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Slajd 1
Alkeny:
Struktura, nazewnictwo,
Termodynamika i kinetyka
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Slajd 2
Węglowodory te zawierają wiązanie podwójne
C C
double bondthe functional group
center of reactivity
Alkeny
wiązanie podwójnegrupa funkcyjna
centrum reaktywności
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Slajd 3
Łańcuchowe alkeny:CnH2n
Pierścieniowe alkeny:CnH2n–2
Molecular Formula of Alkene
CH3CH2=CH2
alken alken cykliczny alken cykliczny alken
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Slajd 4
Nazewnictwo systematyczne alkenów•Należy wybrać najdłuższy łańcuch węglowy zawierającygrupę funkcyjną
1-buten 2-buten 2-heksen
2-propylo-1-heksen
najdłuższy łańcuch węglowy zawiera 8 atomów węgla ale najdłuższy łańcuch zawierający grupęfunkcyjną zawiera 6 atomów węgla stąd właściwa nazwa to heksen.
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Slajd 5
•Podstawniki wymienia się w kolejności alfabetycznej
•Nazwę należy tworzyć tak aby grupa funkcyjna oraz podstawniki miały jak najniższy numer
3,6-dimetylo-3-oktan 5-bromo-4-chloro-1-heptan
2,5-dimetylo-4-oktannie
4,7-dimetylo-4-oktanponieważ 2<4
2-bromo-4-metylo-3-heksannie
5-bromo-3-metylo-3-heksanponieważ 2<3
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Slajd 6
•W cyklicznych alkenach nie ma potrzeby podawania numeru określającego położenie grupy funkcyjnej
3-etylocyklopenten 4,5-dimetylocykloheksen 4-etylo-3-metylocykloheksen
1,6-dichlorocykloheksennie
2,3-dichlorocykloheksenponieważ 1 < 2
5-etylo-1-metylocykloheksennie
4-etylo-2-metylocykloheksenponieważ 1 < 2
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Slajd 7
Dodatkowe nazewnictwowęgiel winylowy
węgiel allilowy
grupa winylowa grupa allilowa
nazwa systematyczna: chloroetan 3-bromopropennazwa zwyczajowa: chlorek winylu bromek allilu
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Slajd 8
Struktura alkenów
sześć atomów węglależy w jednej płaszczyźnie
nałożone bocznie orbitalep tworzą wiązanie π
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Slajd 9
Izomeria alkenów
cis-2-buten trans-2-buten
Związki te nie mają izomerów cis-trans ponieważ podstawniki przy tym samym atomie węgla o hybrydyzacji sp2 są takie same
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Slajd 10
Moment dipolowy izomerów alkenów
cis-2-buten trans-2-buten cis-1,2-dichlorobuten trans-1,2-dichlorobuten
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Slajd 11
Izomeryzacja alkenów wymaga rozerwania wiązaniaπ pomiędzy atomami węgla o hybrydyzacji sp2
cis-2-penten trans-2-penten
izomer cis izomer trans
zerwane wiązanie π
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Slajd 12
Izomeryzacja cis-trans pod wpływem światła
rodopsyna metarodopsyna II(trans-rodopsyna)
wiązanie ciswiązanie trans
światło
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Slajd 13
Izomery E i Z
Który to izomer cis, a który trans?
izomer Z izomer E
wyższy priorytet wyższy priorytet
niższy priorytet niższy priorytet
wyższy priorytet
wyższy priorytetniższy priorytet
niższy priorytet
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Slajd 14
Zasady stosowania oznaczeń E i ZZasada 1: Określić liczbę atomową atomów
bezpośrednio związanych z atomamiwęgla o hybrydyzacji sp2.
izomer Z izomer E
wyższy priorytet wyższy priorytet
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Slajd 15
Zasada 2: Jeśli pierwszy atom nie rozstrzyga,należy rozpatrywać kolejne atomypowiązane z bezpośrednio sąsiadującym.
izomer Z izomer E
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Slajd 16
Zasada 3: Wiązanie wielokrotne traktowane jestjak kilka atomów połączonychwiązaniami pojedynczymi.
izomer Z izomer E
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Slajd 17
Zasada 4: O pierwszeństwie izotopów decydujewiększa liczba masowa.
