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+ X
Y X
C Y
A syn addition
Y C C + X Y X C C A anti addition
H2 catalisador
H H
C C
H H
C C
Complexo alqueno-cat.
C C H H
C C H
catalisador regenerado
O papel do catalisador
H2, Pd
H3C
CH3
H H3C
Pd, 1 atm
CH3C CCH3
H2
(Lindlar) Pd/CaCO3/Pb
H H cis-2-Buteno C C CH2CH3
CH3CH2C CCH2CH3
O Ni OCCH 3
2
H2/Ni2B
CH3CH2
H H (Z)-3-Hexeno
NaBH 4 C2H5OH Ni2B P-2
H3C
CH3
H2 Pd/C
H3C
CH3
CH3 H H H
H3C
CH3
4-Octyne
Li
NHEt
R C C
R R Radical anion Vinylic radical A lithium atom donates an electron to The radical anion acts as a base and removes a the T bond of the alkyne. An electron proton from a molecule pair shifts to one carbon as the of the ethylamine. hybridization states change to sp2. R C C R H Li
R C C
H R H NHEt
R C C
R H Vinylic radical trans-Vinylic anion trans-Alkene The anion acts as a base and A second lithium atom donates an electron to removes a proton from a second molecule of ethylamine. the vinylic radical.
O
H2 Pd/C etanol
CO2Me
H2 Pd/C etanol
Br
H2, Pd/CaCO3 KOH alcolico
HBr
Br
H2, Pt 25oC
HBr
Ni-Raney
S O
H2 SH
CH3CH2CH2CH3
H2S
S
SH BF3
Ni-Raney H2
O O
Desidrog. Hidrog.
HO2C C=C H
H CO2H
Calor de hidrogenao
C C + H H Pt C H C H
(H 120 kJ mol1
CH3CH2CH
H3C C C
Pt
CH3CH2CH2CH3 Butane
CH3CH2CH2CH3 Butane
H H cis-2-Butene (C4H8)
H3C C C
H3C C=C H
CH3 H
E.P. H C=C H3C H (menos energtico) (H = - 27,6 Kcal/mol CH3 cis trans
(H trans (H cis
Curso da reao
R R
R > R
R R
R > H
R R
H > H
R H
H > R
R H
R > H
R H
H > H
H H
H H
Tetrasubstituted
Trisubstituted
Disubstituted
Monosubstituted Unsubstituted
IDH = 1
C7H14O2
C7H14
C7H16 CnH2n + 2
( 2 H, IDH = 1)
Acetato de isopentila II. Presena de elementos do Grupo VII (F, Cl, Br, I) - Substituir o halognio por hidrognio (na prtica acrescentar um H por cada halognio) e comparar a frmula resultante com o alcano correspondente:
C2H3Cl3O2
C2H6
C2H6 CnH2n + 2
IDH = 0 Cloral
OH H OH
Cl3C C
III. Presena de elementos do Grupo V (N, P, As, Sb, Bi) - Subtrair um hidrognio para cada heterotomo e comparar a frmula resultante com o alcano correspondente:
C10H14N2
C10H12
N N
Nicotina
Exerccio
O cariofileno, composto encontrado no leo de cravo, tem a frmula molecular C15H24 e no tem ligao dupla. A reao do cariofileno com excesso de hidrognio, na presena de catalisador de platina, leva ao composto com a frmula C15H28 . (a) Quantas duplas ligaes tem o cariofileno? (b) quantos anis tem a molcula?
CH3O RO Eugenol: R = H Acetato de eugenila: R = Ac Cariofileno
Bonds broken
H C C + H X slow
+C
X
The T electron of the alkene form a bond with a proton from HX to form a carboncation and a halide ion.
H
2a Etapa
H fast C C
X The halide ion reacts with the carboncation by donating an electron pair; the result is an alkyl halide.
Ordem de reatividade: HI > HBr > HCl > HF
Electrophile Nucleophile
H C C
+
H + X C
X C
Electrophile Nucleophile
Regioqumica da adio de HX
H2C=CH2
H C H C H H
HBr
H H C H C
H3CCH2Br
H H C C H H
H Br
H H
Br
Br
H2C
CHCH3 +
HBr
CH3CHCH3 Br 2-Bromopropane
CH2 H
CHCH3 Br
X
CH3CH CH2 + H
CH2 H +
X
CH3CH2CH2 1o
+
Br
CH3CHCH3 2 Step 1
o
Br
CH3CHCH 3
Diagrama de energia livre para adio de HBr ao propeno (G(2) menor que (G(1).
H3C
+C
CH2 + I
Cl
H3C
CH3CH
CH2 + HBr
ROOR
CH3CH2CH2Br
Estereoqumica da adio de HX
CH3CH2CH CH2 + HX * CH3CH2CHCH3 X
(a) H C2H5 CH CH2 H X
C2H5 C+ + X
(a)
X C2H5 C H CH3
CH2
H Achiral, trigonal planar carbocation 1-Butene accepts a proton from HX to form an achiral carbocation.
(b)
C2H5 C
X (R)-2-Halobutane (50%) The carbocation reacts with the halide ion at equal rates by path (a) or (b) to form the enantiomers as a racemate.
