Hoa Huu Co

Ha hc cc hp cht hu c
Phn III HA HC CC HP CHT HU C

Chng 1 I CNG V HA HU C
Ho hc hu c l mt ngnh khoa hc nghin cu v thnh phn, cu to, tnh cht, ng dng ca cc hp cht hu c v cc qu trnh bin i (phn ng) ca chng. Hp cht hu c l cc hp cht ca cacbon tr CO, CO2, axit cacbonic v cc mui cacbonat. Hin nay, con ngi bit n khong di 1 triu hp cht v c v khong 7 triu hp cht hu c. 1. Nhng c im chung ca hp cht hu c Mc d khng c danh gii tht r rt gia cht hu c v cht v c, cc hp cht hu c c mt s c im chung sau y : 1. Trong thnh phn hp cht hu c c th gp hu ht cc nguyn t trong h thng tun hon, song s lng cc nguyn t thng xuyn to nn cht hu c thng khng nhiu : nht thit phi c C, thng c H, hay gp O, N, sau n halogen, S, P,... 2. Lin kt ha hc ch yu trong hp cht hu c l lin kt cng ha tr. 3. Cc hp cht hu c thng d bay hi, km bn i vi nhit v d chy hn hp cht v c. 4. Cc phn ng ca hp cht hu c thng chm v khng hon ton theo mt hng nht nh nn to thnh hn hp sn phm. 2. Phn loi cc hp cht hu c a. Da vo mch C: Chia thnh 3 nhm ln: Cc hp cht mch h gm + Loi no: Mch C ch cha lin kt n. V d dy ng ng ankan CnH2n+2, + Loi cha no: Mch C ngoi lin kt n cn cha lin kt i v lin kt ba. V d anken CnH2n ; cc ankin, ankaien CnH2n 2 ; Cc hp cht mch vng gm: + Vng khng no + Vng no + Hp cht thm: c nhn benzen V d: V d: H2C - CH2 HC = CH CH2 CH2
Hp cht d vng: Ngoi C cn c cc nguyn t khc tham gia to vng. b. Da vo nhm chc Nhm chc l nhm nguyn t gy ra nhng phn ng ha hc c trng cho phn t hp cht hu c. Mt s nhm chc quan trng. Nhm hyroxyl: OH Nhm nitro: NO2 Nhm amin: NH2 Hp cht n chc: Trong phn t c 1 nhm chc. Hp cht a chc: Trong phn t c nhiu nhm chc ging nhau. V d: HOOC R COOH : iaxit
ng c Thin
78
Trng THPT Sn ng s 3
Hp cht tp chc: Trong phn t c nhiu nhm chc khc nhau. V d: cc aminoaxit H2N R COOH, HO CH2 CH2 CHO, 3. Thuyt cu to ho hc Thuyt cu to ho hc do nh bc hc Nga Butlrp ra nm 1861 gm cc lun im chnh. 1. Trong phn t cht hu c, cc nguyn t lin kt vi nhau theo ng ho tr v theo mt th t nht nh. Th t lin kt c gi l cu to ha hc. S thay i th t lin kt s to ra cht mi. Th d: ru etylic v ete metylic u c cng thc phn t C2H6O, nhng chng c cu to ha hc khc nhau: CH3 CH2 OH (ru etylic - cht lng, tan v hn trong nc, tc dng vi Na). CH3 O CH3 (ete metylic- cht kh, gn nh khng tan trong nc, khng tc dng vi Na 2. Trong phn t cht hu c, cacbon c ha tr 4. Nhng nguyn t cacbon c th kt hp khng nhng vi nhng nguyn t ca cc nguyn t khc m cn kt hp trc tip vi nhau thnh nhng mch cacbon khc nhau (mch khng nhnh, c nhnh v mch vng). V d: Mch khng nhnh (mch thng) CH3 CH2 CH2 CH3 Mch nhnh: CH3 CH - CH2 CH3 Mch vng: CH3
3. Tnh cht ca cc cht ph thuc vo thnh phn phn t (bn cht v s lng cc nguyn t) v cu to ha hc (th t lin kt cc nguyn t). Th d: - Ph thuc vo bn cht cc nguyn t: CH4 l cht kh d chy, cn CCl4 l cht lng khng chy. - Ph thuc vo s lng cc nguyn t: C4H10 l cht kh, cn C5H12 l cht lng. - Ph thuc vo th t lin kt cc nguyn t: trng hp CH3 - CH2 - OH v CH3 - O - CH3 ( nu trn). 4. Cc dng cng thc ho hc Cc hp cht hu c c th c biu din bng cc dng cng thc sau: a. Cng thc tng qut (CTTQ): Cho bit thnh phn nh tnh ca hp cht hu c (thnh phn nguyn t cu to nn hp cht) Th d : CxHyOz (x, y, z l nhng s nguyn cha bit) ch cho bit trong phn t c 3 nguyn t : C, H v O. b. Cng thc thc nghim (CTTN): Ch cho bit t l s lng cc nguyn t ca cc nguyn t trong phn t.
ng c Thin
79
Trng THPT Sn ng s 3
V d: CTTN ca etilen (CH2)n, ca glucoz (CH2O)n (n l s nguyn dng, cha xc nh). c. Cng thc n gin nht (CTGN): Ch cho bit t l s lng cc nguyn t ca cc nguyn t trong phn t V d: CTGN ca etilen CH2, ca glucoz CH2O d. Cng thc phn t (CTPT): Cho bit s lng nguyn t ca tng nguyn t trong phn t hp cht hu c, tc l cho bit gi tr ca n. V d: CTPT ca etilen C2H4, ca glucoz C6H12O6, ca benzen C6H6, Lin h vi CTGN trn, h s n i vi etilen : n = 2, vi glucoz: n = 6, e. Cng thc cu to (CTCT): Nu nh cng thc phn t ch cho bit s lng nguyn t ca mi nguyn t trong phn t th cng thc cu to cn cho bit c th t kt hp v cch lin kt cc nguyn t C th vit CTCT di dng y v rt gn. V d: CTCT ca axit axetic.
O H3C OH
Dng rt gn: CH3 COOH 5. Lin kt ho hc trong hp cht hu c Lin kt cng ha tr l loi lin kt ch yu v ph bin nht trong ha hc hu c C hai loi in hnh: a. Lin kt n do mt cp electron to nn v c biu din bng mt gch ni gia hai nguyn t. Ta gi l lin kt . b. Lin kt i do 2 cp electron to nn, c biu din bng 2 gch ni song song gia hai nguyn t : mt gch tng trng cho lin kt bn vng v mt gch tng trng cho lin kt linh ng hn gi l lin kt . c. Lin kt ba do 3 cp electron to nn, c biu din bng ba gch ni song song gia hai nguyn t : mt gch tng trng cho lin kt v hai gch tng trng cho hai lin kt . Lin kt km bn so vi lin kt . Trong cc phn ng ho hc, n thng b t ra phn t lin kt vi 2 nguyn t (hay nhm nguyn t) ca cc nguyn t khc (phn t tham gia phn ng cng). Lin kt n c bn cht lin kt Lin kt i gm 1 lin kt v 1 lin kt . Lin kt ba gm 1 lin kt v 2 lin kt . Khi nguyn t cacbon ch tham gia lin kt n, cc obitan nguyn t lai ho kiu sp3 nh hng theo phng t tm (ht nhn) n 4 nh hnh t din u v l hng ca 4 mi lin kt n ( ). V d cc lin kt trong phn t metan
ng c Thin
80
Trng THPT Sn ng s 3
Khi nguyn t cacbon tham gia lin kt i, cc obitan nguyn t lai ho kiu sp2 nm trong mt mt phng nh hng theo phng t trng tm tam gic u (ht nhn) n 3 nh v l hng ca 3 lin kt n (lin kt ). Obitan p cn li xen ph vi mt obitan p ca nguyn t khc bn cnh to thnh lin kt theo hng vung gc vi mt phng ca tam gic. V d trong phn t etilen: CH2 = CH2 Khi nguyn t cacbon tham gia lin kt ba, cc obitan nguyn t ho tr lai ho kiu sp to ra 2 obitan v to lin kt . Cn 2 lin kt do 2 obitan p cn li tham gia, vung gc vi nhau v vung gc vi trc lin kt . V d trong phn t CH CH: CH CH 6. Hin tng ng phn a. nh ngha: ng phn l hin tng cc cht c cng mt cng thc phn t, nhng c cu to khc nhau nn c tnh cht khc nhau. Cc cht c gi l nhng cht ng phn. V d: C5H12 c 3 ng phn. CH3 CH2 CH2 CH2 CH3 (1) CH3 CH - CH2 CH3 (2) CH3 CH3 CH3 C - CH3 (3) CH3 b. Bc ca nguyn t cacbon Bc ca nguyn t cacbon trong mt phn t c xc nh bng s nguyn t cacbon khc lin kt vi n. Bc ca cacbon c k hiu bng ch s La m (I, II, III,) V d: I III II I CH3 CH - CH2 CH3
I
CH3 c. Cc trng hp ng phn * ng phn cu to. L hin tng ng phn do th t lin kt khc nhau ca cc nguyn t hay nhm nguyn t trong phn t gy ra. Nhm ng phn ny c chia thnh 3 loi: 1) ng phn mch cacbon: thay i th t lin kt ca cc nguyn t cacbon vi nhau (mch thng, mch nhnh, mch vng), cc nhm th, nhm chc khng thay i. V d: Butan C4H10 c 2 ng phn. CH3 CH2 CH2 CH3 : n - butan CH3 CH - CH3 iso butan CH3 2) ng phn v tr ca ni i, ni ba, nhm th, nhm chc Nhm ng phn ny do: S khc nhau v tr ca ni i, ni ba V d:
ng c Thin
81
Trng THPT Sn ng s 3
CH2 = CH CH2 CH3 buten -1 Khc nhau v tr ca nhm th V d: CH3 CH2 CH2 Cl 1 clo propan (propyl clorua)
CH3 CH = CH CH3 buten - 2 CH3 CH CH3 Cl 2 clo propan (isopropyl clorua)
Khc nhau v tr ca nhm chc V d: CH3 CH2 CH2 CH2 OH : butanol -1 CH3 CH CH2 CH3 Ru iso butylic (butanol - 2)
OH 3) ng phn nhm chc Cc ng phn ca nhm ny khc nhau v nhm chc, do tnh cht ho hc hon ton khc nhau. Nhng ng phn nhm chc quan trng l: + Anken - xicloankan V d C3H6 c th l CH2 = CH CH3 (Propen) H2C CH2 (xiclo propan) + Ankaien - ankin - xicloanken V d C4H6 c nhng ng phn sau: CH2 = CH CH = CH2 butaien -1,3 CH C CH2 CH3 butin -1 CH = CH CH2 CH2 xiclobuten xiclopren - 1 CH2 H2C - C = CH2 + Ru - ete V d C3H8O c nhng ng phn. CH3 CH2 CH2 OH : propanol - 1 CH3 CH CH3 propanol - 2 OH CH3 CH2 O CH3 : etyl metylete + Anehit xeton V d C3H6O c 2 ng phn CH3 CH2 CHO : propanal
ng c Thin
CH2 CH2 = C = CH CH3 butaien -1,2 CH3 C C CH3. butin - 2 HC = CH CH CH3 3 metyl CH2 1 metylen
HC = C CH3 1 metyl xiclopren 1
xiclopran
82
Trng THPT Sn ng s 3
CH3 CO CH3 : imetylxeton (axeton hoc propanon). + Axit - este V d C3H6O2 c 3 ng phn CH3 CH2 COOH : axit propionic CH3 COO CH3 : metyl axetat H COO C2H5 : etyl fomiat + Nitro - aminoaxit V d C2H5NO2 c hai ng phn H2N CH2 COOH : axit aminoaxetic v CH3 CH2 NO2 : nitroetan. * Nhm ng phn hnh hc: y l loi ng phn m th t lin kt ca cc nguyn t trong phn t hon ton ging nhau, nhng khc nhau s phn b cc nguyn t hoc nhm nguyn t trong khng gian. c loi ng phn ny. iu kin cn l trong phn t phi c ni i. iu kin l mi nguyn t cacbon ni i phi lin kt vi hai nguyn t hoc nhm nguyn t khc nhau: a b C=C vi a b v c d
c d Ty theo v tr ca cc nguyn t hay nhm nguyn t m ngi ta phn bit hai loi ng phn: ng phn dng cis hoc ng phn dng trans. Cch xc nh dng cis, dng trans: + Khi hai nhm th ln nm cng pha so vi mt phng cha lk i th ta c dng cis + Khi hai nhm th ln nm khc pha so vi mt phng cha lk i th ta c dng trans V d1: buten - 2 (CH3 CH = CH CH3)
CH3 CH3 CH3 H
C=C cis buten - 2
C=C
CH3 H H H trans buten - 2 Vy vit nhanh v y ng phn ca mt cht bt k th chng ta cn: Bc 1: Xc nh xem cht thuc loi hp cht g, no hay khng no. Bc 2: Vit ng phn mch cacbon. Bc 3: Vit ng phn v tr ca lin kt kp v ca nhm chc. Bc 4: Vit ng phn nhm chc. Bc 5: Kim tra xem trong cc ng phn va vit ng phn no c dng ng phn cis-trans khng 7. Hin tng ng ng ng ng l hin tng cc cht c cu to v tnh cht tng t nhau, nhng v thnh phn phn t khc nhau mt hay nhiu nhm CH2. Nhng cht c gi l nhng cht ng ng vi nhau, chng hp thnh mt dy gi l dy ng ng V d: Dy ng ng ankan: CH4, C2H6, C3H8,(CTPT chung CnH2n+2). Dy ng ng anken: C2H4, C3H6, C4H8,(CTPT chung CnH2n).
ng c Thin
83
Trng THPT Sn ng s 3
Ch : Khng phi tt c cc cht c cng cng thc chung u l ng ng ca nhau. V d: khng phi tt c cc ru no n chc c cng thc chung CnH2n+1OH l ng ng. Chng hn CH3 CH2 OH ru bc 1 CH3 CH CH3 Ru bc 2 OH Hn km nhau 1 nhm CH2 nhng c tnh cht ho hc khng hon ton ging nhau khng phi l ng ng ca nhau. Hai cht ng ng lin tip (k nhau) c s nguyn t cacbon Cn v Cn+1 hoc Cn-1. S bin i tnh cht vt l ca cc cht trong dy ng ng thng tun theo mt quy lut chung. V d mch cacbon cng di th nhit nng chy, nhit si tng dn, tan trong nc gim dn. 8. Cch gi tn cc hp cht hu c a. Tn gi thng thng: Khng tun theo quy tc khoa hc no, thng xut hin t xa v bt ngun t nguyn liu hoc tn nh bc hc tm ra, hoc mt a im tm ra hp cht ,... V d: Axitfomic (axit kin); olefin (kh du); axit axetic (axit gim), b. Danh php quc t (danh php IUPAC): gi tn mt hp cht hu c theo danh php quc t, chng ta cn tin hnh theo cc bc sau: Bc 1: Chn mch C chnh l mch C di nht c cha ni i, ni ba, nhm th, nhm chc, Bc 2 : nh s th t cc nguyn t C trn mch chnh (bng ch s rp) xut pht t pha gn nhm chc, ni i, ni ba, nhm th, mch nhnh. Quy tc nh s. u tin nh s ln lt theo th t. Nhm chc ni i ni ba mch nhnh. i vi hp cht tp chc th u tin ln lt: Axit anehit ru. Bc 3: Gi tn.: Tn = v tr nhm th + tn nhm th + tn mch chnh (c ui ph hp vi tng loi cht) + v tr lk bi. + Nu c nhiu nhm th ging nhau th gp chng li v thm cc tip u ng: i (2), tri (3), tetra (4), penta (5), + Ngn cch gia s v ch l du Ch : Hin nay cng tn ti mt s cch gi khc ty trng hp v iu kin nghin cu m chng ta nn s dng cch gi tn cho ph hp. * Tn mch chnh: xut pht t cc hirocacbon no mch thng. Cc hp cht cng loi (cng dy ng ng), cng nhm chc th c ui ging nhau. C th: Hirocacbon no (ankan) c ui an: CH3 CH2 CH3 : propan Hirocacbon c ni i (anken) c ui en: CH2 = CH CH3 : propen Hirocacbon c ni ba (ankin) c ui in: CH C CH3 : propin Hp cht anehit c ui al: CH3 CH2 CHO : propanal Hp cht ru c ui ol:
ng c Thin
84
Trng THPT Sn ng s 3
CH3 CH2 CH2 OH : propanol Hp cht axit hu c c ui oic: CH3 CH2 COOH : propanoic. Hp cht xeton c ui on: CH3 C CH3 propanon (axeton) O ch s nguyn t C c trong mch chnh, ngi ta dng cc phn nn (phn u) sau: Bng 5: Phn nn gi tn cc hp cht hu c S nguyn 1 2 3 4 5 6 7 8 9 10 t C Phn nn Met Et Prop But Pen Hex Hep Oct Non dec * Tn ca nhm th: Trong ho hu c, tt c nhng nguyn t khc hiro (nh Cl, Br, ) hoc nhm nguyn t (nh NO2, NH2,, cc gc hirocacbon CH3 , C2H5 ,) u c coi l nhm th. hm th l cc nguyn t th tn gi l tn nguyn t. Tn gc hirocacbon u xut pht t tn hirocacbon tng ng vi phn ui khc nhau. + Gc hirocacbon no ho tr 1 gi theo tn ca ankan tng ng bng cch thay ui an bng ui yl v c gi chung l gc ankyl. V d: CH3 : metyl, C2H5 : etyl, + Gc hirocacbon cha no ho tr 1 c ui enyl i vi anken, ui nyl i vi ankin v ui -ienyl i vi ien. V d: CH2 = CH : etilenyl (thng gi l gc vinyl) CH C : axetilenyl hay etinyl. + Gc ho tr 2 to thnh khi tch 2 nguyn t H khi 1 nguyn t C hoc tch nguyn t O khi anehit hay xeton. Gc ho tr 2 c ui t -ylien. V d: CH3 CH2 CH = : propylien. 9. Mt s dng phn ng ho hc trong ho hu c a. Phn ng th: L phn ng trong nguyn t (hay nhm nguyn t) b thay th bi nguyn t (hay nhm nguyn t) khc. V d: CH4 + Cl Cl -> CH3Cl + HCl b. Phn ng cng hp: L phn ng trong phn t ca mt cht cng hp vo lin kt i hoc lin kt ba trong phn t ca cht khc. V d: CH3 CH = CH2 + Br2-> CH3 CH = CH2 Br Br CH3 CH = CH2 + Br2-> CH3 CH CH3 sn phm chnh Br CH3 CH2 CH2 sn phm ph Br Trong trng hp phn ng cng hp bt i xng, hng cng ch yu c xc nh theo quy tc cng Maccopnhicop (hay quy tc cng hp bt i xng):
ng c Thin
85
Trng THPT Sn ng s 3
Theo quy tc Maccopnhicop, trong phn cng HX vo lin kt bi bt i xng, nguyn t H (hay l phn mang in tch dng) cng vo nguyn t cacbon c nhiu H hn, cn nguyn t X (hay l phn mang in tch m) cng vo nguyn t cacbon c t H hn. V vy sn phm chnh trong phn ng trn l iso-propyl clorua. Quy tc cng c hiu rng ra vi cc tc nhn l nhng phn t bt i xng chung ch khng ring HX. Sn phm thu c theo quy tc ny l sn phm chnh chim phn ln, cn sn phm thu c ngc quy tc ny l sn phm ph, chim mt t l rt thp. Ch : Khi phn ng cng hp tc nhn bt i c xc tc l cc peoxit th sn phm to thnh theo hng ngc quy tc cng trn l sn phm chnh (sn phm Hopman) c. Phn ng tch HX (HCl, HBr, H2O,): L phn ng tch mt hay nhiu phn t HX khi cc phn t hp cht hu c. Trong nhng phn ng , X c tch ra vi mt H C bn cnh C lin kt trc tip vi X: V d: , CH3 CH CH3 KOH t CH3 CH = CH2 + HBr , ROH
0
Br Trong nhng trng hp phc tp, c nhiu H c th tch ra cng X lin kt vi cc nguyn t C c bc khc nhau, sn phm tch chnh s c xc nh theo quy tc tch Zaixep: Trong phn ng tch HX khi phn t hp cht hu c, nguyn t X s c u tin tch ra cng nguyn t H C bc cao hn. , CH3 CH CH2 CH3 KOH t CH3 CH = CH CH3 + HBr sn phm chnh , ROH
0
Br CH2 = CH CH2 CH2 + HBr sn phm ph d. Phn ng trng hp: L phn ng cng hp lin tip nhiu phn t nh (monome) ging nhau hay tng t nhau thnh phn t ln hay cao phn t (polime) Phn ng trng hp c th xy ra gia hai loi monome khc nhau, khi gi l phn ng ng trng hp. iu kin cc monome tham gia phn ng trng hp l: phn t phi c lin kt kp hoc c vng khng bn. V d: nCH2 = CH2 xt ,t (- CH2 CH2- )n ,p e. Phn ng trng ngng: L phn ng kt hp nhiu phn t nh (monome) to thnh phn t ln polime, ng thi tch ra nhiu phn t nh n gin nh H2O, NH3, HCl, iu kin cc monome tham gia phn ng trng ngng l: phn t phi c t nht 2 nhm chc hoc 2 nguyn t linh ng c th tch khi phn t. Phn ng trng ngng c th xy ra gia hai loi monome khc nhau. V d: nHOOC (CH2)5 NH xt ,t (- CO (CH2)5 NH -)n + nH2O ,p f. Phn ng oxi ho + Phn ng chy (oxi ha hon ton): to thnh CO2, H2O v mt s sn phm khc. V d: CH3OH + 3/2O2 -> CO2 + 2H2O + Phn ng oxi ho nhm chc hoc oxi ho lin kt kp (oxi ho khng hon ton). V d + Oxi ho : ru anehit axit.
0 0
ng c Thin
86
Trng THPT Sn ng s 3
R CH2OH -> R CHO -> RCOOH g. Phn ng kh hp cht hu c: Kh cc nhm chc bin loi cht ny thnh loi cht khc. V d: R CHO -> R CH2OH h. Phn ng este ha: L phn ng gia axit v ru to thnh este. V d: CH3COOH + C2H5OH H SO CH3COOC2H5 + H2O Mun phn ng este ho xy ra hon ton, phi dng cht ht nc (thng hay dng H2SO4 , Al2O3,) i. Phn ng thu phn: L phn ng gia hp cht hu c v nc to thnh hai hay nhiu hp cht mi. V d: CH3COONa + H2O -> CH3COOH + Na+ + OHCH3COOC2H5 + H2O CH3COOH + C2H5OH j. Phn ng crackinh: L qu trnh b gy mch cacbon ca phn t hirocacbon thnh cc phn t nh hn di tc dng ca nhit hoc cht xc tc. crk C3H6 CH4+ C2H4 k. Phn ng refominh: L qu trnh dng nhit v cht xc tc bin i cu trc mch cc hirocacbon: t mch h thnh mch vng, t mch ngn thnh mch di, 10. Cc hiu ng chuyn dch electron a. Hiu ng cm ng + nh ngha: Hiu ng cm ng (k hiu l I) l s dch chuyn my e dc theo mch C di tc dng ht hoc y ca cc nguyn t hay nhm nguyn t.. V d: CH3 CH2 CH2 Cl + Phn loi Quy c: Trong lin kt (C H) nguyn t H c I = 0 - Nhm th c m in ln hn H s ht e gy ra hiu ng cm ng m (I). Hiu ng I tng theo chiu tng ca m in ca nhm th. F > Cl > Br. F > OH > NH2 - Nhm th c m in nh hn H, c +I. Hiu ng +I tng theo bc ca ankyl C(CH3)3 > CH(CH)3 > C2H5 > CH3 - Hiu ng cm ng I gim nhanh khi tng chiu di mch cc lin kt v s n ng khng gian. + ng dng: Hiu ng cm ng I dng gii thch tnh axit - baz ca hp cht hu c: Nhm th gy hiu ng I cng mnh, lm tnh axit ca hp cht cng tng. Nhm th gy hiu ng +I cng mnh lm tnh baz ca hp cht cng tng. b. Hiu ng lin hp + nh ngha: Hiu ng lin hp (k hiu l C) l hiu ng dch chuyn my electron trong h lin hp di tc dng ht hoc y e ca cc nguyn t nhm th. + Phn loi: Nhm th ht electron gy ra hiu ng -C. l cc nhm th khng no. V d:
2 4
CH2 = CH CH = O
ng c Thin
87
Trng THPT Sn ng s 3
Hiu ng ny gii thch s thay i tnh axit - baz ca hp cht hu c c nhm th: Nhm th C lm tng phn cc ca lin kt O H, do lm tng tnh axit. - Nhm th +C (nhm th y electron ) lm tng tnh baz (tc kh nng kt hp proton nh cp electron p khng phn chia) v lm gim tnh axit. V d cc nguyn t H v tr ortho v para trong phn t phenol d b th do hiu ng +C gy ra bi oxi ca nhm OH lm mt e cc v tr ny cao hn.
OH
Chng 2 HIROCACBON
Hirocacbon l nhng hp cht hu c m phn t ch cha cc nguyn t cacbon v hiro. Da vo cu to mch cacbon v bn cht lin kt gia cc nguyn t cacbon, ngi ta thng phn ra ba loi ln: Hirocacbon no (bo ho, trong phn t ch c lin kt n - lin kt ). Hirocacbon khng no (cha bo ho, trong phn t ngoi lin kt n, cn c lin kt i v lin kt ba - ngha l c c lin kt v ). Hirocacbon thm i vi hirocacbon no mch h, ta thy s lin kt gia cc nguyn t C bng s nguyn t cacbon tr i 1. V mi nguyn t C c 4e ho tr (C c ho tr IV) m mi lin kt cn 2e ho tr, nn nu phn t c n nguyn t C th s e ho tr cn lin kt vi H l 4n 2 (n 1) = 2n + 2. Do vy cng thc chung ca hirocacbon no mch h l CnH2n+2. i vi hirocacbon khng no mch h c mt lin kt i (v d anken), ngoi lin kt cn cn 2e ho tr to thnh lin kt gia 2 nguyn t C. Do s e ho tr cn lin kt vi H gim i 2 n v. Do cng thc ca anken l CnH2n. Nu anken c a lin kt i th cng thc chung s l CnH2n+22a. i vi hirocacbon mch h c mt lin kt ba (ankin, v d CH3 C CH) th ngoi lin kt cn 2 lin kt dng ht 4e ho tr. Do s nguyn t H lin kt cng gim i 4 n v (so vi hirocacbon no). Cng thc chung ca ankin s l CnH2n+24 = CnH2n2. i vi hirocacbon vng no: Khi to thnh vng dng mt 2e ho tr nn s e ho tr lin kt vi H gim nn s e ho tr lin kt vi H gim 2 n v (so vi hirocacbon no mch h). Do , cng thc hirocacbon vng no (xicloankan) l CnH2n (ng phn ca anken). Vy cng thc chung ca mi hirocacbon l: CnH2n+22a. n: S nguyn t C trong phn t. a = S lin kt + s vng
I. Hirocacbon no mch h _Ankan