izomer Z izomer E
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Slajd 18
Alkeny są związkami, których cząsteczki sąbogate w elektrony
Nukleofil: bogaty w elektrony atom lub cząsteczka, która dzieli elektrony z elektrofilem
Przykłady nukleofili:
Są nukleoflami
To są nukleofile, bo mają parę elektronów,którą mogą uwspólnić
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Slajd 19
Nukleofile przyciągają atomy lub cząsteczkiposiadające deficyt elektronów (elektrofile)
Przykłady elektrofili:
To elektrofile, ponieważ mogą przyjąćparę elektronów
To elektrofile, ponieważposzukują elektronu
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Slajd 20
Addycja elektrofilowa HBr do alkenów
karbokation 2-bromobutanhalogenek alkilu
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Slajd 21
Zakrzywione strzałki w mechanizmachreakcji
Przesunięcie pary elektronów
Przesunięcie jednego elektronu
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Slajd 22
Wykorzystanie strzałek
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Slajd 23
Diagram przebiegu reakcji
W stanie przejściowym wiązania są częściowo uformowaneProdukty pośrednie mają w pełni uformowane wiązania
postęp reakcji
Ener
gia
swob
odna
energia swobodna substratów
stan przejściowy:
najwyżejenergetyczny
stanreakcji
energia swobodna produktów
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Slajd 24
Termodynamika opisuje własności układu w stanie równowagi
produktysubstraty
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Slajd 25
Parametry termodynamiczne
Zmiana standardowej swobodnej energii Gibbsa (∆G°)
Entalpia (∆H°): ciepło oddawane lub absorbowanepodczas reakcji
Entropia (∆S°): miara nieuporządkowania
∆G° = ∆H° – T∆S°
Jeśli ∆S° jest małe w stosunku do ∆H°, to ∆G° ~ ∆H°
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Slajd 26
Reakcja egzoenergetyczna–∆G°
Reakcja endoenergrtyczna+∆G°
postęp reakcji postęp reakcji
Ener
gia
swob
odna
substrat
substratprodukt
produkt
reakcjiaegzoenergetyczna∆G° ujemna, Keq > 1
reakcjiaendoenergetyczna
∆G° dodatnia, Keq < 1
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Slajd 27
Addycja elektrofilowa HBr do 2-Butenu
W reakcjach wieloetapowych o szybkości reakcjidecyduje jej najwolniejszy etap
Ener
gia
swob
odna
postęp reakcji
produkt pośredni
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Slajd 28
Solwatacja: oddziaływanie pomiędzy rozpuszczalnikiem a cząsteczkami lub jonamizwiązku rozpuszczonego
solwatacja ładunku dodatniego przez cząsteczki wody
solwatacja ładunku ujemnego przez cząsteczki wody
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Slajd 29
Reakcje alkenów
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Slajd 30
Addycja elektrofilowa do alkenów
wiązanie podwójne skała się z wiązania σ i wiązania π
wiązanie π uległo rozerwaniu powstało nowe wiązanie σ
elektrofil nukleofil
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Slajd 31
Addycja halogenowodoru
eten chlorek etylu
2,3-diemtylo-2-buten 2-bromo-2,3-dimetylobutan
cykloheksen jodocykloheksan
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Slajd 32
Jaki produkt powstanie?
2-metylopropen chlorek tert-butylu chlorek izobutylu
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Slajd 33
O kierunku reakcji decyduje tworzenie karbokationu
kation tert-butylowy
kation izobutylowy
chlorek tert-butylujedyny produkt
chlorek izobutylunie powstaje
bardziej stabilnykarbokation
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Slajd 34
Stabilność karbokationów
trzeciorzędowy drugorzędowy pierwszorzędowy kation metylowy
rosnąca stabilność
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Slajd 35
Grupy alkilowe rozpraszają ładunek dodatni stabilizując karbokation
Mapy potencjału elektrostatycznego
kation tert-butylowy kation izobutylowy kation etylowy kation metylowy
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Slajd 36
Delokalizacja elektronów
hiperkoniugacja
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Slajd 37
W reakcjach regioselektywnych jeden z izomerów konstytucyjnychjest głównym lub jedynym produktem
Reguła MarkovnikovaElektrofil przyłącza się do atomu węgla o hybrydyzacjisp2 do którego przyłączonych jest więcej atomów wodoru
2-metylopropen
jedyny produkt
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Slajd 38
Addycja halogenu do alkenów
jon bromoniowy1,2-dibromoetan
wicynalny dibromek
jon bromoniowyetenu
jon bromoniowycis-2-butenu
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Slajd 39
mniej stabilny
bardziej stabilny
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Slajd 40
Tworzenie rodników
nadtlenek alkilu rodnik alkoksylowy
rodnikbromkowy
światło
lub
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Slajd 41
Addycja rodnikowa do alkenów
rozpoczęcie reakcji
rozwinięcie reakcji
zakończenie reakcji
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Slajd 42
Względna stabilność rodnikówalkilowych
rosnąca stabilność
trzeciorzędowy drugorzędowy pierwszorzędowy rodnik metylowy
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Slajd 43
Addycja wodoru do alkenów
2-buten butan
2-metylopropen 2-metylopropan
cykloheksen cykloheksan
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Slajd 44
Katalityczne uwodornienie alkenów
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Slajd 45
Energia potencjalna izomerów pentenu
ener
gia
pote
ncja
lna
najtrwalszynajmniej trwały
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Slajd 46
Względna stabilność podstawionychalkilami alkenów
rosnąca stabilność
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Slajd 47
Zawada steryczna w alkenach
cis-2-buten trans-2-buten
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Slajd 48
Względna stabilność dialkilopodstawionych alkenów
rosnąca stabilność
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