Download - Steroidni hormoni - helix.chem.bg.ac.rs
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Steroidni hormoni
Testosteron Estron
Polni hormoni regulišu razvoj i funkciju reproduktivnih organa;
O H C H3
H
O
H H
O
H
H H
C H3
C H3
O H
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Cikloalkani
Rasprostranjenost u prirodi: “rigid scaffolding”.
Imena: Cikloalkani Ciklopropan, , , etc.
Supstituenti: Cikloalkil. Supstituisani cikloalkani: kod monosupstituisani, položaj supstituenat je “C1”.
etilciklobutan (nije potrebno numerisanje)
Alkilcikloalkani ili cikloalkilalkani?
Manje jedinice se smatraju supstituentima većih!!! 1
2
3
4
5 1-Ciklopropilpentan
(CH2)n ne CnH2n+2
pentilciklopropan IUPAC-novo pravilo:
alkilcikloalkani
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Disupstituisani:
a. Najmanji brojevi za položaj supstituenata
b. Redosled po abecedi
CH3
CH2CH3
1
2
1-etil-2-metilcikloheksan
1 2
4
CH3
1
3 4
Cl
Br
1,2,4 ne 1,3,4
1-bromo-2-hlor-4-metilcikloheksan
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Cikloalkani imaju dve strane.
Sa dva i više supstituenata novi tip izomerije
Supstituenti na istoj strane: cis
Supstituenti na suprotnim stranam: trans Stereoizomeri
Stereoizomeri
Br
F
Trans-1-brom-3-fluorcikloheksan
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Stereoizomeri: su stabilni na sobnoj temperaturi, pretvaranje jednog u drugi moguće samo raskidanjem veza.
Rotameri: konformeri se brzo uravnotežuju rotacijom oko veza
Ista konektivnost (njihovi atomi vezani istim redosledom), ali se razlikuju u prostornom rasporedu
Ova definicija uključuje i rotamere (anti, gauche, itd.).
Definicija stereoizomera:
Steroizomer : rotamer
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Kako možemo kvantifikovati “napon prstena”?
Potrebno je uporediti sa sistemom bez napona.
Toplota sagorevanja kao merilo stabilnosti.
sp3-ugljenik: uglovi veza 109.5°
60° 90° 120°
108°
Napon prstena
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~160
~160
~160
izomeri
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Primena: Relativni energetski sadržaj dva izomerna butana
Račvasti alkani su nešto stabilniji od izomera ravnog niza
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Predviđanje kod cikloalkana :
ΔH°sag (očekivano) (CH2)n: n x 157.4.
Razlika između očekivane i eksperimentalne vrednosti je napon prstena
Kod alkana za svaku dodatu (CH2) grupu prirast od δΔH°sag ~ -157.4.
Na osnovu ovog je moguće predvideti ΔH°sag (očekivano) za CnH2n+2: n x 157.4.
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120° 108°
60° 90° Mali prstenovi (3, 4) Obični prstenovi (5, 6, 7) Srednji prstenovi (8-12) Veliki prstenovi (>12)
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1. Uglovi veza (posebno C3 i C4)
2.Eklipsnost
3.Transanularne interakcije (posebno kod srednjih prstenova)
Napon prstena:
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Eklipsna
Ciklopropan
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Savijene veze kod ciklopropana
Trimetilen diradikal
Slaba veza: 65 kcal/mol
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Ciklobutan: “nabiranjem” se smanjuje eklipsnost
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Ciklopentan: konformacija koverte
Skoro
nezasenjena
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Cikloheksan: cikloalkan bez napona; konformacija stolice
pomeranje
C1,4
Veoma slične vrednosti za izračunatu i eksperimentalno određenu toplotu sagorevanja: -944,4 : -944,5 kcal mol-1
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Newman-ova projekcija
cikloheksana-nezasenjena
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Konformacija lađe, manje stabilna zbog eklipsnih interakcija i transanularnog napona
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…zato se lađa uvija.
Dva moguća oblika uvijene lađe se međusobno izmenjuju preko konformera lađe kao prelaznog stanja
-1.4 kcal mol-1
-1.4 kcal mol-1
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Kako nacrtati cikloheksan u konformaciji stolice
“dole” “gore”
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Promena konformacija cikloheksana
H
H Ea = 10.8
ΔG° = O eq
eq
ax
ax H
H
H H H H
H H H H
( )
( )
Transanularni napon
Eklipsni napon
Stolica Lađa + 6.9 kcal mol-1. Lađa je TS.
