bao gồm các sơ đồ phản ứng hóa học hữu cơ lớp 11 .......................................................................................................................................................................
547.076 GS.TS NGUYEN X U A N T R U O N G S460D „ TT f—^ i CHuol P H A N -JK rn I'—^ h 1^ urnl r^i^* 500°C xt (m>2; CH3CH = CHCH3 + H2 CH2 = CH2 + CH3CH3 Khi C O chat xuc tac, nhiet thich hop, ankan bi oxi hoa khdng hoan toan tao dSn xua't chiia oxi Vi du : n-m>0) CH4 + , CH3CH = CH2 + CH4 > ^" „ Dudri tac dung cua nhidt va xuc tac Fe, Pt, ), cac ankan kh6ng nhOng bi tach hidro tao hidrocacbon khCng no ma bj gay cac li6n k6't C - C d^ tao cac phan tir nho hem • Ne'u mach cacbon dai, oxi hoa c6 the' bi be gay : CHiCH,CH,CH3 + O, + Phan umg phan huy • Phan hiiy boi nhiet: Gia sir ta c6 so d6 : ()()()" c crackinh -> honh(?pY DSc biet: Trong phan umg crackinh s6 mol sau phan umg tSng nhimg kh6'i liromg kh6ng doi VI ham lirong C va H X va Y nhu nx < n y -> P, < P, > HCHO + H2O 200atni.300"C Nhdn xet: khac ^ < " H "hh = " H J O - " C O Cl' + Cr ^ CI •CH3 + a * ^ CH3C1 ankan + 2H,0 -> Cac hidrocacbon thu6c day dong ding ankan va c) Bixorc dut day truy^n Hon hdp X nC02 + (n + DH.O ^- Hoac : no2 > l.Sncoj CH3C1 + cr CH3CH2CH2CH3 + d6ng dang ma thu duoc : "CO2 •CH3 + CI -f CI "^f "x Nhdn xet: Khi d6't chay m6t hay m6t h6n hop cac hidrocacbon thu6c ciing day C H J I H + CI* - ) • 'CHi + HCl •CH3 + *CH3 Pi bi nhiet phan + Phan umg oxi hoa a) Oxi hoa hodn toan Khi dd't cac ankan chay tao CO,, H-,0 va toa nhilu nhiet b) Buorc phat tri^n day truy^n : H + CI* ^ va dxA- = — ta se tinh duoc ny do tinh duoc % ankan =^ nx ' " ' I > 2CH3COOH + H , our-j • PhSn huy bai clo : + C„H„,.3 + (n H- DCU ,„Hs.C^,c.rn, > + 2(n + DHQ AUCj+ D i e u c h e a) Khai then- ti( ddu mo, klii thien nhien qua cue dudng crackinh va chifng cat phc'in doan h) Phuon^ phdp tdn^ mach • Mot so phmmg phap khac a) Tif nhom cachiia : I2H2O (Di^u chd-AI4C, : 2AI2O3 + 9C h) Ti(C vdH C + 2H cachon A l ( O H ) i + 3CH4 ) Al^Q + 6C0T) : Ni ^ CH4 TOOT Tdnghop Vuydc(Phap) 2C„H„„ ,X + 2Na II H I D R O C A C B O N NO, M A C H V O N G ( X I C L O A N K A N ) ( C „ H „ , + 2NaX C„H2„ J Cong thitc chung: (n>3) Chu y: N6'u dung hai loai d3n xua't halogen c6 g6c ankyl khac se thu Tinh chat hoa hoc duoc h6n hop ankan song kho tach khoi vi chiing c6 nhi6t d6 s6i xa'p a) Phdn iOi}> cgng md vdni> ci'ia xiclopropan vd xiclohutan X I bang nhau: R-R R X + R ' X + 2Na • + 2NaX ^' R-R' + 2NaX R'-R' + 2NaX propan + Br2 CH2Br-CH2-CH2Br T6ng hop Konbe (Dure) /,.? - R C O O N a + H O -^2!^ R - R + 2CO,t + c) Phuang phdp gidm much / - Catot Ni Phuong phap Duma : 120°C R H + Na^COj C H , C O O N a + NaOH — CaO C H + Na,COi t' t" Xicloankan vong 5, canh tro len khdng c6 phan ting c6ng ma vong h) Phdn I'rng the Phan ling thd' a xicloankan tuong tu nhu a ankan V i du : a CaO C H , ( C O O N a ) , + 2NaOH — S f i _ ^ CH4 + N a X + Ch Phuong phap crackinh : + HC1 — Q.^: + — i r £ ] H i S — ^ C,„H2„, + C,„ „,,H2,„ ^, + (m > 2, n > m) + > CH,-CH2-CH2-CH3 nhirng dieu ki^n trSn Vidu: • hiompropan Xiclobutan chi c6ng vdi hidro : cachon R C O O N a + NaOH — dihrompropan + HBr ^ C H , - C H - C H B r 2NaOH + H t Anot • > CH,-CH.-CH3 80° C xiclopentan Phuong phap gift nguyen mach cacbon • QHi,, + HT ——> C„H2„ + C,iH2„ - + 2H2 ——> QiH,,, + > (•) Phdn I'fng oxi hoa hodn todn C„H2„+y02 D i tir ancol no, dcm chiic : C „ H , „ , O H + 2HI — \ HCi xiclohexan 1° • + CU Hidro hoa anken, ankin, ankadien tuong iJng : C„H2„,2 + H2O + I2 C6H,2+ 9O2 ^ nCO + nH20 6CO2 + 6H2O »i6uche E l a : CH,CHO Ngoai viec tach trirc ti^'p tuf qua trinh chung cat ddu mo, xicloankan diroc didu che' tuf ankan V i du : F la: Q H G la: C H , H la: C a C ) CH3[CH.]4CH, 1 + Hj Cac phirong trinh hoa hoc : iTng dung (1) A I C , + H , ^ A ( H ) , +3CH4 Ngoai viec dung lam nhien Vitu nhu ankan, xicloankan dugc dung lam dung t", xt xiclohexan Cdch viet dong phdn mach o + benzen vdng Ve vong 16n nha't roi thu nho dan, chii y t6 hop cac loai nhanh (neu c6) • Them cac nguyen t\X H vao mach de dam bao dung hoa tri I V ciia cacbon H,C CH, xiclopropan (3) C H + CI, CHj — CH, CH, C H — CH3 CHj — C H , metylxk opropan xiclohutan (4) 2CH4 (5) 2CH.,C1 + 2Na (6) C,H, + C I , (7) C , H + H C ->C,H,C1 (8) C , H + Br, (9) C,H4 + H,0 (11) CaC, + H , Bai (6) C,H4Br, CjHsOH CH4(OH)3 C , H , + Ca{OH), > C,H6 >C,H4 '''^^"-^ •> Cao su Buna Hg-'»4.so"c ^ C H C H O (15) C,H, + H C ->C,H,C1 (16) C , H + H , (17) C , H , (18) C , H , ^"4Ci.'oo"c (20) nC4H, (21) C4H4 + H , (22) C4H,o ^'-'"^ ) C , H , > C,H4 + H, (19) C4H4 + H , » C4^10 H 3C,H4(OH), + K H + 2MnO, (1)^ CH5OH la: A I C , CH^Cl + HCl C3H5CI (14) C,H, + H , Huong Akn giai CM, + 2NaCl (12) C,H, + H , » (13) C , H , + H , (17) A + HCl '-'"""^ > Q H , + H , (10) C , H + K M n + H O B B A I T A P C H u l P H A N iTNG Dap an > CH3CI 3H • CH, ^"^''^ > CH4 + Na.CO, (2) CH,COONa + N a O H m i , lam nguydn lieu