCO-CH,COOC;H, + C,H,OH. XI135. a) CH;CH,CH,MgBr+'“CO,->CH,CH,CH,'4COOMgBr — CH,CH,CH, “COOH b) chgmger + 4c0, HAL cis,!40n, oF te con,!“cHyMepr CHy- GH, eases cnybu,cu cron eS c#,!tch,cH coon XII.36. X: CHjCH,CH(OH)CH, CH, X1.37. coon Sock | on, riot Sora Oat er rad pd NigH20 ee ye | *OR 2) Hy.Ni i eee HB — gH, Br oo so ee eon (D) (E:Nicotin) XII.38. Axit tropic chia nhém cacboxyl -COOH va nhém ancol bac 1 hoac bac 2. Mat khéc axit tropic c6 thé chuyén hod thanh axit benzoic. Tét c& cdc dit kign dé chi ra 1né chi cé mot mach bén ciia vong benzen: 310CoH 1003 ~CgHyO —CHy ~COOH -OH CoHs ~CyHyO Cy ~CyH; (nh6m mach bén) Axit hydratropic ¢6 cing khung cacbon v6i axit tropic nhumg nhém ~OH duge thay bang -H va mach ben mang nhém ~COOH 1H I Hy pop ed > i " ; Ni OH OH Br ‘Trong axit tropic trong axit aropic trong axit Nhu vay nhiing axit nay cé thé nhu sau: CoHs-CH-COOH +=» C,H, CH-COOH I CH.OH CHy S=—O— 5 hic iratropic Hoae: Ph- CH-CH,-COOH ___ & |» Ph-CH,-CH;COOH PheCly-CH-COOH — (C6 thé axit tropic) (Co thé axit hydratropic) Axit tropic c6 thé c6 3 dang cAu tao Axit atropic 06 thé c6-2 dang ct ta0: CsHsC(=CH, )COOH va C,H;-CH=CH-COOH Axit hidratropic cing 06 thé cé 3 dang cau tao nhu trén, OOH 00H OOH 00H ee 1) KOH Orion 2)HF Na 3H ‘OH ‘OH Gay oH, «a (B) 00H ca oH, KOH SS HBr Kon, HoH ICH MgB ~~ Sy H,OH 1280, is ‘4 2) 20) er ony boot boocyHs on 3XIL40. XIL4L. ‘XI1.42. XIL43. XI1.44 XIL45. 312 ‘Y6u t6 lap thé anh hudng dén phan ting este hod va trong day b vac cdn c6 yéu 6 electron: a) MeOH> n-PrOH >sec-BuOH > tert~pentyl ancol b) CsHsCOOH > 0~CH,CgH,COOH > 2,6~(CHs),CjHj,COOH c) HCOOH > CH,COOH > CH;CH,COOH > (CH;);CHCOOH > (CH;);CCOOH a) AcB2 b) Ank-Al Axit salixylic 66 IkH gitta H cia nhém -OH véi oxi olla nhém cacbonyl lam tang tinh axit, cdn axit_ m-hidroxibenzoic va axit p-hidroxibenzoic c6 IkH lién phan tit. (pKa cita axit o-,m-,p- hidrdxibenzoic lén luot nh sau: 2,97;4,06;4,48) (pKa cita axit o~metoxibenzoic 1a: 4,09). Dua vao phan img th€ electrophin vao nhan thom dé giai thich ‘Axetilen—r CH CHO—> CH,CH OH» cH serge $Now,cu igen -H2O CH3CH,COOH Ht Hy . HNO CH3CH2CH OH <2 CHCH CH NH CHACH,CHOOH + CH CH PHP HSM cyycHycoacH CHE; + 140 a) Axetilen os Chh=CcH, HBL 6H, Br ae CoH. MeBr Axetilen 4 GH Mabe oH 6 gc = cMgBr 2002 Brmgooce =ccooMesr — 2Mg(OH)Br a HOOC-C=C-COOH b) Xem cach giai cha bai 12 cia chuong XII nay. c) | + Axetilen es se cucu HCN, cu,crojen Bou cHoeooH ara a m Axetilen —»cH,COoH —earcticook HQ” noczcooH calico.) Axetilen—=-cH,cooH PZ arctycoon ———$? (BrCH,C00) Ca Pdo OH AS arctt,coctigbr NaN. NCCH,GOH)CH LN Hig HO-E-CH ACH g GOH ‘ CN O COOH O a8 - TRAC NGHI£M : XIL47: B XIL53: C XIL5S9; C XIL65: D XIL71: A ‘XIL77: B XIL83: C XIL48: A XILS4: D XIL60: B XIL66: A XIL72: A XIL78: B RIL 84: B XIL49: A ‘XIL55: C XIL61: A XIL67: A ‘XI173: A XI XIL85: C. XI1.50: C XILS6: C XIL62 :B XIL68: A XIL74: A XIL.80: B XILS1: B XILS57: D XI me XIL69: D XIL75: A XIL81: C 313