4566 Macromolecules, Vol. 43, No. 10, 2010
Chutayothin and Ishida
NMR (50.3 MHz, CDCl3, 298 K): δ 15.2, 20.1 (2C, Ar-CH3),
55.6 (1C, Ar-CH2-N), 60.2 (1C, CH3-O),120.6 -152.5 (6C, Ar).
2.7. Synthesis of Model Compounds C1-C4 in Scheme 11.
Compounds C (Scheme 4) were used as a representative to verify
proposed nitrogen protonation initiation (Scheme 5a).
7.10 (1H, Ar-H), 7.28(1H, Ar-H), 7.50 (H, Ar-H), 10.28 (1H,
CH aldehyde). 13C NMR (50.3 MHz, CDCl3, 298 K): δ 15.1,
20.3 (4C, Ar-CH3), 58.4 (1C, Ar-CH2-O), 75.4 (1C, O-CH2),
110.8 (1C, CH2), 130.2 (1C, CH), 124.4-161.0 (12C, Ar), 187.6
(1C, CH).
2.7.1. Step 1: Synthesis of 3,5-Dimethyl-2-prop-2-enyloxyben-
zaldehyde (Scheme 11, I w II)18. Potassium hydroxide (12.0 g,
0.18 mol) was dissolved in dimethylformamide. 2-Hydroxy-3,5-
dimethyl-benzaldehyde (6.7 g, 0.045 mol) and allyl bromide
(13.1 g, 0.110 mol) were added to the solution. After 5 h, water
was added to the solution. The resulting mixture was extracted
with dichloromethane, washed with water, and dried over
sodium sulfate. Dichloromethane was evaporated using a rotary
evaporator. Further purification was carried out by column
chromatography using gradient solvent (hexane:ethyl acetate).
2.7.5. Step 5: Synthesis of Model Compound VII in Scheme 11
(VI w VII)16. The substances VI were mixed with various amines
in a mole ratio of 1:1. The reactions were carried out in toluene at
140 °C for 12 h. The solvent was then evaporated. Gradient
solution column chromatography (hexane:ethyl acetate) was
performed for purification of the product.
2.7.5.1. VII (Amine=Methylamine) 3-((1Z)-2-azaprop-1-enyl)-
2-[(3,5-dimethyl-2-prop-2-enyloxyphenyl)methoxy]-1,5-dimethylbe-
nzene. The product was obtained as a yellow liquid; yield 70%. 1H
NMR (200 MHz, CDCl3, 298 K) δ 2.35 (12H, CH3), 3.50 (3H,
CH3), 5.20 (2H, CH2), 4.92 (2H, CH2), 5.23 (2H, CH2), 5.89 (1H,
CH), 6.67-7.20 (4H, Ar-H), 8.56 (1H, CH2-N). 13C NMR (50.3
MHz, CDCl3, 298 K): δ 11.6, 20.1 (4C, Ar-CH3), 31.0 (1C, CH3),
58.7 (1C, Ar-CH2-O), 75.4 (1C, O-CH2), 110.8 (1C, CH2),
130.2 (1C, CH), 123.4-161.0 (12C, Ar), 171.6 (1C, CH).
2.7.5.2. VII (Amine=4-Methoxyphenylamine) 1-((1Z)-1-aza-
2-{2-[(3,5-dimethyl-2-prop-2-enyloxyphenyl)methoxy]-3,5-dime-
thylphenyl}vinyl)-4-methoxybenzene. The product was obtained
as a yellow liquid; yield 95%. 1H NMR (200 MHz, CDCl3,
298 K) δ 2.35 (12H, CH3), 3.75 (3H, CH3), 5.20 (2H, CH2), 4.90
(2H, CH2), 5.23 (2H, CH2), 5.90 (1H, CH), 6.60-7.15 (8H,
Ar-H), 8.56 (1H, CH2-N). 13C NMR (50.3 MHz, CDCl3, 298
K): δ 15.2, 20.1 (4C, Ar-CH3), 58.7 (1C, Ar-CH2-O), 56.0
(1C, CH3-O), 75.4 (1C, O-CH2), 110.8 (1C, CH2), 130.2 (1C,
CH), 120.6-160.5 (18C, Ar), 171.6 (1C, CH).
