Upload
others
View
5
Download
0
Embed Size (px)
Citation preview
アリルアニオン・アリルカチオンの13C NMR化学シフト (Me4Si基準,ppm)13C NMR chemical shifts of allyl cation/anions
(G. Olah et al., J. Am. Chem. Soc., 100, 4347 (1978))
Ref.
124
133
26
Ref.
115135
19
Ref. 115
13538
- 両端の等価性,両端と中心炭素の環境の違い,アニオン・カチオンの化学シフト- Equivalence of two termini. Difference between terminal and center. Chemical shift of
cations/anions
HOMO (-9.13 eV)
One of other occupied MOs (-13.49 eV)
Styrene C6H5-CH=CH2
Molecular orbitals with p-character
HOMO (-9.17 eV)
One of other occupied MOs (-14.70 eV)
Phenol C6H5-OH
- Oxygen is involved in p-system
Molecular orbitals with p-character
HOMO (-9.44 eV)
One of other occupied MOs (-14.57 eV)
Toluene C6H5-CH3
Molecular orbitals with p-character
- Methyl group is also involved in p-system !?
HOMO (-10.10 eV)
One of other occupied MOs (-14.57 eV)
propene CH3-CH=CH2
… likewise
HOMO (-9.14 eV)
One of other occupied MOs (-15.47 eV)
2,3-dimethylbut-2-ene (CH3)2C=C(CH3)2
p-system is extended to outer alkyl group!
2-methylpropene (CH3)C=CH2
180 190
but-1-ene CH3CH2CH=CH2
170 180
3.0
1.5
190
4.0
3.5
2,3-dimethylbut-2-ene (CH3)2C=C(CH3)2
190 210 230
4.0
2.0
置換アルケンのUV/visスペクトル UV/vis spectra of substituted alkenes
アルキルカチオン – 空の2pz軌道への電子供与による非局在化
alkyl cations – delocalization by donation of electrons
toward unoccupied 2pz orbital.
methane -13.01 kcal/mol
ethane -18.13 kcal/mol
methyl cation 256.55 kcal/mol
ethyl cation 222.56 kcal/mol
propane -23.62 kcal/mol 2-propyl cation 197.25 kcal/mol
cf. 1-propyl cation 214.36 kcal/mol
HClの解離と水和エネルギー
HCl(aq)
H+(aq) + Cl-(aq)40 kJ/mol
H・ (g) + Cl ・(g)
427 kJ/mol
HCl(g)
5 kJ/mol
Cl-(aq)
322 kJ/mol
H+(g) + Cl-(g)
1347 kJ/mol
H+(aq)
1098 kJ/molH3O
+(g)
686 kJ/mol
H+(g) + H2O (g)
アンモニアのHOMO 水のHOMO
塩基性とHOMOのレベル
C OHCH3
CH3
H3CH
H
EtOH
H2O
MeOH
PhOH
CH3 C CH3
O H
CH3 C OH
O H
CH3 C OH
O
CH3 C CH3
O
CH3 C OCH3
O
CH4
PhCH3
PhNH2
HF
HCl
HI
HNO3
H2SO4
NH4
H3O
EtNH2
NH3
CH2H2C
CHHC
CHH2C CH3
CH3 NO2
CH3COCH2COOCH3
iPr2NH
HN
H2N
Et3NH
Et2NH2
40
30
20
10
0
-10
50
EtNH3
PhNH3
MeOH2
EtOH2
水中での値に換算したpKa値
49
41
35
27
25
20
18
16
15.7
15
10
4.8
3.2
-1.4
-5.2
-7
-10
10.7
9.2
4.6
-1.7
-2.2
-2.4
-6.0
-7.2
16
酸として弱い
酸として強い
(共役塩基が)塩基として強い
(共役塩基が)塩基として弱い
36
有機化学1資料
44
25
44
10
14
36
5
-4
10.8
11
http://employees.csbsju.edu/cschaller/principles%20chem/appendix/appendix%20periodic%20radii.htm
Structure & Reactivity in Organic, Biological and Inorganic Chemistry by Chris Schaller is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported License.