di^u chfi'cac chat khac ^ C4H4 P-'co3.'"c ^ c , H , > (C4He)„ (Cao su buna) > C4H,o ' " " " ^ C H + C,He B la: CH.COONa D la: Q H j Bai Bai CH4 - U C , H — C H , C H O ^ C , H , O H ^ C H , - ^ C H | o Ancol iso-propylic C4H, + H , + H , t 45(rC CH4 + Na.CO, + H , 5) C4H, + H , C4H,„ 6) C4H,o C , H , + CH4 CH4 + 4A1 ( O H ) , CH4 + 4AIC1, A I C , + 6H,S04 ^ CH4 + 2AU(S04), C,H« 3) CH,,CHO + H : 4) C , H , O H OiO t0 C H , C O O H + 2NaOH A I C , + I H O ^ + 2NaOH ^ l' > vi k h u a n CO + H , C H , - C H - CH3 CH4 + C , H , , /^'^f' ^ ) C.H^+ lamlanhnhanh ^ CH4 + H , ^ OH © 1) 2CH,COONa + H , CH4 CH4 + H , 0 CH,COONa + NaOH 7) C H - C H = C H , + H O H > CH4 + Na^CO, 2) C,He + CK '"^"^"'^"^ 3) 2C2H5CI + 2Na ^ 4) C4H,o ) o C,H,,C1 C,H,o + N a a "''^'"^ > C , H , + CH4 5) CH4 + , ) HCHO + H , 600" c 6()()"C 6) H C H O + A g O > CO, + H^O + 4Ag>l © 1) C3H7CI + NaOH,„j„g — ^ CiH^OH + NaCl 2C0, + NaOH + H,T Cty TNHHMTVDVVHKhang 2) C,H70H + CuO — Vift ^ C H - C H - C H O + Cu + H3O ^ Mn" 3) C H , - C H , - C H O + - O , " XI,t 6) n C H , - C = C H >CH3-CH,-COOH I ^ / CH3 I CH3 CH3 -C-CHI 4) C H , - C H - C H O + ^ O > CH3-CH,-COOH 5) CH3 - C H - C H + H C I - > C H - C H - C H , ^ * C H J„ (Bai 5, 6, 7, ban doc tir viet P T H H ciia cac phan urng) ' Bai Viet P T H H cua cac pu thirc hien chuoi bien hoa sau : CI 6) CH3-CH-CH,+NaOH,„a„g a A I O — • A I C — • m e t a n — > • m e t y l c i o r u a — • metilenclorua CH3-CH-CH3 + NaOH — • OH 7) C H - C H - C H clorofoni — • b axitaxetic + C u O ^ C H , - C - C H , + Cu + H O tetraclometan natriaxetat — • m e t a n — ^ m e t y l c i o r u a ^ ^ e t a n — ^ etilen c butan — e t a n OH ^ — e t y l c l o r u a — • b u t a n — • propen — ^ propan Bai Bai a) Cong thirc phan ti'r ciia hidrocacbon A la CiH,, (vong) Hay viet P T H H cua cac phan I'rng theo chuoi sau dudi dang cong thuc cau tao thu gon > B ^ D » E > ^ xt t" ankan A > Polipropilen - +CuO +NaOH B +0, D ^ — E b) Dung cong thuc cau tao viet PTHH ciia cac phan irng theo so d6 sau : cao su isopren i-Br-, " CH, I -C - C H - QH,o —< " - C4H6Br2 D C4H6Br-, ("i9t chat) (hai chat) Hwong dan giai DCjH,, ) C,He+ 2) n C H - C H = C H - XI.I" Bai Hoan cac chu6i phan irng sau : C,H, a A f-CH-CH2- Mir B +D c -CH-CH2I CH2-OCOCH3 CH 3)nCH3-CH-CH2-CH3 > r C H = C - C H = CH xl.t" , f-CH,-C = CH-CH,- 5) n C H - C H - C H - C H , 12 ^ E — * ^ de hidro ^ / c C H — • d C H , CH3 CH CH, A — B b.CHd CH3 CH, 4)nCH2 = C - C H = CH2 + 2H, A | — • A2 — A — • A4 - B2 C CH3-C = CH-CH3^ CH, F — • CH4 F — • Glixeron E • e C2H4Br2 B HjSO^d.t'' F — • H2 NaOOCCH2COONa -£{j^" (-1'""! pluin g C3H6 , , • , irnfi hoa hoc HiTii cir - I\'f>uypn \tiiiii — • _^ C, — • NaOHIg E _ — • C H - C O - C H O ^ AgNO^/NH, 2^A - — B h 1.1 i c l o | * o p a n • C2 Trir&ng F B • D • ,_^„„ E • „ H2SO4 —-— G • G (CjHftO) H (C2H6O) C h u o n g +CI2 D — • H • pohme A K I E N T H t r c C O B A N A n k e n (olefin) / Cong thifc Chung : Cdu tao • k A F • A • B: — • C,fl2, (n >2) T r o n g phan tir c m o t n d i d o i ( C = C ) v d i C l a i h o a sp- t a o g o c 120", phSng t r o n g d o c l i e n k^'t a b^n v a m o t l i e n k e t 7t k e r n b6n n e n a n k e n d d t h a m g i a p h a n irng h o n a n k a n Bai V i e t P T H H ci'ia c h u o i p l i a n i r n g t he o s a d o sau : a CaC2 HIDROCACBON KHONG NO • D • F • N g u y e n tir C k h o n g q u a y diroc q u a n h l i a n ket d d i ( C = C ) l a m xuS't h i e n d d n g CH phan k h o n g g i a n ( d d n g phdn cis trans) Tinh chat vat li < A —•C +HC1^ B i v ^BN a O H c CH4 — • A - • < ^ +2HCI^ B J^—• A ^ G J - * " Cao su Buna • T i r Q - > C la chat k h f , Q C|« l o n g va t r d I6n t d n tai d a n g r a n • N h i e t d d n d n g chay va nhiet d o s d i t u o n g d d i tha'p, t i khd'i h o i n h d , t i n h t a n t r o n g nirdc k e m • C a c a n k e n t h i r d n g phfln c u e (|.i ^ ) va fi,„ > \i„,„„ d o d d cac d d n g phan trans - an ken n d n g c h a y a nhiet d p c a o h o n n h u n g l a i s d i d nhiet d d tha'p h o n so v d i cac d d n g phan cis t i r o n g I'rng CH4-*- D E C2H5OH D — • E — • F — • HCHC • A n k e n hau nhir k h d n g tan t r o n g nude va la nhOng chat k h d n g m a u Tinh chat hoa hoc L i e n ket n c i i a anken k e m ben At hi dut de tao l i e n ket a v d i cac n g u y e n tir +NaOH khac nen dh t h a m g i a phan I'rng c d n g , phan i h i g t r u n g h o p va phan ting o x i hda + Phsin umg cong a) Cgni> // —> ankan C„H2„ + H , Nlian Goi — > C„H2,n.2 xet : K h i g i a i toan ciin l u u y : X la h d n h o p a n k e n va ban d a u , Y la h d n h o p t h u d u p c sau p h a n iJng T a cd : • N e u m o t h i d r o e a b o n m a c h h d phan u'ng vira d u v d i t h e o t i le m o l 1: t h i d d la a n k e n • N e u h a y n h i e u a n k e n c d n g v d i H2 v d i c u n g h i e u suat t h i ta c d the' thay h d n h o p b a n g c d n g t h u c t u o i i g ducmg C - H C-H - + H nank.n p i f = I n Pif C - H - ^, = "umk - n,,„ r ' Chi'i y: K h d n g the' d u n g each neu cac anken c d n g h o p v d i H , k h d n g c u n g h i e u suat Sffcld chuSiphan li-ng hda hpc Httu ca- Nguyln XuQn Tru&ng • 2CH,-Ci l - C H , + 2H,0 — f ^ CH3 - C H - CH3 + C H - C H , - C H , O H V i h6n hop X, Y c6 cung s6 mol C, H nSn d6't chay h6n hop A hay B d^u cho OH cung ke't qua : d6'tX 'o'CO2 va = n^ Ancol isopropylic (spchinh) d6'tY r» sinh d6't X = n^Q va nu r, sinh dot Y + Phan iimg trung hop 'H,o t", xt -> Do lam toan, neu gap h6n hop sau qua Ni/t° dem ddt (h6n hop Y ) thi thay vl ti'nh toan vdi h6n hop Y (thucmg phufc tap hem X ) ta c6 t h i dung cac - < (gia sCr nCH, = (pH MY X, Y o cung dieu kien t°, ap sua't) h) Cdna halogen (CI p Xt [-CH, —CH-]„ CH, polipropilen (PP) cci.^ C„H,„X3 + Phan iimg oxi hoa ! I'' a) Oxi hda hodn toan : Phan ling lam mA't mau dung djch brom dirge dung d l nhan bi6't cac hop chait C„H2„+ chiJa liSn ket doi, lien ket ba • Khd'i lugng ciia binh dung dung dich brom tang I6n la khoi luong ciia anken Ih^p thu • Neu bai toan cho m6t hay mot s6' hidrocacbon mach ho thuoc ciing day d6ng Quy tac Mac-c6p-nhi-c6p : K h i c6ng mot tac nhan bat d6'i H A (axit hoac nucfc) vao liSn ket d6i (C = C) ciia anken thi san p h i m chinh dugc tao dang thu duoc : "CO2 = " H hoac n^o^ = 1-5 n^^^Q ^ MI CH, • CH = CH2 t + H" I cr lankan • C H , - C H - C H C I (spphu) Giai thich quy tac : Do g6'c ankyl day electron lam cho lidn ket 71 bj phan cue, n6n ion duong dd gdn vao cacbon mang didn am va ngugc lai Kha nang phan ling c6ng : H I > HBr > HCl > H F • C6ng H , - > ancol C H , = C H , + H3O '-^—^ CH.CH^OH t" ' Ancbletylic = "H2O ' nc02 • D o t chay h6n hop anken + a n k i n (ankadien) t h i n^.^^ > n^^^Q va (spchinh) CI • * • D6't chay h6n hop ankan + anken ( x i c l o a n k a n ) t h i n^^Q^ > n^^o (cacbon c6 bac tha'p hon) va phdn mang didn am ciia tac nhan (X~) gSn v^o r*CH,-CH-CH3 Cac hidrocacbon thu6c day d6ng dang anken hay xicloankan phAn duong ciia tac nhan (H*) gin vao C ciia n6'i d6i mang di6n am cacbon ciia n6'i d6i mang dien duong (cacbon c6 bac cao hon) V i du : "^^'"^ • K h i d6't chay mot hidrocacbon hay nhidu hidrocacbon thu6c cung day d6ng c) Cons HA (A = halogen, O H " , OSO,H") • ^ Nhan xet : dang tac dung voi brom theo t i le mol 1: thi cac hidrocacbon la anken • polietilen (PE) t", CH, Nhan xet : • I-CH.-CH.-, Br,) C„H,„ + X , (dd) - C - ]„ "CH, = CH, 12 Mx < M Y ^ d (XA') = = A = ^ = m^ = mv va nv < nX [-c Vidu: phan ling dot chay X de ti'nh nco ^ va UH ^ o• Ancol propylic (spphu) ,^ i) Oxi hda khon^ hodn toan V Dung dich KMn04 loang a nhiet d6 thucmg oxi hoa noi d6i ciia anken 1,2- diol 3C„H3„ + 2KMn04 + H , 3C„H2n(OH)2 + M n l + K O H Vi du : 3CH.=CH2 + 2KMn04 + H , ^ 3CH2-CH2 + OH (mau tim) MnO^J-+ K O H OH 17 Toluen tham gia phan ixng brom hoa d6ng ph&n : CH, o + Br,, Fe -HBr Quy t^c th^ tr£n v6ng benzen dang ban va tao san phim g6m hai Khi trfin vong benzen da c6 sSn nhom ankyl (hay cac nh6m - O H , - N H j , -OCH3, ), phan ung th6' vao vong benzen se d l dang hon va uti tifin thd' vao vi O ^ CO t r i ortho hoac para Ngiroc lai, nd'u b vong benzen da c6 sSn nhom - N O j (hoSc Br cdc nhom - C O O H , - S O , H , - C O O R , ) , phan ung the' vao vong se kho hon va uu ti6n the' vao vj t r i meta Phan vfng sunfo hoa Br p-bromtoluen Dun nong benzen voi H2SO4 dam dac d6ng thori chung cat nu6c khoi h6n hop o-bromtoluen phan ling se thu duoc axit benzensunfonic : Clui y: Ne'u kh6ng dung Fe ma chife'u sang (as) thi Br se the nguyfin tijf H d mach nhanh Q H ^ + HOSOjH d) Phan itng ankyl H^C-H H.C-Br o h) Phan • + Br nitro Q H , + C„H3„., CI CsH, + CHjCH^OH o H2SO4 d HO-NOo ^0 ) C6H5CH2CH3 + H2O ) Q H s C H o C H , N6'u anken la propilen ta se thu ducic san ph^m chinh la cumen C,H6 + C H , = C H - C H , + H-,0 "2^^°^ Phan umg cpng Nitrobenzen tac dung voi h6n hop axit H N O , b6c khoi va H , S dam dSc a) Benzen va cac ankyl benzen kh6ng lam mat mau dung dich brom flhu cac d6ng thdi dun nong thi tao m — dinitrobenzen hidrocacbon kh6ng no K h i chid'u sang benzen c6ng vdi clo tao C^HeClj NO, C , H , + 3CU Q) + HO-NO, "^SQ^d, (Qj^ * (hexaclo xiclohexan) ^ ^ N ;)CgnsH, Q H , + 3H, Toluen tham gia phan ung nitro hoa d l dang hon benzen va tao san pham th6' o vj tri oitho va para : o H2SO4 d a) Oxi hoa hoan loan o ^o C „ H „ - + ^Y^O, \ - > nCO, + (n - 3)H20 • NO, NO, p- nitrotoluen 48 !il.iL^QH,2 Phan umg oxi hoa CH, HNO,, CeH^Cl, ^ H2O m- dinitrobenzen CH ) C,H5CH(CH3), (cumen) nitrobenzen NO, —"^^^i C^Hs + C H , = C H , NO, + > QH5C„H,„,, + H C l ^'"^ • Co th^ thay th6' dSn xua't halogen bang ancol hoac anken d ^ ankyl hoa benzen Benzen tac dung voi h6n hop H N O , dac va H2SO4 dam dac tao thiuih nitrobenzen : o QH5SO3H + H2O (phuong phap tang mach cacbon di di6u chS'cac ddng d i n g cua benzen) + HBr hoa H ) hoa • Benzen tac dung v6i ankyl clorua c6 mat ciia AICI3 khan se cho ankylbenzen o > • ' »• o- nitrotoluen + H2O ) Oxi hoa