M Ui tng ca ha hc hu c: Ha hc hu c l mn khoa hc nghin cu thnh phn v tnh cht cc hp cht ca cacbon. Trong thnh phn hp cht hu c,ngoi cacbon cn c nhiu nguyn t khc nh H, O, N, S, P,halogen...nhng cacbon c xem l nguyn t c bn cu to nn hp cht hu c. T xa xa ngi ta bit iu ch v s dng mt s cht hu c trong i sng nh gim (acid axetic long),ru(etanol),mt s cht mu hu c.Thi k gi kim thut cc nh ha hc iu ch c mt s cht hu c nh ur,ether etylic... Cui th k 18 u th k 19, cc nh ha hc chit tch t ng, thc vt nhiu acid hu c nh acid oxalic, acid citric,acid lactic...v mt s base hu c (alcaloid).Nm 1806 ln u tin nh ha hc ngi Thy in Berzelius dng danh t Ha hc hu c ch ngnh ha hc nghin cu cc hp cht c ngun gc ng vt v thc vt.Thi im ny c th xem nh ct mc nh du s ra i ca mn ha hc hu c. Nm 1815 Berzelius a ra thuyt Lc sng cho rng cc hp cht hu c ch c th c to ra trong c th ng vt v thc vt nh mt Lc sng ch con ngi khng th iu ch c .Thuyt duy tm ny tn ti trong nhiu nm nhng dn dn b nh bi cc cng trnh tng hp cc cht hu c t cc cht v c. Nm 1824, nh ha hc ngi c Wohler tng hp c acid oxalic bng cch thy phn dixian l mt cht v c.Nm 1828 cng chnh ng, t cht v c amoni cyanat tng hp c ur .Tip theo Bertholet (Php) tng hp c cht bo nm 1854 v Bulerov (Nga) tng hp ng glucose t formalin nm 1861. Cho n nay hng triu cht hu c c tng hp trong phng th nghim v trn quy m cng nghip.Con ngi khng ch bt chc tng hp cc cht ging thin nhin m cn sng to ra nhiu cht hu c, nhiu vt liu hu c cc k quan trng v qu gi m t nhin khng c . Tuy nhin tn gi hp cht hu c vn c duy tr , nhng khng phi ch vi ngha l cc cht c ngun gc ng vt v thc vt m mang ni dung mi : l cc hp cht ca cacbon. c im ca cc hp cht hu c v phn ng hu c Mc d ra i mun hn ha hc v c nhng cc hp cht hu c rt phong ph v s lng , chng loi. S lng cht hu c cho n nay nhiu gp vi chc ln cc cht v c bit. Nguyn nhn c bn l do cacbon c kh nng to thnh mch di v tn theo nhiu kiu khc nhau. Ni cch khc hin tng ng phn (tc l cc cht c cng thnh phn phn t nhng khc nhau v cu to) l cc k ph bin v c trng trong ha hc hu c. Cu trc phn t ca hp cht hu c c th n gin nhng cng c th rt phc tp, vic xc nh cu trc ca chng nhiu khi rt kh khn , phi s dng nhiu phng php ha hc v vt l hc hin i. Nu nh lin kt ion kh ph bin trong hp cht v c th lin kt ch yu gia cc nguyn t trong phn t hu c li l lin kt cng ha tr. c im ny nh hng nhiu n tnh cht l ha v c bit l kh nng phn ng ca chng. Cc phn ng hu c thng xy ra vi tc chm, khng hon ton v thng theo nhiu hng khc nhau, v vy vai tr ca nhit ng hc, ng hc v xc tc trong ha hu c rt quan trng. Vai tr ca ha hc hu c Cc cht hu c c vai tr rt quan trng trong i sng ca con ngi.Khng nhng hu ht thc phm chng ta n (glucid, protid, lipid), vt dng hng ngy (cellulose, si tng hp, cao su, cht do...) l cc cht hu c m nhiu cht hu c cn l c s ca s sng ( protid, acid nucleic...).Nhin liu cho ng c t trong ,cho nh my nh xng, du l hn hp hidrocarbon mch di ngn khc nhau.Cc vt liu hu c nh, khng han g, tin s dng, nhiu mu sc a dng ang ngy mt thay th cho cc kim loi, hp kim trong nhiu lnh vc, k c nhng lnh vc tng nh khng th thay th c nh bn dn, siu dn...Do tt c nhng c im trn, ha hc hu c c tch ra nh mt ngnh khoa hc ring i hi nhng phng php nghin cu v thit b ngy cng hin i hn, i hi n lc khng ngng ca cc nh ha hc khng nhng bt chc thin nhin tng hp nn cc cht phc tp phc v cho nhiu lnh vc ca cuc sng m cn vt xa hn c thin nhin.T c s ha hc hu c, c rt nhiu ngnh nghin cu ng dng ra i: ha cng nghip, ha du, cng nghip dt, ha thc phm, dc phm, v ha m phm.

Chng 1CU TO CA HP CHT HU C

MC TIU1.Gii thch c cch hnh thnh cc loi lin kt: - Lin kt d cc - Lin kt cng ha tr - Lin kt cho nhn - Lin kt hydro2.Trnh by c cu to in t cacbon cc trng thi lai ha sp, sp2 , sp3. NI DUNG1. Cu to nguyn t - 2 kiu orbital:

orbital s( hnh cu) orbital p - Cu hnh e ca 1 s nguyn t:H (Z=1)1s1C (Z=6)1s22s22p2N (Z=7)1s22s22p3O (Z=8)1s2 2s22p4 S (Z=16)1s22s22p63s23p4 Cl (Z=17)1s22s22p63s23p52. Lin kt trong ho hc hu c2.1. Lin kt d cc (Lin kt in ho tr) - Lin kt ion sinh ra do lc ht tnh in gia cc in tch ca nhng ion mang in tch tri du nhau - Trong ha hu c: Lin kt ion trong cc phn t mui ca acid carboxylic v mui amoni:

2.2. Lin kt cng ho tr - Lin kt c hnh thnh gia 2 nguyn t ging nhau hoc gia 2 nguyn t c m in khng khc nhau nhiu bng cch gp chung e (tng trng bng 1 gch). V d:

- Lin kt cng ho tr thun tu: gia 2 nguyn t c m in nh nhau- Lin kt cng ho tr phn cc: gia 2 nguyn t c m in khc nhau cha n mc tr thnh thun tu ion.2.3. Lin kt cho - nhn (Lin kt phi tr)- Lin kt to bi cp e khng phn chia ca 1 nguyn t (cht cho) v orbital cn trng ca mt nguyn t khc (cht nhn):

2.4. Lin kt hydro - Lin kt hnh thnh do lc ht tnh in gia H ( lin kt trong 1 phn t) vi 1 nguyn t c m in mnh, kch thc b (N, O, F...) 1 phn t khc hoc trong cng 1 phn t .a. Lin kt hydro lin phn t:

acid acetic

alcol methylicb. Lin kt hydro ni phn t:

3. Cu trc in t ca carbon & s lai ho cc orbital. Lin kt Sigma & lin kt Pi. C (1s2 2s2 2px 2py) C (1s2 2s 2px 2py 2pz)

(ho tr 2) (ho tr 4)3.1. Lai ho sp3 (lai ho t din)- 1 orbital 2s + 3 orbital 2px, 2py, 2pz 4 orbital lai ho sp3, trc to gc 109028':

Cc orbital lai sp3

Lin kt - Lin kt xen ph theo trc orbital lin kt3.2. Lai ho sp2 (lai ho tam gic) - 1 orbital 2s + 2 orbital 2px, 2py 3 orbital lai ho sp2 - 3 orbital nm trn 1 mt phng, trc to gc 1200 Lin kt - xen ph bn ca 2 orbital 2p c trc song song & vung gc mt phng 3.3. Lai ho sp (lai ho ng thng): phn t Acetylen ( C2H2) - 1 orbital 2s + 1 orbital 2p 2 orbital lai sp - Trc ca 2 orbital nm trn ng thng, gc 1800

2 orbital lai ho sp4. S to chui carbon. Cu trc khng gian ca cc khung carbon. Gc & nhm chc.4.1. Chui Carbon - mch h - mch vng, d vng*Mch h

mch vng no

d vng

4.2. Cu trc khng gian khung Carbon 2 yu t: - Tnh nh hng cc orbital - Kh nng quay ca nhm th xung quanh lin kt n to ra cc hnh dng khc nhau cu dng V d ethan: Cng thc phi cnh Cng thc Newman (Niumen)

* Mch carbon bo ho* Mch carbon khng no4.3. Nhm chc- Nhm nguyn t (hoc nguyn t ) gy ra tnh cht ho hc c trng nht ca tng loi cht- V d mt s nhm chc thng gp trong ho hu c:OHHydroxyl (alcol, phenol)amid