1. ng ng ng phn danh php a. ng ng: Cng thc chung ca dy l CnH2n+2 vi n 1.Tn gi chung l ankan hay parafin Cht n gin nht l metan CH4 (metan). Tt c cc hp cht c cng cng thc chung hp thnh mt dy ng ng ca metan CH4. b. ng phn: T C1- C3: khng c hin tng ng phn T C4: c ng phn mch cacbon: khng nhnh (thng) v c nhnh. V d:
ng c Thin
88
Trng THPT Sn ng s 3
C4H10: c hai ng phn: CH3 CH2 CH2 CH3 v CH3 CH(CH3) CH3 c. Danh php: + Danh php thng: Tt c cc ankan u tn cng bng ui an. Bn ankan u dy c tn gi xut pht t ngun gc lch s. Cc ankan khc c tn gi xut pht t cc s m. Tn gi ca mt s ankan u dy c gii thiu trong bng sau: Bng 5: Tn gi mt s ankan u dy Cng thc Tn gi Cng thc Tn gi Metan Hexan C6H14 CH4 Etan Heptan C7H16 C2H6 Propan Octan C8H18 C3H8 Butan Nonan C9H20 C4H10 Pentan Decan C10H22 C5H12 Vi ankan mch nhnh: Tn gi ca mt s ankan mch nhnh c gi theo quy c sau: + phn bit vi trng hp mch C c nhnh, ngi ta thm vo trc tn gi ca ankan mch thng tip u ng : n (normal ngha l bnh thng). + Nu nguyn t C th 2 c 1 nhnh CH3 th thm trc tn gi tip u ng: iso + Nu nguyn t C th 2 c 2 nhnh CH3 th thm trc tn gi tip u ng: neo V d: C5H12: c ba ng phn: 1, CH3 CH2 CH2 CH2 CH3 n - pentan 2, CH3 CH(CH3) CH2 CH3 iso - pentan 3, CH3 C(CH3)2 CH3 neo pentan + Danh php quc t (danh php IUPAC): gi tn ankan theo danh php quc t, chng ta tin hnh qua cc bc sau: - Bc 1: Chn mch C di nht lm mch chnh - Bc 2: nh s th t cc nguyn t C ca mch chnh t pha no gn nhnh - Bc 3: Gi tn: Tn ankan = s ch v tr nhnh + tn nhnh + tn mch chnh V d: 1 CH3 2CH2 3CH 4CH 5CH2 6CH3 Cl 2. Tnh cht vt l Nhit nng chy, nhit si tng dn khi tng s nguyn t C trong phn t. Bn cht u l kh, cc cht c n t 5 17 l cht lng, khi n 18 l cht rn. u khng tan trong nc nhng d tan trong cc dung mi hu c 3. Tnh cht ho hc * c im cu to: Phn t CH4: H C H H H CH3 3 Clo 4 metyl hexan
ng c Thin
89
Trng THPT Sn ng s 3
Cu trc phn t:
. Trong phn t ch c lin kt n (lin kt ) to thnh t 4 obitan lai ho sp3 ca nguyn t C, nh hng kiu t din u. Do mch C c dng gp khc. Cc nguyn t c th quay tng i t do xung quanh cc lin kt n. Hin tng ng phn do cc mch C khc nhau (c nhnh khc nhau hoc khng c nhnh). Phn ng c trng l phn ng th. a. Phn ng th + Th clo v brom: Khi chiu sng hoc un nng hn hp ankan v clo (hoc Brom), phn ng din ra v to thnh hn hp sn phm CH4 + Cl2 askt CH3Cl CH3Cl + Cl2 askt CH2Cl2 + HCl CH2Cl2 + Cl2 askt CHCl3 + HCl askt CHCl3 + Cl2 CCl4 + HCl C CH4 + Br2 >100 CH3Br + HBr Iot khng c phn ng th vi ankan. Flo phn hu ankan km theo n. Nhng ankan c phn t ln tham gia phn ng th m du hn v u tin th nhng nguyn t H ca nguyn t C bc cao. V d: CH3 CH2 CH3 + Cl2 askt CH3 CHCl CH3 + HCl + Th vi HNO3 (hi HNO3 200oC 400oC). C2H6 + HO NO2 H SO C2H5 NO2 + H2O b. Tc dng ca nhit : + Phn ng phn hy -> C + H2 V d nhit phn metan: CH4 1000 C + 2H2 C + Phn ng tch hiro -> anken + H2: ( 400 900oC, xc tc Cr2O3 + Al2O3)
0
hoc
Al O ,t CH3 CH2 CH2 CH3

2 3
CH 3 CH = CH CH 3 + H 2 ( spc) CH 2 = CH CH 2 CH 3 + H 2 ( spp )
+ Phn ng crackinh -> ankan + anken (mch nh hn) C4H10 t

0
C 2 H 6 + C 2 H 4 CH 4 + C 3 H 6
c. Phn ng oxi ho: + Phn ng chy: sn phm chy l CO2 v H2O. CH4 + 2O2 t CO2 + 2H2O + Oxi ho khng hon ton: CH4 + O2 -> C + 2H2O CH4 + 2Cl2 t C + 4HCl CH4 + O2 NO , 700 HCHO + H2O C CH4 + 1/2O2 Cu , 250 C ,100 atm CH3OH
0 0 0 0
ng c Thin
90
Trng THPT Sn ng s 3
4. iu ch a. iu ch metan: + Ly t cc ngun thin nhin: kh thin nhin, kh h ao, kh du m, kh chng than . + Tng hp C + 2H2 Ni ,500 CH4 C ,t CO + 3H2 xt CH4 + H2O ,t CH3COONa + NaOH CaO CH4 + Na2CO3 Al4C3 + 12H2O -> 4Al(OH)3 + 3CH4 b. iu ch cc ankan khc + Ly t cc ngun thin nhin: kh du m, kh thin nhin, sn phm crackinh. + Tng hp t cc dn xut halogen: R - Cl + 2Na + Cl - R' R - R' + 2NaCl V d: CH3 Cl + 2Na + C2H5 Cl t CH3 CH2 CH3 + 2NaCl CH3 CH3 + 2NaCl CH3 Cl + 2Na + Cl CH3 t + T cc mui axit hu c R COONa + NaOH CaO R - H + Na2CO3 ,t 5. ng dng Dng lm nhin liu (CH4 dng trong n x hn, ct kim loi). Dng lm du bi trn. Dng lm dung mi. tng hp nhiu cht hu c khc: CH3Cl, CH2Cl2, CCl4, CF2Cl2, c bit t CH4 iu ch c nhiu cht khc nhau: hn hp CO + H2, amoniac, CH CH, ru metylic, anehit fomic II. Anken (olefin) 1. ng ng ng phn danh php a. ng ng: Cng thc chung ca dy l CnH2n vi n 2.Tn gi chung l anken hay olefin Cht n gin nht l etilen C2H4. Tt c cc hp cht c cng cng thc chung hp thnh mt dy ng ng ca etilen C2H4. b. ng phn: T C2- C3: khng c hin tng ng phn T C4: c ng phn v: + Mch cacbon: khng nhnh (thng), c nhnh v mch vng (xicloankan). + ng phn v v tr ca lin kt i + C th c ng phn hnh hc (ng phn cis, trans) V d: C4H8: c cc ng phn: 1, CH2 = CH CH2 CH3 2, CH3 CH = CH CH3 3, CH2 = C(CH3) CH3 Buten - 2 (CH3 CH = CH CH3) c ng phn hnh hc:
0 0 0 0 0 0
CH3
CH3
H
CH3
H
H
C=C cis buten - 2