khong hoan toan • Khac voi etilen va axetilen, benzen kh6ng phan iJng vdi dung djch K M n • Toluen va cac ddng dang dun nong voi dung dich K M n (hoac K2Cr207) se bi o x i hoa mach nhanh (nhom ankyl) tao mu6'i va axit hiru co Phan iJng dimg de nhan bie't toluen 49 QH5CH3 + 2KMn04 -> Q H s C O O K + 2Mn024 + K O H + H.O Nhqn xet: Nd'u nh6m ankyl d vong benzen dhi hem nhom -CH3 thi phan ling 1, ) Phcin ling trung hcrp n C H = CH2 oxi hoa mach nhanh v3n iru tifin xay or vj tri a d6'i vdi vong QH,CH2 - ^ C H j R KMNO, > QH5COOK + Chung cat nhua than da va rifominh din mo thu duoc m6t luong 16n benzen, toluen va naphtalen (diing c6ng nghidp) + Dehidro hoa d6ng vong hexan va heptan thu duoc benzen va toluen CH,(CH,),CH3 2Z"QH,-^4H, - C6H5 C6H5 """^ ) Q H C O O H Dieu che benzen va aren r-CH-CH, "•^"••^ polistiren (PS) v (•) Phan ifng oxi hoa Giong nhu etilen, stiren lam mat mau dung djch KMn04 va bi oxi hoa nhom vinyl, vong benzen vSn gi& nguyen ' ' " ' '' ' 3QH5CH = CH + 2KMn04 + ^ -> BQHjCHCOH) - CHjOH + 2Mn02 + 2KOH Phan ling tren dung d^ nhan bie't stiren , Naphtalen CftHjCHj + 4H2 + Ca'u tao phan tir va tinh chat vat li + Dehidro hoa xicloankan hoac metyl xicloankan • Naphtalen c6 c6ng thiic phan tir CioHg, duoc ca'u tao boi hai nhan benzen c6 chung m6t canh + Trime hoa axetilen SCH, ^ C,H, 6"6 + Ankyl hoa benzen de A\iu che'ddng dang ciia benzen > QH5QH,,,,, + HCl Q H , + C H , , , , ,C1 Naphtalen la chat rSn mau trlng, t„, = 80°C, t, = 2\Q°C, thang hoa a nhiet d6 thucmg, c6 miii dac trung (mui bang phie'n) Kh6ng tan nuoc, + Cong H2 vao mach nhanh khdng no C.H5CH = CH, + tan dung moi hihi co Ni, t° -» C^HjCH^CHj + Tir benzen va etilen de diau che' etylbenzen '' + Tinh chat hoa hoc Naphtalen duoc coi nhu g6m vong benzen giap nen c6 tinh thom tuong C^H, + CH, = CH, — i i ^ ^ QH5CH2CH3 tu benzen II S T I R E N VA N A P H T A L E N tj Phan irng the CH=CH, Stiren + CS'u tao va tinh chat v$t li • Stiren (vinylbenzen, phenyletilen) c6 c6ng thirc ca'u tao : • Stiren la chat long kh6ng mau, nhe hon nude va kh6ng tan nu6c Naphtalen de tham gia phan iJng the' hon benzen San ph^m the'vao vi tri (vi tri a) la san phdm chinh Br Br ™ + HBr ^ t l = - ° C , t ^ = 145°C + Tinh chat hoa hoc a) Phan ifng cpng Tuong tu nhu anken, stiren c6 phan ihig c6ng halogen (Q,, Brj), hidrohalogenua (HCl, HBr) vao nhom vinyl HNO3 _iM2i^ + H,0 h) Phan irng cgng hidro (hidio hoa) C6H5CH=CH2 + Br, - » C^HjCBr-CH^Br C6H,CH=CH, + HCl ^ CeHjCHCl-CHj Ni, 15()»C ^ CQIC-^ tetralin 50 , ZOO^C, 35 atm decalin 51 CtyTlVHTrMTV c) Phan I'fn^ oxi hoa Naphtalen kh6ng bi oxi hoa bcri dung dich KMn04 Khi c6 VjOj 1km xiic tac, nhiet d6 cao no bi oxi hoa boi oxi khdng O,(kk) V , „ 350" - 45()"C ^ / CO Anhidrit phtalic B BAI TAP C H u l PHAN UNG B^i Xac djiih A, B, C D, I , K, L va viet PTHH cua cac phan ihig sau : 1500°C A -> B + C Ni,l"C D + C ^ E A + J -> K + HCl 7.L + I ->• T N T + > C^li,,C\ HCl D Ta tha'y chi c6 chat c6 CTCT la: CH3-(pH-(|;H-CH3 4.D + I -> T N B + dugrc dong phan : K + D U — L + HCl CH3 V Hu(hig Ahn giai Quan sal toan b6 phuong trinh chira hoan va riit nhan xet : - Trong cac phuong trinh chi cho bi6't m6t so chat cac phan iJng (4, 5, 6, 7) - Trong cac phucrtig trinh chi cho biet dieu kien a cac phan ung (1,3) - Dira vao cac dir kidn da biet da' tim moi lien he giiJa cac chat - a phirong trinh biet duoc D hoac I la C^Hs hoac HNO, - a phiromg trinh bi6't duoc L hoac la CeHjCH, hoac HNO, Ket luan : D la C.H^; L la C^H^CH.,; I la HNO., - Dira vao pha.i ung (3) dieu kien (Ni, t°) suy luan E la C^U, va C la H - Dira vao phan ung (1) di^u kidn (1500°C) suy luan A la CH4 va B la C H - Dua vao phan ling (5)) suy luan J la CUva K la CH3CI 3CH4 C6H, + 3H, J -CH-CHi CH3 CH3 CH3 - C - (1-clo 2,3-dimetylbutan) CH-CH3 CH3 CH3 (2-cIo 2,3-dimetylbutan) Br Br CH2-C-CH=CH2 C H'3 Br CH2= (^-CU-CHj CH3 CH2=C =C-iH-CH2 Br CH3 -> C.H, (Co d^ng cis va d^ng trans) Ni.l'- + 3HO-NO2 c lljS()4 C,H, + CH,C1 aski CH2-CH3 + 3H2O 0,N CH4 + CI, NO, -> CH,C1 + HCI ^'"-^ > C,H5-CH., + HCI CH3 CH3 + 3HO-NO2 H2SO4 Br Jr :H2 NO2 CI-CH2-CH CH3 ^'^'^'"'^ > CH=CH + 3H, 3CH=CH Knang 0,N NO NO2 + 3H2O rip Bai a) Xac dinh CTCT cua C^H^, bifi't rang tac dung vdri CI, theo ti 16 mol 1:1 ta chi thu duoc dong phan Goi ten d6ng phan b) Isopren c6 the' c6ng hop brom theo ti le mol 1:1 theo each d^ tao d6ng phan vj tri Viet CTCT ciia cac d6ng phan c) Cho aren c6 c6ng thiic QHIQ Viet CTCT va goi ten cdc d6ng phan ciia A Hirdng dkn giai a Nam c6ng thurc ca'u tao c6 th^ c6 ciia C6H,4 (hoc sinh tu vie't) Theo phan ung : C,H,4 + CI, B uvvn Ten goi : (A) etylbenzen (B) o-dimetylbenzen ( hoac o-xilen, hoac 1,2-dimetylbenzen) (C) m-dimetylbenzen ( hoac m-xilen, hoac 1,3-dimetylbenzen) (D) p-dimetylbenzen ( hoac p-xilen, hoac 1,4-dimetylbenzen) Bai Thuoc chiJa ghe DEP (dietyl phtalat) duac di^u che tir nguon nguyfin lifiu Bai diu la naphtalen theo so d6 cac qua trinh chuyen hoa va hidu sua't sau : B O Oj (kk), VO, 