2.7.5.3. VII (Amine = 4-Methylphenylamine) 3-[(1Z)-2-Aza-
2-(4-methylphenyl)vinyl]-2-[(3,5-dimethyl-2-prop-2-enyloxyphenyl)-
methoxy]-1,5-dimethylbenzene. The product was obtained as a
yellow liquid; yield 90%. 1H NMR (200 MHz, CDCl3, 298 K) δ
2.35 (15H, CH3), 5.20 (2H, CH2), 4.92 (2H, CH2), 5.23 (2H,
CH2), 5.89 (1H, CH), 6.67- 7.14 (8H, Ar-H), 8.56 (1H,
CH2-N). 13C NMR (50.3 MHz, CDCl3, 298 K): δ 11.6, 20.1
(5C, Ar-CH3), 60.2 (1C, Ar-CH2-O), 75.4 (1C, O-CH2),
110.8 (1C, CH2), 130.2 (1C, CH), 123.0-160.2 (18C, Ar), 171.6
(1C, CH).
2.7.5.4. VII (Amine=Aniline) 3-((1Z)-2-Aza-2-phenylvinyl)-
2-[(3,5-dimethyl-2-prop-2-enyloxyphenyl)methoxy]-1,5-dimethyl-
benzene. The product was obtained as a yellow liquid; yield
80%. 1H NMR (200 MHz, CDCl3, 298 K) δ 2.35 (12H, CH3),
5.20 (2H, CH2), 4.92 (2H, CH2), 5.22 (2H, CH2), 5.90 (1H, CH),
6.67- 7.50 (9H, Ar-H), 8.56 (1H, CH2-N). 13C NMR (50.3
MHz, CDCl3, 298 K): δ 11.6, 20.1 (4C, Ar-CH3), 60.5 (1C,
Ar-CH2-O), 75.4 (1C, O-CH2), 110.8 (1C, CH2), 130.2 (1C,
CH), 123.0-165.0 (18C, Ar), 171.6 (1C, CH).
2.7.6. Step 6: Synthesis of Model Compounds VIII in
Scheme 11 (VII w VIII)17. The various amine based phenoxy
model compounds (0.1 g) from step 5 were reduced by using
sodium borohydride (1.5 equiv) in the presence of potassium
carbonate (0.38 equiv), dissolved in methanol and dichloro-
methane solution (50:50).
1
The product was obtained as a yellow liquid; yield 60%. H
NMR (200 MHz, CDCl3, 298 K): δ 2.30 (6H, CH3), 4.41-4.47
(2H, CH2), 5.28-5.45 (2H, CH2), 6.00-6.20 (1H, CH), 7.28
(1H, Ar-H), 7.50 (1H, Ar-H), 10.32 (1H, CH aldehyde). 13C
NMR (50.3 MHz, CDCl3, 298 K): δ 15.0, 20.2 (2C, Ar-CH3),
75.6 (1C, O-CH2), 110.8 (1C, CH2), 130.2 (1C, CH), 125.6-
160.5 (6C, Ar), 187.2 (1C, CH aldehyde).
2.7.2. Step 2: Synthesis of (3,5-Dimethyl-2-prop-2-enyloxy-
phenyl)methan-1-ol (Scheme 11, II w III)19. Sodium borohyd-
ride (2.52 g, 0.067 mol) and potassium carbonate (2.3 g,
0.017 mol) were mixed with methanol at room temperature.
Then, 3,5-dimethyl-2-prop-2-enyloxybenzaldehyde ((8.3 g, 0.044
mol), from step 1) was added dropwise and reacted overnight.
The solution was dissolved in 20 mL dichloromethane and
washed with 20 mL water, followed by drying over sodium
sulfate. The product was obtained as a colorless liquid; yield
1
98%. H NMR (200 MHz, CDCl3, 298 K) δ 2.26 (6H, CH3),
4.33-4.36 (2H, CH2), 4.65 (2H, CH2), 5.25-5.48 (2H, CH2),
6.00-6.20 (1H, CH), 6.90 (1H, Ar-H), 6.97(1H, Ar-H). 13C
NMR (50.3 MHz, CDCl3, 298 K): δ 15.1, 20.2 (2C, Ar-CH3),
55.4 (1C, CH2-OH), 75.5 (1C, O-CH2), 110.8 (1C, CH2), 130.2
(1C, CH), 125.6-160.5 (6C, Ar).
