2

2.1. C s l thuyt

2.1.1. Mt s khi nim

Terpen L hp cht hirocacbon c cng thc tng qut (CTTQ) (C5H8)n, n 2. Phn t cc hp cht ny c mch nhnh l cc nhm CH3 xut hin mt cch chu k trong mch.

Terpenoit L cc dn xut cha oxi ca terpen nh ancol, cc anhit v axeton.

Quy tc Isopren Khi nhit phn phn ln cc terpen v terpenoit u thu c cc isoprene iu cho php khng nh rng cu trc b khung cc terpen v terpenoit trong thin nhin c cu to bi cc n v isoprene.

Quy tc ny c ngh bi Wallach (1887) v Ruzica (1921).

2.1.2. Monoterpen v monoterpenoit (C10)

Monoterpen v monoterpenoit l nhng cht long d bay hi, l thnh phn chnh ca mt s ln tinh du thm thu c t hoa, l hoc qu

C th chia thnh ba nhm:

Monoterpen monoterpenoit mch h

Monoterpen monoterpenoit mt vng.

Monoterpen monoterpenoit hai vng (bixiclo).

2.1.2.1. Monoterpen monoterpenoit mch h

Cc hp cht ny phn ln c khung 2,6 dimetyl octan

a) Myrcen v Ocimen ( CTTQ: C10H16)

* Myrcen (s: 1660C 1680C): l mt monoterpen ph bin trong t nhin. Tn ti dng v ( dng ph bin hn). Phn ln cc sn phm trong t nhin dng - myrcen.

* Tnh cht:

-

Nh vy myrcen c ba lin kt i.

- Myrcen c cu trc dien lin hp cu dng cis do c th tham gia phn ng Diels Alader vi cc dienophin ( VD: Acrokin, acrylonitrin)

- Phn ng ozon phn myrcen to sn phm: axeton, focmanehit v mt xeton diandehit.

-

Nh vy myrcen c cu to tong ng l 3 metylen 7 - metyl octa 1,6 dien.

Trong k ngh - myrcen c iu ch bng cch thy phn - pinen ( Hsut 90%).

* Ocimen:

Ocimen c bn dng ng phn:

- Thy phn - pinen 1750C thu c cis - - ocimen.

- un nng cis - - ocimen 185 1900C to thnh ng phn alloocimen.

* Tnh cht:

Nh vy, ocimen c ba lin kt i.

- Ocimen to sn phm cng vi anhit maleic chng t hai trong ba ni i lin hp.

- Phn ng ozon phn ocimen to sn phm: fomanhit, axton, axit axetic, axit malonic, v anhit levunic CH3COCH2CH2CHO.

Ocimen thng c s dng iu ch ocimenol (2,6 dimetylocta 5,7 dien 2 ol).

b) Cc terpenoit dng ancol

* Geraneol, nerol, linalool ( CTTQ: C10H18O)

Geraneol, nerol, linalool c mi thm d chu, c mt trong nhiu loi tinh du khc nhau.

Geraneol c trong hn 200 loi, c nhiu trong tinh du hoa hng, tinh du s, v trong tinh du cam.

Nerol c trong hn 50 loi v cng c trong tinh du hoa hng, tinh du s nhng hm lng it hn Geraneol.

Linalool c trong tinh du chanh, tinh du r ca cy nin kiu hay ht mi.

Trong mi trng axit, ba ancol ny c th chuyn ha ln nhau. Tuy nhin, geraneol thng chuyn ha thnh linalool, cn nerol th chuyn ha thnh .

iu ny chng t rng nerol c cu hnh cis v geraneol c cu hnh trans.

Geraneol, nerol, linalool l cc sn phm c gi tr trong cng nghip hng hiu. Cc dn xut este, c bit l cc axetat u l cc cht thm quan trng.

Geraneol, nerol, linalool c bn tng hp t

* Citronellol (CTTQ: C10H20O)

Citronellol c nhiu trong tinh du hoa hng (35% - 55%) v trong tinh du s. C th tng hp Citronellol t p pinen, t geraneol (nerol):

c) Cc terpenoit dng anhit

* Geraneal, neral (CTTQ: C10H16O):

Citral l thnh phn quan trng ca monoterpenoit mch h. Tn ti di hai dng ng phn: Citral a ( trans hay Geraneal), Citral b ( cis hay neral)

Citral c trong hn 150 loi tinh du khc nhau. C nhiu trong tinh du s chanh (85%). Citral c thu t phng php chng ct tinh du s chanh hoc c tng hp t Geraneol hoc nerol.