460-480"C O + San phim phu etan Axetilen H = 75% D o II H i r i n g dan giai n rr^)0+ 2C,H,OH-ai4- COOC2H5 o + H2O XI, t'' 1.2QH2 Daps6': 90,44kg Bai poll «tiren D A Hex an uitiobeiizen B Tolueu 'I Stiien Hirong dan giai Q H Pd ->C,H,+3H2 300° C Q H s + HNO3 ^ QH, + CH,C1 + CH:=CH2 QH, ^'"^ > H.O Q H , C H + HCl QH5-CH2-CH3 QH,-CH=CH3 n C H , - C H = CH2 >r-CH-CH2-^ I C6H5 + CH5CI Q H - C H , - C H , C A QHjNO, + QH,-CH3-CH3 — ^ Q H , Ni.t" + H, ^"^'-^ > Q H , - C H , - C H , + HCl -> QH,-CH=CH, +H, > QH,o H5£hill_> Q H e + QH4 Q H i o QH3 + 2H, - ^ ^ ^ QH3 + H,0 C H , C H O Q H O H C,H,2 QH4 QH4 + H , Ti'nh khdi liromg naphtalen d^ didu che 100 kg thuoc DEP ^ -112^ + H, + QH, 2HI CH,CHO Ni,t° -)• photpho 200° c QH5OH ^ Q H , + I2 + H2O Cly TNHHMTVDWHKhang Sarad chudiphan urng hda hpc Hihi ccr-NguySn Xu&n Tru&ng DAN XUAT HIDROCACBON Chuofng A K l f i N T H U C C O B A N tu halogen hang nhom -OH + CH3CH2CH3CI DAN X U A T HALOGEN - A N C O L - PHENOL Propyl clorua NaOH K h a i niem, ph^n loai, dong ph^n, danh phap niem QH,C1 CHjCHXH.OH + NaQ ancol propyl ic R C H = C H C H - X + H2O I D A N X U A T H A L O G E N a) Khdi T i n h chat hoa hoc ^) Phan ling thenguyen Vift + 2NaOH RCH=CHCH,-OH 3OO°c,20Oa.n, ^ Q H , O N a I, ) Phan i(ng tdch hidro > -CH3 CH3 1 Djnh nghla, phan loai, dong phan, danh phap lodofom a) Dinh CH2=CHF florua nghia Ancol la nh&ng hop chat hiru co ma phan tir c6 nhom hidroxyl ( - O H ) lien ke't QHjCH^Br true tiep vdi nguyen tir cacbon no benzyl bromua Thidu: Ten thay the': Br CI2CHCH3 1,1 -dicloetan j^,,^.,,, v|, II A N C O L CHI3 Vinyl Etyl magie bromua » , CH3 Tdn gdc hidrocacbon + halogennua Metylclorua CH3CH.-Mg-Br Vidu: C H j C f - CH3 T6n g6c churc : CH,a ^ ' ^ > d) Co che phan i(ng the nguyen tii halogen + Danh phap Ten th6ng thircmg : '' c) Phan vtng voi Mg CHrC-B"^ + D6ng phan FCH.CH.CHj CH2=CH-CH2-CH3 dSn xu^t bac c) Dong phan vd danh phdp -flobutan KBr + H , san phSim chinh ^ ^ ^ ^ ^ Br Dua theo ca'u tao cua g6c hidrocacbon ngircri ta phan cAc loai sau: + Bac ciia dan xuSit halogen bang bac cua nguyfin tir C lifen k^t vod nguydn tir halogen - > CH,=CH, + *- CH3-CH=CH-CH3 va dan xua't chura d6ng thcfi m6t vai halogen khac - KOH logi DSn xua't halogen g6m c6 d i n xua't flo, d i n xutft clo, dSn xua't brom, dSn xu^t iot + + — ^ 1,3-dibrom benzen C2H,OH; CH,=CHCH20H h) Phan logi + Theo ca'u tao g6'c hidrocacbon : Ancol no, ancol kh6ng no, ancol thom + Theo so luong nhom hidroxyl: Ancol don chiic, ancol da chiJc ) Ddng phan , Ddng phan nhom churc : Thi du C H j O H va CH3OCH3 ' D6ng phan mach cacbon CH3CH2CH2CH2OH va CH3-CH-CH2OH CH3O-H CH3 : Ttn g6c chirc : Ancol + ten g6'c hidrocacbon + ic Ancol etylic - Ancol anlylic Ancol benzylic CH2=CH2 R-CH2OH RCH=0 CuO + R1-C-R2 CuO -R2 2-metylbutanol-1 + Ancol chay tao COi tiep v&i nguyen ti( cachon no Chuant^ trinh hoa hoc mai gpi loai hop chat Id ancol Ancol Id ten chifc hcki hoc, rum Id ten ud'ng c6 chvCa ancol + Cu + h HoO CH.,OH T i n h chat hoa hoc + Phan ling chung cua ancol - Ancol tac dung vdi k i m loai k i ^ m tao ancolat va giai phong H2 Na -> RO-Na -)• 2CO, + +30, lian k6t voi C bac va c6 n6'i d6i thi chuy^n andehit Ancol CO nhom -OH lien ket vdi C bac va c6 n6'i d6i thi chuyfi'n xeton ^ CH,CHO ciing lidn k6't vdi nguyen tir C bac thi t u loai di •phan tijr H2O chuyen andehit + l/ZH, R-CH(OH)2 R-CHO + H^.O Ancol hau nhu khong phan ling duoc vdi N a O H , ma nguoc lai natri ancolat lai A n c o l CO nhom -OH bj thuy phan hoan toan phan tir H2O chuyen xeton + H-OH ^ RO-H + Ancol CO nhom -OH Glixerol hoa tan duoc Cu(OH)2 tao phiic tan mau xanh da trod ttt HiO HO-CH2 CH2-QH (i:H-0-Cu-0- CH2-OH CH2-OH "HO-CHZ D6ng(II) glixerat h) Phan iJtng the nhom -OH cua ancol + HBr + HA CH,Br + H , ->R-A Phan ihig tdch H2O + Tach nuoc lien phan tir + H,0 'CH+ H2O cijng lien ket vdi nguydn tir C bac thi t u loai di phan chuyen axit R-C(OH), HO-CH2 (J:H-0H +HO-CU-OH + H O - C H HO-CH2 cung lidn k6't voi nguyen tif C bac thi t u loai di R,-C(OH)2-R2 -> R.-CO-R: + H.O NaOH Phan ung rieng ciia glixerol CH2-OH 3H2O Ancol CO nhom -OH Ancol CO nhom -OH Natri ancolat RO-Na -1 phan ling toa nhi^u nhiet CH,=C(OH)CH, ^ CH,COCH, a) Phan i(ng the'H cua nhom -OH ancol R-OH + va H^O, Mot so ancol khong ben CH:=CHOH etylic c) H2O + Ancol bac bi oxi hoa manh se dut mach cacbon Chu y : Truac day ta gpi rum la chat hHu ca, phan ti( c6 nhom OH lien kit trUc R-OH + xeton CH3 CH,OH Cu + Ancol bac bi oxi hoa nhe xeton T6n thay the : Tdn hidrocacbon tuong irng + V j tri nhom ( - O H ) + o l CH3-CH-CH2-CH2OH - H2O ' + andehit Thi du : - + + Ancol bac ! bj oxi hoa andehit Thi du : QH,CH20H H,0 J} Phan I'fng oxi hod OH d) Danh phcip CH,=CHCH,OH CH3OCH3 140"C H;S04(I CH3-CH2OH I CH5OH H2S04d OH-CH3 + Tach nude n6i phan tijf Ddng phan vi tri nhom O H : C H , C H , C H , C H , O H va CHjCHCH^CHj - + -> R-COOH + H2O Phan ling trung gian ciia phan ling loai HnO ciia ancol vdi xt H2SO4: +H-O-SO3H • CH3CH2OH CH2-CH2 k OSO^H CH3CH2-O-SO3H + H2O CH2=CH2 + H2SO4 Co ch6 phan ung tach H2O tir m6t phan t i j ancol (ca ch6 SN,) : C H - C H - C H - C H + H^ OH • CH3-CH2-CH-CH3 ^OH, -H20 Sadd chudiphan irng hda hpc HOu ca-Nguyen Xuan Trir&ng fj) Phan Crng the a vdng therm CH,-CH2 -^CH-CHj CHj-CH-'^qH-CHj H OH O CH3-CH=CH-CH3 san pham chinh — H -*• CH3-CH2-CH=CH2 san ph^m phu Dun anken v6\O va dung chat xiic tac thich hop thi thu duoc ancol + NaOH ^ + 2NaOH CfiHsONa C^HjCl + HCI '"-P CeHjONa + NaCI +CO2 + H2O C6H5OH + + H2O NaHCOj Q H f i CH2=CHCH3 C6H5CH(CH3)2 Q2kk.H2S04^ C e H g O H + H + CH3OH Fe So di^u che khac : CH3CH2OH + Thuy phan dSn xua't halogen dd kiem : CH5-CI + C!2 C6H5CI + Hidrat hod anken : H.O Trang Br 2,4,6-Tribromphenoi CfiHft + 3HBr c) Dieu che chung CH2=CH2 W BrrgiBr Br, (1 „/ M.,\wV Dieu che a) Phuan^ phap + NaCI h) Dieu che etanol B B A I T A P C H u l P H A N tTNG Bail Ngoai phuong phap Xvtn etanol duoc di^u che' bSng phuong phap Ifen men tinh b6l (C,H,„05)„ + nH^O ™ » QH12O6 Tiiibbot Glucozo CftU,20C2H5-0-C2H5+H20 (9) - ^ l 2 d ! £ _ ^ c H = C H - C H = C H + H + H t (10) C H O H + H C l — C H , C + H O (11) > QH4 R-COOH+C2H,OH< "2S04(d).t°c , R C O O _ C H + H (12) ^ CH 2''6 C2H,OH > C2H5OH +HC1 C2H5CI + H O + CuO C2H5OH + 3O2 '"'^ > C H C H O +Cu i + H O (13) '"'^ > C O + H O (14) Bai B a i (7) (8) (9) (10) (11) (12) (13) (14) ->C2H,ONa Propan-2-ol dimetylxeton -^CH2=CH2 (C2H5)20 propan-l-ol propen • -^CH,=CH-CH=CH, CH3-CH2-CH2OH ^RCOO-C,H5 CH2=CH-CH3 + H , CH3-CH2-CH3 ^CH2=CH-CH, + H , +a ^ aski > CH,-CH, - C H , -> C H - C H - C H CH3CHO + H2 '"'^ > C H , O H + NaCl ( ) Ni.t^C +NaCl (4) > CH3 - C - CH3 + Cu + H2O (5) OH ,2C,H,OH + 2CO O OH > C H - C H - O H (3) len men nr,>u,32"C (3) >CH3CH20H (1) C H - C H - C H + CUO C2H5CI + NaOH (2) CI (Spc) ->C02 CI "2S04(1) (1) CH3-CH-CH3+HC1 C H - C H - C H +NaOH CH2 =CH2 + H2O 10 Htfo'ng d a n giai -^QHjCl -^CHjCHG isopropylclorua propan Htfo'ng d a n giai C^H.jO, (6) »r C 2y^2'^5 H N a + ^ H t (7) C H O H + Na lam lanh nhanh (9) O H , + C I C H O H + NaCl (5) ,T ( ) C H - C - C H + H, II O •> CH,-CH-CH, I OH (6) H propen CH3-CH-CH3 H,SO.,,„, >170"C CH2 = C H - C H + H,0 (7) Bai + HjO/OH A, OH CH2=CH-CH3 + H3O CH3-CH-CH3 "2-'^"4""^"g> ) (8) OH CH3-CH-CH3 KOH,ancol,l"c + H, Propen — ^ * CH2 = C H - C H +Ha > + 0,/xt, t" B -— ^ +OAt.r (4) > D + C1, 1:1 (2) H,0/OH (9) (.'5) CI (6) Hirong dan giai CH2 = C H - C H + H C ->CH3-CH-CH3 (10) C H = C H - C H + H2 CI (Spc) Ni,l" ^CH3-CH2-CH3 , ^ (1) (A) Bai C H - C H - C H +CI2 GCCjHgO) askl,l:l ^ C H - C H C l - C H +HC1 (2) (A| :spchinh) C H - C H - C H +CI2 askt,l:l •>CH3-CH2-CH2C1+HC1 (2') (A, :spphu) K (CjHgO) M i hop chat hOu co c6 so nguydn tir cacbon khdng qua va kh6ng chiJa halogen Xac dinh cac chat A, B, D, E , F, G, K Vid't cac PTHH minh hoa (Ung vdri m6i mQi ten la PTHH) Hudtig dSn giai Sa CO thi la: CoH 2"2 „ „ CH3CHO i CH3-CHCI-CH, +H2O OH" - j - C H ^ - C H O H - C H j + HCl (3) (B) CH, -CHOH - C H + ^ >CH3 - C O - C H + H O (4) (D) C2H5OH C H - C H -CH2CI +H2O- CH, OH" - > C H - C H - C H H + HC1 (5) (E) HCHO CH3OCH3 CH30H- ^ C H - C H - C H H + ^ — ^ ^ ^ ^ C H - C H - C H O + H (6) PTHH ciia cac phan ung : 2CH4 15(K)"c,lani lanh nhanh HgS04.H;S04.X() C ^ C H C H O C H , + H,0 CH,CHO + H, CH4 + O, ^'''"^ ) CH,CH,OH (I) (2) (3) "'•'"'^ ) HCH=0 + H,0 (4) ^'•'"'^ ) C H O H (5) HCH=0 + H, 2CH3OH (F) ^ C H , + 3H, "2S04d^c."*""c ^ C H O C H + Hfi a Hoan cac PTHH sau : i a) Br-CftH4CH,Br + NaOH (dd loang, nong) b) Br-C,H4CH,Br + NaOH (dd dac, nong) c) CH3CH,Br + Mg \) CH,CH,MgBr tac dung vcM CO, sau thuy phan san ph^m thu diroc irong dung dich axit HBr J e) CH,CHBrCH,CH3 tac dung vdi dd NaOH/H,0 ,t° f) CH,CHBrCH,CH, tac dung vdi dd KOH/ancol,t° Huofng d-kn giai (6) a) Br-C,H4CH,Br MaOH (dd loang, nong) -fy-r.-W}'' P^'J ^ Br-C6H4CH,OH + NaBr 64 'srrao cniioipnnn ung nuu wyt' iirni LU —itguycn /luuii nuung b) B r - Q H C H B r + 2NaOH (dd dac, nong) c) CHjCHjBr + Mg N a O - Q H i C H i O H + NaBr + H.O p a i Viet P T H H cua cac chuOi phan ling : a) D i ^ u che' ancol etylic tir than da, da v6i va cac chat v6 co c5n thie't khac b) Dieu che' ancol metylic tir nhOm cacbua va cac chat v6 co c&n thie't khac ) CH,CH,MgBr d) CH,CH:MgBr + C O , C H i C H , COOMgBr CH3CH,COOMgBr + H B r C H ^ C H , C O O H + MgBr, ^ , , G(ri y : a) CaCO, ^ CH3CH(OH)CH,CH3 + NaBr -> C H , C H = C H C H , „ p „ + K B r + H , f) CH2=CHCH2CH3 + K B r + H O Viet P T H H cua cac pu hoan chu6i pu sau : b Butan - > — brombutan ^ b u t - - e n - > CH3CH(OH)CH2CH3 Hirong dan giai + CU — ^ + H,0 ) X, > QH,0 Xac djnh chat X va vie't cong thiic ca'u tao thu gon cua X ^ ^r>;H' ' Hudrng d i n giai JPxiaCH^CH j.