2.7.3. Step 3: Synthesis of (3,5-Dimethyl-2-prop-2-enyloxy-
phenyl)methyl methylsulfonate and 3-(Chloromethyl)-1,5-di-
methyl-2-prop-2-enyloxybenzene (Scheme 11, III w IV þ V)20.
Product from step 2 (4.0 g, 0.02 mol) was added into a triethy-
lamine (3.2 g, 3.13 mmol) and dimethyl-4-pyridilamine (0.12 g,
1.00 mmol) solution of dichloromethane at -78 °C. Chloro-
methylsulfone (3.64 g, 3.12 mmol) was added via syringe. After 3
days at -30 °C, the suspension was diluted with additional di-
chloromethane (40 mL), and the resulting solution was washed
successively with 1 N HCl, water, and 1 N NaOH. Then, the
solution was dried over sodium sulfate and was evaporated after
drying overnight. The product was obtained as a white solid;
1
yield 70%. H NMR (200 MHz, CDCl3, 298 K) δ 2.27 (6H,
CH3), 4.39-4.42 (2H, CH2), 4.63 (2H, CH2), 5.25-5.52 (2H,
CH2), 6.02-6.22 (1H, CH), 6.98 (1H, Ar-H), 7.05 (1H, Ar-H).
13C NMR (50.3 MHz, CDCl3, 298 K): δ 15.1, 20.3 (2C,
Ar-CH3), 30.1 (CH3-S), 41.2 (1C, Ar-CH2-Cl), 55.4 (1C,
Ar-CH2-O), 75.5 (1C, O-CH2), 110.8 (1C, CH2), 130.2 (1C,
CH), 125.3-160.0 (6C, Ar).
2.7.6.1. VIII (Amine = Methylamine) ({2-[(3,5-Dimethyl-2-
prop-2-enyloxyphenyl)methoxy]-3,5-dimethylphenyl}methyl)met-
hylamine. The product was obtained as a brown liquid, yield
80%. 1H NMR (200 MHz, CDCl3, 298 K) δ 2.35 (15H, CH3),
3.66 (2H, CH2), 5.20 (2H, CH2), 4.92 (2H, CH2), 5.23 (2H, CH2),
5.89 (1H, CH), 6.67-7.14 (4H, Ar-H). 13C NMR (50.3 MHz,
CDCl3, 298 K): δ 11.6, 20.1 (4C, Ar-CH3), 33.0 (1C, CH3), 48.0
(Ar-CH2-N), 58.9 (1C, Ar-CH2-O), 75.4 (1C, O-CH2),
110.8 (1C, CH2), 130.2 (1C, CH), 123.0-160.0 (12C, Ar).
2.7.6.2. VIII (Amine=4-Methoxyphenylamine) ({2-[(3,5-Di-
methyl-2-prop-2-enyloxyphenyl)methoxy]-3,5-dimethylphenyl-
methyl)(4-methoxyphenyl)amine. The product was obtained as
a dark brown liquid, yield 95%. 1H NMR (200 MHz, CDCl3,
298 K) δ 2.35 (12H, CH3), 3.75 (3H, CH3), 4.32 (1H, CH2-N),
2.7.4. Step 4: Synthesis of 2-[(3,5-dimethyl-2-prop-2-en-
yloxyphenyl)methoxy]-3,5-dimethylbenzaldehyde (Scheme 11,
IV þ V w VI)21. Under nitrogen, the substance from step 3
(3.3 g, 0.016 mol) and 2-hydroxy-3,5-dimethylbenzaldehyde
(3.6 g, 0.024 mol) in the presence of NaI (4.8 g, 0.030 mol) in
dimethylformamide were added dropwise at -30 °C to a well
stirred mixture of fine KOH powder (4.3 g, 0.064 mol) in
dimethylformamide. The reaction mixture was stirred at -30 °C
for 30 min and 1 h at -20 °C. The mixture was then allowed to
warm to room temperature and was stirred at room temperature
for overnight. The product was obtained as a white solid; yield
1
76%. H NMR (200 MHz, CDCl3, 298 K) δ 2.26 (6H, CH3),
2.31 (6H, CH3), 4.28-4.31 (2H, CH2), 4.92 (2H, CH2),
5.19-5.41 (2H, CH2), 5.92-6.10 (1H, CH), 7.00 (1H, Ar-H),