OetherC=Nimin

OOperoxydN=Onitroso

SHmercapto (thioalcol, thiophenol)NO2nitro

alkoxy carbonyl (ester)CNnitril

NH2aminoN=Cisonitril

OCH3methoxyN=Nazo

carbonylSO3Hsulfonic

formylcarboxyl

Chng 2HIU NG IN T TRONG HO HU C

MC TIU1. Nu c cc loi hiu ng cm ng, hiu ng lin hp, hiu ng siu lin hp v tnh cht ca chng. 2. Bit c mt s ng dng ca cc hiu ng trn. NI DUNG Mt in t trong lin kt cng ha tr thng c phn b khng ng u gia 2 nguyn t ca lin kt, khi y phn t cht hu c b phn cc. S phn cc c th xy ra ngay trng thi tnh hoc cng c th ch xut hin nht thi trng thi ng (khi phn t b tc ng bi cc yu t ca mi trng). Bn cht ca s phn cc khc nhau cn tu thuc vo cu to phn t (phn t c h thng lin kt nh th no). Nh vy cu to phn t c nh hng n s phn b mt in t,nh hng gi l hiu ng in t trong phn t. C cc loi hiu ng: Hiu ng cm ng I Hiu ng lin hp C, M Hiu ng siu lin hp H 1. Hiu ng cm ng (Inductive effect): K hiu l I Kho st phn t n -propan C3H8 v phn t n-propylclorid C3H7Cl

Trong phn t n -propylclorid, lin kt C1 Cl b phn cc v pha nguyn t clor v nguyn t clor c m in ln hn. Nguyn t clor mang mt phn in tch m - v nguyn t carbon mang mt phn in tch dng + . V C1 mang in tch dng nn cp in t lin kt ca lin kt C2 C1 b dch chuyn v pha carbon C1. Kt qu l lin kt C2 C1 cng b phn cc theo. Nguyn t C2 mang mt phn in tch dng. n lt lin kt C3 C2 cng chu nh hng nh vy v kt qu nguyn t carbon C3 mang mt phn in tch dng. Nhng 1+ > 2+ > 3+ .Cc lin kt cng chu nh hng nh th v kt qu c s phn cc ca lin kt C H. Hydro tr nn linh ng hn. Hin tng ny khng ch xy ra vi phn t propan. Nh vy nh hng s phn cc ca lin kt C -Cl lm cho cc lin kt khc b phn cc theo v ton phn t b phn cc. Nguyn t clo l nguyn t gy nh hng cm ng.S phn cc hay s chuyn dch mt in t trong cc lin kt gi l hiu ng cm ng. Hiu ng cm ng k hiu l I hoc I(ch u ca inductive) phn loi cc nhm nguyn t theo hiu ng cm ng ngi ta quy c rng nguyn t hydro lin kt vi carbon trong C - H c hiu ng I = 0. Nhng nguyn t hay nhm nguyn t X c kh nng ht in t (CX) mnh hn hydro c coi l c hiu ng - I (hiu ng cm ng m). Nhng nguyn t hay nhm nguyn t Y c kh nng y in t (YC) mnh hn hydro c coi l nhng nhm c hiu ng +I (hiu ng cm ng dng)

1.1. Hiu ng cm ng + I Thng thy cc nhm alkyl (R-) v cc nhm mang in tch m. Trong dy cc nhm alkyl, hiu ng cm ng +I tng theo phn nhnh hay l bc ca nhm .

Trong dy cc nhm mang in tch m, nhm c m in nh hn l nhm c hiu ng + I ln hn .

1.2. Hiu ng cm ng - I L hiu ng rt ph bin cc nhm khng no, cc nhm mang in tch dng v cc nhm ng vi nhng nguyn t c m in ln (nh cc halogen, oxy, nit). S bin thin mc mnh yu ca hiu ng - I trong cc nhm nguyn t tun theo mt s quy lut: Nguyn t carbon lai ha sp c -I ln hn nguyn t carbon lai ha sp2 v sp3 Nhm mang in tch dng c hiu ng -I ln hn nhm c cng cu to nhng khng mang in tch.

Cc nguyn t ca nhng nguyn t trong cng mt chu k nh hay trong cng mt phn nhm chnh ca h thng tun hon, hiu ng -I cng ln khi nguyn t tng ng cng bn phi (trong cng chu k) hoc cng pha trn trong cng phn nhm -F > -Cl > -Br > -I -F > -OR > -NR2 > -CH3. -OR > -SR > -SeR m in cng tng th hiu ng cm ng - I cng ln Biu hin c th ca hiu ng cm ng l nh hng ca cc nhm th khc nhau n lc acid v lc base ca cc acid carboxylic no v ca cc amin. Hiu ng - I tng, lc acid tng. Khi thay th hydro ca CH3 trong acid acetic bng cc halogen c m in khc nhau th tnh acid thay i. Nguyn t halogen c hiu ng -I ht in t nh hng n s phn ly ca nhm O -H.

c im quan trng ca hiu ng cm ng l hiu ng cm ng lan truyn trn mch lin kt v yu dn khi chiu di ca mch carbon tng ln.

2. Hiu ng lin hp (cng hng) 2.1. H thng lin hp H thng lin hp l mt h thng: Cc lin kt bi (i, ba) lun phin vi lin kt n.

H thng cha nguyn t cn cp in t p t do khng lin kt trc tip vi nguyn t carbon c lin kt bi.

Phn t cha h thng lin hp l phn t lin hp. 2.2. c im ca h thng lin hp Trong phn t khng ch c lin kt i hoc lin kt n ring:

Cc nguyn t to h lin hp lun nm trong mt mt phng v trc ca cc oirbtal p song song vi nhau v thng gc vi mt phng cha cc lin kt .

Phn t lin hp bao gi cng c nng lng thp hn nng lng ca nhng phn t khng lin hp tng ng. V mt in t gn nh gii ta ng u trn cc nguyn t to h thng lin hp v to thnh mt orbital phn t gii ta trn ton b phn t.

Orbital phn t trong h thng lin hp rt d bin dng v d phn cc khi cu to ca phn t lin hp c mt nguyn t chnh lch v m in. Nh vy trong h lin hp c s tng tc gia cc orbital p vi nhau. S tng tc gi l hiu ng lin hp. 2.3. Hiu ng lin hp C (M) Hiu ng lin hp l hiu ng sinh ra do s phn cc ca lin kt c lan truyn trong h thng lin hp 2.4. Phn loi hiu ng lin hp Cn c vo s dch chuyn in t ca cc in t . C hai loi hiu ng lin hp: Hiu ng lin hp + C v Hiu ng lin hp- C Hiu ng lin hp - C Nu thay th nguyn t hydro trong nhm CH2 ca butadien bng nhm CH = O, nhm ny tham gia lin hp vi orbital phn t ca butadien. Nh c c tnh phn cc ca nhm CH =O nn ton b orbital mi hnh thnh ca phn t b dch chuyn mt phn v pha nguyn t oxy.

Nhm CH = O c hiu ng lin hp theo c ch ht in t nn c gi l nhm c hiu ng - C. Cc nhm c hiu ng - C l nhng nhm khng no c cng thc chung C =Y, CZ v mt s nhm khc khng cha carbon nh - NO2, - SO3H... Hng chuyn dch in t trong h thng c nhm vi hiu ng - C c m t bng mi tn cong. Nhm c hiu ng -C thng c thm hiu ng cm ng - I. Cc nhm chc c hiu ng -C :

Hiu ng lin hp +C - Cc nguyn t hay nhm nguyn t c hiu ng lin hp +C l nhng nhm c kh nng y in t. Cc nhm ny thng c nguyn t mang cp in t p t do. Chnh cp in t p ny lin hp vi cc lin kt trong h thng lin hp.

- Cc nhm c hiu ng + C : -NH2 > -OH ; -O- > -OH -F > -Cl > -Br > -I -NR2 > -OR > -SR > -SeR - Cc nhm c hiu ng + C thng c thm hiu ng cm ng - I. Hiu ng lin hp c ng dng rng ri gii thch c ch phn ng,cc cu to trung gian, bn ca cc ion, tnh acid -base ... 3. Hiu ng siu lin hp (Hyperconjugate effect) Ngoi s lin hp - v p - nu trn cn c s lin hp - gia cc orbital ca cc lin kt C H trong nhm alkyl v orbital ca ni i, ni ba hay vng thm. S tng tc lin hp gia orbital ca lin kt C - H vi orbital ca lin kt i, ba hoc h thng lin hp gi l hiu ng siu lin hp. - Hiu ng siu lin hp c k hiu l H. - Hiu ng siu lin hp khng nhng lm thay i bn cht ca lin kt i m cn lm thay i c tnh cht ca lin kt n C - H. -Hiu ng siu lin hp lm thay i hng cng hp vo lin kt i. -Hiu ng siu lin hp nh hng n tnh cht linh ng ca lin kt C -H trong gc alkyl. -Hiu ng siu lin hp tng theo s lng lin kt C -H v tr . CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C - -Hiu ng siu lin hp v hiu ng cm ng +I lun xy ra cng hng. -Hin tng phn b li mt in t cn c th c trong cc trng hp h thng carbanion v carbocation.