ng c Thin
91
Trng THPT Sn ng s 3
C=C
CH3
c. Danh php: + Danh php thng: Tn gi ca cc anken xut pht t tn ankan tng ng, ch i ui an thnh ui ilen: Cng thc Tn gi Cng thc Tn gi Hexilen C6H12 Etilen Heptilen C7H14 C2H4 Propilen Octilen C8H16 C3H6 Butilen Nonilen C9H18 C4H8 Pentilen Decilen C10H20 C5H10 + Danh php quc t (danh php IUPAC): gi tn anken theo danh php quc t, chng ta tin hnh qua cc bc sau: - Bc 1: Chn mch C di nht cha lin kt i lm mch chnh - Bc 2: nh s th t cc nguyn t C ca mch chnh t pha no gn lk i - Bc 3: Gi tn: Tn anken = s ch v tr nhnh + tn nhnh + tn mch chnh (i ui an -> en) + v tr lk i V d: 1 CH3 2CH = 3C 4 CH 5CH2 6CH3 Cl 2. Tnh cht vt l Theo chiu tng ca n (trong cng thc CnH2n), nhit si v nhit nng chy tng. n = 2 4 : cht kh n = 5 18 : cht lng. n 19 : cht rn. u t tan trong nc, tan c trong mt s dung mi hu c (ru, ete,) 3. Tnh cht ho hc * c im cu to: Mch C h, c th phn nhnh hoc khng phn nhnh. Trong phn t c 1 lin kt i: gm 1 lin kt v 1 lin kt . Nguyn t C lin kt i tham gia 3 lin kt nh 3 obitan lai ho sp2, cn lin kt nh obitan p khng lai ho. c bit phn t CH2 = CH2 c cu trc phng. CH3 3 Clo 4 metyl hexen
-2
Do c lin kt nn khong cch gia 2 nguyn t C = C ngn li v hai nguyn t C ny khng th quay quanh lin kt i v khi quay nh vy lin kt b ph v. Do lin kt trong lin kt i km bn nn cc anken c phn ng cng c trng, d b oxi ho ch ni i v c phn ng trng hp. a. Phn ng cng hp + Cng hp H2: ,t CH2 = CH2 + H2 Ni CH3 CH3 + Cng hp halogen: Lm mt mu nc brom nhit thng. ,t CH2 = CH2 + Cl2 Ni CH2 CH2
0 0
ng c Thin
92
Trng THPT Sn ng s 3
Cl Cl (Theo dy Cl2, Br2, I2 phn ng kh dn.) + Cng hp hirohalogenua HX (sn phm theo quy tc cng Maccopnhicop) O CH3 CH = CH2 + HCl H CH3 CH CH2 (spc)
2
Cl
(Theo dy HCl, HBr, HI phn ng d dn) + Cng hp H2O (un nng, c axit long xc tc): Cng tun theo quy tc Maccpnhicp: Nhm - OH nh vo C bc cao CH3 CH = CH2 + H OH H CH3 CH CH2 (spc) ,t
+
OH H b. Phn ng trng hp: C xc tc, p sut cao, un nng p , xt ,t nCH2 = CH2 (- CH2 CH2 -) n etilen poli etilen (PE) c. Phn ng oxi ho + Phn ng chy (phn ng oxi ha hon ton)
0
CnH2n +
0 3n O2 t nCO2 + nH2O 2
+ Phn ng oxi ho khng hon ton: To thnh ru 2 ln ru hoc t mch C ch ni i to thnh anehit hoc axit. R CH = CH2 + [O] + H2O -> R CH CH2 4. iu ch a. iu ch etilen: Tch nc khi ru etylic CH3 CH2 OH H SO , CH2 = CH2 + H2O 170 C Tch H2 khi etan: ,t CH3 CH3 Fe CH2 = CH2 + H2 Crackinh ankan mch ln hn: CH3 CH2 CH3 Crk CH4 + CH2 = CH2 Cng hp H2 vo axetilen , CH CH + H2 Pd CH2 = CH2 t b. iu ch cc anken khc: Thu t ngun kh ch bin du m. Tch H2 khi ankan: ,t CnH2n + 2 Fe CnH2n + H2 Tch nc khi ru R CH2 CH2 OH H SO , R CH = CH2 + H2O 170 C Tch HX khi dn xut halogen: ,t R CH2 CH2 X + KOH R OH R CH = CH2 + KX + H2O Hoc: R CH2 CH2 X KOH R CH = CH2 + HX , R OH ,t Tch X2 t dn xut ihalogen: R CHX CH2X + Zn t R CH = CH2 + ZnX2 (Phn ng trong dung dch ru vi bt km xc tc). 5. ng dng
2 4 0 0 0 0 2 4 0 0 0 0
KMnO4
OH
OH
ng c Thin
92
Trng THPT Sn ng s 3
Dng sn xut ru, cc dn xut halogen v cc cht khc. trng hp polime: polietilen, poliprpilen. Etilen cn c dng lm qu mau chn.
III. Ankin
1. ng ng, ng phn, danh php a. ng ng: Cng thc chung CnH2n2 (n 2) Cht n gin nht l axetilen CH CH. Cc cht c cng cng thc chung nh trn v c cu to tng t axetilen hp thnh dy ng ng ca axetilen. b. ng phn: Hin tng ng phn l do mch C khc nhau v do v tr ni ba khc nhau. Ngoi ra cn ng phn vi ankaien v hirocacbon vng. c. Danh php: Tng t nh cch gi tn anken nhng c ui in. V d: HC C CH CH2 CH3 CH3 3 metyl pentin - 1 2. Tnh cht vt l Khi n tng, nhit si v nhit nng chy tng dn. n = 2 4 : cht kh n = 5 16 : cht lng. n 17 : cht rn. u t tan trong nc, tan c trong mt s dung mi hu c. V d axetilen tan kh nhiu trong axeton. 3. Tnh cht ho hc * c im cu to: Trong phn t c mt lin kt ba (gm 1 lin kt v 2 lin kt ). c bit phn t axetilen c cu hnh ng thng ( H C C H : 4 nguyn t nm trn mt ng thng). Trong phn t c 2 lin kt lm di lin kt C C gim so vi lin kt C = C v C C. Cc nguyn t C khng th quay t do quanh lin kt ba. Do , cc ankin c nhng tnh cht c trng ca lin kt nh: phn ng cng, trng hp; ngoi ra do nguyn t H lin kt ba tng i linh ng nn cc ankin c H lin kt vi C lin kt ba (ankin -1) cn c phn ng th ion kim loi c trng. a. Phn ng cng: C th xy ra theo 2 nc. + Cng H2 (to, xc tc): , HC CH + H2 Pd CH2 = CH2 t ,t CH2 = CH2 + H2 Ni CH3 CH3 + Cng halogen (lm mt mu nc brom) O HC CH + Br2 H BrHC = CHBr O BrHC = CHBr + Br2 H Br2HC CHBr2 + Cng hirohalogenua HX (HCl, HCN, CH3COOH,): 120oC 180oC vi HgCl2 xc tc ,t HC CH + HCl HgCl CH2 = CHCl (vinyl clorua) Vinyl clorua c dng trng hp thnh nha P.V.C: nCH2 = CHCl xt , p (- CH2 CH - )n (PVC) ,t
0 0 2 2 2 0 0
ng c Thin
93
Trng THPT Sn ng s 3
Cl Phn ng cng HX c th xy ra n cng: ,t HC CH + 2HCl HgCl CH3 CHCl2 (1,1 diclo etan) CH COO ) ,t HC CH + CH3 COOH ( Zn CH3 COO CH = CH2 (vinyl axetat) HC CH + HCN CuCl ,NH CH2 = CHCN (vinyl xianua) i vi cc ng ng ca axetilen, phn ng cng tun theo quy tc Maccpnhicp. V d: HC C CH3 + HCl -> CH2 = CCl CH3 + Cng H2O: Cng tun theo quy tc Maccpnhicp:
2 0 3 2 0 2 3
,80 C HC CH + H2O Hg CH2 = CH OH -> CH3 CHO (andehit axetic) ,t CH3 C CH + H2O Hg CH3 C = CH2 -> CH3 C CH3
0 2+ 0
2+
OH O b. Phn ng trng hp Cl 2HC CH CuCl HC C CH = CH2 , NH C 3HC CH C , 600 C6H6 c. Phn ng th ion kim loi: Ch xy ra i vi axetilen v cc ankin khc c ni ba cacbon u mnh R C CH: 2R C CH + Ag2O NH 2R C CAg (mu vng nht) + H2O du HC CH + Ag2O NH AgC CAg + H2O du Hay c th vit l: R C CH + AgNO3 + NH3 R C CAg + NH4NO3 OH ,t HC CH + 2CuOH Cu - C C Cu ( nu)+ 2H2O Khi cho sn phm th tc dng vi axit li gii phng ankin: AgC CAg + 2HNO3 -> HC CH + 2AgNO3 d. hn ng oxi ho ankin + Phn ng chy CnH2n -2 + O2 t nCO2 + (n - 1)H2O Phn ng to nhit + Oxi ho khng hon ton (lm mt mu dung dch KMnO4) to thnh nhiu sn phm khc nhau. V d: HC CH + [O] + H2O -> HOOC COOH axit oxalic dd KMnO4 Khi oxi ho ankin bng dung dch KMnO4 trong mi trng H2SO4, c th gy ra t mch C ch ni ba to thnh anehit hoc axit. 4. iu ch a. iu ch axetilen: + Tng hp trc tip 2C + H2 3000 C2H2 C + T metan 2CH4 1500, C2H2 + 3H2 C l ln + Thu phn canxi cacbua CaC2 + 2H2O -> Ca(OH)2 + C2H2 + Tch hiro ca etan ,t CH3 CH3 Fe C2H2 + 2H2
4 0 3 3 _ 0 0 0 0 0
ng c Thin
94
Trng THPT Sn ng s 3
b. iu ch cc ankin khc: + Tch hirohalogenua khi dn xut ihalogen (tch kim ru) ,t CH2 CH R + 2KOH R OH C2H2 + 2KCl + 2H2O
0
Cl Cl + Phn ng gia axetilenua vi dn xut halogen CH3 I + Ag C C Ag + I CH3 -> CH3 C C CH3 + 2AgI 5. ng dng ca ankin Ch c axetilen c nhiu ng dng quan trng. thp sng (kh t n). Dng trong n x hn, ct kim loi. Dng tng hp nhiu cht hu c khc nhau: anehit axetic, cao su tng hp (policlopren), cc cht do v cc dung mi, Cng thc chung l : CnH2n2 (n 3). Cht tiu biu l: butadien 1, 3 v isopren (2 metyl butaien 1, 3) 1. Cu to C 2 lin kt i trong phn t. Cc ni i c th: v tr lin nhau: C = C = C v tr cch bit: C = C C C = C H lin hp: C = C C = C Quan trng nht l cc ankaien thuc h lin hp. Ta xt 2 cht tiu biu l: Butaien : CH2 = CH CH = CH2 v CH2 = C CH = CH2 isopren CH3 2. Tnh cht vt l Butaien l cht kh, isopren l cht lng (nhit si = 34oC). C 2 cht u khng tan trong nc, nhng tan trong mt s dung mi hu c nh: ru, ete. 3 Tnh cht ho hc Phn t Ankadien c 2 lin kt , do n c nhng tnh cht ha hc c trng ca loi lin kt ny: phn ng cng, phn ng trng hp, Nhng quan trng nht l 2 phn ng sau: a. Phn ng cng: + Cng halogen lm mt mu nc brom CH2 = CH CH = CH2 + Br2 -> brom, cc ni i s b bo ho. + Cng H2
0
IV Ankaien (hay iolefin)
CH 2 Br CH = CH CH 2 Br (80%) CH 2 Br CHBr CH = CH 2 (20%)
CH2 = CH CH = CH2 + H2 Pd ,eol , 12 tan C + Cng hirohalogenua CH2 = CH CH = CH2 + H - Br ->

0
CH 3 CH = CH CH 3 CH 3 CH 2 CH = CH 2
CH 3 CH = CH CH 2 Br (80%) CH 3 CHBr CH = CH 2 (20%)
b. Phn ng trng hp n CH2 = CH CH = CH2 Na , p (- CH2 CH = CH CH2 -)n cao su Buna ,t

ng c Thin
95
Trng THPT Sn ng s 3
nCH2 = C CH = CH2 xt , p (- CH2 C = CH CH2 -)n cao su isopren ,t

0
CH3 CH3 4. iu ch a. Tch hiro khi hirocacbon no: Phn ng xy ra 600oC, xc tc Cr2O3 + Al2O3, p sut thp. CH3 CH2 CH2 CH3 CH2 = CH CH = CH2 + 2H2 CH3 CH2 CH2 CH3 CH2 = C CH = CH2 + 2H2 CH3 CH3 b. iu ch t ru etylic hoc axetilen: ,t 2CH3CH2OH ZnO CH2 = CH CH = CH2 + H2 + 2H2O (hoc khi xt: Al2O3, ,MgO 0 500 C) Cl 2HC CH CuCl HC C CH = CH2 , NH ,t HC C CH = CH2 + H2 Pd CH2 = CH CH = CH2
0 4 0
Cc hirocacbon thm quen thuc nh benzen (C6H6), toluen (C6H5 CH3), etylbenzen (C6H5 C2H5) v cc ng ng ca n c cng thc chung CnH2n-6 vi n 6. Ngoi ra, c cc aren mch nhnh khng no nh stiren C6H5 CH = CH2, phenylaxetilen C6H5 C CH,hoc c nhiu nhn benzen nh naphtalen, antraxen. Hirocacbon thm in hnh l benzen. 1. Benzen C6H6 v ankyl benzen a. Cu to - ng phn - tn gi + Cu to Phn t benzen c cu to vng 6 cnh u.
V. Hirocacbon thm (Aren)
Mi nguyn t C trong phn t benzen tham gia 3 lin kt vi 2C bn cnh v H nh 3 obitan lai ho sp2 nn tt c cc nguyn t C v H u nm trn cng mt phng. Cn mi lin kt th 4 (lin kt ) c to nn nh obitan 2p c trc vung gc vi mt phng phn t. Khong cch gia cc nguyn t C trong phn t l bng nhau nn my electron p ca nguyn t C xen ph u vi 2 my electron 2p ca 2 nguyn t C bn cnh, do trong phn t benzen khng hnh thnh 3 lin kt ring bit m l mt h lin kt thng nht gi l h lin hp thm, quyt nh nhng tnh cht thm c trng ca nhn benzen: va th hin tnh cht no, va th hin tnh cht cha no. V th CTCT ca benzen thng c biu din bng my cch sau:
Gc hirocacbon thm
ng c Thin
96
Trng THPT Sn ng s 3
Khi tch bt 1H khi phn t benzen ta c gc phenyl C6H5 Khi tch bt 1H khi nguyn t C trn nhn benzen ca 1 phn t hirocacbon thm ta c gc aryl. Nu tch 2H th c gc phenylen v arylen + ng phn V cc lin kt C C trong nhn benzen ng nht nn benzen ch c 3 ng phn v tr. Nu hai nhm th hai C ln cn ta c ng phn ortho (vit tt l o) hoc nh s 1, 2. Nu hai nhm th cch nhau mt nguyn t C (mt nh lc gic) gi l ng phn meta (vit tt l m) hoc 1, 3. Nu hai nhm th hai nguyn t C i nh gi l ng phn para (vit tt l p) hoc 1, 4. + Tn gi: Tn = s ch v tr nhnh + tn nhnh + benzen V d: Cc ng phn ca iclobenzen C6H4Cl2.
Cl
Cl Cl
Cl
Cl
Cl
Ortho iclobenzen meta - iclobenzen para iclobenzen 1, 2 iclobenzen 1, 3 iclobenzen 1, 4 iclobenzen b. Tnh cht vt l Benzen l cht lng khng mu, rt linh ng, c mi c trng, t0s = 80oC. Benzen nh hn nc, khng tan trong nc, nhng tan nhiu trong cc dung mi hu c nh ru, ete, axeton. Benzen l dung mi tt ho tan nhiu cht nh Cl2, Br2, I2, S, P,cht bo, cao su. Nhng cht n gin nht trong dy ng ng ca benzen l cht lng, nhng ng ng cao hn l cht rn. Benzen c dng lm nguyn liu u iu ch thuc nhum, thuc cha bnh, si tng hp, cht do, phenol, nitrobenzen, anilin. Benzen l mt trong nhng dung mi hu c tt nht. c. Tnh cht ho hc ca benzen Do c c im cu to c bit nh trn, benzen c c tnh cht ca hp cht no c tnh cht ca hp cht cha no. Benzen tng i d tham gia phn ng th, tng i kh tham gia phn ng cng v phn ng oxi ha. Tnh cht gi l tnh thm. Cc ng ng ca benzen cng c tnh thm; ngoi ra chng cn c tnh cht ca nhnh ankyl. + Phn ng th: Vi halogen nguyn cht (Cl2, Br2) phn ng xy ra nhit thng c v bo st xc tc: C6H6 + Br2 Fe C6H5Br + HBr (brombenzen)
Ch : Bnh thng benzen khng lm mt mu nc brom.

ng c Thin
97
Trng THPT Sn ng s 3
Toluen tham gia phn ng th d dng hn so vi benzen v to ra hai ng phn ov p-
Nu khng c bt st v hn hp c chiu sng th phn ng s xy ra nhnh ankyl
Phn ng nitro ho: Vi HNO3 bc khi, c mt H2SO4 c, un nng nh. C6H6 + HO NO2 H SO C6H5 NO2 + H2O ,t
2 4 0
Nitrobenzen li phn ng vi HNO3 to thnh m initrobenzen :
Toluen tham gia phn ng th nitro d dng hn benzen v to thnh hn hp sn phm
* Quy lut th nhn benzen: Khi trn nhn benzen c sn nhm th y electron (nhm ch cha cc lk n_Nhm th loi 1) nh: NH2, NR, OH, OCH3, gc ankyl R, (+C, +H lm mt electron cc v tr ortho v para tng), th phn ng th xy ra d dng hn so vi benzen v sn phm phn ng nh hng th vo v tr o , p Khi trn nhn benzen c sn nhm th ht electron (nhm th loi 2) nh NO2, SO3H, COOH, CHO ( C lm tng mt electron v tr meta), th phn ng th xy ra kh khn hn so vi benzen v nh hng th vo v tr m .
Khi c nhm th loi 1 Phn ng vi H2SO4 c

ng c Thin
khi c nhm th loi 2
98
Trng THPT Sn ng s 3
C6H6+ HO HSO3 170 C6H5 HSO3 + H2O 180 C Phn ng vi dn xut halogen AlCl khan ,t C6H6 + CH3 Cl C6H5 CH3 + HCl + Phn ng cng: Kh xy ra hn hirocacbon cha no, mch h. Cng hp hiro C6H6 + 3H2 Ni ,180 C6H12 (xiclo hexan) C Cng hp clo v brom C6H6 + 3Cl2 askt C6H6Cl6 (hexaclo xiclohexan hay 666) + Phn ng oxi ho: Benzen khng b oxi ha bi cc cht oxi ho mnh nh: KMnO4. Cc cht oxi ho mnh (nh KMnO4) oxi ho nguyn t C ca mch nhnh nh trc tip vi nhn benzen:
3 0 0
C6H5 CH2 CH3 + [O] -> C6H5 COOH + CO2 + H2O C6H5 CH2 CH2 CH3 + [O] -> C6H5 COOH + CH3 COOH d. iu ch * iu ch benzen Chng ct nha than . T axetilen: C 3HC CH C , 600 C6H6 T xiclohexan. C6H12 Fe,600 C6H6 + 3H2 C T n - hexan. C6H14 xt , p C6H6 + 4H2 ,t * iu ch cc hirocacbon thm khc
0 0 0
AlCl khan ,t C6H6 + CH3 Cl C6H5 CH3 + HCl C6H5 CH3 + 2NaCl C6H5 Cl + 2Na + CH3 Cl t 2. Gii thiu mt s hirocacbon thm khc a) Tuloen C6H5 CH3: l cht lng (nhit si = 111oC), c mi ging benzen, khng tan trong nc, tan trong mt s dung mi hu c. b) Etylbenzen C6H5 CH2 CH3 l cht lng khng mu, c mi ging benzen (nhit si = 136oC), t tan trong nc. Ngoi cc tnh cht ca hirocacbon thm cn c phn ng tch H2: C6H5 CH2 CH3 Fe,600 C6H5 CH = CH2 + H2 C
3 0 0
ng c Thin
99
Trng THPT Sn ng s 3
c) Stiren C6H5 CH = CH2 l cht lng (nhit si = 145oC). t tan trong nc, tan nhiu trong ru, ete, xeton. D tham gia phn ng cng ni i ca mch nhnh. C6H5 CH = CH2 + Br2 -> C6H5 CHBr - CH2Br Phn ng trng hp xy ra rt d dng khi c mt cht xc tc: C6H5 CH = CH2 xt , p (- CH CH2 - ) n ,t
0
C6H5 Polistiren l cht rn trong sut, d gia cng nhit, dng lm vt liu in, dng c gia nh. Stiren ng trng hp vi butaien to thnh cao su butaien stiren.(cao su Buna - S) d) Xilen C6H4(CH)3 : c 3 dng.
CH3
CH3 CH3
CH3
CH3
CH3
O xilen
m xilen
p xilen
e) Hirocacbon thm c nhiu vng benzen iphenyl C6H5 C6H5 : cht rn, tan trong ru, ete. Naphtalen C10H8:
Cht rn Antraxen C14H10
VI. Dn xut halogen

1. Dn xut halogen ca hirocacbon no a. Cu to Do m in ca nguyn t halogen (X) ln nn mi lin kt C-X b phn cc ng k v nguyn t X linh ng d tham gia phn ng. Theo chiu t Cl -> Br -> I linh ng ca nguyn t X trong phn t dn xut tng ln. -Cch gi tn: Theo danh php th. V d 1 CH3 2CH2 3CH 4CH 5CH2 6CH3 Cl CH3 3 Clo 4 metyl hexan b. Tnh cht vt l - Ba cht CH3Cl, CH3Br, C2H5Cl l cht kh. Cc cht khc l cht lng, rn, khng mu. - Khng tan trong nc, d tan trong cc dung mi hu c. c. Tnh cht ho hc + Phn ng thu phn trong mi trng kim:
ng c Thin
100
Trng THPT Sn ng s 3
Ha hc cc hp cht hu c ,t 0 R X + H2O NaOH R OH + HX
Hoc
,t R X + NaOH H O R OH + NaX
2 0
,t CH2 CH2 + 2NaOH H O CH2 CH2

2
Cl
Cl OH
0
OH
OH
CH3 C(Cl)3 + 3NaOH H O CH3 C OH + 3NaCl ,t

2
OH + Phn ng tch HX:

,t R CH2 CH2 X + KOH R OH R CH = CH2 + KX + H2O Hoc: R CH2 CH2 X KOH R CH = CH2 + HX , R OH ,t + Phn ng tch X2 t dn xut ihalogen:
0 0
R CH = CH2 + ZnX2 R CHX CH2X + Zn t
+ Tc dng vi NH3 R Cl + NH3 -> R NH2 + HCl + Tc dng vi Na

R R + 2NaX R X + 2Na + X R t
0
d. iu ch - Phn ng th ca halogen vo hirocacbon no.

/ t CnH2n + 2 + aX2 askt CnH2n + 2 aXa + aHX
0
- Phn ng cng HX vo hirocacbon cha no.