^'^.,,: + C1,, as ^1 +NaOH • 7, • Y + CUO X3 V » andehit benzoic Xac dinh chat X 1.) '1^ C,H,C1 + HCl C2H5CI + M g ^ C I in- Bai Cho s o d sau : a Etan —>cloetan —>etyl magie clorua a CaO— CaC, — Q H ^ ^ (^U,-^ C2H5OH Bai6.Chosod6chuy^nh6a:X ^ C H , C H B r C H : C H , + K O H ^I1S£L£ Bai H ^ b) AI4C3 ^ C H ^ C H , O H t" e) CH^CHBrCHjCHj + NaOH feVp- Hudrng dSn giai - C.H,MgCl Hudmg dSn giai Cha't X la ancol benzylic b CH3CH2CH3CH3 + Br, - ^ C H j C H B r C H C H j + HBr CHjCHBrCH.CH, + K O H > CH3-CH=CH-CH3 + K B r + H , CH3-CH=CH-CH, + H,0 Bai Hoan day chuy^n hoa sau : R_CH3 ^ ) R-CH,C1 ) R-CH,OH "^g"'" ) > CH3-CH(OH)-CH2-CH, Bai Tiretilen c6 the di6u che cac chat sau day : 1,2-dibrometan ; 1,1-dibrometan; (4) (5) vinyl clorua va poli(vinyl clorua) Viet PTHH ciia cac pu Hm'mg dSn giai Hudng d i n giai So d6 tren the' hien m6'i quan he giffa hidrocacbon, dSn xua't halogen, ancol, Di^u che' 1,2-dibrom andehit va axit cacboxylic Co the' hoan so d6 trucmg hop khai quat CH3=CH + Br, - > C H , B r - C H , B r nhu sau : D i ^ u che 1,1 -dibrom CH,Br-CH,Br + 2KOH ^ C H ^ C H + 2KBr + H , (1) R - C H , + CI2 (2) R-CH2CI R-CH2CI + NaOH ^ + HCl R-CH2OH+ NaQ CHsCH +2HBr-^CHiCHBr, Dieu che' vinylclorua C H , = C H , + CU |(3) CH,C!-CH,C1 CH,C1-CH,C1 + K O H CH.= CHCl + K C l + H , Bai Viet PTHH cua cac pu thuc hien chu6i pu sau : A ^i'y |7()"C > B tl22 H2S04l.)ang , D "2^Q4'^ > E ^•J^P( (4) R - C H O H + CuO — ^ R - C H O + Cu + H2O R - C H O + O2 '2 -' > 2R-COOH Tir trucmg hop khai quat b tren, G V co the' cho HS van dung vio cac trUcmg hop cuthe'ma-Rla-H,-CH3,-C2H5, li Hoan so d6 chuye'n hoa sau bang cac phuong trinh hoa hoc a Etan - > cloetan —> etyl magie clorua - ^ ^ ^ ^ CHj-CHBr-CHBr-CHj b Butan Hirotig dan giai — brombutan - > b u t -2- en - > CH3CH(OH)CH2CH3 j , ^ CH.(C1)CH(C1)-CH(C!)CH3 (3) C H , ( C l ) C H ( C l ) - C H ( C i ) C H , + N a O H - ^ CH3(OH)CH(OH)-CH(OH)CH3 CHjCHBrCHjCH, + HBr CH,CHBrCH,CH, + K O H '^^"s"" > C H , - C H = C H - C H , + H.O ) C H , - C H = C H - C H , + K B r + H.O ^ X • CH,-CH(OH)-CH,-CH, 114 Xac dinh cac chat A , B, D c6 thd' c6 va hoan chu6i biS'n hoa du6i dang CTCT thu gon so d6 sau : r-^ - ' v/ i i , v(,,r;\p: Bai 10 CH,CHO - QH^OH ^ CH4O - CH,COOH - CHjCOONa -* CH4 CnH^ ^ » CH3CHO Hirong dan giai (1) C H , C H O + H : ) CH,CH.OH (2^ C H , C H : O H + C u O — ^ C H , C H O + Cu + H.O (3) C H , C H O + Br, + lUO Hirong dan giai > CH,COOH + HBr (4) C H , C O O I I + NaOH : CO the la C H : = C H , / CH:=CHC1 / CH,CHC1: / RCOOCH=CH2 - AC • \ : Neu B la C H , = C H , thi D la C H , C H , O H > CH,COONa + H^O Neu B Id C H ,=CHCI thi D la C H , C H C I : (5) CH.COONa + NaOM > C H , + Na.CO, Bai 15 i}-^'-' Bai 11 ( X ) CO cong tlu'rc phaii tir dang Q H , , , © va thoa man so phan ihig saii: a (Cf,H IoO^)n (X, ^ y " (Y) > (Y) ) (T) + C2H5OH CfiH, O^, CH3COOH CH3COOC2H5 (Z) ^ ^ f " > (Z) "^.^^^^!,' ) C H , C2H5CI - ^ C o H s O H - ^ C H j C H O — C H C O O H Xac dinh X va hoan lhanh chutJi trdn Hu(Vng dan giai Huong dan giai X hi C H C O O C H M ) C H ; C O O C , H , + NaOH — ^ (2) C H , C H , O H + ^ O , C H , C H : O H + CH,COONa Bai 12 Cho clui6i bieii hoa C H , ^ (Y) ^ — ) C H + Na.CO, (X) ^ QH,A (Z) CH.COOCH.s Vay ( X ) , HircVng d^n giai - Ne'u X la C.H, till Y la CH,CHO va Z la CH,COOH hoac CH.,CH,OH - Neu X la C H , C H O thi Y la C H , C H , O H va Z la CH3COOH >C4H7C1, ^ >C4H|„0, (Z): CH:(C1)CH(C1)-CH(C1)CH, ( T ) : CH,(OH)CH(OH)-CH(OH)CH, >CH,(Cl)CH(CI)-CH(OH)CH, ± ;? > C,H,C1 CH,COOC,H, ^O: xt.l + H:0 ) + H^O '"'^ > C H , C H O + Cu + H , CH,COOH CH,CHCI, CH3CHO CH.COOH CaC.-Uc\H2 CHjONa + (7) C H C I + NaOH ^ „ + (10)CH,COOH " "2"-'° > C H O H + NaCl CH3CI CH3OH HCHO '=••' QH.o QH, + CK Hiro-ng dan giai QH, + CH, > CH2=CHCH3C1 + HCl + ^ CH3COOH C,H,OH ^ X -> -> C H C O O C H , + H,0 CH4 Y i t ^ P -> Z X, Y, Z C O the' la nh&ng chat nao ? Hiring d^n giai Truong hop X la CH3CHO Y la C^HjOH Z la CH3COOH C H , + H,0 70 xt, t CO i 16 Hoan chu6i phan irng : C,H, CH4 HCl IH, ^C3H6-^ai2=CHCH2Cl-^CH2aCH(OH)CH2Cl-iH-giixerol ^ + Ni,t" (8) HCHO + H, ^ H C H O + Cu + H , - CH3CI CI, (9)CH30H 4Al(OH)3 > 2CH3 OH (5) C H O H C H O H + CuO "'-'"'"^ > C,H4 + H , • CH3COOC2H5 > CH4 + NaXO, CH,COONH4 + 2Ag + 2NH4NO3 > QH5OH 10 CH3CI >I70°C C H O H >Cl C H j O H - ^ CH3COOH > 3CH4 + (4) CH4 + O, + NaQ HO Hirdng dan giai (6) C3H,OH ' (3) 2CH4 + O, CH3CHO + 2AgN03 + 3NH3 — ^ QH4 + H , •- (2) CH,COONa + NaOH " f > CH,=CHC1 t°c V ^ H C H O ^ ^ CD A I C + 12H,0 C H , + 3H, + HQ ^^''f'^ * ^i CHjCOONa + - H , CH,COONa + NaOH > CH4 + Na.CO, TriTomg hap X la CH^CHO Y la C H , O H Z la QH^ Q H , + H2O > CH^CH.CH.CH, " " ^ ' ^ > CH4 + CH.=CHCH,, CH.CH^CHXHj > CH3OH CH3OH + CO ) CH3COOH M CH3COOCH, + H2O Tmang hop HCHO - > C,H, A ) C^HjOH CH3=:CH-CH=CH, + 2H, HCHO + H , CH,COOCH, +NaOH - > CH,COONa + CH3OH ) CH2=CH-CH=CH, + H + 2H2O 2CH,OH Trifcmghopl HCHO -)• CH3OH -> CH3COOH -> CH3COOCH3 - > CH3COONa CH,COOH + CH3OH ^ > CH.CHO CH3CHO + H , pai 18 Hoan chudi phan ling : HCHO - > A ^ B - > D Natri axetat Hudng &kn giai Bai 17 Hoan chudi phan ung : 6HCHO QH,A C^H^OH ^ CH3COOH CH,COONa ' ' > C,H,20, '"'"""^ > 2CH,OH + 2C0, C^HsOH + - O '| ) CH,COOH + H , ) HOCH.