Chng 3NG PHN HC

MC TIU1.Trnh by c cc loi ng phn gp trong ha hu c.2.c c tn cu hnh cc hp cht hu c dng Z,E v R,SNI DUNGng phn l nhng hp cht c cng cng thc phn t, c cu trc khc nhau tnh cht l ho khc nhau .Da vo c im cu trc ngi ta chia thnh hai loi ng phn:- ng phn phng- ng phn lp th (ng phn khng gian)1. ng phn phng1.1. ng phn v tr mch C v tr nhm chcV d: *C4H10 c 2 ng phn mch cacbon:

*C3H8O c 2 ng phn v tr nhm chc:

1.2. ng phn cu to: ho chc khc nhau V d: *C2H6O ng vi 2 hp cht CH3CH2OH:ethanol (cht lng)CH3OCH3 : ether methylic (cht kh)1.3. H bin (tautomerism) nh ngha:mt cht c thnh phn nguyn t, khi lng phn t xc nh nhng tn ti dng hn hp cn bng ca cc ng phn d dng chuyn ho ln nhau ceton enol: Ethyl acetoacetat

lactam lactim:

2. ng phn lp th S phn b khc nhau trong khng gian ca cc nhm th. ng phn hnh hc ng phn cu dng ng phn quang hc2.1. ng phn hnh hc hp cht c lin kt C=C, C=N, N=N hp cht vng no2.1.1. ng phn ca hp cht ethylenic S phn b khc nhau trong khng gian ca cc nhm th so vi lin kt i

iu kin: C cha lin kt i phi lin kt vi 2 nguyn t hoc 2 nhm nguyn t khc nhau: R1 R2 v R3 R4 H danh php Z E - Danh php cis-trans khng r rng trong trng hp c cc nhm th khc H gn vo C lin kt i. - Danh php Z E: theo v tr ca cc nhm th u tin + 2 nhm th u tin cng 1 pha lin kt i Z ("Zusammen" - cng) ~ cis + 2 nhm th u tin khc pha lin kt i E ("Entgegen" - ngc li) ~ trans

* Qui tc u tin Cahn - Ingold Prelog: -Da trn nguyn t s ca nguyn t lin kt trc tip vi cacbon lin kt i:I > Br > Cl > S > F > O > N > C > H -Nu ging nhau xt tip cc nguyn t lp II, lp III... -Lin kt i hoc ba tnh bng hai hoc ba lin kt n vi nguyn t lin kt CH2Br CH2Cl CH2OH CH2CH3 CH3

2.1.2. ng phn hnh hc cc hp cht c lin kt >C=N & N=N

2.2. ng phn cu dng Cu dng l 1 trong v s phn b tc thi trong khng gian ca cc nguyn t trong phn t do s quay xung quanh lin kt n ng phn cu dng (ng phn quay) l cc cu dng c nng lng cc tiu V d:Xt cu dng ca n-butan:

Cng thc phi cnh

Cng thc hnh chiu Newman2.3. ng phn quang hc ng phn quang hc l ng phn c lin quan n s khc nhau v gc quay ca mt phng nh sng phn cc.2.3.1. nh sng phn cc

S phn cc k2.3.2. Cht hot quang-Cht quay phi (hu tuyn): (+) -Cht quay tri (t tuyn): (-) * 2 loi: - do cu trc tinh th: thch anh, NaClO3, ZnSO4... - do cu trc phn t: cc cht hu c V d: (+)-glucose, (+)-penicilin, (+)-campho, (+)-glyceraldehyd (-)-menthol, (-)-ephedrin, (-)-glyceraldehyd2.3.3. quay cc ring (xc nh bng phn cc k)Dung dch: Cht lng nguyn cht: : Tr s gc quay o c, t0 : Nhit , oC : di sng (DNa = 589,3nm) l: Chiu di khong ng nh sng truyn qua dung dch,dung mi c: Nng mu, g/100 ml dung dch d: T trng cht lng, g/ml2.3.4. iu kin xut hin tnh hot quang Phn t c tnh khng trng vt - nh (chirality) (chiral xut pht t t Hy Lp cheir bn tay) cu to phn t bt i xng

a b c d 2-butanol Acid lactic2.3.5. Cc cht hot quang c nguyn t Ca. Hp cht c 1C: glyceraldehyd []D25 = -8,7O []D25 = +8,7O

ng phn i quang (enantiomers): hai dng ng phn i xng nhau nh vt & nh ca n trong gng, quay cc ring cng tr s, tri du (+), (-) Hn hp racemic - hn hp c s phn t bng nhau ca mi dng i quang khng hot quang (b tr ngoi phn t) V d: 50% D(+)-glyceraldehyd, []D25 = +8,7O 50% L(-)-glyceraldehyd, []D25 = -8,7O ()-glyceraldehyd, []D25 = 0 Hp cht c 1C: 1 ng phn hu tuyn (+) 1 ng phn t tuyn (-) hn hp racemic () Hp cht c nC: 2n cht hot quang 2n-1 cp i quang 2n-1 hn hp racemic Cu hnh C: Cu hnh D, L: Cu hnh tng i (so snh vi glyceraldehyd) D - nhm th c trng pha phi mch C L - pha tri

Cu hnh R, S: Cu hnh tuyt i (Qui tc Cahn-Ingold-Prelog, 1955) Cabcd theo th t u tin nhm th C: a > b > c > d

V d glyceraldehyd:

b. Hp cht c nhiu nguyn t C: nC 2n ng phn quang hc Hp cht c 2C ging nhau: Acid tartric 4 cng thc ng phn:

(I) & (II) cp i quang hn hp racemic (III) & (IV) dng meso, khng hot quang (b tr ni phn t do phn t c mt phng i xng) Cu hnh tuyt i:

Hp cht c 2C khc nhau: Xt cc cp i quang ca tetrose: 2,3,4-trihydroxybutanal:

4 ng phn c th c:

nhng ng phn quang hc khng i quang (diastereomers) (I) & (III), (I) & (IV) (II) & (III), (II) & (IV)

Tip u ng erythro, threo ch cu hnh 2C tng t erythrose, threose

2.3.8. Tch i quang t hn hp racemic -Phng php kt tinh -Phng php sinh hc: mt s vi sinh vt ng ho mt trong hai i quang cn li i quang kia -Phng php ho hc:Hn hp racemic + tc nhn hot quang hn hp hai ng phn quang hc khng i quang phn lp gii phng cc i quang bng phn ng thch hp2.3.9. ngha ca ng phn quang hc -Nhiu cht hot quang c ngun gc t sinh vt: mt s vitamin, hormon, aminoacid, glucid -Cc ng phn quang hc c hot tnh sinh hc & tc dng dc l khc nhau. V d: Asparagin: (+) v ngt (-) v ng () khng v Adrenalin: ng phn (-) tc dng co mch ln gp 15 ln so vi ng phn (+)

Chng 4CC PHN NG HU C PHN LOI PHN NG - C CH PHN NG

MC TIU1.Trnh by c cc c ch phn ng thng gp trong ha hu c.2.Vit v gii thch c cc c ch phn ng : th (S), cng hp (A), tch loi (E)NI DUNG Qu trnh thay i (t chc li) orbital phn t di nh hng ca nhng iu kin bn ngoi & bn trong vi s to thnh h thng mi khc bit vi trng thi ban u ca cc nguyn t trong phn t v c tnh nng lng & v tr tng h. Cc yu t nh hng ti vP : to, p sut, xc tca. Bn cht & cu trc ca cc cht trung gian Phn ct ng ly

-Xy ra th kh, trong dung mi khng phn cc -Xc tc: to, nh sng, peroxyd -Gc t do: CH3, C2H5, Cl .... Phn ct d ly

-C mang in tch (+) carbocation. V d:

-C mang in tch (-) carboanion. V d:

- Phn ng d ly (phn ng ion) xy ra trong dung mi phn cc vi xc tc l acid hoc base.b. Cu trc & bn ca cc cht trung gian Gc t do R thng c cu trc phng, mt s c cu trc hnh thpCH3 CH3CH2 (CH3)2CH (CH3)3C CH3 C6H5CH2 (C6H5)2CH (C6H5)3C Carbocation R+ - bn: in tch (+) gii to bn tng +I, +M lm tng bn V d: +I: CH3+ CH3CH2+ (CH3)2CH+ (CH3)3C+ +M: CH3+ C6H5CH2+ (C6H5)2CH+ (C6H5)3C+ Carbanion R- - bn: bn tng khi c nhm ht e -I, -M lm tng bn V d: CH3- (CF3)2 CH- (C6H5)2CH- CH3CH2CH2- CH2=CH-CH2- (CH2=CH)2CH- 1. Phn loi tc nhn phn ng 1.1. Tc nhn i nhn (Nucleophile): - Tc nhn c cp e khng phn chia: cc base Lewis - Cc anion H , H2N , HO , RO , RS , RCOO Hal , HSO3 , NC , RCC1.2. Tc nhn i e (Electrophile) E+ - Cc ion dng, cc acid Lewis

BF3 , AlCl3 , ZnCl2 , FeCl1.2. Gc t do (Free radical) - Nguyn t hoc nhm nguyn t cha e c thn: Cl , Br , H3C , HO ...2. Phn loi phn ng2.1. Theo kt qu phn ng - phn ng th (S - Substitution):

- phn ng cng hp (A - Addition):

- phn ng tch loi (E - Elimination):

- phn ng chuyn v (Rearrangement):Trong cc loi phn ng k trn c lc c th xy ra s chuyn v lm chuyn ch mt nguyn t hay nhm nguyn t no trong phn t.Phn ng xy ra c s chuyn i v tr trong phn t gi l phn ng chuyn v.