CnH2n + X2 CCl CnH2nX2
4
- Phn ng gia HX v ru (c H2SO4 ) R OH + HX -> R X + H2O e. Gii thiu mt s cht + CH2Cl - CH2Cl (icloetan) l cht lng, dng ho tan nha, cht bo. + CHCl3 (clorofom) l cht lng, dng lm dung mi, gy m. + CCl4 (tetraclorua cacbon) l cht lng, dng lm dung mi ho tan cao su, cht bo, du m. + Freon - 12 (CCl2F2) l cht kh, khng mu, khng mi, khng chy, khng c. Dng lm cht sinh hn trong my lnh. Tuy vy, n c nhc im ln l ph hu tng ozon bo v Tri t, cho nn ngi ta ang tm cch hn ch sn xut v s dng n. 2. Dn xut halogen ca hirocacbon cha no a. Cu to phn t Nguyn t X (halogen) c th nh vo C ni i hoc nguyn t C khc.
ng c Thin
101
Trng THPT Sn ng s 3
V d, ng vi CTPT C3H5Cl c 3 cht. ClCH = CH CH3 Hoc CH2 = CH CH2 Cl hoc CH2 = C CH3 Cl C lin kt bi (i hoc ba) trong phn t. b. Tnh cht ho hc Phn ng cng v phn ng trng hp: CH2 = CH CH2 Cl + Cl2 -> CH2 CH CH2 Cl Cl Cl nCH2 = CH CH2 Cl (- CH2 CH - )n
xt , p ,t 0
c. Phn ng thy phn Nguyn t X linh ng v d tham gia phn ng trao i - d b thu phn khi c mt kim. CH2 = CH CH2 Cl + H2O OH CH2 = CH CH2 OH + HCl ,t
CH2Cl
VII. Ngun hirocacbon trong thin nhin

1. Kh thin nhin Thnh phn ch yu ca kh thin nhin l metan (90 - 98%), cn li l eta, propan, butan v mt s ng ng cao hn, ngoi ra cn mt lng nh H2S, N2, ng dng: * Dng lm nhin liu * Dng lm nguyn liu ho hc iu ch hiro, axetilen, cao su nhn to, cht do, nhiu cht tng hp khc. V d: 2CH4 1500 C2H2 + 3H2 C T axetilen c th tng hp nhiu cht khc.
0
2. Du m a. Thnh phn ca du m Du m l cht lng c snh, mu nu sm, c mi c trng, nh hn nc. Du m nm trong nhng ti du su di t. Du m l hn hp hirocacbon c th thuc cc loi: no mch h, vng no, thm. Ngoi ra, cn cha nhng lng nh cc cht hu c khc trong phn t c O, N, S Trong du m thnh phn hirocacbon lng l ch yu, c ho tan hirocacbon kh v rn. b. Cc sn phm chng ct du m + Sn phm nh ca du m gm: Khi chng ct phn on du m thu c cc sn phm nh ghi bng sau: Tn phn Nhit si, S C trong ng dng o on C phn t Kh < 40 C1 - C4 Nhin liu, nguyn liu THHC. Xng nh 40 - 200 C5 - C11 Nhin liu, dung mi Ligorin 120 - 240 C8 - C11 Nhin liu, dung mi Du thp 150 - 310 C12 - C18 Nhin liu , thp sng Nhin liu, ng c iezen Du nng 300 - 450 C15
ng c Thin
102
Trng THPT Sn ng s 3
Phn cn li ca du m sau khi chng ct sn phm nh gi l mazut. Chng phn on mazut thu c: + Du nhn: bi trn. + Vazlin: bi my. + Parafin: lm nn thp sng. + Cui cng l hc n dng lm nha ri ng. * Crackinh du m Crackinh l qu trnh "b gy" phn t hirocacbon mch di (bng nhit v bng xc tc) thnh cc hirocacbon mch ngn hn. V d: crk C8 H18 C4H10 + C4H8 Octan butan buten crk C16H34 C8H18 + C8H16 C 2 phng php crackinh Crackinh bng nhit: Thc hin 500 - 600oC, p sut vi chc atm. Xng thu c theo phng php ny cha nhiu anken. Crackinh bng xc tc: Thc hin nhit thp hn, cht xc tc thng dng l nhm silicat. Xng thu c bng phng php crackinh ny c cht lng cao v cha nhiu ankan mch nhnh, xicloanken v aren. 3. Than Khi nung nng than ln khong 1000o C trong iu kin khng c khng kh, cc hp cht hu c ln trong than bay ra, cn li than cc. Hi bay ra khi chng than c ngng t v phn tch thnh: 1. Kh l cc: H2, CH4, oxit cacbon, NH3, N2, C2H4, 2. Nha than : l cht lng nht, mu thm, khi chng phn on thu c. Du nh (nhit si < 170oC) cha hirocacbon thm. Du trung (nhit si = 170 - 230oC) cha phenol, naphtalen, piriin Du nng (nhit si = 230 - 270oC) cha naphtalen v cc ng ng ca n, cresol, Du antraxen (nhit si = 270 - 360oC) cha antraxen, phenantren. Cn li (khong 60%) l nha than , dng ri ng, lm vt liu xy dng. 3. Nc amoniac Ho tan NH3 v cc mui amoni nh (NH4)2CO3, NH4Cl,
ng c Thin
103
Trng THPT Sn ng s 3
Chng 3 NHNG HP CHT HU C C NHM CHC I. Ru (ancol)

1. Cng thc - cu to - cch gi tn a. Cng thc tng qut R(OH)n vi n 1. R l gc hirocacbon c bit ru no, n chc, mch thng c CTPT : CnH2n+1OH. b. Cu to Nhm hiroxyl OH vi mi lin kt O - H phn cc ng k. Gc R c th l mch h no hay cha no hoc mch vng. V d: CH3 OH, CH2 = CH CH2 OH, C6H5 CH2 OH. Nhm OH c th nh vo nguyn t C bc 1, bc 2, bc 3 to thnh cc ru tng ng bc 1, bc 2, bc 3. V d: CH3 CH3 CH2 OH CH3 CH CH3 CH3 C CH3
OH OH Ru bc 1 Rou bc 2 Ru bc 3 Ru khng bn khi: + Nhiu nhm OH cng nh vo 1 nguyn t C. + Nhm OH nh vo nguyn t C c ni i. V d: R CH OH -> R CH = O + H2O OH OH R C OH -> R - COOH OH CH3 C = CH2 -> CH3 C CH3 OH
ng c Thin
CH2 = CH OH -> CH3 CHO
104
Trng THPT Sn ng s 3
* Hin tng ng phn: ru c th c cc loi ng phn: + Mch C khc nhau. + V tr ca cc nhm OH khc nhau. + Ngoi ra ru n chc cn ng phn l ete oxit R O R'. V d: Cht n gin C3H8O c 3 ng phn. CH3 CH2 CH2 OH; CH3 CH(OH) CH3; CH3 CH2 O CH3 c. Cch gi tn + Danh php thng Tn ru = Tn gc hirocacbon tng ng + ic. V d: CH3 CH2 OH ru etylic + Danh php quc t (IUPAC) Tn ru = tn hirocacbon tng ng + ol + v tr nhm OH CH3 CH2 CH2 OH Propanol - 1 CH3 CH(OH) CH3 propanol - 2 2. Tnh cht vt l i vi ru no, n chc, mch h CnH2n+1OH : Khi n = 1 12 ; ru l cht lng, n > 12 l cht rn, nhit si ca ru cao hn ca hirocacbon no hay dn xut halogen c KLPT xp x v trong ru c hin tng lin hp phn t nh lin kt H, do s bay hi kh khn. OHOH R R Tt c cc ru n chc u nh hn nc. Ba cht u (metanol, etanol, propanol) tan v hn trong nc l do khi ho tan ru vo nc, gia cc phn t ru v cc phn t nc hnh thnh lin kt hiro: OHOH H R Sau tan gim nhanh khi n tng. 3. Tnh cht ho hc a. Tc dng vi kim loi kim. C2H5 OH + Na -> C2H5 ONa + 1/2H2 Cc ancolat l cht rn, tan nhiu trong ru tng ng, b thu phn hon ton. C2H5 ONa + H2O -> C2H5OH + NaOH b. Phn ng este ho vi axit hu c v v c (xt: H2SO4 c) C2H5 OH + H Cl C2H5Cl + H2O C2H5 OH + H OCOCH3 CH3COOC2H5 + H2O Cc phn ng este ho u thun nghch, khng hon ton. Mun phn ng xy ra hon ton theo chiu thun phi dng H2SO4 c ht nc. Phn bit: Ru bc 1: phn ng chm, khng hon ton. Ru bc 2: phn ng rt chm. Ru bc 3: gn nh khng xy ra phn ng. c. Phn ng tch nc To ete: 2C2H5OH H SO , C2H5OC2H5 + H2O 140 C To olefin: C2H5OH H SO , CH2 = CH2 + H2O 140 C
2 4 0 2 4 0
ng c Thin
105
Trng THPT Sn ng s 3
Trong phn ng tch nc ca ru to anken, sn phm chnh ca phn ng tun theo quy tc tch Zaixep. d. Phn ng tch hiro: Cho hi ru qua bt Cu hay bt Fe nung nng. Ru bc 1 anehit. Ru bc 2 xeton. R-CH2OH + CuO t RCHO + Cu + H2O Hay ,t R-CH2OH + 1/2O2 CuO RCHO + H2O e. Phn ng oxi ho khng hon ton (m du): R-CH2OH + 1/2O2 -> RCOOH +H2O C2H5H + 1/2O2 men gim CH3COOH + H2O 4. iu ch a. Thu phn este v dn xut halogen RCOOR + H2O NaOH RCOONa + ROH b. Cng H2O vo anken CnH2n + HOH t CnH2n + 1OH c. Kh anehit v xeton ,t RCHO + H2 Ni R-CH2OH d. Cho glucoz ln men c ru etylic men r- u, 320C C6H12O6 2C2H5OH + 2CO2 5. Gii thiu mt s ru n chc a. Ru metylic CH3OH L cht lng, khng mu, nh hn nc, tan v hn trong nc, c mi c trng, nhit si = 65oC. Rt c: ung phi d m, ung nhiu d cht. Dng iu ch anehit fomic, tng hp cht do, lm dung mi. iu ch: + Tng hp trc tip: CH4 + 1/2O2 Cu , 250 C ,100 atm CH3OH + Bng cch chng g b. Ru etylic CH3 CH2 OH L cht lng, nh hn nc, tan v hn trong nc, c mi thm, nhit si = 78,3oC. C ng dng rt ln trong thc t: ch to cao su v mt s cht hu c tng hp khc nh este, axit axetic, ete lm dung mi ho tan vecni, dc phm, nc hoa. c. Ru butylic C4H9OH C 4 ng phn l nhng cht lng, t tan trong nc hn 3 cht u dy ng ng. C mi c trng. d. Ru anlylic CH2 = CH CH2OH L cht lng khng mu, mi xc, nhit si = 97oC c dng sn xut cht do. Khi oxi ho ch ni i to thnh glixerin: CH2 = CH CH2OH + [O] -> CH2OH CHOH CH2OH iu ch i t propilen CH2 = CH CH2OH + Cl2 500 CH2 = CH CH2Cl + HCl C CH2 = CH CH2Cl + NaOH t CH2 = CH CH2OH + NaCl 6. Ru a chc
0 0 0 0 0 0 0
ng c Thin
106
Trng THPT Sn ng s 3
CH2 CH2
CH2 CH CH2
OH OH OH OH OH Etylenglicol Glixerol a. Phn ng c trng Do c nhiu nhm OH trong phn t nn phn cc ca cc nhm O - H tng, nguyn t H y linh ng hn so vi ru n chc. Do vy ngoi nhng tnh cht chung ca ru, chng cn c nhng tnh cht ring ca ru a chc: in hnh l phn ng ho tan Cu(OH)2 to thnh dung dch mu xanh lam. CH2 OH CH2 O O CH2 2 + Cu(OH)2 -> Cu + 2H2O CH2 OH CH2 O O CH2 HH ng etylenglicolat b. Gii thiu mt s ru a chc: + Etylenglicol CH2OH CH2OH L cht lng dng xiro, khng mu, khng mi, c v ngt, c, tan nhiu trong nc, nhit si = 197oC. iu ch: + i t etilen CH2 = CH2 + [O] -> CH2OH CH2OH CH2Cl CH2Cl + 2NaOH -> CH2OH CH2OH + 2NaCl Etylenglicol c th trng ngng vi iaxit to thnh polime dng lm si tng hp + Glixerol CH2OH CHOH CH2OH L cht lng dng xiro, khng mu, khng mi, c v ngt, tan nhiu trong nc, nhit si = 290oC (khi si ng thi phn hy) Phn ng este ho vi HNO3 (khi c mt H2SO4): CH2 OH CH2ONO2 CH OH + 3HO NO2 H SO CHONO2
2 4
+ 3H2O
CH2ONO2 Nitroglixerin (glixerintrinitrat) Nitroglixerin l cht lng nh du, rt c, km bn, khi va chm mnh gy n. Dng lm thuc n iamit (75% nitroglixerin, 25% t trng bn l v silic ca mt loi rong cht) 4C3H5(ONO2)3 -> 12CO2 + 6N2 + O2 + 10H2O iu ch: + X phng ho cht bo. + Ln men glucoz khi c mt NaHSO3 C6H12O6 NaHSO C3H5(OH)3 + CH3CHO + CO2 + Tng hp t propilen Cl CH2 = CH CH3 + Cl CH2 = CH CH2Cl + CH2Cl CHCl CH2Cl ,500 C ,t NaOH glixerin ng dng: + Dng sn xut thuc n nitroglixerin. + Trong sn xut thc phm, dc phm, hng liu, thuc da, vi, mc, kem nh rng.
3 2 0 2 0
CH2 OH
ng c Thin
107
Trng THPT Sn ng s 3
II. Phenol
1. Cu to phn t ca phenol Phenol l dn xut ca hirocacbon thm trong mt hay nhiu nguyn t H ca nhn benzen c thay th bng nhm OH. V d:
CH3
OH
CH3 OH
CH3
OH
OH
Phenol o crezol m crezol p - crezol y ch xt mt cht tiu biu l C6H5 OH. Trong phn t phenol c hiu ng lin hp (+C) : My electron ca cp e khng tham gia lin kt trong nguyn t O b dch chuyn v pha nhn benzen: kt qu lm tng phn cc ca lin kt O H. Nguyn t H linh ng, d tch ra lm phenol c tnh axit. Mt khc, do hiu ng lin hp dng (+C) ca nhm OH lm mt e cc v tr ortho v para trn nhn benzen tng ln, do phn ng th vo cc v tr ny d hn benzen. O H
2. Tnh cht vt l Phenol l cht tinh th khng mu, nhit nng chy = 42oC. nhit thng, phenol t tan trong nc, khi un nng tan tng ln. to > 70oC tan v hn vo nc. Phenol tan nhiu trong ru, ete, clorofom, Phenol c, c tnh st trng, lm bng da. 3. Tnh cht ho hc Trong phn t nhm phenol c nhm OH nn phenol cng c phn ng th nguyn t hiro ca nhm OH. Mt khc do c vng benzen nn phenol cn cho phn ng th brom vo vng benzen. a. Phn ng vi kim loi kim Tng t nh ru, khi cho kim loi kim (Na, K) vo phenol nng chy, thy phn ng xy ra mnh lit, kh hiro thot ra nhanh : 2C6H5OH + 2Na -> 2C6H5 ONa + H2 Natri phenolat b. Phn ng vi baz Khc vi ru, phenol d phn ng vi baz. Khi cho phenol dng rn hoc nng chy vo dung dch natri hiroxit, phenol tan dn, dung dch tr thnh trong sut : C6H5OH + NaOH -> C6H5ONa + H2O Natri phenolat (tan trong nc) Nh vy phenol phn ng c c vi kim loi kim v baz. iu chng t phenol c tnh axit, do phenol cn c gi l axit phenic.
ng c Thin
108
Trng THPT Sn ng s 3
Tuy vy tnh axit ca phenol rt yu. Phenol khng i c mu qu tm thnh . Phenol b axit cacbonic y ra khi natri phenolat : C6H5ONa + CO2 + H2O -> C6H5OH + NaHCO3 Tnh axit ca phenol mnh hn ca ru. l do nh hng ca gc phenyl C6H5 n nhm OH. Thc t ru khng phn ng c vi dung dch baz. c. Phn ng vi brom Nh nc brom vo dung dch phenol, thy kt ta trng xut hin tc thi :
OH Br + 3Br2 Br OH Br + 3HBr
2, 4, 6 tribromphenol (Trng) d. Phn ng vi dung dch HNO3

OH NO2 + 3HNO3 NO2 OH NO2 + 3H2O
2, 4, 6 trinitrophenol (axit picric) Axit picric c nhiu ng dng trong y hc: dng pht hin nc tiu, l tc nhn lm thuc hm mu, lm dc phm tr bnh st rt, giun mc, u ma, axit khan v mui ca n c bit nguy him bi kh nng d gy n khi b va chm nh, n c s dng lm thuc n trong lu n, bom, Qua phn ng trn ta thy, cc nguyn t hiro trong gc phenyl ca phenol d tham gia phn ng th hn cc nguyn t hidro trong phn t benzen. l do nh hng ca nhm OH n gc phenyl nh hng ca gc phenyl n nhm hiroxyl v nh hng ca nhm hiroxyl n gc phenyl c gi l nh hng qua li gia cc nguyn t trong phn t. 4. iu ch phenol a. Tch t nha chng than . b. i t benzen. C6H6 + Cl C6H5Cl ddNaOH C6H5ONa H C6H5OH , Fe ,t ,t NaOHrn, t0 5. ng dng ca phenol Phenol c dng trong nhiu lnh vc khc nhau : - Cng nghip cht do : phenol l nguyn liu iu ch nha phenolfomaehit, nha bakelit - Cng nghip t ha hc : T phenol tng hp ra t poliamit. - Nng dc : T phenol iu ch c cht dit c di v kch thch t thc vt 2,4 - D ( l mui natri ca axit 2,4 iclophenoxiaxetic). - Phenol cng l nguyn liu iu ch mt s phm nhum, thuc n (axit picric). - Do c tnh dit khun nn phenol c dng trc tip lm cht st trng, ty u, hoc iu ch cc cht dit nm mc (ortho - v para - nitrophenol)
2 0
+
ng c Thin
109
Trng THPT Sn ng s 3
6. S lc v ru thm Cng thc: C6H5 R OH. Trong R l gc hirocacbon mch h. C6H5 CH2OH C6H5 CH2 CH2OH (ru benzylic) (ru phenyletylic) C hai u l cht lng, t tan trong nc, tan c trong mt s dung mi hu c nh ru etylic, ete, axeton, C 2 u tham gia phn ng nh ru no, mch h, bc nht mt ln ru.
III. Amin
1. Cng thc cu to Amin l dn xut ca NH3 khi thay th mt hay nhiu nguyn t H bng gc hirocacbon. Cng c th xem amin nh dn xut ca hirocacbon khi thay th nguyn t H bng nhm NH2. Phn loi: bc ca amin: Ty theo s nhm nguyn t H trong phn t NH3 c thay th ta c cc amin c bc khc nhau: V d: CH3 NH2 metyl amin (amin bc 1) (CH3)2NH imetyl amin (amin bc 2) (CH3)3N trimetyl amin (amin bc 3) Trong phn t amin (ging trong phn t NH3), nguyn t N c 1 cp electron cha tham gia lin kt. Do , amin c kh nng kt hp proton (H+), th hin tnh baz. Nu R l gc no mch h, c khuynh hng y electron, lm tng in tch m N, lm tng kh nng kt hp H+, ngha l lm tng tnh baz. Amin bc cao c tnh baz mnh hn amin bc thp. Nu R l nhn benzen, c khuynh hng ht electron, ngc li lm gim tnh baz ca amin (tnh baz yu hn NH3) 2. Tnh cht vt l a) Cc amin mch h: Nhng cht n gin nht (CH3 NH2, C2H5 NH2) l nhng cht kh, tan nhiu trong nc, c mi c trng ging NH3. Khi khi lng phn t tng dn, cc amin chuyn dn sang lng v rn, tan trong nc cng gim dn. V d. Cht : CH3CH2, (CH3)2NH, C2H5NH2, C2H4(NH2)2 Nhit si 6,3oC +6,9oC +16,6oC +116,5oC b) Cc amin thm: l nhng cht lng hoc cht tinh th, c nhit si cao, mi c trng, t tan trong nc. 3. Tnh cht ho hc Trong cc phn t amin, nguyn t N cn mt i e cha tham gia lin kt, amin c khae nng nhn proton (H+) th hin tnh baz. Ni chung amin l nhng baz yu, c phn ng tng t NH3. a) Tnh baz Cc amin mch h tan c trong nc cho dung dch c tnh baz, lm qu tm chuyn mu xanh. CH3NH2 + HOH CH3NH4+ + OH Anilin (C6H5 NH2) v cc amin thm khc do tan t trong nc, khng lm xanh giy qu.
ng c Thin
110
Trng THPT Sn ng s 3
Phn ng vi axit to thnh mui. RCH2NH2 + HCl -> RCH2NH3Cl Cc mui ca amin l cht tinh th, tan nhiu trong nc. Khi cho cc mui ny tc dng vi kim mnh li gii phng amin. RCH2NH3Cl + NaOH -> RCH2NH2 + NaCl + H2O b) Cc iamin: Cc iamin c th tham gia phn ng trng ngng vi cc iaxit to thnh polime (xem phn iaxit) c) Amin thm: Nhm NH2 c nh hng hot ho nhn thm v nh hng th vo v tr o-, p-. V d:
NH2 Br + 3Br2 Br NH2 Br + 3HBr
Do nh hng ca nhm NH2, tnh bn ca nhn benzen gim xung, d b oxi ho (v d bng hn hp K2Cr2O7 + H2SO4) cho nhiu sn phm khc nhau. V d:
NH2 O
+[2O] O
+ NH3
(K2Cr2O7 + H2SO4) 4. iu ch a) Kh hp cht nitro bng hiro mi sinh: RNO2 + 3Zn + 6HCl -> RNH2 + 3ZnCl2 + 2H2O b) Phn ng gia NH3 vi R X (X = Cl, Br, I) RX + 2NH3 C H RNH2 + NH4X OH Phn ng c th tip tc cho amin bc cao: RNH2 + RX + NH3 C H R2NH + NH4X OH c) Phng php Sabatie C2H5OH + NH3 350 C2H5NH2+ H2O C 5. Gii thiu mt s amin a) Metylamin CH3 NH2 L cht kh, c mi ging NH3, tan nhiu trong nc, trong ru v ete. b) Etylamin C2H5 NH2 L cht kh (nhit si = 16,6oC), tan v hn trong nc, tan c trong ru, ete. c) Hecxametyliamin H2N (CH2)6 NH2: L cht tinh th, nhit si = 42oC. c dng ch nha tng hp poliamit, si tng hp. d) Anilin C6H5 NH2: L cht lng nh du, nhit si = 184,4oC. c, c mi c trng. t tan trong nc nhng tan tt trong axit do to thnh mui. trong khng kh b oxi ho c mu vng ri mu nu. Dng sn xut thuc nhum (en anilin), sn xut thuc cha bnh. e) Toluin CH3 C6H4 NH2 Dng ortho v meta l cht lng. Dng para l cht kt tinh. iu ch bng cch kh nitrotoluen.
2 5 2 5
0
ng c Thin
111
Trng THPT Sn ng s 3
IV. Andehit fomic v dy ng ng

