Professional Documents
Culture Documents
Kinetic and Organic Reaction Mechanism
Kinetic and Organic Reaction Mechanism
Pertemuan ke-6
Reactive Intermediate.
Radical, carbene, nitren, carbocation, carbanion, aryn.
1
Kinetic and Organic Reaction Mechanism
Chapter 4
Reactive Intermediate
References
E. V. Anslyn, D. A. Dougherty: Modern Physical Organic Chemistry, University Science Books, 2006.
R. A. Moss et al.: Reactive Intermediate Chemistry, Wiley, 2004.
D. E. Evans: Harvard University; Advanced Problems in Organic Chemistry and Chemical Biology, 2006.
I. Fleming: Molecular Orbitals and Organic Chemical Reactions, Wiley, 2009.
A. Rauk: Orbital Interaction Theory of Organic Chemistry
F.A. Carroll: Perspectives on Structure and Mechanism, Brooks/Cole, 1998.
T. H. Lowry, K. S. Richardson: Mechanisms and Theory in Organic Chemistry, Harper Collin, 1987.
F. A. Carey, R. J. Sundberg: Advanced Organic Chemistry, Kluver Academic, 1990.
R. Bruckner: Advanced Organic Chemistry, Elsvier, 2002.
2
Kinetic and Organic Reaction Mechanism
Huckel Molecular Orbital (HMO) and substituents
Note: definition of substitution designation (I. Fleming) ... for further discussion
3
Kinetic and Organic Reaction Mechanism
Reaction Intermediates - Intermediates as Local area Minimum
Intermediate vs. transition state
4
Kinetic and Organic Reaction Mechanism
Reaction intermediates - intermediates
The Appearance of reactive (short-lived) intermediates is an endothermic process
... ETS ~ EIntermediate (late TS)
E.g. carbocation:
5
Kinetic and Organic Reaction Mechanism
Reaction intermediates - intermediates
Bell(s)–Evans(s)–Polanyi principle:
6
Kinetic and Organic Reaction Mechanism
Radical - history
• Radical (= "free") on carbon - unpaired electron and charge 0.
• Gomberg (1900):
7
Kinetic and Organic Reaction Mechanism
Radicals - conjugation = stability
Examples of long-living radicals (hydrazyl is commercially available):
Etc.
8
Kinetic and Organic Reaction Mechanism
Radicals - Detection and Identification
EPR ... spin of electron
The energy difference between the two quantum states:
ΔE = h = geH0
... g: spectroscopic resolution factor (magnet torque and electron torque
ratio; 2,002 for e-);
e: is Bohr's magneton (9,27x10-21 erg / gauss); Ho: Magnetic field size
- hyperfine signal splitting in the methyl radical (1: 3: 3: 1) (cleavage due
to electron interaction - 3 equivalent protons)
13
erg (1 erg = 10−7 joule) … ergon (řecky) = práce
Kinetic and Organic Reaction Mechanism
Radicals - Detection and Identification
Signal splitting in the ethyl radical:
10
Kinetic and Organic Reaction Mechanism
Radicals - Structure
Alkyl radicals: both planar and pyramidal ... inversion (analogy to ammonia)
Pro. chlorination of (S) -1-chloro-2 methylbutane
or
racemáte
11
Kinetic and Organic Reaction Mechanism
Radicals - Structure
Spectroscopy: The EPR distinguishes the planar and pyramidal structure
- the methyl radical is almost planar, ie carbon is sp2 (type p-orbital ... radical);
- the trifluoromethyl radical is pyramidal, ie sp3 (hybrid orbit ... radical)
... ie EWG substitute: interaction of SOMO (2p) and LUMO )
(Pauling: due to the high electronegativity of F, the C-F bond has more p character
than C-H)
12
Kinetic and Organic Reaction Mechanism
Radicals - Structure
• t-Butyl according to EPR is not planar from steric and electron (interaction
with bonds) reasons:
•Rigid formations such as 1-adamantyl and 7-norbornyl radicals exist but their
stability and rate of formation are low:
13
Kinetic and Organic Reaction Mechanism
Radicals - Stabilization
Different interactions:
15
Kinetic and Organic Reaction Mechanism
Radicals - Structure and hyperconjugation
Loss of planarity in radicals with EDG also thanks to:
hyperconjugation of the orbital with an adjacent bond, e.g., ethyl radical:
16
Kinetic and Organic Reaction Mechanism
Radicál - Appearance
17
Kinetic and Organic Reaction Mechanism
Radicál - Appearance
18
Kinetic and Organic Reaction Mechanism
Radicál - Appearance
AIBN
(azobis-
isobutyronitril)
19
Kinetic and Organic Reaction Mechanism
Radicál - Appearance
Photochemistry - Radicals and Biradics
20
Kinetic and Organic Reaction Mechanism
Radicáls – radical traps (spin)
- Intramolecular capture
26
Kinetic and Organic Reaction Mechanism
Radicáls – radical traps (spin)
2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)
... radar trap; additions to reactive groups; biomolecules
... detection by MS, NMR, etc.