-CHO - > CH2(OH)-CH,OH - > CH3CHO ^ CH3COONa Huong dan giai 2HCHO '° > HOCH3-CHO Trirofnghon A la CH3COOCH=CH3 B la CH^OH D la CH3CHO HOCH3-CHO + H : CH3COOH + CH=CH - > CH,COOCH=CH CH3(OH)-CH30H CH,COOCH=CH2 + NaOH - > CH3COONa + CH3CHO CH,CHO+ - O " > CH3COOH > CH3(OH)-CHoOH > CH3CHO + H2O CH3CHO + Cu(OH), + NaOH Bai 19 Hoan chudi phan ifng : " C H , O H + CuO — ^ A CH3CHO + Cu + H , CH.,OH + O, > CH3COOH + H3O Tmomg han A la CH3COOCH=CH2 B la CH3CHO D la CHjCOONa > CHjCOONa + Cu.O + SH.O ^ B ^ D F F + N : + H3O Hir()rng dan giai CHjCOOH + CH=CH -> CH3COOCH=CH3 CH3COOCH=CH, + NaOH -> CH3C00Na + CH3CHO XlaCHjCOONHjCH^CHj CHjCOONa + HCl ^ CH3COOH + NaCl CH3CHO+ - O , ) CH,COOH " CHjCOONHjCH.CH, + NaOH -> CHjCOONa + NHjCHjCHj + H^O CH3CHO + 2Cu(OH)3 + NaOH CHjCOONa + Cu.O + SH.O D la HCHO GlaC,H,A, CHjCOONa + NaOH CH4 + O, A la CHjCOONa "'" ElaCH,CH,NH, BlaCH4 FlaC,H,OH > CH4 + Na.COj > HCHO + H , 73 sffao cfiuoi pnan ifng hoa hoc Horu cff- 6HCHO QH.jO, Tvguym:xaatf^wimg^ Chircmg — > QH,,0, "'""^^'^ ) Q H , O H + ZCO, N H j C H j C H , + HNO2 CH.CH.OH + N + H , Bai 20 Hoan chudi phan ung : B CH,„0, ' X Biet X d6'i xiing U A K I E N T H i r C C O B A N I ANDEHIT VA XETON Dinh nghia va danh phap ^ D a) Dinh F g6'c hidrocbon hoac nguyfin tir H Nhom - C H = la nhom chufc cua andehit G no dugc goi la nhom cacbandehit + Xeton la nhirng hop chat cacbonyl ma phan tir c6 nhom > C = lifin ke't vdi hai H i r i n g dan giai gdc hidroeacbon X la C H , O O C - C O O C , H , AIa(COONa)2 B la (COO)2Ca D la ( C O O H ) , E la C H , O H F la C H , = C H , G la H O C H - C H O H CH,OOC-COOC,H, + 2NaOH ^ (COONa), + ZQHsOH (COONa), + CaCK ^ (COO),Ca + NaCl (COO):Ca + H:S04 ^ (COOH), + CaSO^ CH,OH h) Danh phap + Andehit - - 3CH:=CH, + K M n + H ^ H O C H , - C H : O H + M n O , + K O H ) (COOH), + T f i n t h a y t h e : Ten hidroeacbon + A l Vidu: ) CH,=CH: + H^O H O C H , - C H , + O, ng/mi + Andehit la nhirng hop chat cacbonyl ma phan tii c6 nhom - C H = Hen kfi't vdi T+O.ixt) E ANDEHIT - XETON - AXIT CACBOXYLIC CH3CHO QH,CHO Etanal Benzandehit Ten thucrtig : Mot so andehit don gian diroc goi theo ten th6ng thircmg c6 ngu6n goc lich sir V i du : H.O HCHO CH3CHO Fomandehit Axetandehit • ,/ Xeton - ' 1:) T6n thay thd': G6m t6n hidroeacbon tuong ung + on ,j, Vi'du: - CH3COCH3 CH,COCH2CH3 Propan-2-on Butan-2-on ' Ten goc chiJc : Ten g6'c hidroeacbon lien ke't vdi nhom C = + xeton V i du : CH3COCH2CH3 CH3COQH, Etyl metyl xeton Metyl phenyl xeton E T i n h chat hoa hoc ^o) Phan + ifn^ipn}> Phan ung c6ng H , (phan ihig khir) Vidu: CH3CHO CHj-p-CHj O + H2 + H2 Ni.t° Ni,t" CH3CH2OH CH3-(^H-CH3 OH Cty TNHrrMTVDVVH + Phan ling cpng H , HCN CHj-f-CH, + HCN Axit khong no : CN I CHj-^-CHj O CH2=CH-COOH Xianohidhn ' t; •• + Tac dung voi dd BIS va dd kali pemanganat RCH=0 + Bf: + H:0 ^ R-COOH + 2HBr Xeton khong lam mat man dd tren v\o kho bi oxi hoa + Tac dung vdi dd AgNO,/NH, (phan umg trang bac) AgNO, + N H , + H , -> |Ag(NH,)2]OH + N H N O , Phirc tan Ttfamol - Phuong phap chung de didu che andehit va xeton la oxi hoa nhe ancol bac 1, bac - tuonig irng bflng CuO Di6u che fomandehit * Tir ancol etylic : - 2H2O 2HCH0 + Axit 2-metyl propanoic CH:=CH-COOH C.H.COOH Axit acrylic Axit benzoic Ten thong thuoiig cua cac axit c6 lien quan den nguon goc tim chung HCOOH CH,COOH Axit fomic Axit axetic Tinh chat hoa hoc + H2O H,0+ + R-COO [RCOOH] Axit cacboxylic la axit yeu, tiiy vay chiing cung c6 ddy du ti'nh chat ciia m6t axit h) Phcin O2 HCHO + I'fni; tan thdnh dan xndt axit + Phan iirng voi ancol (phan irng este hoa): H2O RCOOH 02-^^5Wi£!v 20"C^ CH3COCH3 + CeHjOH II A X I T C A C B O X Y L I C t)inh nghla, phan loai, danh phap a) Diiih H}>hTa Axit cacboxylic la nhChig hop chat hiru co ma phan tir c6 nhom cacboxyl Axit no don chiic : CTTQ: C„H„„,COOH (n > 0) Goi la CTTQ day dong diing cua axit fomic + Phdn i'fni> d i-oc Ancol RCOOR' + H.O Este (RC0)20 HOOCR H,0 hidrocaihon + Phan urng the a goc no : CH3CH2CH2COOH + CH3CH2CHCICOOH CI2 + HCl + Phan u-ng the o g6'c thoin : COOH COOH + (-COOH) lien ket true tiep voi nguyen tirC hoac nguyen tir H h) Phiin loai 4^ R'OH + Phan lirng tach H^O lien phftn tir: RCOOH '•"2-2.H2SO4 + Axit cacboxylic 2CH3CH=0 Oxi hoa cumen roi cha' hoa v6i axit sunfuric thu duoc axeton cung vdi phenol - J ! K., cang Ion thi ti'nh axit cang manh va nguoc lai Dieu che axeton : (CH3)2-C6H5 ' [H30^][RC00-] + O2 + it CH,CH(CH,)COOH Axit etanoic R-COOH Di6u che axetandehit : 2CH2=CH2 Danh phap a) Tinh axit va dnh hir(hif> ii'ia nhom the * Tir hidrocacbon : + Tir metan : - Axit no, da churc : HOOC-CH,-COOH CH,COOH t)ieu che CH4 + HC-COOH Theo lUPAC : axit + ten hidrocacbon tuong ung + oic RCH=0 + | A g ( N H , ) : | O H - > RCOONH4 + 2Ag + 3NH, + H.O 2C2H5OH CH Axit thom : C^H^COOH OH h) Phan I'Oifi oxi hod u] Khang Wft H7O HNO, NO2 axit benzoic axit m-nitrobenzoic + Phan ihig c6ng vao g6c kh6ng no : CH,CH=CHCOOH + Br, - CHjCHBrCHBrCOOH 77