1. Cng thc - cu to - cch gi tn a. Cng thc tng qut: R(CHO)m, m 1. R c th l H hoc gc hirocacbon v c bit R c th khng c hp cht OHC CHO trong m = 2. Anehit fomic v cc cht ng ng CH3 - CH = O, C2H5 - CH = O, C3H7 - CH = O hp thnh mt dy ng ng, c cng thc chung: CnH2n+1CH = O (n 0) v cn c gi l dy ng ng ca anehit no n chc. b. Cu to phn t Trong phn t c nhm CHO lin kt vi gc R (no hoc cha no). Cu to ca nhm - CHO c th m t:
O C H
Hin tng ng phn xut hin do: + Mch C khc nhau. + V tr cc nhm chc. + ng phn vi xeton v ru cha no. V d: Anehit C3H7 CHO c cc ng phn 1, CH3 CH2 CH2 CHO 2, CH3 CH(CH3) CHO 3, CH3 CO CH2 CH3 4, CH2 = CH CH2 CH2OH 5, CH3 - CH = CH CH2OH 6, CH2 = C(CH3) CH2OH c. Cch gi tn + Danh php thng: Tn = anehit + tn axit tng ng. V d. H CHO : anehit fomic. CH3 CHO : anehit axetic. + Danh php quc t: Thm ui al vo tn hirocacbon no tng ng (v s C). V d. H CHO : metanal CH3 CHO : etanal. CH2 = CH CH2 CHO : butenal. 2. Tnh cht vt l - Anehit fomic th kh, cc ng ng tip theo th lng. Nhit si ca anehit thp hn ca ru tng ng v gia cc phn t anehit khng c lin kt hiro. V d: etanal si 210C cn ru etylic si 78,30C. tan trong nc gim dn khi tng s nguyn t C trong phn t. 3. Tnh cht ho hc Phn ng ha hc ca anehit xy ra ch yu nhm chc anehit. a. Phn ng oxi ho: + Phn ng trng gng: Tc dng vi AgNO3 trong NH3. RCHO + 2AgNO3 + 3NH3 + H2O -> RCOONH4 + 2Ag + 2NH4NO3 ( C th vit dng n gin: RCHO + Ag2O NH RCOOH +2Ag
3
n Ag
nandehit
=2 : 1)
ng c Thin
112
Trng THPT Sn ng s 3
Nu R l H : HCHO + 4AgNO3 + 6NH3 + 2H2O -> (NH4)2CO3 + 4Ag + 4NH4NO3 ( + Phn ng vi Cu(OH)2: ,t RCHO + 2Cu(OH)2 NaOH RCOOH + Cu2O + 2H2O (mu gch) Cc phn ng ny l cc phn ng c trng nhn bit anehit. + Vi oxi khng kh c mui Mn2+ xc tc:
0
n Ag nandehit
= 4: 1)
RCHO +
2+ 0 1 O2 kk Mn RCOOH ,t 2
b. Phn ng kh anehit: Kh anehit bng H2 chng ta thu c ru bc nht. ,t RCHO + H2 Ni RCH2OH c. Cng hp HX:
0
CN
O R C H
h
+ HCN
OH
d. Phn ng trng hp anehit: C nhiu dng. * To polime:

CH2 O 3HCHO H2SO4 CH2 O CH2 O
nHCHO (- CH2 O)n

BF3
6HCHO Ca (OH ) C6H12O6 e Phn ng trng ngng: Gia anehit fomic v phenol to thnh polime phenolfomanehit.
2
OH
OH CH2
OH CH2
OH
(n + 2)
+ (n + 1)CH2 = O
+ (n + 1)H2O
n
Ngoi nhng tnh cht trn (tnh cht ca nhm chc andehit), cc andehit cn c tnh cht ca gc hirocacbon nh: gc no c phn ng th, gc cha no c phn ng cng,... V d CH2 = CH CHO + HBr -> CH2Br CH2 CHO (Phn ng cng y tri vi quy tc Maccopnhicop). 4. iu ch Tch H2 khi ru bc nht. Oxi ho m du ru bc nht. Hp nc vo axetilen c anehit axetic. C2H2 + HOH Hg CH3CHO ,80 C Thu phn dn xut th 2 ln halogen: RCHCl2 + OH- -> RCH(OH)2 -> RCHO + H2O
2+ 0
ng c Thin
113
Trng THPT Sn ng s 3
5. Mt s anehit thng gp a. Fomanehit HCHO (andehit fomic) L cht kh, c mi xc, tan nhiu trong nc. Dung dch 37 40% gi l fomon (hay fomalin)dng nhiu trong y hc. iu ch: + Trc tip t CH4. CH4 + O2 600 , HCHO + H2O 800 C NO + Oxi ha ru metylic nh oxi khng kh nhit 500 7000C, c xc tc Cu hoc Pt hoc Ag. Anehit fomic c nhiu ng dng quan trng trong cng nghip i sng : + Sn xut cht do phenolfomanehit, keo urefomanehit. + Do c tc dng dit vi khun, c bit vi khun gy thi ra, nn dung dch formanehit c dng ngm xc ng vt, thuc da, ty u... b. Anehit axetic CH3 CHO L cht lng, tan nhiu trong nc, nhit si = 52,4oC, b oxi ho thnh axit acrilic, b kh thnh ru anlylic. iu ch bng cch cho axetilen tc dng vi nc: ,80 C C2H2 + HOH Hg CH3CHO
09 2+ 0
V. Xeton
1. Cu to Cng thc tng qut ca xeton c dng: R C R O Trong R, R' l nhng gc hirocacbon c th ging hoc khc nhau. V d. CH3 C CH3 CH3 C C2H5 O O Axeton etyl metylxeton 2.Tnh cht vt l Axeton l cht lng, cc xeton khc l cht rn, thng c mi thm. Axeton tan v hn trong nc, cc xeton khc c tan gim dn khi mch C tng. Axeton dng lm dung mi v nguyn liu du tng hp mt s cht hu c. 3. Tnh cht ho hc Kh nng phn ng km anehit a. Kh b oxi ho. Khng c phn ng trng gng v khng c phn ng vi Cu(OH)2. Khi oxi ho mnh th t mch cacbon. To thnh axit cacboxylic. CH3 C C2H5 + [O] -> CH3COOH + C2H5COOH O etyl metylxeton b. Phn ng cng Kh bng H2 thnh ru bc 2. CH3 C C2H5 + H2 -> CH3 CH(OH) C2H5 O
ng c Thin
114
Trng THPT Sn ng s 3
etyl metylxeton 4. iu ch Tch H2 khi ru bc 2: Oxi ho ru bc 2. Thy phn dn xut th 2 ln halogen: R CHCl2 R + HOH -> R CH(OH)2 R -> R CO R +H2O Cng nc vo ng ng ca axetilen R C CH + HOH -> R CO CH3
VI. Axit axetic v dy ng ng

1. Cng thc - cu to - cch gi tn a. Cng thc. Axit hu c (cn gi l axit cacboxylic) l nhng hp cht hu c m phn t c mt hay nhiu nhm cacboxyl (COOH) lin kt vi gc hirocacbon. Cng thc tng qut: R(COOH)n R c th l H hay gc hirocacbon. + R = 0, n = 2 axit oxalic: HOOC COOH + Nu R l gc hirocacbon cha no, ta c axit cha no. + Nu R c nhm chc khc cha axit, ta c axit tp chc. Axit no, n chc c cng thc tng qut: CnH2n + 1COOH (n 0) b. Cu to: Trong nhm:
O C O H
Do nguyn t O ht mnh cp electron lin kt ca lin kt i C = O lm tng phn cc ca lin kt O H. Nguyn t H tr nn linh ng, d tch ra. Do vy tnh axit y th hin mnh hn nhiu so vi phenol.
O C O H
*nh hng ca gc R n nhm - COOH: + Khi R l gc ankyl c hiu ng cm ng +I (y electron) th lm gim tnh axit. Gc R cng ln hay bc cng cao. +I cng ln, th tnh axit cng yu. V d: Tnh axit gim dn trong dy sau. CH3COOH > C2H5COOH > (CH3)2CHCOOH + Khi trong gc R c nhm th gy hiu ng cm ng I (nh F > Cl > Br > I hay NO2 > F > Cl > OH) th lm tng tnh axit. V d: Tnh axit tng theo dy sau. CH3COOH < CH2Br COOH < ClCH2 - COOH + Khi trong gc R c lin kt bi: gy hiuc ng I lm tng tnh axit: V d: CH2 = CH COOH > CH3 CH2 - COOH + Khi c 2 nhm COOH trong 1 phn t, do nh hng ln nhau nn cng lm tng tnh axit. * nh hng ca nhm COOH n gc R:
ng c Thin
115
Trng THPT Sn ng s 3
Nhm COOH ht electron gy ra hiu ng I lm cho H nh C v tr tr nn linh ng, d b th. V d: CH3 CH2 COOH + Cl2 -> CH3 CHCl - COOH c. Cch gi tn + Tn thng thng: Thng bt ngun t tn ngun nguyn liu u tin dng tch c axit. V d Axit fomic (axit kin), axit axetic (axit gim) + Danh php quc t: Tn axit = Tn hirocacbon tng ng(c nguyn t C ca nhm chc) + oic. CH3 CH2 COOH : propanoic CH2 = CH CH2 COOH : butenoic. Bng 6: Tn gi ca mt s axit no n chc
Cng thc H - COOH CH3 - COOH CH3 - CH2 - COOH CH3 - CH2 - CH2 - COOH
(CH3)2CH - COOH
Tn thng thng Axit fomic Axit axetic Axit propionic Axit n - butiric Axit iso - butiric
Tn quc t Axit metanoic Axit etanoic Axit propanoic Axit butanoic Axit 2 - metylpropanoic
2. Tnh cht vt l ca axit no, n chc mch h (CnH2n+1 COOH) Ba cht u dy ng ng l cht lng, c v chua, tan v hn trong nc, in li yu trong dung dch. Nhng cht sau l cht lng, ri cht rn, tan gim dn. Nhit si tng dn theo n. Gia cc phn t axit cng xy ra hin tng lin hp phn t do lin kt hiro.
O ... H C O H ... O O C
Do , axit c nhit si cao hn anehit v ru tng ng Th d : Nhit si ca axit axetic l 1180C, ca ru etylic l 78,30C. 3. Tnh cht ho hc Phn ng ha hc ca axit cacboxylic xy ra ch yu nhm cacboxyl. l phn ng th nguyn t hiro ca nhm COOH (tnh axit), phn ng th c nhm hiroxyl ca nhm COOH (phn ng este ha). a. Tnh axit Cc axit trong dy ng ng ca axit axetic c y tnh cht ca axit yu + Trong dung dch nc in li ra ion H+ (H3O), lm giy qu (axit yu). RCOOH + HOH RCOO- + H3O+ R cng nhiu C, axit in li cng yu. + Phn ng trung ho RCOOH + NaOH -> RCOONa + H2O + Ho tan kim loi ng trc H trong dy hot ng: 2CH3COOH + Zn -> (CH3COO)2Zn + H2 + y mnh axit yu hn ra khi mui: 2CH3COOH + CaCO3 -> (CH3COO)2Ca + CO2 + H2O
ng c Thin
116
Trng THPT Sn ng s 3
b. Phn ng do nhm OH ca COOH + Phn ng este ho vi ru: c H2SO4 c lm xc tc CH3COOH + C2H5OH CH3COOC2H5 + H2O c im ca phn ng este ha l thun nghch. Mun cn bng chuyn dch sang pha to thnh etyl axetat cn cho d mt trong hai cht u (ru etylic hoc axit axetic), ng thi chng ct ly ngay etyl axetat ra khi hn hp phn ng. Ngoi vai tr xc tc, axit sunfuric c cn c tc dng ht nc sinh ra chuyn dch cn bng sang pha to thnh este. + Phn ng to thnh halogenua axit: RCOOH + PCl5 -> RCOCl + PCl3 + HCl + Phn ng hp H2 to thnh anehit ,t RCOOH + H2 Ni RCHO + H2O + Phn ng to thnh anhirit axit: O 2RCOOH P (RCO)2O + H2O + Phn ng to thnh amit v nitrin RCOOH + NH3 -> RCOONH4 RCOONH4 t RCONH2 + H2O amit P O ,t RCONH2 RCN + H2O Nitrin Do phn t axit cn cha gc hirocacbon nn ngoi nhng tnh cht nu trn, axit cn th hin cc tnh cht ca gc R: phn ng th, cng, trng hp,
0 2 5 0 2 5 0
4. iu ch a. Thu phn este CH3COOC2H5 + H2O CH3COOH + C2H5OH Nu qu trnh thy phn xy ra trong mi trng kim th sn phm phn ng l x phng v phn ng c gi l phn ng x phng ha. b. Oxi ho cc hirocacbon Oxi ho hirocacbon no bng O2 ca khng kh vi cht xc tc (cc mui Cu2+, Mn2+, Cr3+,) P = 7 20 atm v un nng s thu c axit bo c t 10 -20 nguyn t C trong phn t. c. T anehit ,t RCHO + 1/2O2 Mn RCOOH d. Thy phn dn xut trihalogen RCl3 + NaOH -> RC(OH)3 -> RCOOH e. Tng hp qua nitrin RCN + H2O -> RC(OH)3 -> RCOOH 5. Gii thiu mt s axit a. Axit fomic H COOH L cht lng, khng mu, tan nhiu trong nc, c mi xc, nhit si = 100,5oC. Trong phn t c nhm chc anehit CHO nn c tnh kh mnh ca anehit. V d: HCOOH + 2AgNO3 + 4NH3 + H2O -> (NH4)2CO3 + 2Ag + 2NH4NO3 5HCOOH + 2KMnO4 + 3H2SO4-> 5CO2 + K2SO4 + 2MnSO4 + 8H2O Axit fomic c trong nc kin, trong mt s tri cy, trong m hi ng vt. iu ch: c th iu ch t CO v NaOH (cho CO i qua kim nng)
2+ 0
ng c Thin
117
Trng THPT Sn ng s 3
CO + NaOH t HCOONa 2HCOONa + H2SO4 -> 2HCOOH + Na2SO4 Axit fomic c dng lm cht kh trong ngnh nhum, tng hp cc hp cht hu c khc. b. Axit axetic CH3 COOH L cht lng, khng mu, tan nhiu trong nc, c mi chua, xc, nhit si = 118,5oC. iu ch : ngoi cc phng php chung, axit axetic cn c iu ch bng nhng cch sau. + i t axetilen. C2H2 + HOH , Hg C CH3CHO + O ,Mn CH3COOH ,80 + Cho ru etylic ln men gim C2H5OH mengiam CH3COOH + H2O + Chng kh g: trong lp nc c 10% CH3COOH. Trung ho bng vi thnh (CH3COO)2Ca. Tch mui ra ri ch ho bng H2SO4 thu axit axetic. - ng dng: + Axit axetic c dng iu ch mt s mui axetat kim loi dng lm cht cm mu trong cng nghip nhum (nh nhm axetat, st axetat, crom axetat), lm nguyn liu sn xut bt sn (nh ng axetat, ch axetat). + Axit axetic l mt trong nhng nguyn liu iu ch xenluloz axetat dng cho cng nghip sn xut t nhn to, phim khng chy. + Axit axetic cn c dng iu ch mt s este lm cht thm (xem bi este) lm thuc cha bnh (aspirin). + Dung dch axit axetic 2 - 5% (sn phm ca qu trnh ln men gim t ru etylic, ng, mt) c dng lm gim n. c. Axit bo c KLPT ln Quan trng nht l C15H31COOH C17H35COOH (axit panmitic) (axit stearic) C hai u c cu to mch thng, khng phn nhnh. L nhng cht rn nh sp, khng mu. Khng tan trong nc nhng tan nhiu trong dung mi hu c. Phn ng vi kim v tan trong dung dch kim. RCOOH + NaOH -> RCOONa + H2O Mui ca cc axit ny vi Mg v kim loi kim th (Ca, Ba, ) khng tan trong nc. Mui natri ca axit panmitic n - C15H31COOH v stearic n - C17H35COOH c dng lm x phng. d. Gii thiu mt s axit cha no + Axit acrylic CH2 = CH COOH L cht lng khng mu, mi xc, tan v hn trong nc, tan nhiu trong ru, ete. Este ca axit acrylic dng sn xut cht do. + Axit metacrylic: CH2 = C COOH
2+ 0 2 2+
CH3 L cht lng khng mu, tan c trong nc, ru, ete. Este ca n vi ru metylic c trng hp ch to thu tinh hu c (plexiglat). CH3
ng c Thin
118
Trng THPT Sn ng s 3
nCH2 = C COOCH3 xt , p - CH2 = C ,t