* Citronellal (CTTQ: C10H18O)

C trong hn 50 loi tinh du khc nhau. Nhng c nhiu trong tinh du s Jawa, tinh du bch n chanh.

Citronellal c th oc iu ch t s chng ct tinh du hoc c tng hp t citral hoc citrol.

Hoc c tng hp t :

2.1.2.2. Monoterpen monoterpenoit mt vng

a s cc hp cht loi ny c khung 1 metyl 4 isopropyl xiclohexan (p menthan), ch c 6 cht tn ti trng thi thin nhin l:

a) Limonen (C10H16, s: 175,5 176,50C)

L hirocacbon terpen ph bin sau . N c hm lng ln trong tinh du cam, tinh du chanh, bc h cayc mi thm mt.

Limonen c th c iu ch bng cch tch nc terpineol:

b). Cc terpenoit mt vng dng ancol

* Mentol (C10H20O):

L hp cht monoterpenoit vng ph bin v quan trng nht. Phn ln mentol c tch t tinh du bc h (70 80%). Mentol trong trng thi t nhin tn ti dng quay tri.

Mentol (3 hiroxi p menthan)

C 8 ng phn quang hc, 4 bin th raxemat v 4 ng phn hnh hc: D,L Mentol (e,e,e); D,L Neolmentol (e,a,e); D,L Isomentol (e,e,a); D,L neoisomentol (e,a,a).

Trong tinh du bc h, D,L mentol c mi thm d chu, cn D,L isomentol v neomentol c mi kh chu.

ngi ta c th tng hp mentol nh sau:

Hay

* C10H18O:

l mt ancol bc ba tn ti trong t nhin c ba dng +, - , . Ngi ta thng iu ch t :

* 1,8 Cineol C10H18O (s: 174,40C)

1,8 - Cineol c trong tinh du bch n, trm. L mt este ng phn ca . Do khi hirat ha cis 1,8 terpinhidrat th thu c 1,8 - Cineol .

c) Cc terpenoit mt vng dng anhit

* Menton (C10H18O)

Mentol c trong tinh du bc h, tn ti hai dng: menton (e,e) v Isomenton (a,e), d dng c iu ch bng phn ng oxi hoa mentol:

2.1.3. Monoterpen monoterpenoit hai vng

C nm loi hp cht monoterpen hai vng c bn sau:

a) Dn xut ca Pinan

Trong nhm ny v Pinen l hai hp cht ht sc quan trng v l cht c s iu ch cc hp cht khc.

Ngun nhin liu ca , Pinen l tinh du thng.

Trong cng thc cu to c hai C*, theo l thuyt phi c bn ng phn quang hc, nhng thc t ch c hai ng phn: D,L pinen; D,L pinen.

Nguyn nhn l do hp cht cu, 2C* phi cng quay mt lc do s ng phn gim i mt na.

H pinen c tm quan trng c bit dng iu ch cc hp cht khng vng, n vng hoc hp cht h camphan di tc dng xc tc axit.

Tnh cht ca ng phn dn xut pinan l vng bn cch c th m d dng.

Phn ng xc tc bng axit:

Trong dung dch axit pinen to thnh terpin, terpin c dng iu ch vi cht lng cao.

Thc t, mt lng ln c iu ch trc tip t tinh du thng bng phn ng Bertram Walbaum:

Phn ng nhit phn pinen to thnh cc hirocacbon trong c limmin, myrcen, ocimen v alloocimen. Nhng hp cht ny dng lm nguyn liu u tng hp mt s ln cc tinh cht trong k ngh nc hoa.

Ha hc ca , pinen ng vai tr quan trng trong s pht trin hp cht hu c ni chung do c nh hng ng k n s pht trinca h thng hai vng cng nh nhng hiu bit v c ch phn ng.

b) Dn xut ca Bornan (Camphan): Camphor

Camphor l cht kt tinh khng mu, n: 1800C, c tnh quang hot. Trong thin nhin camphor tn ti hai dng + , - c trong tinh du cy long no. Camphor tng hp thng dng raxemic. Cng thc cu to c ngh bi Brect (1893).

Camphor c ngha quan trng trong ha hc terpenoit c th c iu ch t , pinen.