Mt s phn ng th, cng hp, tch loi c th xem l phn ng oxy ha kh.V trong qu trnh phn ng c s thay i s oxy ha ca mt hay nhiu nguyn t trong phn t.Cc phn ng c s tng v gim s oxy ha (hay s nhng v thu in t) gi l phn ng oxy ha kh.2.2. Theo cch sp xp li lin kt - Phn ng ion (d ly): + Phn ng i nhn + Phn ng i in t - Phn ng gc (ng ly)2.3. Theo s phn t tham gia vo giai on quyt nh vP -Phn ng n phn t -Phn ng lng phn t -Phn ng phn t s cao hnBng phn loi cc phn ng hu cP th (S)P cng hp (A)P tch loi (E)P chuyn v

Th i nhnTh i in tTh gcCng hp i nhnCng hp i in tCng hp gcTch loin PTTch loilg PT

SN1, SN2SESRANAEARE1E2

3. C ch phn ng C ch phn ng: con ng chi tit m cc cht tham gia phn ng phi i qua to thnh sn phm cui, gm cc giai on c bn ca phn ng, s phn ct lin kt c & hnh thnh lin kt mi... & nhng d kin khc ca phn ng.3.1. Phn ng th Qu trnh trong di tc dng ca cc tc nhn xy ra s th nguyn t hay nhm nguyn t trong phn t bng nguyn t hay nhm nguyn t khc.3.1.1. P th i nhn SN (Nucleophilic Substitution)a. P th i nhn n PT SN1: b. Th i nhn lng phn t SN2: c. Th i nhn ni phn t SNi:d. Phn ng th i in t lng phn t SE2: 3.1.3. Phn ng th gc SR (Radical Substitution):xy ra vi hp cht noPhn ng SR l phn ng dy chuynPhn ng SR thng to ra hn hp cc sn phm khc nhau.3.2. Phn ng cng hpPhn ng cng hp l qu trnh chuyn lin kt thnh lin kt .3.2.1. Cng hp i in t AE (Electrophilic Addition)3.2.2. Cng hp i nhn AN (Nucleophilic Addition)3.2.3. Cng hp gc AR (Radical Addition)3.3. Phn ng tch loi E (Elimination)Phn ng tch loi l phn ng trong c hai nguyn t hoc nhm nguyn t b loi khi phn t m khng c thay th bng nhng nguyn t hoc nhm nguyn t khc.Thng th hai nhm b loi t hai nguyn t carbon cnh nhau v sn phm ca phn ng l cc hp cht khng no:Tu thuc vo cu to ca R trong RX v iu kin phn ng, cc phn ng tch loi c th xy ra theo c ch n phn t (E1) hoc lng phn t (E2).Phn ng tch loi v phn ng th i nhn lun tranh chp nhau.3.3.1. Tch loi n phn t (E1) Nu gc R trong RX l bc ba (hoc bc hai), dung mi phn cc mnh, phn ng xy ra qua giai on to hp cht trung gian l carbocation (nh phn ng SN1).3.3.2. Tch loi lng phn t E2Nu gc R trong dn cht halogen RX l bc mt (hoc bc hai), c mt ca base mnh, phn ng xy ra qua trng thi chuyn tip.3.4. Phn ng chuyn v (Rearrangement)Phn ng chuyn v l phn ng gy ra s thay i v tr ca mt s thnh phn cu trc (nguyn t, nhm chc, lin kt bi) trong phn t.Phn ng chuyn v thng xy ra theo c ch d ly. Phn ng chuyn v theo c ch gc t gp trong ho hu c.

Chng 5CC PHNG PHP TINH CH V XC NHCU TRC CC HP CHT HU CMC TIU1.Trnh by c cc phng php tinh ch hp cht hu c.2.Xc nh cu trc cc hp cht hu c bng phng php ph.NI DUNG1.Cc phng php tinh ch- Kt tinh li cht rn- Ct phn on (P thng, P gim) cht lng - Cc phng php sc k ( sc k ct, sc k lp mng,sc k kh lng, sc k lng hiu nng cao) phn lp, tinh ch2.Cc tiu chun tinh khit Xc nh cc hng s vt l: tonc, tos, n, , , cc s liu ca cc phng php ph3.Xc nh cng thc phn t. -Phn tch nh tnh nguyn t -Phn tch nh lng nguyn t+ Cng thc nguyn+ Khi lng phn t4.Khi nim v 1 s phng php ph kho st cu trc phn tXc nh cu trc phn t hp cht hu c bng cc Phng Php ph4.1.Ph t ngoi kh kin (UV Vis): Ph electron Thng tin v cu trc electron (lin kt bi, h lin hp) phn tch nh lng4.2.Ph hng ngoi (IR) Xc nh cc nhm chc, cc lin kt ... (xc nh tnh ng nht ca hp cht nghin cu so vi cht mu)4.3.Ph cng hng t ht nhn (NMR) 1H-NMR nhn bit loi proton & s proton mi loi 13C-NMR nhn bit s cacbon & v tr cacbon trong phn t4.4.Khi ph (MS) Xc nh khi lng phn t Xc nh cc on cu trc

Chng 6HIDROCARBON MCH H

MC TIU1. c c tn cc alkan thng dng,nu c ha tnh ca alkan .2. Xc nh ng phn hnh hc, danh php Z-E ,tnh cht ha hc ca alken.3. Trnh by c tn gi, tnh cht ha hc ca alkyn v vit s cc phn ng chuyn ha to thnh sn phm.4. Nu c ha tnh ca cc ien lin hp.

NI DUNG Hydrocacbon mch h : 2 loi-Hydrocacbon no : Alkan-Hydrocacbon khng no : Alken, Alkyn, Ankadien 1. Ankan (CnH2n+2 )Alkan l nhng hidrocacbon no mch h, c cng thc chung CnH2n+2 (n 1). Metan: CH4 (n=1), etan: C2H6 (n=2), propan: C3H8 (n=3), c thnh phn cu to ch khc nhau mt hay nhiu nhm CH2, chng hp thnh mt dy ng ng.1.1. Cu trc phn t Phn t alkan ch c nhng nguyn t Csp3 vi gc ha tr 109,5o do mch cacbon thng l ziczac v tn ti dng xen k (dng bn).

1.2. ng phn - ng phn cu to: ng phn v mch cacbon (cc alkan phn nhnh v khng phn nhnh).Bt u t butan C4H10 xut hin ng phn v mch cacbon

- ng phn lp th: + ng phn quang hc: khi n 7 cn c th c ng phn quang hc nu trong phn t c nguyn t cacbon bt i.

+ ng phn cu dng: Cng thc phi cnh Cng thc Newman

1.3. Danh php - Tn ring (tn thng thng): theo ngun gcMetan (CH4), etan (C2H6), propan (C2H6), butan (C4H10)- Tn hp l: ly metan lm c sCH3-CH3 metylmetan

- Danh php quc t (IUPAC) Chn mch chnh l mch thng di nht. nh s carbon trn mch chnh sao cho tng cc ch s ch v tr ca nhm th l mt s nh nht (theo IUPAC). Nu mch nhnh khc nhau khong cch nh nhau so vi hai carbon u mch chnh th phi nh s t u no c mch nhnh vi s carbon t nht Nu mch nhnh c s phn nhnh th phi nh s mch nhnh bt u t v tr gn vi mch chnh.

Cch gi tn: Tn cc gc (mch nhnh) v ch s ch v tr cc gc gn vo mch chnh. Tn gc (mch nhnh) ln lt t n gin n phc tp. Dng cc t Hylp (di, tri, tetra, penta, hexa, hepta, octa) ch s lng cc nhm th ging nhau v gi tn ca hydrocarbon no c s carbon tng ng vi s carbon trong mch chnh. 1.4. Phng php iu ch alkan 1.4.1. Phng php gi nguyn mch carbon 1.4.1.1. Kh ha hydrocarbon cha no

1.4.1.2. Kh ha dn xut halogen Tc nhn kh c th l Zn /H+ hoc acid hydroiodic c (HI)

1.4.1.3. Kh ho alcol Tc nhn kh l HI c (80%), nhit 180-200C v c mt phosphos

1.4.1.4. Kh ha acid v dn xut acid

Phn ng dng iu ch alkan c mch carbon ln. Kh ester d hn acid. 1.4.1.5. Thy phn hp cht c kim

1.4.2. Phng php lm tng mch carbon 1.4.2.1. Phn ng Wurtz

1.4.2.2. Phn ng in phn dung dch mui acid (phn ng Kolbe) 1.4.3. Phng php lm gim mch carbon Ct khan mui kim, kim th ca acid carboxylic vi vi ti, xt s thu c hydrocarbon c mch gim 1 carbon so vi acid carboxylic.