0
CH3 COOH n Thy tinh hu c rt cng, khng gin v trong sut. Polimetyl metacrylat c dng ch to lng knh, thu knh, vt liu cho k thut laze, lm rng gi + Axit sorbic CH3 CH = CH CH = CH COOH Cht tinh th mu trng, t tan trong nc. Dng bo qun thc phm. + Axit oleic CH3 (CH2)7 CH = CH (CH2)7 COOH L cht lng nh du. C trong du ng, thc vt di dng este vi glixerin, c bit c ti 80% trong du oliu. Phn ng vi hiro to thnh axit stearic. Mui oleat ca Na, K dng lm x phng git. Cc oleat ca Ca, Mg khng tan trong nc. e. Gii thiu mt s axit a chc + Axit oxalic HOOC COOH L cht tinh th, thng dng C2H2O4 . 2H2O. Khi un nng d b mt CO2. HOOC - COOH t CO2 + HCOOH D b oxi ho 5HOOC COOH + 2KMnO4 + 3H2SO4 -> 10CO2 + K2SO4 + 2MnSO4 + 8H2O Axit oxalic c dng lm cht kh v chun xc nh nng KMnO4.trc khi tin hnh th nghim iu ch HCOONa 400 NaOOC COONa + H2 C NaOOC COONa + 2HCl -> HOOC COOH + 2NaCl + Axit aipic HOOC (CH2)4 COOH Dng sn xut nha tng hp (amit), si tng hp (nilon 6,6) iu ch Oxi ha xiclohexan (ly t du m). f.Gii thiu mt s axit thm + Axit benzoic C6H5 COOH L cht tinh th hnh kim, khng mu, nhit si = 122,4oC. t tan trong nc lnh, tan nhiu hn trong nc nng. C tnh st trng, c dng trong y hc, bo qun thc phm, tng hp cc hp cht hu c (thuc nhum) iu ch: Oxi ho toluen c xc tc C6H5CH3 + [O] -> C6H5COOH + Axit phtalic C6H4(COOH)2 Thng gp dng ortho v para.
0 0
Co o H
Co o H Co o H
v
ng c Thin
Co o H
119
Trng THPT Sn ng s 3
Axit ortho - phtalic l cht tinh th, tan nhiu trong nc nng. Khi un nng, khng nng chy m b mt nc to thnh anhirit phtalic.
Co o H Co o H t0 CO CO O + H2O
iu ch bng cch oxi ho naphtalen

Co o H Co o H +9/2O2 +2CO2 + H2O
+ Axit salixilic HO C6H4 COOH L cht tinh th, nhit nng chy = 159oC, t tan trong nc, tan trong cc dung mi hu c. Dng lm thuc st trng, ch thuc cha bnh, bo qun thc phm. g. Gii thiu mt s axit c nhm chc pha tp + Axit glyconic: HO CH2 - COOH L cht tinh th khng mu, tan nhiu trong nc. Tnh axit mnh hn axit axetic (K = 1,48 . 104). C trong nhiu loi thc vt (c ci ng, nho), trong qu cha chn. + Axit lactic ( hiroxi propionic)
CH3 - CH - Co o H OH
L cht tinh th, khng mu, ht m mnh v chy ra. Tan nhiu trong nc. C trong sa chua, to thnh khi ln men lactic mt s cht ng. V d.
C6H12O6
2CH 3 - CH - Co o H OH
Axit lactic c dng trong cng nghip thuc nhum (cm mu), cng nghip thuc da, cng nghip thc phm v dc phm. + Axit malic (axit to)
Ho o C - CH - CH2 - Co o H OH
L cht tinh th, tan nhiu trong nc. C cha trong mt s qu (to, nho). Dng trong cng nghip thc phm. + Axit tactric
Ho o C - CH - CH - Co o H OH OH
L cht tinh th, tan nhiu trong nc. C nhiu trong cc loi qu, c bit l nho (nn c tn l axit ru vang) Mui kali - natri tactrat.
ng c Thin
120
Trng THPT Sn ng s 3
KOOC CHOH CHOH COONa Ho tan c Cu(OH)2 to thnh dung dch Feling, dng lm thuc th anehit v cc hiratcacbon.
Ko o C - CH - CH - Co o N a O O
Cu
+ Axit limonic hay axit xitric (axit chanh)

OH Ho o C - CH2 - C - CH2 - Co o H COOH
L cht tinh th, tan nhiu trong nc. C nhiu trong chanh v mt s qu chua khc.
VII. Este Cht bo

1. Cu to v gi tn a. Cng thc Este l sn phm ca phn ng este ho gia axit hu c hoc axit v c vi ru. V d: CH3COOH + HOCH3 CH3COOCH3 + H2O CH3CH2OH + HCl CH3CH2Cl + H2O C th phn este thnh cc loi Loi 1: Este ca axit n chc v ru n chc c cng thc cu to chung RCOOR Gc R v R' c th ging nhau, hoc khc nhau, c th l gc hirocacbon no hoc khng no Nu R v R' u l gc no mch h th CTPT chung ca este l: CnH2nO2 (n 2) Loi 2: Este ca axit a chc v ru n chc. Cng thc chung l R - (COOR')n, trong R' l gc ru ho tr 1. Loi este ny c: este trung ho v este axit. V d: CH3 OCO (CH2)4 COO CH3 imetyl aipat CH3 OCO (CH2)4 COOH metyl hiroaipat Loi 3: Este ca axit n chc v ru a chc. Cng thc chung l (R - COO)n - R'. V d:
C17H35 - Co O - CH2 C17H35 - Co O - CH C17H35 - Co O - CH2
H2SO4
Hoc:
CH3 - Co O - CH2 C2H5 - Co O - CH2
b. Tn gi Tn thng thng ca este c gi nh sau Tn este = Tn gc hirocacbon ca ru + tn gc axit ( i ui ic -> at) V d: CH3COOC2H5: etyl axetat
ng c Thin
121
Trng THPT Sn ng s 3
CH2 = CH COOCH3: metyl acrylat 2. Tnh cht vt l Este ca cc ru n chc v axit n chc (c s nguyn t C khng ln lm) thng l cht lng, d bay hi, c mi thm d chu ca cc loi hoa qu khc nhau. Nhng este c KLPT cao thng l cht rn. Nhit si ca este so vi axit cng CTPT thp hn v khng c s to thnh lin kt hiro. Cc este t tan trong nc (so vi axit v ru to ra n), nhng tan nhiu trong cc dung mi hu c. 3. Tnh cht ho hc Tnh cht ho hc quan trng nht ca este l phn ng thy phn (phn ng vi nc). Qu trnh thy phn c thc hin trong dung dch axit hoc baz. a. Trong dung dch axit : un nng este vi nc, c axit v c xc tc, phn ng to ra axit cacboxylic v ru. Nhng cng trong iu kin , axit cacboxylic v ru li phn ng vi nhau cho este. Th d : CH3COOC2H5 + HOH CH3COOH + C2H5OH Phn ng theo chiu t tri sang phi l phn ng thy phn este, phn ng theo chiu t phi sang tri l phn ng este ha. Vy phn ng thy phn este trong dung dch axit l phn ng thun nghch. b.Trong dung dch baz : un nng este trong dung dch natri hiroxit, phn ng to mui ca axit cacboxylic v ru. Th d : CH3COOC2H5 + NaOH t CH3COONa + C2H5OH l phn ng khng thun nghch, v khng cn axit cacboxylic phn ng vi ru to li este. Phn ng ny cn c gi l phn ng x phng ha. Ngoi kh nng tham gia phn ng thy phn, cc este cn c cc phn ng c trng ca cc gc hirocacbon : gc no -> phn ng th; gc cha no -> phn ng cng, trng hp, 4. iu ch a. Thc hin phn ng este ho CH3COOH + C2H5OH CH3COOC2H5 + HOH b. T mui v dn xut halogen ca hirocacbon CH3COOAg + C2H5Cl -> CH3COOC2H5 + AgCl c. T halogenua axit v ancolat. CH3COCl + NaOCH3 -> CH3COOCH3 + NaCl d. T anhirit axit v ru (CH3CO)2O + HOCH3 -> CH3COOCH3 + CH3COOH 5. Gii thiu mt s este thng gp a. Etyl axetat CH3 COO C2H5 L cht lng khng mu, mi c trng, nhit si = 77oC. t tan trong nc. c dng lm dung mi cho hp cht cao phn t v dng ch to sn. b. Isoamyl axetat CH3COOCH2CH2CH (CH3)2
ng c Thin
H+
0
H+
122
Trng THPT Sn ng s 3
L cht lng khng mu, mi l, nhit si = 142oC Hu nh khng tan trong nc. Dng lm dung mi v lm cht thm trong ngnh thc phm v hng liu c. Este ca cc loi hoa qu. To thnh mi thm ca cc hoa qu. V d Etyl fomiat HCOO C2H5 : mi ru rum Amyl fomiat HCOO C5H11 : mi anh o. Etyl butyrat C3H7 COO C2H5 : mi m Isoamyl butyrat C3H7 COO C5H11 : mi da. d. Este ca axit acrylic v axit metacrylic C 2 este u d trng hp to thnh cc polime poliacrilat trong sut, khng mu. V d: CH3 nCH2 = C COOCH3 xt , p - CH2 = C ,t
0
COOH n Polimetyl metacrylat Polimetyl acrilat dng sn xut mng keo, da nhn to. Polimetyl metacrilat dng ch thu tinh hu c c trong sut cao hn thu tinh silicat, cho tia t ngoi i qua, ch rng gi, mt gi. 6. Lipit _Cht bo a. Thnh phn Cht bo (ngun gc ng vt, thc vt) l este ca glixerin vi axit bo (axit hu c mt ln axit mch thng, khi lng phn t ln). Cc cht bo c gi chung l glixerit. Cng thc tng qut ca cht bo.
R1 - Co O - CH2 R2 - Co O - CH R3 - Co O - CH2
CH3
Mt s axit bo thng gp. Axit panmitic: C15H31COOH Axit stearic: C17H35COOH Axit oleic: C17H33COOH Axit linoleic: C17H31COOH Thng gp cc glixerit pha tp. V d:
C15H31 - Co O -CH2 C17H33 - Co O - CH C17H35 - Co O - CH2
Trong R1, R2, R3 c th ging nhau hoc khc nhau.
Trong cht bo, ngoi este ca glixerin vi axit bo cn c mt lng nh axit dng t do c c trng bi ch s axit. Ch s axit ca mt cht bo l s miligam KOH cn thit trung ho axit t do trong mt gam cht bo. V d: Mt cht bo c ch s axit bng 9 - Ngha l trung ho 1 gam cht bo cn 9 mg KOH
ng c Thin
123
Trng THPT Sn ng s 3
b. Tnh cht vt l Cc cht bo thc t khng tan trong nc nhng tan nhiu trong ru, ete v cc dung mi hu c khc. ph thuc thnh phn axit trong cht bo: nu cht bo ch yu t axit no th th rn (m), ch yu t axit cha no th th lng (du). Cht bo ng vt : glixerit ca axit no panmitic, stearic nn th rn. Cht bo thc vt : glixerit ca axit cha no oleic nn th lng. c. Tnh cht ho hc: Do cht bo l este ca glixerin vi cc axit bo nn phn ng c trng ca cht bo cng l phn ng thy phn. S thy phn cc cht bo c thc hin trong cc mi trng nh sau: + Trong mi trng nc hoc axit Cht bo t tan trong nc nn khng b thu phn bi nc lnh hay nc si. thu phn cht bo phi un nng trong nc p sut cao (25atm) t n nhit cao (220oC):
R1 - Co O - CH2 R2 - Co O - CH R3 - Co O - CH2 +3H2O CH2 - OH CH - OH CH2 - OH + R1 - Co OH R2 - Co OH R3 - Co OH
C th dng axit v c (axit sunfuric long) tng tc phn ng thu phn. Axit bo khng tan trong nc, c tch ra. +Trong mi trng kim (phn ng x phng ho): Nu cht bo vi kim :
R1 - Co O - CH2 R2 - Co O - CH +3NaOH R3 - Co O - CH2 t0 CH2 - OH CH - OH CH2 - OH + R1 - Co ONa R2 - Co ONa R3 - Co ONa
Cc mui to thnh l x phng tan trong dung dch. Khi thm NaCl vo hn hp phn ng, x phng s ni ln thnh lp, ng c. Glixerin tan trong dung dch c tch bng cch chng phn on. Cc glixerit cha no (du thc vt) c kh nng tham gia phn ng cng H2, d b oxi ha cc lin kt i: + Phn ng cng hiro (s hiro ho) bin glixerit cha no (du) thnh glixerit no (m). V d: ,t (C17H33COO)3C3H5 + 3H2 Ni (C17H35COO)3C3H5 + Lm mt mu dung dch KMnO4. + B oxi ho bi oxi ca khng kh. d. ng dng ca cht bo Dng lm thc phm: khi n, nh men ca dch ty, cht bo b thu phn thnh axit bo v glixerin ri b hp th qua mao trng rut vo bn trong rut. Nh qu trnh tiu ho n bin thnh nng lng nui c th. e. S chuyn ha lipit trong c th: Cht bo l mt trong nhng thnh phn c bn trong thc n ca ngi, v n gi mt vai tr quan trng trong qu trnh dinh dng. Khi b oxi ha chm trong c th, cht bo cung cp nhiu nng lng hn cht m (protit) v cht bt (gluxit): 1 gam cht bo cho khong 38,87 kJ, trong khi 1 gam cht m cho khong 23,41 kJ, cn 1 gam cht bt cho khong 17,56 kJ.
0
ng c Thin
124
Trng THPT Sn ng s 3
V cht bo khng tan trong nc, nn chng khng th trc tip thm qua mao trng rut i vo c th. Nh c men ca dch tu v dch trng, cht bo b thy phn thnh glixerin v axit bo. Glixerin c hp th trc tip, cn axit bo khi tc dng vi mt bin thnh dng tan v cng c hp th qua mao trng rut vo thnh rut. glixerin v axit bo kt hp vi nhau. Cht bo mi c tng hp i vo mu v chuyn vo m m. T cc m ny, cht bo li c th i ti cc m v c quan khc. y cc cht bo b thy phn v b oxi ha chm thnh kh cacbonic v hi nc, ng thi gii phng nng lng cung cp cho s hot ng ca c th. Khi n nhiu cht bo, hoc khi cht bo trong c th khng c oxi ha ht th lng cn d c tch li thnh nhng m m. 7. X phng v cc cht ty ra tng hp a. Thnh phn X phng l mui ca kim loi kim (Na, K) vi cc axit bo khi lng phn t ln (c mch cacbon di > 12 nguyn t C) Cc axit bo ch yu sn xut x phng l panmitic, stearic, oleic. X phng rn l hn hp mui Na ca cc axit bo, ch yu l natri stearat, natri panmiat. Cc x phng K u l x phng lng. b. iu ch x phng + Ho tan cc axit bo vo dung dch kim (xa) RCOOH + NaOH -> RCOONa + H2O Cc axit bo c th iu ch t du m bng cch oxi ho cc parafin c s nguyn t cacbon ln hn 30 bng oxi (khng kh) c mui mangan xc tc: RCH2CH2R +
2+ 5 O2 Mn RCOONa + RCOONa + H2O 2
+ un nng cht bo vi kim (x phng ho cht bo) c. Tc dng ty ra ca x phng Phn t x phng gm Mt gc hirocacbon mch di (v d C15H31, C17H35, C17H33,) kh tan trong nc nhng d tan trong cc dung mi khng cc (nh du, m). Mt nhm phn cc (l COONa hay COOK) c kh nng in li thnh ion nn d tan trong nc,nhng khng tan trong du m. V vy x phng c tnh cht c bit l tnh hot ng b mt. X phng lm gim sc cng b mt ca nc, lm cho nc d thm t cc git du, m v cc cht bn trn b mt. Khi git, ra bng x phng, gc R ca phn t x phng bm vo cht bn, nhm phn cc (COONa) chuyn (ho tan) cht bn vo nc di dng nh tng hay huyn ph, do lm sch vt git, ra. Mt khc, x phng l mui ca axit yu nn phn t x phng b thu phn to ra mi trng kim gip cho vic nh tng ho cht keo: RCOONa + HOH -> RCOOH + NaOH Trong nc cng x phng to thnh cc mui panmiat, oleat, stearat (canxi, magie, st) kt ta, do x phng mt tc dng ty ra. d. Cc cht ty ra tng hp Ngoi x phng thng, hin nay ngi ta cn dng nhiu loi cht ty ra tng hp khc nhau. cng l nhng cht hot ng b mt, thuc my loi sau. + Nhng cht ty ra sinh ion (iongen) Phn t gm gc hirocacbon R v nhm phn cc. Ngoi loi R - COONa, cn c nhng cht hot ng b mt nh ion phc tp.
ng c Thin
125
Trng THPT Sn ng s 3
V d: Cc ankyl sunfat: R O SO3Na (R c > 11C) Cc ankyl sunfonat: R SO3Na, iu ch bng cch. RH + HO SO2 OH -> RSO2 OH + NaOH R O SO3Na (R c 10 20 nguyn t C) Cc ankyl aryl sunfonat: R C6H4 SO3Na Nhng cht hot ng b mt nh cation phc tp. V d : C18H37NH3Cl; C16H33(CH3)3NCl; + Nhng cht ty ra khng sinh ion Phn t cha gc R khng phn cc v cc nhm phn cc nh OH, O (ete). V d: ROH + nCH2 CH2 -> R (O CH2 CH2)n OH O R : c th c ti 18C, n : c th bng 6 30 tu theo cng dng. Cc cht ty ra trn vn gi c tc dng ty ra c trong mi trng axit v nc cng.
VIII. Gluxit
Gluxit l nhng hp cht hu c tp chc, c cha nhiu nhm hiroxyl (- OH) v c nhm cacbonyl (- CO -) trong phn t. Gluxit bao gm nhiu loi khc nhau, quan trng nht l cc loi sau y: a) Monosaccarit l nhng gluxit n gin nht, khng b thu phn thnh nhng gluxit n gin hn. V d: glucoz, fructoz (C6H12O6), riboz (C5H10O5) b) Oligosaccarit l nhng sn phm ngng t t 2 n 10 phn t monosaccarit vi s tch bt nc. Quan trng nht l cc isaccarit hay ioz c cng thc chung C12H22O11. Cc isaccarit ny b thu phn to thnh 2 phn t monosaccarit. V d thu phn saccaroz. C12H22O11 + HOH -> C6H12O6 + C6H12O6 c) Polisaccarit l nhng hp cht cao phn t. Khi b thy phn, polisaccarit to thnh mt s ln phn t monosaccarit. V d: Tinh bt, xenluloz, glicogen u c cng thc chung l (C6H10O5)n. (C6H10O5)n + nHOH -> nC6H12O6 1. Monosaccarit a. Cng thc v cu to (C6H12O6) Monosaccarit l nhng hp cht tp chc m trong phn t ngoi nhm cn c nhiu nhm chc OH nhng nguyn t cacbon k nhau. Nu nhm dng anehit (c nhm CH = O), ta gi monosaccarit l anoz, nu nhm dng xeton, ta c xetoz.
CH 2 - OH
CHO (CH - OH)4 CH2 - OH
C=o
C=O (CH - OH) 3 CH 2 - OH
Anoz
ng c Thin
xetoz
126
Trng THPT Sn ng s 3
Tu theo s nguyn t cacbon trong phn t, monosaccarit (anoz v xetoz) c gi l trioz (3C), tetroz (4C), pentoz (5C), hexoz (6C), heptoz (7C). Nhng monosaccarit quan trng u l hexoz v sau l pentoz. V d: glucoz, fructoz, Ngoi ng phn cu to (anoz v xetoz), monossaccarit cn c ng phn khng gian gi l ng phn quang hc, mi ng phn khng gian li c tn ring. b. Cu to dng mch h ca glucoz. Glucoz tham gia phn ng trng bc v kh c Cu2+, do vy phn t phi c nhm chc anehit (CH = O). Glucoz tc dng vi (CH3CO)2O sinh ra pentaeste C6H7O(OCOCH3)5, chng t trong phn t c 5 nhm -OH; cc nhm -OH c th to phc cht mu xanh lam khi tc dng vi Cu(OH)2 (tng t nh glixerin). T cc kt qu thc nghim, ngi ta thy rng glucoz l mt pentahiroxi anehit c mch thng khng phn nhnh.
CHO (CH - OH)4 CH2 - OH
Do s phn b khc nhau ca cc nhm OH trong khng gian, glucoz c nhiu ng phn khng gian. Glucoz thin nhin, c gi l D-glucoz (c nhm OH ti C5 bn phi) phn bit vi mt ng phn iu ch trong phng th nghim l L-glucoz (nhm OH bn tri). Cng thc cu to ca cp i quang nh sau:
CHO
H HO H H C C C C OH H OH OH HO H HO HO
CHO
C C C C H OH H H
CH2 - OH
D glucoz
CH2 - OH
L glucoz
c. Cu trc dng vng ca glucoz Ngoi dng mch h, glucoz cn c cc dng mch vng 6 cnh hoc 5 cnh: Dng vng 6 cnh c gi l glucopiranoz v vng ny c dng ca d vng piran, cn vng 5 cnh c gi l glucofuranoz v c dng d vng furan.
CH 2 - OH
H HO
CH2 - OH
O
H OH H
OH H
HO
OH H OH H
H OH H
OH
Glucopiranoz glucofuranz. Glucopiranoz bn hn rt nhiu so vi glucofuranz. d. Tnh cht vt l - trng thi t nhin Monosaccarit l nhng cht rn khng mu, c v ngt, d tan trong nc, khng tan trong dung mi hu c, c kh nng lm quay mt phng nh sng phn cc. Trong thin nhin, glucoz c trong hu ht cc b phn c th thc vt: r, l, hoa v nht l trong qu chn. Glucoz cng c trong c th ngi, ng vt. Trong mt ong c trn 30% glucoz. Trong mu ngi lun cha mt t l glucoz khng i l 0,1%. Fructoz trng thi t do trong qu cy, mt ong. V ngt ca mt ong ch yu do fructoz.
ng c Thin
127
Trng THPT Sn ng s 3
e. Tnh cht ho hc + Phn ng ca nhm anehit CH = O Tnh oxi ho nhm chc anehit thnh nhm chc axit. Khi glucoz tr thnh axit gluconic. + Phn ng trng gng. CH2OH (CHOH)4 CHO + Ag2O NH CH2OH (CHOH)4 COOH + 2Ag + Phn ng vi Cu(OH)2 (trong mi trng kim) CH2OH (CHOH)4 CHO + 2Cu(OH)2 -> CH2OH (CHOH)4 COOH + Cu2O + 2H2O (mu gch) + B oxi ho trong mi trng trung tnh v axit, v d nh: CH2OH (CHOH)4 CHO + HOBr -> CH2OH (CHOH)4 COOH +HBr - Tnh kh : Khi cho monosaccarit tc dng vi H2 thu c ru 6 ln ru. CH2OH (CHOH)4 CHO + H2 -> CH2OH (CHOH)4 CH2OH + Phn ng ca cc nhm OH (tnh cht ca ru a chc) Phn ng vi Cu(OH)2 cho dung dch mu xanh lam. - To este cha 5 gc axit trong phn t. + Phn ng ca glucoz dng vng: Nhm OH nguyn tr C1 trong phn t glucoz dng vng linh ng hn cc nhm OH khc nn d dng to ete vi cc phn t ru khc (v d vi CH3OH) to thnh glucozit:
3
CH2 - OH
H HO
CH2 - OH
H OH + HO - R H HO
O
H OH H
O
H OH H
H + HOH O-R
OH
OH
To este c cha 5 gc axit mt ln axit. V d glucoz phn ng vi anhirit axetic (CH3CO)2O to thnh pentaaxetyl glucoz + Phn ng ln men Di tc dng ca cc cht xc tc men do vi sinh vt tit ra, cht ng b phn tch thnh cc sn phm khc. Cc cht men khc nhau gy ra nhng qu trnh ln men khc nhau. V d: Ln men etylic to thnh ru etylic. C6H12O6 -> 2C2H5OH + 2CO2 Ln men butyric to thnh axit butyric: C6H12O6 -> CH3 CH2 CH2 COOH + 2H2 + 2CO2 Ln men lactic to thnh axit lactic: C6H12O6 -> 2CH3 CHOH - COOH Ln men limonic to thnh axit limonic: C6H12O6 + 3O -> HOOC CH2 COH(COOH) CH2 - COOH f. iu ch + Qu trnh quang hp ca cy xanh di tc dng ca bc x mt tri, to thnh glucoz v cc monosaccarit khc: 6CO2 + 6H2O -> C6H12O6 + 6O2 + Thu phn i, polisaccarit c trong thin nhin (nh saccaroz, tinh bt, xenluloz) di tc dng ca axit v c hay men.
ng c Thin
128
Trng THPT Sn ng s 3
C12H22O11 + HOH -> C6H12O6 + C6H12O6 (glucoz) (fructoz) (C6H10O5)n + nH2O -> nC6H12O6 + Trng hp anehit fomic 6HCHO Ca (OH ) C6H12O6 (glucoz) g. ng dng: Glucoz l thc n c gi tr cho ngi. Trong y hc dng lm thuc tng lc (huyt thanh glucoz) cho ngi bnh, v glucoz d c tiu ho v cung cp nhiu nng lng cho c th. Glucoz l nguyn liu tng hp vitamin C. Trong cng nghip, glucoz c dng trng gng, trng rut phch (bnh thu). 2. isaccarit isaccarit l loi gluxit phc tp hn, khi thu phn cho hai phn t monosaccarit. Nhng monosaccarit tiu biu v quan trng l saccaroz, mantoz, lactoz u c cng thc phn t C12H22O11. a. Tnh cht vt l Tt c cc isaccarit u l nhng cht rn khng mu, kt tinh c v tan tt trong nc. Saccaroz c nhiu nht trong cy ma, c ci ng, cy tht nt. (Lng Saccaroz trong nc ma p c khong 20%, trong nc c ci ng khong 10 - 20% b. Tnh cht ha hc + Phn ng thu phn H Saccaroz + HOH Glucoz + fructoz H Mantoz + HOH 2Glucoz Lactoz + HOH -> glucoz + galactoz (Lactoz l isaccarit c trong sa) + Tnh cht ca nhm anehit Saccaroz khng c nhm chc anehit nn khng tham gia phn ng trng gng v phn ng vi Cu(OH)2. Mantoz v lactoz khi ho tan trong dung dch chuyn mt phn sang dng tautome c nhm chc anehit nn c phn ng trng gng v phn ng vi Cu(OH)2. + Tnh cht ca ru a chc (tc dng vi Cu(OH)2) v tham gia phn ng to ete v este (phn ng ca ru nhiu ln ru). c. iu ch Cc isaccarit c iu ch t cc ngun nguyn liu thin nhin. V d Saccaroz ly t ma, c ci ng. Saccaroz trong ma tc dng vi sa vi to thnh dung dch canxi saccarat trong sut. Khi sc CO2 vo dung dch canxi saccarat li to thnh saccaroz: C12H22O11. CaO. 2H2O + CO2 -> C12H22O11 + CaCO3 + 2H2O Mantoz l cht ng ch yu trong mch nha (ng mch nha). N l sn phm ca s thu phn tinh bt. Lactoz c trong sa ngi, ng vt (v vy cn c tn l ng sa). Ngoi ra cng tm thy c lactoz trong thc vt. 3. Polisaccarit Polisaccarit l nhng gluxit c cu thnh bi nhiu n v monosaccarit ni vi nhau bng nhng lin kt glicozit. Nhng polisaccarit thng gp: tinh bt, xenluloz, a. Tinh bt (C6H10O5)n + Cu to: Tinh bt l hn hp cc polisaccarit (C6H10O5)n, khc nhau v s n v cu trc ca chui polime. Tinh bt c trong c v ht nhiu loi cy.
2
ng c Thin
129
Trng THPT Sn ng s 3
Cc phn t tinh bt gm 2 loi: Loi amiloz cu to t chui polime khng phn nhnh gm cc mt xch - glucoz mch vng vi n vo khong 200 400 v c khi ti 1000. Gia 2 mt xch l mt cu oxi ni nguyn t C1 ca gc th 1 vi nguyn t C4 ca gc th 2. Cu oxi ny c gi l lin kt -1, 4 glicozit.
CH2 - OH
H
CH2 - OH
H 1 H O 4
O
H OH H
O
H OH H
... O 4
H 1
O ...
OH
OH
Loi amilopectin: Chui polime c s phn nhnh, h s n t 600 - 6000. S hnh thnh mch nhnh l do lin kt - 1,6 glicozit, c biu din nh sau:
CH2 - OH
H
O
H OH H
... O
H 1
O 6
OH H
CH2
5
... O 4
H OH H
H 1
O ...
OH
T l amiloz v amilopectin thay i tu theo tng loi tinh bt, amiloz thng chim 20% v amilopectin chim khong 80%. + Tnh cht vt l: Tinh bt cu to t nhng ht nh c hnh dng v kch thc khc nhau, phn ngoi ca ht tinh bt cu to t amilopectin, phn bn trong cu to t amiloz. Tinh bt l cht bt v nh hnh, mu trng, khng tan trong nc lnh. Khi un si, ch mt phn nh tinh bt tan vo nc, cn phn ch yu tinh bt b phng ln to thnh dung dch keo gi l h tinh bt. + Tnh cht ho hc: H tinh bt + dung dch iot dung dch mu xanh. Tinh bt khng tham gia cc phn ng kh (phn ng trng gng v vi Cu2+) v trong phn t khng c chc anehit. Phn ng thu phn tinh bt thnh glucoz xy ra khi un nng vi xc tc axit v c long hoc nh cc enzim, phng trnh tng qut: (C6H10O5)n + nH2O H nC6H12O6 ,t (glucoz) giai on trung gian c th sinh ra cc extrin (C6H10O5)x (x < n) v mantoz. Qu trnh thu phn din ra theo s sau:
+
0
Tinh bt
Amilaza H2O
extrin Amilaza Mantoz H2O
Mantaza H 2O
Glucoz
+ S to thnh tinh bt t CO2 v H2O: Nng lng mt tri c l cy hp th, chuyn qua cc sc t: clorofin (mu xanh lc), carotin (mu da cam), xantofin (mu vng) v dng thc hin qu trnh quang hp. 6CO2 + 6H2O -> C6H12O6 (glucoz) n C6H12O6 -> (C6H10O5)n + nH2O (tinh bt) + ng dng ca tinh bt Lm lng thc cho ngi v ng vt. iu ch glucoz. iu ch mch nha.
ng c Thin
130
Trng THPT Sn ng s 3
iu ch ru etylic H vi. b. Xenluloz (C6H10O5)n + Cu to phn t: Khc vi tinh bt, cu to phn t ca xenluloz c nhng c im sau: n rt ln ( t 6000 12000 ). Chui polime ca xenluloz l mch thng khng phn nhn, v vy n to thnh si (si bng, si gai, si ay) trong cc chui polime c xp theo cng mt phng v xut hin lc tng tc gia cc chui . Mi mt xch (1 mt xch glucoz) c 3 nhm OH, trong 1 nhm chc ru bc 1 v 2 nhm chc ru bc 2. nhn mnh c im ny, ngi ta thng vit cng thc phn t ca xenluloz nh sau: [C6H7O2(OH)3]n + Tnh cht vt l Xenluloz l cht rn mu trng, khng mi, khng v, c dng si, c tnh thm nc. Xenluloz khng tan trong nc, ete, ru nhng tan trong mt s dung mi c bit nh dung dch Sveze gm Cu(OH)2 trong NH3 c, dung dch H2SO4 c. + Tnh cht ho hc: Bn hn tinh bt (khng to mu xanh vi iot) To thnh este [C6H7O2(OH)3]n + 3nHNO3 -> [C6H7O2(ONO2)3]n + 3nH2O Trinitroxenluloz l cht n mnh, c dng lm thuc sng khng khi. Khi este ho khng hon ton s thu c mono, initroxenluloz dng ch sn, lm phim, keo dn, iu ch t axetat Cc cht trn c iu ch bng phn ng gia xenluloz v anhirit axetic c H2SO4 xc tc: [C6H7O2(OH)3]n + 3n(CH3CO)2O -> [C6H7O2(OCOCH3)3]n + 3nCH3COOH Xenluloz axetat khng d chy nh xenluloz nitrat, c dng ch t nhn to, nha, sn. iu ch t Visco: khi ch ho vi kim c (NaOH) xenluloz b phng ln thnh xenluloz kim l sn phm th khng hon ton. [C6H7O2(OH)3]n + nNaOH -> [C6H7O2(OH)2ONa]n + nH2O Xenluloz kim khi ch ho vi CS2 to thnh xenluloz xantogenat [C6H7O2(OH)2ONa]n + nCS2 -> [(OH)2C6H7O2 O C S - Na]n S Xenluloz xantogenat ho tan trong dung dch kim long thnh dung dch rt nht gi l visco. Khi p visco chy qua l nh vo dung dch axit s thu c si xenluloz hirat, l t visco. [(OH)2C6H7O2 O C S - Na]n + nH2SO4 -> nCS2 + nNaHSO4 + [C6H7O2(OH)3]n S Phn ng thu phn xenluloz. Xenluloz kh b thu phn hn tinh bt. Phi un nng lu vi axit v c long p sut cao, xenluloz thu phn hon ton thu c glucoz: (C6H10O5)n + nH2O H nC6H12O6 ,t (glucoz) + Xenluloz trong t nhin - ng dng
+
0
ng c Thin
131
Trng THPT Sn ng s 3
Xenluloz c nhiu trong si bng (98%), si ay, gaiTrong g c khong 50% xenluloz. Xenluloz c dng lm giy, lm vi, si, t nhn to (v d t visco), thuc sng khng khi, cht do (xenluloit), sn, sn xut ru etylic.
IX. Aminoaxit protit