* T Bornylclorua n caphen n Isobornylfocmiat u c s chuyn v Wagner Mecrwei.

2.2. Bi tp

Bi 1: Myrcen C10H16 (X) l terpen c tch ra t tinh du cy Nguyt qu. Myrcen cng 3 H2 thu c hirocacbon (Y) C10H22. Ozon ha Myrcen ri thy phn cho cc sn phm sau:

a. Da vo quy tc isopren ca terpen hy cho bit cng thc cu to ng ca myrcen (X) v hirocacbon (Y).

b. Hon thnh s bn tng hp cc ancol terpenoit t pien.

Gii: a.

Bi 2: a. Hy xc nh cng thc cu to ca hp cht c cng thc phn t C10H18O theo d kin thc nghim sau:

- Cng hai phn t H2 khi c Ni xc tc, nhit .

- Tham gia phn ng trng gng.

- B oxi ha ct mch cho: CH3COCH3, HOOC(CH2)2CH(CH3)CH2COOH.

b. Da vo quy tc isoprene hy xc nh cng thc cu to ng cho cht A.

Gii:

a. + 2H2 trong c hai lin kt

tham gia phn ng trng gng A c nhm CHO. Nh vy : c 1 lin kt i v 1 lin kt , c nhm CHO Cng thc cu to ca :

b. Da vo quy tc isoprene Cng thc cu to ng ca :

Bi 3: a. Hy xc nh cng thc cu to ca hp cht c cng thc phn t C10H16O theo d kin thc nghim sau:

- Cng ba phn t H2 khi c Ni xc tc, nhit .

- Tham gia phn ng trng gng.

- B oxi ha ct mch cho: axeton, axit oxalic, axit CH3COCH2CH2COOH

b. Da vo quy tc isoprene hy xc nh cng thc cu to ng cho cht A.

c. c hai ng phn A1, A2; Kh chn lc A1, A2 thu c B1, B2 tng ng c cng thc phn t C10H18O. Khi c axit H2SO4 long, c xc tc, c hai cht B1, B2 u tham gia phn ng vng ha to terpenoit, B1 phn ng nhanh hn B2. Hy xc nh cng thc cu to ca A1, A2, B1, B2, vit cc phn ng xy ra.

d. T pinen, thnh phn chnh trong tinh du thng, ngi ta nhit phn thu myrcen l nguyn liu iu ch B1, B2 bng cch hirat ha myrcen vi xc tc l H2SO4. Sau bng phng php chng ct phn on tch bit B1, B2. Hy vit c ch phn ng hirat ha myrcen v phng trnh phn ng xy ra.

Gii:

+ 3H2, tham gia phn ng trng gng, suy ra l hp cht anhit cha no hai . b oxi ha ct mch cho: CH3COCH3, HOOCCOOH, CH3COCH2CH2COOH. Vy cng thc cu to ca :

b. Da vo quy tc isoprene, cng thc cu to ng ca l:

c. Hai ng phn ca :

Bi 4: Limonen C10H16 c tm thy trong v cam, v chanh, v bi. Limonen cng hai phn t H2 thu c p mentan C10H20. Oxi ha Limonen bi KMnO4 to thnh hp cht:

a. Cng thc cu to c th c phn ng vi sn phm oxi ha.

b. Da vo quy tc ispren hy cho bit cng thc cu to ng ca Limonen.

c. T Limonen vit cc phn ng iu ch terpineol v 1,8 Cineol.

Gii:

c.

Bi 5: Geraneal l hp cht t nhin c cng thc phn t C10H16O. Geraneal tham gia phn ng vi hyroxylamin v tham gia phn ng trng gng.

a. Khi hiro ha Geraneal c mt Pt, ngi ta thu c sn phm (C10H22O). khng cn phn ng trng gng, nhng khi un nng vi axit H2SO4 th to thnh hirocacbon (C10H20) m khi ozon phn cho metanal v dimetyl 2,6 heptanal. Vit cc phn ng, cho bit cng thc cu to , B.

b. Khi ozon phn Geranial cho sn phm: CH3COCH3, anhit levulinic CH3COCH2CH2CHO v glyoxal OHCCHO. Vit cng thc khai trin phng ca Geranial v cc ng phn c th c. Bit rng trong mi trng axit, Geraniol, mt ancol c mch cacbon hon ton ging vi Geranial chuyn thnh sn phm chnh Linalol.

c. Geranial tham gia phn ng ngng t andol vi axeton trong mi trng kim, tch nc to sn phm xeton cha no, cht ny trong mi trng axit b vng ha to hai sn phm ionon, ionon. Vit phng trnh phn ng xy ra.