1.5. Tnh cht l hc Nhit si v nhit nng chy tng dn khi s carbon tng.Nhng ng phn no c hnh dng gn gang (gn vi hnh cu) th thng c nhit si thp hn nhng nhit nng chy cao hn so vi ng phn c hnh dng km gn gng. Ankan khng tan trong nc. D tan trong ether, trong cc hydrocarbon khc v trong cc dn xut halogen. 1.6. Tnh cht ha hc Trong phn t alkan ch c 2 loi lin kt: C-H v C-C. Chng l nhng lin kt hu nh khng phn cc. 1.6.1. Phn ng th - Tnh cht ca lin kt C - H 1.6.1.1. Phn ng halogen ha -Tc dng vi halogen

Phn ng xy ra theo c ch gc t do, c xc tc nh sng hoc nhit cao. 1.6.1.2. Phn ng nitro ha - Tc dng vi HNO3

1.6.1.3. Phn ng sulfon ha

1.6.2. Cc phn ng thuc lin kt CC 1.6.2.1. Nhit phn v cracking nhit cao khng c oxy khng kh, cc phn t alkan b phn hy hoc b gy mch carbon to thnh alkan v hydrocarbon cha no c mch carbon ngn hn. Qu trnh gi l qu trnh cracking. CnH2n+2 CxH2x+2 + CyH2y ( n = x + y )1.6.2.2. Oxy ha v t chy Khi t chy alkan to CO2 v hi nc ng thi gii phng nng lng.

Chnh v vy cc alkan nh metan, butan, octan ... c dng lm nhin liu. 2.Anken (CnH2n) Alken cn gi l olefin. Chng l nhng hydrocarbon cha no, khng vng, trong phn t c mt ni i. Alken c cng thc tng qut CnH2n (n 2)2.1. ng phn 2.1.1. ng phn cu to Ngoi ng phn v mch carbon, alken cn c cc ng phn do v tr ca ni i. Do alken c s ng phn cu to nhiu hn alkan c cng s carbon tng ng. 2.1.2. ng phn hnh hc - ng phn cis-trans Cc nhm th khng th quay t do chung quanh lin kt i m tn ti mt cch tng i v hai pha ca lin kt i. Do alken c ng phn hnh hc. Hai nhm th cng pha so vi mt phng th gi l ng phn cis. Hai nhm th khc pha so vi mt phng th gi l ng phn trans. V d: 2-buten cho 2 dng ng phn cis trans khc nhau:

2.2. Danh php - Tn thng thng: gi tn alken bng cch ly tn alkan c s carbon tng ng thay tip v ng ''an'' thnh ''ylen''.

Danh php ny ch gi tn nhng alken n gin -Danh php IUPAC: + Gi tn nh hydrocarbon no v thay v ng ''an'' bng v ng ''en'' + Chn mch chnh l mch di nht cha lin kt i . + nh s carbon trn mch chnh sao cho ni i c s b nht. V tr nhnh + Tn nhnh + S ch v tr ni i + Tn mch chnh + en

2.3. Phng php iu ch 2.3.1. Tch hydro halogenid t cc dn xut monohalogen 2.3.1.1.Phn ng tch loi E1 alkylhalogenid

2.3.1.2. Phn ng tch loi E2 alkylhalogenid Phn ng E2 xy ra trong iu kin c base mnh v dung mi km phn cc.

2.3.2. Tch loi nc t alcol 2.3.2.1. pha lng un nng alcol vi acid mnh (H2SO4, H3PO4) hoc vi KHSO4 s to alken.

2.3.2.2. pha hi Alcol di tc dng ca Al2O3 350 - 400C cng to alken 2.3.3. T dn xut dihalogen S tng tc gia dihalogen trn 2 carbon lin nhau vi bt kim loi (Zn,Cu) s thu c alken.

2.3.4. Phng php dehydro ho, cracking hydrocarbon no

Cc alken cng c to thnh khi nhit phn , cracking cc hydrocarbon no. 2.4. Tnh cht l hc Ba thnh phn u tin ca dy ng ng iu kin thng l cc cht kh. Cc thnh phn trung bnh l nhng cht lng. Cc thnh phn cao hn l cht rn.ng phn cis c nhit nng chy thp hn nhng li c nhit si cao hn so vi ng phn trans. 2.5. Tnh cht ha hc 2.5.1. Phn ng cng hp 2.5.1.1. Phn ng hydro ho c xc tc

2.5.1.2. Phn ng cng hp i in t (AE) C 2 giai on sau: Giai on I

Giai on II Quy tc Markonikov Trong phn ng cng hp, tc nhn khng i xng (HX...) tc dng vi mt alken khng i xng th nguyn t hydro ca HX s tn cng vo nguyn t carbon ca ni i c nhiu hydro hn, cn X s tn cng vo nguyn t carbon cn li ca ni i.

2.5.2. Hydroboran ha 6RCH=CH2 + B2H6 2(RCH2CH2)3B 2.5.3. Phn ng oxy ha Alken b oxy ha bi cc cht oxy ha khc nhau. 2.5.3.1. Vi KMnO4

2.5.3.2. Vi ozon (O3 )

2.5.3.3. Vi cc peroxyd Alken b oxy ha bng cc peracid. Sn phm to thnh l cc oxiran (epoxyd) 2.5.4. Phn ng trng hp (phn ng polymer ha) Phn ng trng hp cc alken hoc cc hp cht cha no khc c tm quan trng c bit trong cng nghip ha hc. C th c s chung nA (A)n. A l cc monomer, (A)n l cht cao phn t (polymer), n l h s trng hp. 2.5.5. Phn ng th 2.5.5.1. Th v tr allyl Tu theo cu to s th vo v tr allyl xy ra cc iu kin khc nhau

2.5.5.2. Th vo v tr vinyl 3.Alkyn( CnH2n-2 ) Alkyn hoc hydrocarbon acetylenic l hp cht khng vng cha no c cha mt lin kt ba ng vi cng thc chung CnH2n-2 (n 2).3.1. Danh php 3.1.1. Danh php IUPAC Cc alkyn u c tn cng l yn. Mch chnh l mch di nht c lin kt ba. nh s mch chnh sao cho lin kt ba c s nh nht. V tr nhnh + Tn nhnh + V tr lin kt ba + Tn mch chnh + yn

3.1.2. Danh php hp l - Danh php acetylen Cc alkyn n gin c xem nh dn xut ca acetylen CH3CCH : Methyl acetylen (CH3)2CHCCCH3 : Methylisopropylacetylen F3C-CCH : Trifluoromethyl acetylen 3.2. ng phn Cc alkyn c ng phn cu to v mch carbon v ng phn c v tr ca ni ba . Khc vi alken, cc alkyn khng c ng phn lp th. 3.3. Tnh cht l hc Cc alkyn hu nh khng tan trong nc, tan tt trong cc dung mi hu c t phn cc.3.4. Tnh cht ha hc 3.4.1. Tnh acid ca alkyn

3.4.2. Phn ng cng hp 3.4.2.1. Cng hp vi hydro Alkyn tc dng vi hydro c xc tc to thnh alkan

3.4.2.2. Phn ng cng hp i in t

3.4.2.3. Cng hp i nhn Khc vi alken, cc alkyn tham gia phn ng cng hp vi cc cht i nhn nh alcol, amin, acid carboxylic, amid, HCN to thnh cc hp cht tng ng. 3.4.2.4. Phn ng carbonyl ho vo lin kt ba

3.4.3. Phn ng trng hp

*Mt s alkin in hnh:Mt s poliaxetilen phn lp t ngun thc vt c dng lm thc phm hay l cht thm. V d: norcapilen c trong cy ngi dm v falcarinon pht hin trong cy carum h hoa tn, trong hng dng

Hin nay ngi ta cng cha bit r vai tr ca lin kt ba trong mi thm ca thc phm. Mt s poliaxetilen khc u c c tnh. Mt s khc li c ch, v d nh alkinyl xeton nh capelin c tc dng chng nm da

1,7-etinylestradiol c dng lm thuc kim sot sinh theo k hoch. N c dung lm thuc trnh thai thay th cho hormone c trong thin nhin, bi v n c hiu lc hn trong nga thai v do c th dng vi liu nh hn. Chng 7HYDROCARBON CYCLANIC

MC TIU1. Gi c tn cc loi cycloalkan: 1 vng, 2 vng. 2. Vit v trnh by c cu dng ca cyclohexan. NI DUNG Hydrocarbon cyclanic (cyclan, cycloankan) l nhng hydrocarbon no mch vng. Nguyn t carbon trng thi lai ha sp3. C nhiu loi hp cht vng no. Hp cht n vng: Monocycloalkan Hp cht a vng: Polycycloalkan. Phn chia hp cht a vng thnh cc loi sau: Hp cht a vng ngng t, Hp cht a vng c mch cu carbon, Hp cht a vng spiran. 1. Monocycloalkan 1.1. Danh php Gi tn alkan tng ng v thm tip u ng ''cyclo'' Nu trong phn t c mch nhnh th gi tn mch nhnh t n gin n phc tp. nh s cc nguyn t carbon trn mch vng xut pht t mch nhnh n gin v nh s theo chiu sao cho tng s cc ch s ch mch nhnh l nh nht.

1.2. ng phn Monocycloalkan c s ng phn nhiu hn s ng phn ca alkan c s carbon tng ng. V d: C8H16 c cc ng phn vng 3, 4, 6, 7, 8 cnh. 1.3. bn vng ca vng Cc hp cht c vng 3, 4 cnh km bn hn so vi vng 5, 6 1.4. Tnh cht ha hc ca cycloalkan Cc vng 3, 4 cnh th hin tnh cht cha no. Phn ng cng hp v vng b ph v. Phn ng th halogen khi c xc tc l nh sng

Cyclohexan b dehydro ha khi c xc tc l Pt hoc Pd.