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Prevođenje jedne konformacije stolice u drugu
100,000 times/sec
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Konformacionom inverzijom aksijalni vodonici se pretvaraju u ekvatorijalne i
obrnuto
Ove dve strukture su identične. Šta se dešava sa supstituisanim cikloheksanima?
Gº = 0
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Supstituisani cikloheksani
ΔG° = +1.7 Kcal/mol
odnos=95:5
gauche
H H
CH3
Transanularne 1,3 diaksijalne
interakcije
H
CH3
ax eq
Konformaciona analiza: Aksijalni i ekvatorijalni metilcikloheksani nemaju iste energije
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Aksijalno-ekvatorijalni konformeri
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Konformaciona analiza: ΔG° mogu biti aditivne. Razmotrimo dimetilcikloheksane:
ΔG° = 0
ΔG° = +3.4!
ΔG° = 0
1,1-dimetilcikloheksan
Cis-1,4-dimetilcikloheksan CH3
CH3
CH3
CH3
CH3
CH3
H3C
CH3
CH3
H3C
diaksijalni
diekvatorijalni Trans-1,4-dimetilcikloheksan
CH3
CH3
Ali:
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Najveća grupa favorizuje jednu konformaciju:
ΔG° = 3.4-5 = -1.6 ax
eq
eq
ax
ax eq
+1.7
+1.7 -5
Veliki supstituenti kaoterc-Bu, „zaključava“ konformaciju
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Br COOH
H3C
H3C
Br
COOH
ΔG° = ?
Problem:
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Br COOH
H3C
H3C
Br
COOHΔG° = +2.56
+1.70 +1.41
-0.55
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sve-cis-heksametilcikloheksan:
sve-trans-heksametilcikloheksan:
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Srednji prstenovi: transanularne interakcije
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biciklo[2.2.1]heptan (norbornan)
Biciklo[4.4.0]dekan (dekalin), trans i cis
Biciklični, kondenzovani, policiklični, polihedralni alkani
kondenzacija
trans cis
H
H
H
H
most
zaključana lađa
Napraviti model i pokušati konformacionu inverziju!!!!
H
H
ekvatorijalne C-C veze trans-dekalin
H
H
aksijalne C-C veze ekvatorijalne C-C veze
cis-dekalin
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Ugljovodonici sa naponom: Da li postoji granica? Egzotični poliedri: Pet Platonskih
ili kosmička čvrsta tela (Platon 350 BC)
Tetrahedran
(vatra)
Kuban
(zemlja)
Dodekahedron
(“eter”)
Da li je moguće napraviti Platonska tela sa ugljeničnim skeletom(CH)n ?
ikosahedron (voda) i oktahedron (vazduh)
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Maier, Sekiguchi, 2002, tetrakis(trimethylsilyl)- tetrahedrane.
m.p. 135°C ! Strain: 130 kcal mol-1
Strain: 166 kcal mol-1
Strain: 60 kcal mol-1
Eaton, 1964, cubane, C8H8
Maier, 1978, tetra-t-Bu- tetrahedrane. Substituted C4H4
Paquette, 1982, dodecahedrane, C20H20, 12 faces
m.p. 202°C
m.p. 126°C
m.p. 430°C !
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Sekiguchi, Angew. 2005, 5821
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Oktanitrokuban: Novi
eksploziv i raketno gorivo
Eaton, Adv. Mat., 2000.
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Alotropi ugljenika: Cn
a truncated icosahedron
Benzene
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Zuo, J. M. et al. Science 2003, 300, 1419
Atomic Resolution Imaging of a Carbon Nanotube
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Ugljenične nanotube: novi materijali za budućnost
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Karbociklični proizvodi u prirodi
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Steroidi: tetraciklični proizvodi
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Prikazati sledeća jedinjenja u najstabilnijim konformacijama:
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Za svaki par izomera a-d odrediti koje jedinjenje je stabilnije (nacrtati odgovarajuće konformacije stolice):
a)
b)
c)
d)