H OH
+C
O +
HO3SO OH C
H C
S O
H CH 2 H OSO H 3 H3C C CH 3
H3C
H2O, heat
Isopropyl alcohol
C OH
CH 3CH2OH
OH
H3O+
Mecanismo da hidratao
CH3 H 3C C CH2 H H O
+
1a
Etapa
slow
H 2C H 3C C+
H +
H O H
2a Etapa
H O H
fast
CH3
3a Etapa
H3C CH3H C CH3 O
+
H H + O H fast H3C
CH3 C CH3 O H + H
H O
+
Regioqumica e rearranjos
H3C C CH2 + HOH H3C 2-Methylpropene (isobutylene)
CH 3 H3C C CH 2 H H O
+
H3O
o
25 C
OH tert-Butyl alcohol
very slow CH 3 H3C C H + CH 2+ H O H
Praticamente no ocorre
H2SO4 H2O
OH H3C C CH CH3
Adio de X2 a alquenos
CH3CH2CH CH2 + Cl2 9oC CH3CH2CH Cl CH2 (97%) Cl
CH3CH
CHCH 3 +
Cl2
9 C
CH3CH Cl
CHCH 3 (100%) Cl
Br2
+ Br2
Br Br vic-Dibromide (colorless)
no appreciable reaction
Mecanismo da adio de X2
1a Etapa
C
+
C Br
Br Bromide ion
H Br H Br
Bromonium ion
Br
Br C
+ Br
Br C C + Br
Br
Bromonium ion
2a Etapa
Estereoqumica da adio de X2
H H H Br2 CCl4 Br + enantiomer H H
Br H trans-1,2-Dibromocyclopentane
Br H Bottom attack
H
+
H H
H Br Br
Br
Br+
Cyclopentene
Carbocation intermediate
Br
Br
Br
Br
(b)
(b) (a)
(a)
Br
Br
trans-1,2-Dibromocyclopentane enantiomers
Br Br2
6 1 2 3 6 1 2 3
inversion at C1
Br
Cyclohexene
Br Br Br Diequatorial conformation
Br
trans-1,2-Dibromocyclohexane
Reaes estereoespecficas
H3 C H C C H Br2 CH3 CCl4 Br CH3 H C C Br H
trans-2-Butene
Me H H Me Br
Br C C H Me
C
Me C H
H Me
Br
Br Me H C
Br C
+
trans-2-butene
H Me
Br C Me H C
Me
Br
Br
anti-addition
H3 C H3 C
C C
H Br2 H CCl4
Br H
CH3 H C C Br
CH3 H Br C C Br H
cis-2-Butene
CH3 (2S,3R)
CH3 (2S,3S)
Br H Me H C C H Me Me cis-2-butene Br Br H Me C
+
Me H Me
H C C
Br H Me
C
Br + Br H Me C C
Br C Br
H Me
Me
Br
anti-addition
Br H H 3C C C
HCH 3 Br
H H3C
H CH3
H Br H Br
cis-2-butene reacts with bromine to The bromonium ion reacts with the yield an achiral bromonium ion and bromide ions at equal rates by paths (a) a bromide ion. [Reaction at the and (b) to yield the two enantiomers in other face of the alkene (top) would equal amounts (i.e., as the racemic form). yield the same bromonium ion.]
Br H H3C C C
CH3 H Br
H H3C
CH3 H
H Br H Br
trans-2-Butene reacts with bromine yo yield chiral bromonium ions and bromide ions. [Reaction at the other face (top) would yield the enantiomer of the bromonium ion as shown here.]
When the bromonium ions react by either path (a) or path (b), they yiled the same achiral meso compound. [Reaction of the enantiomer of the intermediate bromonium ion would produce the same result.]
X OH Halohydrin (major)
C C X
+
X X vic-Dihalide (minor)
C + X
1a Etapa
C
H X H X
Halonium ion
H C + O H H X C C
H H O H X H C C O + H O H
+
Protonated Halohydrin halohydrin The protonated hallohydrin loses a Here, however, a water molecule acts as the nuclephile and attacks a proton (it is transferred to a molecule of water). This step produces the carbon of the ring, causing the halohydrin and hydronium ion. formation of a protonated halohydrin.
Halonium ion
Regiosseletividade
H3C C H3C CH2 Br2 CH3 H3C
H
CH2 Br H
OH2
+OH2
H3C
C CH3
CH2Br H3C
H OH C CH2Br
Mapa de contorno vermelho indica rea relativamente negativa e azul indica reas relativamente positiva (ou nemos negativa).
CH3 (73%)
Br Cl Cl Br Cl
Cl
Cl
Cl Cl
Halomon: in preclinical evaluation as a cytotoxic agent against certain tumor cell types
OCH 3 Br
3
Tetrachloromertensene
Br Br OH Br O
Cl
(3R)- and (3S)-Cyclocymopol monomethyl ether: show agonistic or antagonistic effects on the human progesterone receptor, depending on which enantiomer is used
Br Cl Br
O O Br
Kumepaloxane: a fish antifeedant synthesized by the Guam bubble snail Haminoea cymbalum, presumably as a defense mechanism for the snail.
(3E)-Laureatin:
HO H O O O H H O H H O H H O H O H O H H O H H H O O
H O