2. Hp cht a vng 2.1. Hp cht a vng c lp

2.2. Danh php hp cht vng ngng t Hp cht vng ngng t l nhng hp cht m cc vng c cnh chung vi nhau.

2.3. Hp cht a vng c mch cu carbon Hp cht vng c cu l hp cht khng c cnh chung nhng c cc nguyn t carbon chung cho cc vng. Nguyn t carbon chung l nguyn t u cu.

C th c hp cht 3, 4 vng

Chng 8HYDROCARBON TERPENIC

MC TIU1. Nu c cch phn loi v gi c tn cc terpen v dn cht ca chng. 2. Nu c tnh cht ha hc v ng dng ca chng trong cc loi tinh du gp trong thin nhin. NI DUNG1. nh ngha v phn loi Hydrocarbon Terpenic (terpen) l nhng hydrocarbon cha no c cng thc chung (C5H8)n (n = 2,3,4,5,6...m ), c to thnh bng cc n v isopren lin kt vi nhau dng mch h hay mch vng, theo nguyn tc cng hp ''u - ui''.

Gi tr n c dng phn loi terpen: n = 1 Hemiterpen C5H8 ; n = 2 Monoterpen (C5H8)2 n = 3 Sesquiterpen (C5H8)3; n = 4 Diterpen (C5H8)4 n = 6 Triterpen (C5H8)6 ; n = 8 Tetraterpen (C5H8)8 trong c Carotenoid n = n Polyterpen (C5H8)n cao su Terpen tn ti trong thin nhin ph bin trong tinh du thc vt (thu c bng cch ct ko theo hi nc hay chit bng dung mi hu c cc b phn thc vt). Trong tinh du, ngoi terpen cn c cc dn xut oxy ca chng, thng l alcol, aldehyd, ceton, acid. Tt c c gi chung l terpenoid Cc terpenoid c dng cu to khng vng hoc cu to vng, n vng hay a vng. 2. Monoterpen C10H16 C 3 loi monoterpen: Monoterpen khng vng (c 3 lin kt i) Monoterpen 1 vng (c 2 lin kt i) Monoterpen 2 vng (c 1 lin kt i) 2.1. Monoterpen khng vng Myrcen.

Ocimen 2.1.1. Cc dn xut ca monoterpen khng vng Cc alcol ca monoterpen khng vng.

Geraniol v Nerol l cc ng phn cis v trans vi nhau.

Geraniol, Nerol, Linalol, Citronellol l thnh phn ch yu trong mt s tinh du lm hng liu: hoa hng, cam, chanh, s, geranium... Cc aldehyd ca monoterpen khng vng.

Citral, citronellal c nhiu trong tinh du s, tinh du bch n. 2.1.2. Tnh cht ca cc monoterpenoid khng vng S ng vng xy ra theo hng to khung p -mentan.

S ng vng xy ra theo hng to vng ionon Tng hp -ionon v -ionon Ionon c trong thin nhin, l thnh phn quan trng trong nhiu hng liu v c trong thnh phn cu to ca caroten v vitamin A. Citral ngng t vi aceton c xc tc base hoc acid th to thnh ionon. Ty huc vo tc nhn ng vng c th to -ionon hoc -ionon. Xc tc l acid phosphoric th -ionon c to thnh ch yu; xc tc l acid sulfuric th -ionon l ch yu. Phn ng to ionon qua nhiu giai on:

2.2. Monoterpen 1 vng 2.2.1. Limonen v ng phn Cc hp cht thuc loi monoterpen 1 vng c khung p-cymen hoc khung p-mentan Khung p-mentan l hexahydro-p-cymen

Tt c cc monoterpen 1 vng c cng thc C10H16 mang khung mentadien Tng hp limonen

Limonen c nhit si 175-176C. Limonen c tnh quang hot. (+)Limonen c trong tinh du cam, chanh, (-)Limonen c trong tinh bc h, chanh, ()Limonen c trong tinh du thng. nhit 250C limonen b racemic ha. Phn t limonen cn gi l dipenten v c th xem limonen nh 2 phn t penten ng vng vi nhau. 2.2.2. Tnh cht chung ca monoterpen 1 vng Phn ng cng hp. Cng hp vi HX ( X = Cl, Br ,HO- )

Cng hp vi halogen:

Phn ng oxy ho:

2.2.3. Cc dn xut ca monoterpen 1 vng (Terpenoid 1 vng) a. Alcol vng no

-Menthol. Menthol l thnh phn ch yu trong tinh du bc h (Mentha piperita ). Menthol c tnh quang hot. Trong thin nhin ch tn ti dng (-) menthol. Menthol dng kt tinh nng chy 34C. Nhm OH ca menthol c th b ester ha to ester v oxy ha to menthon (p-mentanon-3). Menthol c nhiu ng dng trong dc phm, thc phm.Menthol c chit xut t tinh du bc h hoc tng hp ha hc.

-cis-Terpin Terpin dng kt tinh khng mu, khng mi. Hai nhm OH ca 1,8-dihydro-p-mentan v tr cis gi l cis-terpin-1, 8. Terpin c ngm mt phn t nc gi l terpin hydrat, c t nc = 115-117C c quy nh l loi dc dng. Terpin d dng mt mt phn t nc to -terpineol hoc cineol (eucalyptol), ngoi ra cn to -terpineol v limonen. Terpin c tng hp t -pinen hoc t 1,8-dicloro-p-mentan. Terpin c dng lm thuc ho nh tc dng long m, st trng h hp.

-Cineol -1,8 (Eucalyptol). Cineol c th c 2 loi, cineol -1, 4 v cineol-1,8. Cineol-1, 8 l thnh phn ch yu ca tinh du Eucalyptus (tinh du trm, bch n). Loi nc t terpin -1, 8 cng thu c cineol-1,8. C th xem cineol l mt ether ni phn t c cu trc loi bicyclo c carbon chung v mt nguyn t carbon trn mt mch cu c thay th bng nguyn t oxy. Cineol c tc dng st trng ng h hp.

-Ascaridol Ascaridol c cng thc phn t C10H16O2. Nu cineol l oxyd th ascaridol l peroxyd. Ascaridol c trong tinh du giun. Ascaridol c to thnh khi chiu nh sng vo -terpinen c xc tc clorophyl. Phn ng theo c ch gc t do. Kh ha ascaridol c xc tc to thnh terpin -1,4. Ascaridol c s dng lm thuc ty giun.

b. Alcol c 1 lin kt i. L nhng monoterpenoid 1 vng khng no.

Terpineol c iu ch t terpin.

2.3. Monoterpen 2 vng (bicyclo) Cng thc cu to c bn ca cc monoterpen 2 vng c cc loi sau:

Chia monoterpen 2 vng thnh 3 loi ph thuc v ln ca vng th hai. Loi 1: Vng 6 cnh ngng t vi vng 3 cnh c caran v thuyan. Loi 2: Vng 6 cnh ngng t vi vng 4 cnh c pinan. Loi 3: Vng 6 cnh ngng t vi vng 5 cnh c camphan, iso-camphan, fenchan, isobornilan. C th gi tn theo danh php IUPAC ca cc cht trn nh sau: Caran: 3,7,7-trimethyl bicyclo[4.1.0]heptan Thuyan: 1-isopropyl-4-methylbicyclo[3.1.0]heptan Pinan: 2,6,6-trimethylbicyclo[3.1.1]heptan Camphan (Bornan): 1,7,7-trimethylbicyclo[2.2.1]heptan Isocamphan: 2,3,3-trimethylbicyclo[2.2.1]heptan Fenchan: 1,3,3-trimethylbicyclo[2.2.1]heptan Isobornilan: 2,7,7-trimethylbicyclo[2.2.1]heptan Trong cc loi hp cht ny th nhm hp cht thuc dy pinan v camphan c nhiu ng dng v l thuyt cng nh thc t. 2.3.1. Nhm pinan Pinan khng tn ti dng t do trong thin nhin. Hp cht cha no c mt ni i ca pinan l pinen. Pinen c nhiu ng dng. - Pinen Pinen c 2 loi: -Pinen (2,6,6-trimethylbicyclo[3.1.1]hepten-3(3)). -Pinen (6,6-dimethylbicyclo[3.1.1]hepten-2(10)).

Pinen l thnh phn ch yu ca tinh du thng. -pinen chim 65-90%, -pinen chim 5-20%. iu ch: nha thng + Na carbonat em ct ko theo hi nc thu c tinh du thng. Ct phn on tinh du thng thu c -pinen v -pinen. 2.3.2. Nhm Camphan. Dn xut quan trng ca camphan (bornan) l Camphor v Borneol. Camphor 1,7,7-trimethylbicyclo[2.2.1]heptanon-2

Tnh cht ca camphor. Camphor l cht rn nng chy 179C, c tnh quang hot. Camphor c 2 nguyn t carbon bt i xng (1 v 4), nhng ch c mt cp i quang v mt racemic. (+)Camphor v (-)Camphor c trong tinh du long no Cinnamomum camphora, thu c bng cch ct ko theo hi nc. ()Camphor thu c bng phng php tng hp t Camphor -pinen. Camphor to oxim. Chng ct camphor c mt ca ZnCl2 hoc P2O5 s to thnh p-cymen. T camphor c th to thnh borneol. Borneol Borneol l alcol no ca bornan (camphan). Cu trc lp th ca borneol v isoborneol: Borneol c cu hnh endo. Nhm gem-dimetyl pha trn mt phng vng cyclohexan. Nhm OH nm pha di mt phng . iso-Borneol c cu hnh exo. Nhm gem-dimethyl v nhm OH u pha trn mt phng ca vng cyclohexan.

