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tertiary (3), depending on the number of carbons bonded to the carbon with the halogen atom.
The halogen atom in halides is often denoted by the symbol X. Uses:
pesticides, refrigerants (freons), solvents, synthetic intermediates, anestesi lokal (kloroetana) dan hisap (1-bromo-1kloro-2,2,2-triflouroetana), plastik yg dipake dlm piringan hitam, tas, pipa dll (PVC)
There are other types of organic halides. These include vinyl halides, aryl halides, allylic halides and benzylic halides. Vinyl halides have a halogen atom (X) bonded to a CC double bond. Aryl halides have a halogen atom bonded to a benzene ring. Allylic halides have X bonded to the carbon atom adjacent to a CC double bond. Benzylic halides have X bonded to the carbon atom adjacent to a benzene ring.
Nomenclature:
common names: alkyl halide (fluoride, chloride, bromide, iodide)
IUPAC names: use rules for alkanes halogen = halo (fluoro, chloro, bromo, iodo)
Cl
CH3CH2CH2CH2-Br n-butyl bromide 1-bromobutane 1o CH3CHCH3 isopropyl chloride 2-chloropropane 2o
Nomenclature
Physical Properties
Alkyl halides are weak polar molecules. They exhibit dipole-dipole interactions because of their polar CX bond, but because the rest of the molecule contains only CC and CH bonds, they are incapable of intermolecular hydrogen bonding.
Carbocation Stability
The effect of the type of alkyl halide on SN1 reaction rates can be explained by considering carbocation stability. Carbocations are classified as primary (1), secondary (2), or tertiary (3), based on the number of R groups bonded to the charged carbon atom. As the number of R groups increases, carbocation stability increases.
following characteristics:
Reaction occurs with inversion at reacting center Follows second order reaction kinetics rate = k [Nu:-][RX]
CH 2CH 3 (R)-2-Butanol
Higher transitionstate energy level (red curve) = slower reaction (larger G).
The carbon atom in (a) bromomethane is readily accessible resulting in a fast SN2 reaction. The carbon atoms in (b) bromoethane (primary), (c) 2-bromopropane (secondary), and (d) 2-bromo-2-methylpropane (tertiary) are successively more hindered, resulting in successively slower SN2 reactions.
The Nucleophile
Neutral or negatively charged Lewis base Reaction increases coordination at nucleophile Neutral nucleophile acquires positive charge Anionic nucleophile becomes neutral See Table 11-1 for an illustrative list
reaction
The Solvent
Solvents that can donate hydrogen bonds (-OH or
NH) slow SN2 reactions by associating with reactants Energy is required to break interactions between reactant and solvent Polar aprotic solvents (no NH, OH, SH) form weaker interactions with substrate and permit faster reaction
Rate-Limiting Step
The overall rate of a reaction is controlled by the rate
of the slowest step The rate depends on the concentration of the species and the rate constant of the step The highest energy transition state point on the diagram is that for the rate determining step (which is not always the highest barrier) This is the not the greatest difference but the absolute highest point (Figures 11.8 the same step is ratedetermining in both directions)
intermediate should lead to loss of chirality A free carbocation is achiral Product should be racemic
SN1 in Reality
Carbocation is biased to react on side opposite
leaving group Suggests reaction occurs with carbocation loosely associated with leaving group during nucleophilic addition Alternative that SN2 is also occurring is unlikely
remains associated, then product has more inversion than retention Product is only partially racemic with more inversion than retention Associated carbocation and leaving group is an ion pair
this mechanism
Controlled by stability of carbocation
Delocalized Carbocations
Delocalization of cationic charge enhances
stability Primary allyl is more stable than primary alkyl Primary benzyl is more stable than allyl
group is H2O, which is still less reactive than halide p-Toluensulfonate (TosO-) is excellent leaving group
Nucleophiles in SN1
carbocation, reaction rate is not affected normally affected by nature or concentration of nucleophile
Opposite of addition
Generates an alkene Can compete with substitution and decrease yield,
predominates
a base abstracts a proton from the carbocation E2: Concerted (one step) transfer of a proton to a base and departure of leaving group
begins to depart Transition state combines leaving of X and transfer of H Product alkene forms stereospecifically
E2 Reaction Kinetics
One step rate law has base and alkyl halide
Transition state bears no resemblance to reactant or
product Rate = k[R-X][B] Reaction goes faster with stronger base, better leaving group
E2 Stereochemistry
Predicting Product
trans-diaxial to be anti periplanar (app) in approaching transition state (see Figures 11-19 and 1120) Equatorial groups are not in proper alignment
V = k [RX]
Stereochemistry of E1 Reactions
E1 is not stereospecific and there is no requirement
for alignment Product has Zaitsev orientation because step that controls product is loss of proton after formation of carbocation
Comparing E1 and E2
Strong base is needed for E2 but not for E1
E2 is stereospecifc, E1 is not
E1 gives Zaitsev orientation
Alkana dpt bereaksi dg halogen (Cl2 atau Br2) dg adanya energi (h dan kalor)
H3C H
+ Cl
Cl
cahaya panas
H3C
Cl
+ HCl
metana
kloro metana
Halogenasi aromatik dipake untuk mendapat aril halida melalui suatu reaksi substitusi elektrofilik aromatik
Br
+ Br2