Gii:b.

Mt khc:

T ta c cu to ca Geranial :

ng phn hnh hc:

Bi 6: Hy biu din cc ng phn cu dng ca mentol c tch ra t tinh du bc h.

Gii:

Mentol c 3C* nn c 8 ng phn quang hc tng ng 8 cu dng.

Bi 7: Campho c dng lm sn, vecni, thuc tr su, thuc bo qun Trong y-dc, n c s dng lm thuc gim au, gy m v kh trng. Ngy nay, campho c th c tng hp t - pinen, mt thnh phn ca nha cy thng.

-pinen

campho

Hy xut mt quy trnh tng hp campho t -pinen.

Bi 8: Xitral (CH3)2C=CHCH2CH2C(CH3)=CHCH=O c trong tinh du chanh, gm 2 ng phn a v b.

a) Cu to phn t xitral c tun theo qui tc isoprenoit hay khng? Hai cht a v b thuc loi ng phn no? Hy vit cng thc cu trc v gi tn h thng hai ng phn .

b) tch ring hai ng phn a v b, ngi ta s dng semicacbazit v axit v c. Hy nu vn tt qu trnh thc nghim .

c) Kh xitral ri chuyn ho sn phm A theo s :

Vit cng thc cu to ca A, B, C v hon thnh s cc phn ng. Gii thch qu trnh chuyn ha to thnh C.

b) Tch ring hai ng phn a v b:

c) Cng thc cu to ca A, B, C. Gii thch qu trnh chuyn ha to thnh C.

Bi 9: Hp cht hu c A cha 79,59 % C; 12,25 % H; cn li l O ch chim mt nguyn t trong phn t. Ozon phn A thu c HOCH2CH=O ; CH3[CH2]2COCH3 v CH3CH2CO[CH2]2CH=0. Nu cho A tc dng vi brom theo t l mol 1:1 ri mi ozon phn sn phm chnh sinh ra th ch thu c hai sn phm hu c, trong s c mt xeton. un nng A vi dung dch axit d dng thu c sn phm B c cng cng thc phn t nh A, song khi ozon phn B ch cho mt sn phm hu c duy nht.

a. Xc nh cng thc cu to v gi tn A.

b. Tm cng thc cu to ca B v vit c ch phn ng chuyn ho A thnh B.

Bi 10: T tinh du bc h ngi ta tch c (-)-menton (trans-2-isopropyl-5-metylxiclohexanon). Khi ch ha (-)-menton vi axit hoc kim, n chuyn mt phn thnh xeton ng phn (+)-isomenton. Khi ch ha (-)-menton vi anhirit axetic trong dung dch natri axetat th thu c hai ng phn A v B c cng thc phn t C12H20O2.

a. V cc cu trc ng phn lp th ca (-)-menton.

b. Dng cng thc cu trc, hy gii thch s to thnh (+)-isomenton, A v B t (-)-menton.

Bi 11: Hp cht A1 l dn xut ca eugenol c kh nng kch thch sinh trng thc vt. T eugenol c th tng hp A1 theo hai cch sau:

Hy gii thch v so snh kh nng phn ng ca hai cch tng hp trn.

Bi 12: Xitral (C10H16O) l mt monotecpen-anehit c trong tinh du chanh. Oxi ha xitral bng KMnO4 thu c axit oxalic, axeton v axit levulinic (hay axit 4-oxopentanoic). T xitral ngi ta iu ch iu ch vitamin A.

a. Xc nh cu to v vit tn h thng ca xitral.

b. Vit s cc phn ng chuyn ha xitral thnh

c. sinh ra c ln mt lng ng k cht ng phn cu to l -ionon, khng th tch ra bng cch chng ct.

Trnh by c ch to thnh -ionon cng vi Nu phng php tch ring hai ng phn .

d. T axetilen, v cc ho cht cn thit, hy iu ch vitamin A.

( Dng lm thuc ho long m)

H mt vng

Hp cht dy camphan

, - pinen

Kim/ ancol

EMBED ChemWindow.Document

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