Acid camphorsulfonic C th sulfon ha camphor to thnh acid. S sulfon ha xy ra v tr 10 hoc v tr 8.

3. Sesquiterpen (C5H8)3 Sesquiterpen c 3 n v isopren. 3.1. Phn loi Sesquiterpen khng vng c 4 lin kt i. Sesquiterpen 1 vng c 3 lin kt i. Sesquiterpen 2 vng (bicyclo) c 2 lin kt i. Sesquiterpen 3 vng (tricyclo) c 1 lin kt i. 3.2. Cc hp cht sesquiterpen 3.2.1. Sesquiterpen khng vng Farnesen C15H24: tn ti 2 dng ng phn v .

Cc dn xut c oxy ca farnesen l Nerolidol, Farnesol, acid Farnesenic.

3.2.2. Sesquiterpen 1 vng C cc khung c bn Bisabolan, Eleman, Humulan, Germacran.

Cc sesquiterpen c khung bisabolan l bisabolen (C15H24), Zingiberen (C15H24), Bisabolen c 3 ng phn do khc nhau v v tr ca lin kt i.

3.2.3. Sesquiterpen 2 vng: Bicyclosesquiterpen. Sesquiterpen 2 vng c cc cht nh Cadinen, Selinen, Azulen Cadinen Hai cng thc ng phn c th c:

Selinen C 2 ng phn.

Cc dn xut cha oxy ca salinen l Eudesmol v Santonin.

Guaiazulen Phn ln cc tinh du u cha cc hp cht c mu xanh hoc tm. Cc cht mu c khung azulen v sesquiterpen l guaiazulen. Dn xut cha oxy ca guaiazulen l guaiol.

4. Diterpen (C5H8)4 Diterpen c cng thc phn t (C5H8)4 gm 4 n v isopren. C 2 loi diterpen: Diterpen khng vng v diterpen vng 4.1. Diterpen khng vng Phytol Phytol l dn xut cha oxy ca diterpen khng vng c cng thc phn t C20H40O, l cht lng, nhit si 145C/ 0,03mmHg. Phytol c 1 lin kt i v mt chc alcol bc nht. Thy phn chlorophyl thu c Phytol. Phytol l mt phn cu trc ca vitamin E v vitamin K. Cng thc cu to ca Phytol nh sau:

Trong cng thc cu to ca vitamin K1 v nhm vitamin E c gc phytyl.

Dy vitamin E thuc nhm tocopherol gm 2 thnh phn cu to l croman v gc phytyl hydro ha.

4.2. Diterpen vng Diterpen 3 vng u c khung carbon 1-methyl-7-isopropylphenanthren hydro ha.

Cc diterpen vng loi ny gm c: acid abietic, acid sapietic, acid neo-abietic, acid palustric, acid pimaric, acid iso-pimaric. Chng u l nhng hp cht c 2 ni i c v tr khc nhau. Chc acid ti nguyn t carbon s 1 ca vng. Acid abietic l dn xut cha oxy tiu biu ca diterpen 3 vng (tricycloditerpen). Acid abietic c trong thnh phn ca collophan ph thi khi chng ct nha thng. Acid abietic l cht rn nng chy 170-174C.

5. Triterpen (C5H8)6 Triterpen c cng thc phn t (C5H8)6. Cht tiu biu thuc triterpen l squalen. Squalen c cu trc khng vng, c 6 lin kt i. C 4 n v isopren, trong c 2 n v isopren kt hp vi nhau theo "ui" v "ui". Cng thc cu to nh sau:

6. Tetraterpen (C5H8)8 Tetraterpen c cng thc phn t (C5H8)8 gm 8 n v isopren. Tetraterpen c dng vng v dng khng vng. Carotenoid thuc loi tetraterpen. 6.1. Carotenoid Nhng hp cht thuc dy caroten gi l carotenoid c cng thc cu to nh sau:

Khung carbon ca carotenoid c cu trc polyisopren. Carotenoid l cc cht mu thc vt hoc ng vt c mu vng hoc vng cam caroten v lutein kt hp vi chlorophyl. Khi kt hp vi chlorophyl, carotenoid c tc dng nh l mt cht nhy cm quang ha. Trong cc loi nm khng cha chlorophyl th mu ca nm l mu ca cc carotenoid. Carotenoid tan c trong du, m v vy cc lipid v cc lipoid u c mu vng nht. Carotenoid kt hp vi acid sulfuric m c v vi dung dch SbCl3 trong cloroform to mu xanh m (Phn ng Carr -Price). ng dng phn ng Carr -Price nh lng carotenoid. Mt s carotenoid l hydrocarbon nh caroten, mt s khc l dn xut cha oxy ca caroten nh xanthophyl, acid carotenoid , ester ca xanthophyl. 6.1.1. Caroten Caroten c cng thc phn t C40H56. C cc ng phn ,,, v -caroten. Caroten chit c t c c rt, v vy hp cht ny u tin c tn gi l carotin sau ny i thnh caroten. Caroten chit t c rt c 15% ng phn , 85% ng phn v khong 0 - 1% ng phn -caroten. -Caroten -Caroten c nhit nng chy 184-185C, cha 11 lin kt i v cha 2 vng -ionon trong phn t. Khng quang hot.

Khi tip xc ngoi khng kh -caroten b oxy ha v chuyn thnh mu tm, mu c trng ca vng -ionon.

-Caroten -Caroten l ng phn ca -caroten, nng chy 187-187,5C. -Caroten d chuyn thnh -caroten. Trong phn t -caroten c vng -ionon v vng -ionon. -Caroten c mt carbon khng i xng nn -caroten quang hot v quay phi.

- Caroten Nhit nng chy 176,5C, khng quang hot. C 12 lin kt i. Trong phn t c mt vng -ionon. C th xem phn t -caroten gm mt na phn t -caroten v mt na phn t licopen kt hp li vi nhau.

6.1.2. Licopen Cng thc phn t C40H56, c 13 lin kt i trong phn t. Licopen l mu ca c chua. Phn t khng quang hot v khng c vng ionon.

6.1.3. Vitamin A Cng thc phn t C20H30O. Cc vitamin A c ngun gc t -caroten, nh l mt na phn t -caroten v cha nhm chc alcol. Vitamin A1 v A2 khc nhau mt lin kt i trong vng.

Vitamin A cn gi l Retinol v n c th thu c khi kh ha Retinal. Cc caroten cn gi l tin sinh t A. C th minh ha s chuyn ha Licopen c trong c chua thnh vitamin theo s :

Chng 9AREN - HYDROCARBON THM

MC TIU1. Gii thch cu to ca nhn thm. 2. Gi tn c cc hydrocarbon thm. 3. Trnh by cc tnh cht ha hc ca benzen: c ch SE.

NI DUNG 1. Benzen v nhn thm 1.1. Cu to benzen Benzen c cng thc phn t C6H6. 1.1.1. Cc dng cng thc c in

Cc cng thc trn khng gii thch y tnh cht ha hc c trng ca benzen. 1.1.2. Khi nim hin i v cu to benzen Benzen bn vng, kh tham gia phn ng cng hp, kh b oxy ha v d tham gia phn ng th. Tnh cht c trng ny ca benzen gi l "tnh thm". Vy: "Tnh thm " l kh nng ca mt hp cht: D cho phn ng th, kh cho phn ng cng hp v phn ng oxy ha C th tng trng cng thc cu to ca benzen nh sau:

1.2. Nhn thm Benzen l hp cht c tnh thm c bn nht . Nhng hp cht khc c cu to vng phng, cha no v lin hp c s electron p to h thng lin hp tha mn v cng thc Huckel 4n+2 u c tnh thm tng t benzen. V d: V cc nhn thm vi cc gi tr n khc nhau.

2. Danh php v ng phn V tr nhnh + tn nhnh + benzen

Nu cc ng ng c 2 gc alkyl gn vo nhn benzen th 2 nhm ny c th cc v tr khc nhau. Chng l nhng ng phn ca nhau.

3. Phng php iu ch 3.1. Phng php dehydro ha cc cycloalkan

3.2. Phng php trimer ha

3.3. Phng php Wurtz -Fittig

3.4. Phng php alkyl ha theo phn ng Friedel - Crafts y l phng php iu ch cc ng ng ca benzen (Xem tnh cht ha hc ca hydrocarbon thm).

4. Tnh cht l hc Cc ng ng ca benzen l nhng cht lng, mt s l cht rn. Chng u c mi c trng. 5. Tnh cht ha hc T cu to lin hp ca vng benzen, hydrocarbon thm c cc loi phn ng: Phn ng th i in t vo nhn benzen. Phn ng cng vo vng benzen. Phn ng oxy ho. 5.1. Phn ng th i in t trn vng benzen Phn ng th tin hnh trong mi trng acid mnh hoc c mt mt cht xc tc. Acid mnh hoc xc tc c tc dng chuyn ha tc nhn phn ng thnh dng i in t Y+ (electrophile).