23
Kinetic and Organic Reaction Mechanism
Radicáls – reaction
E.g.
- Fragmentation
- addition
- elimination
24
Kinetic and Organic Reaction Mechanism
Radicáls – reaction
Chain reactions
25
Kinetic and Organic Reaction Mechanism
Carbens – Structure
Neutral particles with a non-bonding electron pair:
Linier Non-linier
27
Kinetic and Organic Reaction Mechanism
Carbens – Stabilization
X: ... restituent increases the energy of 2p orbitals (increases the separation between
2p and energy); ie the baseline is S0
Z, C ... reduce the separation between 2p and energy; ie the multiplicity is usually T1
28
Kinetic and Organic Reaction Mechanism
Carbens – Detection and Identification
- reaction
29
Kinetic and Organic Reaction Mechanism
Carbens – Formation
The formation of carbenes (in singlet state):
Diazoalkanes or dialkylazirins
or hv
or hv
• N-nitrosoureas diazoalkanes
base
30
Kinetic and Organic Reaction Mechanism
Carbens – Formation
The formation of carbenes (in singlet state):
• Tosylhydrazon
• -Elimination reaction
base base-H
(carbenoid)
carbenoid: a singlet carbene stabilized by association with metal 36
Kinetic and Organic Reaction Mechanism
Carbens – Formation
Triplet Carben may originate directly by sensitization (spinning law!)
37
Kinetic and Organic Reaction Mechanism
Carbens – Reaction
Reaction of singlet carbenes (examples)
- dimerization
- cyclopropanation
33
Kinetic and Organic Reaction Mechanism
Carbens – Reaction
Reaction of triplet carbenes (examples)
- cleavage of hydrogen (tunneling - triplets only)
34
Kinetic and Organic Reaction Mechanism
Carbens – Reaction
Reaction of triplet carbenes (examples)
- Addition to double bonds
35
Kinetic and Organic Reaction Mechanism
Nitrenes
R N
Similar to carbenes: the triplet is a biradical and basic state:
- the energy of the triplet nitrogen (NH) is 36 kcal / mol (151 kJ / mol)
lower than the singlet (Coulomb repulsion decreases, T is less reactive
than the singlet)
36
Kinetic and Organic Reaction Mechanism
Nitrenes
The emergence of,
for example,:
azide
or apparently even in the Hofmann rearrangement (amide + NaOH + Br2)
37
Kinetic and Organic Reaction Mechanism
Carbocation
Carbene ions (CH3+), ie formally "carbenic”
38
Kinetic and Organic Reaction Mechanism
Carbocation-Structure
Hybridization sp2 - planar
41
Kinetic and Organic Reaction Mechanism
Carbocation
Electronic effects
Reactions - rearrangements
42
Kinetic and Organic Reaction Mechanism
Carbocation-Structure
Group migration is very fast: NMR
1,2-migration
43
Kinetic and Organic Reaction Mechanism
Carbocation-Rearranggement
44
Kinetic and Organic Reaction Mechanism
Carbocation-Emmergence
1960 (Oláh): alkyl carbene is formed in the presence of superacids
or
45
Kinetic and Organic Reaction Mechanism
Carbocation-Reactivity
Reaction in water
Lifetime in water
46
You do a lot of work before you really convince yourself that you have
observed something, particularly in a field where for decades and
decades people have tried and failed.
47
Kinetic and Organic Reaction Mechanism
Carbocation-Non-classical ion
"Classic" example: 2-norbornyl cation:
48
Kinetic and Organic Reaction Mechanism
Carbanions
-
sp3 hybridized carbon: H3C:
C … HOMO does not change; but the reactivity with respect to the 58
electrophile is lower due to the lower carbon coefficient
Kinetic and Organic Reaction Mechanism
Carbanions-Stabilization
Carbon acid acidity - delocalization
The mixture of negative charge orbitals with the methyl orbital denies
the logical reduction of acidity by increasing the number of alkyls due
to their electron donor effect.
anion anionradicál
anionradicál
53
Kinetic and Organic Reaction Mechanism
Aryne
o-benzyn