1. Aminoaxit Aminoaxit l nhng hp cht hu c tp chc, trong phn t ca chng c cha ng thi nhm chc amino (-NH2) v nhm chc cacboxyl (-COOH). a. Cu to: Cng thc tng qut : (NH2)x R (COOH)y Aminoaxit l hp cht hu c tp chc, c cha c nhm NH2 (baz) v nhm -COOH (axit) trong phn t. C th coi aminoaxit l dn xut th NH2 vo nguyn t H gc R ca axit cacboxylic, khi nhm NH2 c th nh vo nhng v tr khc nhau (, , ,) trn mch C. C C C COOH Cc aminoaxit c trong cc cht anbumin t nhin u l -aminoaxit. C nhng aminoaxit trong s nhm NH2 v s nhm COOH khng bng nhau. Tnh axit - baz ca aminoaxit tu thuc vo s nhm ca mi loi. b. Tnh cht vt l Cc aminoaxit u l nhng cht tinh th, nng chy nhit tng i cao ng thi b phn hu. Phn ln u tan trong nc, v ngt, t tan trong dung mi hu c. c. Tnh cht ho hc Aminoaxit c nhm amino, ng thi c nhm cacboxyl trong phn t nn chng va c tnh baz va c tnh axit. Trong dung dch t ion ho thnh lng cc: H2N R COOH H3N+ R COO To mui vi c axit v kim: H2N R COOH + NaOH -> H2N R COONa + H2O H2N R COOH + HCl -> ClH3N R COOH Phn ng este ho vi ru. H2N R COOH + HO C2H5 H2N R COOC2H5 + H2O Phn ng trng ngng to polipeptit + Trng ngng gia 2 phn t to ipeptit. 2H2N R COOH -> H2N R CO NH R COOH + H2O Nhm CO NH c gi l nhm peptit Trng ngng to ra polipeptit nH2N R COOH -> [- NH R CO -]n + nH2O Cc polipeptit thng gp trong thin nhin (protein) d. iu ch. + Thu phn cc cht protein thin nhin
Protein + HOH t aminoaxit
0
H+
+ Tng hp T dn xut halogen ca axit. ClCH2 - R COOH + 2NH3 -> H2N R COOH + NH4Cl Tng hp nh vi sinh vt. e. ng dng
ng c Thin
132
Trng THPT Sn ng s 3
Aminoaxit c coi l cht c s xy dng nn cc cht protit trong c th ng vt v thc vt. Nhiu aminoaxit c dng trong y hc cha bnh, lm thc n nui c th ngi bnh. Mui natri ca axit glutamic (thng c gi l m chnh hay bt ngt) c dng lm gia v cho thc n. Mt s aminoaxit c dng lm nguyn liu sn xut t tng hp. f. Gii thiu mt s aminoaxit + Cc aminoaxit thin nhin c trong protein Glixin: H2N CH2 COOH Alanin: CH3 CH COOH NH2 Cn gi l - aminoaxit propionic.
- Valin CH3 - CH - CH - Co o H
CH3 NH2
- Leuxin: CH3 - CH - CH2 - CH - Co o H

CH3
- Axit glutamic
NH2 Ho o C - CH 2 - CH - Co o H
NH2
L tinh th khng mu, tan trong nc, cho v chua. Mui mononatri glutamat (m chnh) c v ngt ca tht, dng lm gia v.
- Phenyl alanin: C6H5 - CH2 - CH - Co o H
NH2
+ Cc aminoaxit dng Axit - aminocaproic. H2N (CH2)5 COOH Khi trng ngng to thnh poliamit dng ch to t capron. [- HN (CH2)5 CO -]n Axit - aminoenantoic. H2N (CH2)6 COOH Khi trng ngng to thnh polime ch to si tng hp enan.
2. Protit
a. Thnh phn - cu to Thnh phn nguyn t ca protein gm c: C, H, O, N, S v c P, Fe, I, Cu. Protein l nhng polime thin nhin cu to t cc phn t aminoaxit trng ngng vi nhau. S to thnh protein t cc aminoaxit xy ra theo 3 giai on. + Giai on 1: To thnh chui polipeptit nh s hnh thnh cc lin kt peptit. + Giai on 2: Hnh thnh cu trc khng gian dng xon (nh l xo) ca chui polipeptit nh cc lin kt hiro gia nhm CO - ca vng ny vi nhm NH ca vng tip theo.
C = O ... H - N
dng xon, gc R hng ra pha ngoi. + Giai on 3 cc chui polipeptit dng xon cun li thnh cun nh s hnh thnh lin kt ho hc gia cc nhm chc cn li trong gc aminoaxit ca chui polipeptit.
ng c Thin
133
Trng THPT Sn ng s 3
Vi cch cu to nh vy t hn 20 aminoaxit to thnh hng ngn cht protein khc nhau v thnh phn, cu to trong mi c th sinh vt. Mi phn t protein vi cu hnh khng gian xc nh, vi nhm chc bn ngoi hnh xon mang nhng hot tnh sinh hc khc nhau v thc hin nhng chc nng khc nhau trong hot ng sng ca c th. b. Tnh cht: + Cc protein khc nhau to thnh nhng cun khc nhau. C 2 dng chnh. Hnh si: nh t tm, lng, tc. Hnh cu: Nh anbumin ca lng trng trng, huyt thanh, sa. + Tnh tan: rt khc nhau C cht hon ton khng tan trong nc (nh protein ca da, sng, tc) C protein tan c trong nc to dung dch keo hoc tan trong dung dch mui long. Tnh tan ca mt s protein c tnh thun nghch: nu tng nng mui th protein kt ta, nu gim nng mui protein tan. + Hin tng bin tnh ca protein Khi b un nng hay do tc dng ca mui kim loi nng hoc ca axit (HNO3, CH3COOH), protein b kt ta (ng t) km theo hin tng bin tnh. Khi , cc lin kt hiro, lin kt mui amoni, lin kt isunfua, lin kt este b ph hu v lm mt hot tnh sinh hc c trng ca protein. + Tnh lng tnh ca protein V trong phn t protein cn c nhm - NH2 v - COOH t do nn c tnh baz v tnh axit tu thuc vo s lng nhm no chim u th. Trong dung dch, protein c th bin thnh ion lng cc +H3N - R - COO-. Khi tng s in tch dng v in tch m ca ion lng cc bng khng th protein c gi l trng thi ng in. + Thu phn protein H H Protein + H cc polipeptit + H cc peptit + H cc axit amin O , O , O + Phn ng c mu ca protein Tng t peptit v aminoaxit, protein tham gia phn ng cho mu. Phn ng biure: Cho protein tc dng vi mui ng (CuSO4) trong mi trng kim cho mu tm do s to thnh phc cht ca ng (II) vi hai nhm peptit. Phn ng xantoproteinic: Cho HNO3 m c vo protein s xut hin mu vng. Nguyn nhn do phn ng nitro ho vng benzen cc gc aminoaxit to thnh cc hp cht nitro dng thm c mu vng. c. Phn loi protein Gm 2 nhm chnh: + Protein n gin: ch cu to t cc aminoaxit, khi thu phn hu nh khng to thnh cc sn phm khc. Cc protein n gin li c chia thnh nhiu nhm nh. V d: Anbumin: Gm mt s protein tan trong nc, khng kt ta bi dung dch NaCl bo ho nhng kt ta bi (NH4)2SO4 bo ho. ng t khi un nng. C trong lng trng trng, sa. Globulin: Khng tan trong nc, tan trong dung dch mui long, ng t khi un nng. C trong sa, trng. Prolamin: Khng tan trong nc, khng ng t khi un si. C trong la m,ng. - Gluein: Protein thc vt tan trong dung dch kim long. C trong thc go. Histon: Tan trong nc v dung dch axit long.
2
ng c Thin
134
Trng THPT Sn ng s 3
Protamin: L protein n gin nht. Tan trong nc, axit long v kim. Khng ng t khi un nng. + Cc protein phc tp: Cu to t protein v cc thnh phn khc khng phi protein. Khi thu phn, ngoi aminoaxit cn c cc thnh phn khc nh hiratcacbon, axit photphoric. Protein phc tp c chia thnh nhiu nhm. Photphoprotein: c cha axit photphoric. Nucleoprotein: trong thnh phn c axit nucleic. C trong nhn t bo ng, thc vt. Chromoprotein: c trong thnh phn ca mu. Glucoprotein: trong thnh phn c hiratcacbon. Lipoprotein: trong thnh phn c cht bo. d. S chuyn ho protein trong c th Protein l mt thnh phn quan trng nht trong thc n ca ngi v ng vt ti to cc t bo, cc cht men, cc kch thch t, xy dng t bo mi v cung cp nng lng. Khi tiu ho, u tin protein b thu phn (do tc dng ca men) thnh cc polipeptit (trong d dy) ri thnh aminoaxit (trong mt) v c hp th vo mu ri chuyn n cc m t bo ca c th. Phn ch yu ca aminoaxit ny li c tng hp thnh protein ca c th. Mt phn khc tng hp cc hp cht khc cha nit nh axit nucleic, kch thch tMt phn b phn hu v b oxi ho cung cp nng lng cho c th. ng thi vi qu trnh tng hp, trong c th lun xy ra qu trnh phn hu protein qua cc giai on to thnh polipeptit, aminoaxit ri cc sn phm xa hn, nh NH3, ure O = C(NH2)2 to thnh CO2, ncQu trnh tng hp protein tiu th nng lng, qu trnh phn hu protein gii phng nng lng. e. ng dng ca protein Dng lm thc n cho ngi v ng vt. Dng trong cng nghip dt, giy dp, lm keo dn. Mt s protein dng ch to cht do (nh cazein ca sa).
Chng 3 HP CHT CAO PHN T V VT LIU POLIME