Tc nhn Y + s tng tc vi nhn benzen ti v tr c mt electron cao nht

C cc loi phn ng th i in t vo vng benzen nh sau: 5.1.1. Phn ng halogen ha Phn ng brom ha c s chung:

5.1.2. Phn ng nitro ha

5.1.3. Phn ng sulfonic ha

5.1.4. Alkyl ho hydrocarbon thm Thay th nguyn t hydro ca nhn thm bng gc alkyl. Tc nhn phn ng l alkyl halogenid RX vi xc tc l cc acid Lewis nh AlCl3 khan (phn ng Friedel -Crafts) hoc FeBr3, FeCl3.

5.1.5. Phn ng acyl ha 5.2. Phn ng cng hp ca hydrocarbon thm 5.2.1. Cng hp vi hydro

5.2.2. Phn ng cng halogen

5.3. Phn ng oxy ha

5.4. S nh hng trong phn ng th i in t

Cc nhm th trn l nhm th loi I

Cc nhm th trn l nhm th loi II Quy tc nh hng - Quy tc Holleman (Holleman Arnold Frederich 1859-1953) Nu trn nhn benzen c mt nhm th loi I (nhm tng hot) th nhm th ny nh hng cc nhm th mi vo v tr ortho v para ca vng benzen.

Nu trong nhn benzen c sn mt nhm th loi II (nhm h hot) th nhm ny s nh hng nhm th mi vo v tr meta trn nhn benzen.

Chng10DN XUT HALOGEN V HP CHT C KIMMC TIU 1. Gi c tn cc alkylhalogenid v arylhalogenid 2. Trnh by v so snh c tnh cht ha hc ca RX v ArX 3. c c tn theo danh php cc loi hp cht c kim. 4 Trnh by c ha tnh ca hp cht c Magnesi (thuc th Grignard). 5. Nu c ng dng ca cc hp cht c kim trong tng hp hu c. NI DUNG1.Dn xut halogen Nu thay th mt hay nhiu nguyn t hydro ca hydrocarbon bng mt hay nhiu nguyn t halogen th thu c dn xut halogen.

C cc loi hp cht halogen sau: Halogenoalkan, Halogenocycloalkan. Halogenoalken, Halogenocycloalken. Halogenoalkyn Halogenoaren. Tu thuc s lng nguyn t halogen c trong phn t c th c hp cht monohalogen v polyhalogen. Cc halogen hydrocarbon c nhiu ng dng quan trng. Chng c kh nng phn ng cao v vy hp cht halogen l nguyn liu u trong tng hp hu c. 1.1. Danh php 1.1.1. Danh php IUPAC Gi tn hydrocarbon tng ng v thm tn halogen nh mt tip u ng. Chn mch chnh l mch di nht cha halogen. nh s sao cho v tr halogen l b nht. Gi tn theo th t: S ch v tr v tn halogen + S ch v tr v tn mch chnh

+ Tn hydrocarbon ng vi mch chnh

Nu phn t c nhiu halogen cng loi th dng cc ch di, tri, tetra... ch s lng nguyn t halogen. Nu phn t c nhiu halogen khc loi th gi tn halogen theo th t a, b, c.. hoc theo th t " ln ".

1.1.2. Danh php thng thng Ngi ta xem dn xut halogen l sn phm thay th ca HX (HX RX). V vy c tn gi: Tn gc hydrocarbon + tn halogenid.

Vn thng gi tn mt s hp cht halogen theo tn quen dng nh cc haloform.

1.2. ng phn S ng phn ty thuc cu to ca mch carbon v v tr ca halogen.

1.3. Phng php iu ch C th iu ch cc hp cht halogen nh alkylhalogenid, vinylhalogenid, allylhalogenid, halogenoaren, benzylhalogenid theo cc phn ng ha hc c phn hydrocarbon. Cn ch rng cc hp cht fluor kh iu ch theo cc phng php nh iu ch cc hp cht clor, brom v iod. 1.3.1. Halogen ha alkan (xem phn alkan). 1.3.2. Cng hp HX vo alken (xem phn alken). 1. 3.3. Phn ng gia HX vi alcol 1.3.3.1. T alcol Khi alcol tc dng vi HX to thnh dn xut halogen theo s :

1.3.3.2. Phn ng gia phosphor halogenid hoc thionylclorid vi alcol. Alcol tc dng vi phosphotriclorid hoc phosphopentaclorid u to thnh dn xut monohalogen.

Alcol phn ng vi thionylclorid SOCl2 xy ra theo c ch sau:

1.3.3.3. iu ch dn xut monofluor Cho dn xut monoclor tc dng vi bc fluorid:

1.3.3.4. iu ch cc hp cht monohalogenoaren Thc hin phn ng th i in t gia halogen v aren hoc un nng mui diazoni (phn ng Sandmeyer).

3.3.5. iu ch cc dn xut polyhalogen Cc dihalogen c iu ch bng cch cho aldehyd hoc ceton tc dng vi phosphopentahalogenid PX5.

Cc phn ng cng hp halogen vo alken, alkyn u c kh nng to thnh cc cht di hoc tetrahalogen. S clo ha toluen c xc tc nh sng thng thu c hn hp mono v polyclorid 1.4. Tnh cht l hc Ngoi mt vi cht trng thi hi nh fluoroetan, clorometan, bromometan... phn ln cc dn xut halogen l cc cht lng khng mu hoc cc cht rn. Hp cht halogen khng tan trong nc nhng tan nhiu trong cc dung mi hu c. 1.5. Tnh cht ha hc 1.5.1. Cu to v kh nng phn ng Trung tm phn ng ca cc dn xut halogen l lin kt C -X. m inca halogen ln hn ca carbon. Lin kt C -X l lin kt cng ha tr phn cc.u m ca lin kt lch v pha halogen. Kh nng phn ng ca cc dn xut halogen ph thuc vo bn cht ca halogen. Kh nng phn ng tng theo th t RI > RBr > RCl > RF. Dn xut iod c kh nng phn ng cao v phn cc ca lin kt C -I ln nht so vi cc lin kt C -X khc. phn cc ca cc lin kt C -X ph thuc vo m in v kch thc ca nguyn t X. m in ca X cng nh v kch thc nguyn t X cng ln th lin kt C -X cng d phn cc. Kh nng phn ng ca dn xut halogen cn ph thuc vo c im ca gc hydrocarbon lin kt vi halogen. C th chia thnh 3 loi dn xut halogen theo kh nng phn ng: Kh nng phn ng bnh thng l cc dn xut alkyl v cycloalkyl halogenid.

Kh nng phn ng thp l cc dn xut cha cc gc hydrocarbon cha no v gc hydrocarbon thm, trong nguyn t halogen X lin kt trc tip vi carbon c lin kt i hoc nhn thm. Nguyn nhn kh nng phn ng thp l do cp in t p trn halogen lin hp vi gc hydrocarbon.

Kh nng phn ng cao l hp cht c cu to allylic.

S khc nhau ca 3 loi hp cht trn c cn c vo phn ng thy phn:

Kh nng phn ng gim dn theo cu trc ca gc R nh sau:

1.5.2. Phn ng th i nhn Cc dn xut halogen tham gia nhiu loi phn ng th khc nhau nh phn ng thy phn, th amin, to ether.... 1.5.2.1. Phn ng th i nhn ca hp cht alkyl halogenid Phn ng th xy ra gia alkyl halogenid RX v tc nhn i nhn Y - theo s :

Ty thuc vo cu to ca dn xut halogen, tc nhn i nhn, dung mi phn ng c th xy ra theo c ch lng phn t SN2 hoc n phn t SN1.

Bng phn ng th i nhn, t hp cht halogen to ra nhiu hp cht c cc nhm chc khc nhau.

Dn xut halogen tc dng vi cc alcolat hay phenol trong mi trng kim to thnh ether ROR' hoc ArOR' (phn ng Williamson).

1.5.2.3. Phn ng th i nhn ca hp cht halogenoaren S th xy ra kh khn, i hi nhit cao v p sut.

Nu trn nhn thm c nhm ht in t th phn ng xy ra d dng hn. Phn ng th gia clorobenzen v NH3 xy ra theo c ch "tch -cng" hoc ''c ch aryn" Phn ng th loi ny cng xy ra i vi cc tc nhn i nhn l cyanid CN-

1.5.3. Phn ng tch loi (Xem phn iu ch alken) 1.5.4. Phn ng vi kim loi 1.5.4.1. Tc dng vi natri Cc dn xut halogen mch thng cng nh vng thm u tc dng vi natri kim loi to thnh hydrocarbon (phn ng Wurtz v Wurtz - Fittig).

Phn ng ny cho php iu ch nhng hydrocarbon c s lng carbon ty . 1.5.4.2. Dn xut halogen tc dng vi nhiu kim loi hot ng khc Dn xut halogen tc dng vi kim loi to thnh hp cht c kim c nhiu ng dng v thc t cng nh l thuyt. c bit l phn ng ca hp cht halogen vi magnesi to thuc th Grignard (xem phn hp cht c kim).