I. nh ngha polime Nhng hp cht c khi lng phn t rt ln (thng t hng ngn ti hng triu n v cacbon) do nhiu mt xch lin kt vi nhau c gi l hp cht cao phn t hay polime. Th d : Cao su thin nhin, tinh bt xenluloz, l nhng polime thin nhin. Cao su buna, polietilen, polivinyl clorua l nhng polime tng hp. II. Cu trc v phn loi 1. Thnh phn ho hc ca mch polime a) Polime mch cacbon: Mch C bo ho. V d polietilen. (- CH2 CH2 - )n Mch C cha bo ho. V d cao su Buna: (- CH2 CH = CH CH2 - )n Polime cha nguyn t halogen th. V d P.V.C:
(- CH2 - CH - n ) Cl
Ru polime. V d ru polivinylic:
ng c Thin
135
Trng THPT Sn ng s 3
(- CH2 - CH - n ) OH
Polime dn xut ca ru. V d polivinyl axetat:

(- CH2 - CH - n ) OCOCH 3
Cc polime anehit v xeton. V d poli acrolein.

(- CH 2 - CH - ) n CH = O
Polime ca axit cacboxylic. V d poliacrylic:

(- CH2 - CH - n ) COOH
Polime nitrin (c nhm - C N). V d poliacrilonitrin:

(- CH2 - CH - n ) CN
Polime ca hirocacbon thm. V d polistiren:

(- CH2 - CH - n ) C6H5
b) Polime d mch: Trn mch polime c nhiu loi nguyn t. Mch chnh c C v O. V d poliete (poliglicol): (- CH2 CH2 O -)n polieste (polietylenglicol terephtalat) (- O - CH2 CH2 O CO C6H5 CO - )n Mch chnh c C, N. V d polietyleniamin : (- NH CH2- CH2 NH -)n Mch chnh c C, N, O. V d poliuretan : (- CO NH R NH -)n 2. Cu to hnh hc ca mch polime Cc phn t polime thin nhin v tng hp c th c ba dng sau. a) Dng mch thng di: Mi phn t polime l mt chui mch thng di, do cc mt xich polime kt hp u n to ra. b) Dng mch nhnh: Ngoi mch thng di l mch chnh, cn c cc mch nhnh do cc monome kt hp to thnh. c) Dng mch li khng gian: Nhiu mch polime lin kt vi nhau theo nhiu hng khc nhau. V d trong cao su lu ha, trong cht do phenolfomanehit. III. Tnh cht ca polime 1. Tnh cht vt l L nhng cht rn tinh th hoc v nh hnh tu thuc vo trt t sp xp cc phn t polime. Khi cc phn t polime sp xp hn n to thnh trng thi v nh hnh. - Cc polime khng bay hi, do khi lng phn t ln v lc lin kt gia cc phn t ln - Hp cht polime khng c nhit nng chy xc nh do mt polime l hn hp ca nhiu phn t c khi lng phn t khc nhau. Phn ln cc polime khi un nng th u mm ra ri chy nht. Mt s polime b phn hu khi un nng.
ng c Thin
136
Trng THPT Sn ng s 3
- Phn nhiu polime kh tan trong cc dung mi. C loi polime hon ton khng tan trong cc dung mi. Th d : Teflon (- CF2 - CF2 -)n. Mt s polime c cu trc mch thng thng c tnh n hi (cao su), c tnh mm mi v dai (t capron). Nhng polime c cu trc mng khng gian thng c tnh bn c hc cao, chu c ma st va chm. Th d: nha bakelit ( phenolfomaehit). Mt s polime c tnh cch in, cch nhitTh d: polietilen, polyvinyl clrorua, nha bakelit 2. Tnh cht ho hc Ph thuc thnh phn v cu to ca polime. Phn ln cc polime bn vng ho hc (i vi axit, kim, cht oxi ho). C cht rt bn vi nhit v ho cht, v d nh teflon ( - CF2 - CF2 - )n. Mt s polime km bn vi tc dng ca axit v baz. V d: Len, t tm, t nilon b thu phn bi dung dch axit hoc kim do c nhm peptit. Nhng polime c lin kt i trong phn t c th tham gia phn ng cng. V d phn ng lu ho cao su. IV. iu ch polime 1. Phn ng trng hp L qu trnh cng lin tip nhiu phn t nh ging nhau hoc tng t nhau (monome) thnh phn t ln (polime), Trong qu trnh ny khng c s tch bt cc phn t nh nn thnh phn nguyn t ca polime v monome ging nhau. Phn t monome tham gia phn ng trng hp phi c lin kt kp hoc c vng khng bn. V d: nCH2 = CH2 xt , 200 C (- CH2 CH2 -)n ,1000 atm
0
n CH2 - CH2 O
(- CH2 - CH2 - O -)n
Phn ng trng hp c th xy ra gia 2 loi monome khc nhau, khi gi l ng trng hp.
nCH2 = CH + n CH2 = CH - CH = CH 2 CN Na, xt, t0 (- CH2 - CH - CH - CH = CH - CH )n 2 2 CN
2. Phn ng trng ngng l qu kt hp lin tip nhiu phn t nh (monome) thnh phn t ln (polime) ng tch ra nhiu phn t nh, n gin nh H2O, NH3, HCl, c th tham gia phn ng trng ngng, cc phn t monome phi c t nht 2 nhm chc c kh nng phn ng hoc 2 nguyn t linh ng c th tch khi phn t monome. Trng ngng nhng monome cng loi: V d: nH2N CH2 COOH t (- HN CH2- CO -)n + nH2O Trng ngng gia cc monome khc nhau: Gia iamin v iaxit: n HOOC (CH2)4 COOH + n HN2 (CH2)6 NH2 t (- CO (CH2)4 CO HN (CH2)6 NH -)n + nH2O T nilon 6,6 Gia iaxit v ru 2 ln ru: nHO (CH2)2- OH + n HOOC C6H4 COOH t
0 0 0
ng c Thin
137
Trng THPT Sn ng s 3
(- O (CH2)2 O - CO C6H4 - CO)n + nH2O (t lapxan) V. ng dng ca polime 1. Cht do a) nh ngha: cht do l nhng vt liu polime c tnh do, tc l c kh nng b bin dng di tc dng bn ngoi v gi c bin dng sau khi ngng tc dng. b) Thnh phn: Thnh phn c bn: l 1 polyme no . V d thnh phn chnh ca bnit l cao su, ca xenluloit l xenluloz nitrat, ca bakelit l phenolfomanehit. Cht ho do: tng tnh do cho polime, h nhit chy v nht ca polime. V d ibutylphtalat, Cht n: tit kim nguyn liu, tng cng mt s tnh cht. V d aming tng tnh chu nhit. Cht ph gia: cht to mu, cht chng oxi ho, cht gy mi thm. c) u im ca cht do: Nh (d = 1,05 1,5). C loi xp, rt nh. Phn ln bn v mt c hc, c th thay th kim loi. Nhiu cht do bn v mt c hc. Cch nhit, cch in, cch m tt. Nguyn liu r. d) Gii thiu mt s cht do Polietilen (P.E) (- CH2 CH2 -)n: iu ch t etilen ly t kh du m, kh thin nhin, kh than . L cht rn, hi trong, khng cho nc v kh thm qua, cch nhit, cch in tt. Dng bc dy in, bao gi, ch to bng thm khng, lm thit b trong ngnh sn xut ho hc, sn tu thu. Polivinyl clorua (P.V.C)
(- CH2 - CH - n ) Cl
Cht bt v nh hnh, mu trng, bn vi dung dch axit v kim. Dng ch da nhn to, vt liu mng, vt liu cch in, sn tng hp, o ma, a ht Polivinyl axetat (P.V.A)
iu ch bng cch : cho axit axetic tc dng vi axetilen, ri em trng hp sn phm: Dng ch sn, keo dn, da nhn to. Polimetyl acrilat
v polimetyl metacrilat
CH3 (- CH2 - CH - n ) OCOCH 3
iu ch bng cch trng hp cc este tng ng. L nhng polime rn, khng mu, trong sut. Polimetyl acrilat dng sn xut cc mng, tm, lm keo dn, lm da nhn to
ng c Thin
138
Trng THPT Sn ng s 3
Polimetyl metacrilat dng lm thu tinh hu c. Polistiren (- CH2 - CH - n )

C6H5
Dng lm vt liu cch in. Polistiren d pha mu nn c dng sn xut cc dng dn dng nh cc o, lc Nha bakelit: Thnh phn chnh l phenolfomanehit. Dng lm vt liu cch in, chi tit my, dng gia nh. bonit: l cao su rn c ti 25 - 40% lu hunh. Dng lm cht cch in. Tflon (- CF2 - CF2)n rt bn nhit, khng chy, bn vi cc ho cht. Dng trong cng nghip ho cht v k thut in. 2. Cao su Cao su l nhng vt liu polime c tnh n hi, c ng dng rng ri trong i sng v trong k thut. a) Cao su thin nhin: c ch ho t m cy cao su. Thnh phn v cu to: l sn phm trng hp isopren.
nCH2 = C - CH = CH 2 CH3 (- CH2 - C = CH - CH -)n 2 CH3
n t 2000 n 15000 Mch polime un khc, cun li nh l xo, do cao su c tnh n hi. Cao su khng thm nc, khng thm khng kh, tan trong xng, benzen, sunfua cacbon. Lu ho cao su: Ch ho cao su vi lu hunh lm tng nhng u im ca cao su nh: khng b dnh nhit cao, khng b dn nhit thp. Lu ho nng: ung nng cao su vi lu hunh. Lu ho lnh: Ch ho cao su vi dung dch lu hunh trong CS2. Khi lu ha, ni i trong cc phn t cao su m ra v to thnh nhng cu ni gia cc mch polime nh cc nguyn t lu hunh, do hnh thnh mng khng gian lm cao su bn c hc hn, n hi hn, kh tan trong dung mi hu c hn.
H3C S ... - CH2 - C = CH - CH2 - ... S ... - CH2 - C = CH - CH2 - ... H3C S
b) Cao su tng hp: Cao su butaien (hay cao su Buna) (- CH2- CH = CH CH2 -)n L sn phm trng hp butaien vi xc tc Na. Cao su butaien km n hi so vi cao su thin nhin nhng chng bo mn tt hn. Cao su isopren.
(- CH2 - C = CH - CH -)n 2 CH3
C cu to tng t cao su thin nhin, l sn phm trng hp isopren vi khong 3000.

ng c Thin
139
Trng THPT Sn ng s 3
Cao su butaien stiren (Cao su Buna - S)

(- CH2 - CH - CH - CH = CH - CH )n 2 2 C6H5
C tnh n hi v bn cao: Cao su butaien - nitril: sn phm trng hp butaien v nitril ca axit acrilic.
(- CH2 - CH - CH - CH = CH - CH )n 2 2 CN
Do c nhm C N nn cao su ny rt bn vi du, m v cc dung mi khng cc. 3. T tng hp a) Phn loi t: T c phn thnh: T thin nhin: c ngun gc t thc vt (bng, gai, ay) v t ng vt (len, t tm) T ho hc: chia thnh 2 loi. + T nhn to: thu c t cc sn phm polime thin nhin c cu trc hn n (ch yu l xenluloz) v bng cch ch to ho hc ta thu c t. + T tng hp: thu c t cc polime tng hp. b) T tng hp: T clorin: l sn phm clo ho khng hon ton polivinyl clorua.
(- CH2 - CH - CH - CH -)n Cl Cl Cl
Ho tan vo dung mi axeton sau p cho dung dch i qua l nh vo b nc, polime kt ta thnh si t. T clorin dng dt thm, vi dng trong y hc, k thut. T clorin rt bn v mt ho hc, khng chy nhng bn nhit khng cao. Cc loi t poliamit: l sn phm trng ngng cc aminoaxit hoc iaxit vi iamin. Trong chui polime c nhiu nhm amit - HN - CO - : + T capron: l sn phm trng hp ca caprolactam ( - HN (CH2)5 CO -)n (n > 250) + T enan: l sn phm trng ngng ca axit enantoic ( - HN (CH2)6 CO -)n (n > 250) + T nilon (hay nilon): l sn phm trng ngng hai loi monome l hexametyliamin v axit aipic n HOOC (CH2)4 COOH + n HN2 (CH2)6 NH2 t (- CO (CH2)4 CO HN (CH2)6 NH -)n + nH2O T nilon 6,6 Cc t poliamit c tnh cht gn ging t thin nhin, c dai bn cao, mm mi, nhng thng km bn vi nhit v axit, baz. Dng dt vi, lm li nh c, lm ch khu. T polieste: ch to t polime loi polieste. V d polietylenglicol terephtalat. nHO (CH2)2- OH + n HOOC C6H4 COOH t (- O (CH2)2 O - CO C6H4 - CO)n + nH2O (t lapxan) T lapsan rt bn c hc, bn nhit v bn vi axit, baz hn t nilon.
0 0
ng c Thin
140
Trng THPT Sn ng s 3

Hoa Huu Co

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hoa Huu Co

Uploaded by

Copyright:

Available Formats

Ha hc cc hp cht hu c

Phn III HA HC CC HP CHT HU C

CH3 CH = CH CH3 buten - 2 CH3 CH CH3 Cl 2 clo propan (isopropyl clorua)

HC = C CH3 1 metyl xiclopren 1

C=C cis buten - 2

I. Hirocacbon no mch h _Ankan

Al O ,t CH3 CH2 CH2 CH3

+ Phn ng crackinh -> ankan + anken (mch nh hn) C4H10 t

C=C cis buten - 2

IV Ankaien (hay iolefin)

CH 2 Br CH = CH CH 2 Br (80%) CH 2 Br CHBr CH = CH 2 (20%)

CH2 = CH CH = CH2 + H2 Pd ,eol , 12 tan C + Cng hirohalogenua CH2 = CH CH = CH2 + H - Br ->

CH 3 CH = CH CH 2 Br (80%) CH 3 CHBr CH = CH 2 (20%)

b. Phn ng trng hp n CH2 = CH CH = CH2 Na , p (- CH2 CH = CH CH2 -)n cao su Buna ,t

nCH2 = C CH = CH2 xt , p (- CH2 C = CH CH2 -)n cao su isopren ,t

V. Hirocacbon thm (Aren)

Ch : Bnh thng benzen khng lm mt mu nc brom.

Toluen tham gia phn ng th d dng hn so vi benzen v to ra hai ng phn ov p-

Nu khng c bt st v hn hp c chiu sng th phn ng s xy ra nhnh ankyl

Nitrobenzen li phn ng vi HNO3 to thnh m initrobenzen :

Toluen tham gia phn ng th nitro d dng hn benzen v to thnh hn hp sn phm

Khi c nhm th loi 1 Phn ng vi H2SO4 c

khi c nhm th loi 2

Cht rn Antraxen C14H10

VI. Dn xut halogen

Ha hc cc hp cht hu c ,t 0 R X + H2O NaOH R OH + HX

,t CH2 CH2 + 2NaOH H O CH2 CH2

CH3 C(Cl)3 + 3NaOH H O CH3 C OH + 3NaCl ,t

OH + Phn ng tch HX:

R CH = CH2 + ZnX2 R CHX CH2X + Zn t

+ Tc dng vi NH3 R Cl + NH3 -> R NH2 + HCl + Tc dng vi Na

d. iu ch - Phn ng th ca halogen vo hirocacbon no.

- Phn ng cng HX vo hirocacbon cha no.

VII. Ngun hirocacbon trong thin nhin

Chng 3 NHNG HP CHT HU C C NHM CHC I. Ru (ancol)

CH2 = CH OH -> CH3 CHO

2, 4, 6 tribromphenol (Trng) d. Phn ng vi dung dch HNO3

IV. Andehit fomic v dy ng ng

d. Phn ng trng hp anehit: C nhiu dng. * To polime:

nHCHO (- CH2 O)n

VI. Axit axetic v dy ng ng

nCH2 = C COOCH3 xt , p - CH2 = C ,t

iu ch bng cch oxi ho naphtalen

+ Axit limonic hay axit xitric (axit chanh)

VII. Este Cht bo

Trong R1, R2, R3 c th ging nhau hoc khc nhau.

C=O (CH - OH) 3 CH 2 - OH

extrin Amilaza Mantoz H2O

IX. Aminoaxit protit

- Leuxin: CH3 - CH - CH2 - CH - Co o H

Chng 3 HP CHT CAO PHN T V VT LIU POLIME

Polime dn xut ca ru. V d polivinyl axetat:

Cc polime anehit v xeton. V d poli acrolein.

Polime ca axit cacboxylic. V d poliacrylic:

Polime nitrin (c nhm - C N). V d poliacrilonitrin:

Polime ca hirocacbon thm. V d polistiren:

(- CH2 - CH2 - O -)n

Polimetyl metacrilat dng lm thu tinh hu c. Polistiren (- CH2 - CH - n )

C cu to tng t cao su thin nhin, l sn phm trng hp isopren vi khong 3000.

Cao su butaien stiren (Cao su Buna - S)

You might also like