g,16.2 mmol) and 4 (9.0 g, 8.3 mmol) in xylene/DMF (150
mL/150 mL) was stirred at 160 °C for 40 h. The reaction
was cooled to room temperature, and 300 mL of hexane was
added. The nonpolar organic phase was isolated and washed
with H2O (3 × 40 mL) and 90% EtOH (4 × 25 mL). The
organic phase was then dried over Na2SO4, and the solvent
removed in vacuo to yield 8.5 g of 5.1H NMR (300 MHz,
CDCl3, δ): 0.76-1.49 (m, 180H), 3.42 (dd, J ) 8.1 and
13.4 Hz, 1H), 3.54 (dd, J ) 6.6 and 13.4 Hz, 1H), 7.68 (dd,
J ) 3.0 and 5.4 Hz, 2H), 7.82 (dd, J ) 3.0 and 5.4 Hz, 2H).
Amine-Terminated Polyisobutylene (PIB-NH2) (6). A
solution of hydrazine hydrate (18 mL, 314 mmol) and 5 (8.0
g, 6.97 mmol) in 400 mL of 1:1 ethanol/heptane was heated
to reflux for 20 h. The reaction was allowed to cool to room
temperature, and 50 mL of H2O was added. The organic
phase was then washed first with H2O (3 × 40 mL) and
then with 90% EtOH (4 × 25 mL). The heptane phase was
dried over Na2SO4 and the solvent removed under vacuum
to yield 7.5 g of 6.1H NMR (300 MHz, CDCl3, δ): 0.76-
1.49 (m, 180H), 2.43 (dd, J ) 7.5 and 12.4 Hz, 1H), 2.60
(dd, J ) 5.4 and 12.4 Hz, 1H).
Dansyl-Labeled Polyisobutylene (PIB-Dansyl) (7). A
solution of dansyl chloride (0.337 g, 1.25 mmol), 6 (0.5 g,
0.5 mmol), and triethylamine (3.0 mL, 0.42 mmol) in 20
mL of chloroform was refluxed for 24 h. The solvent was
removed under reduced pressure and the residue taken up
100 mL of hexane and washed with 90% EtOH (3 × 20
mL). The organic phase was dried over MgSO4, the solvents
were removed under reduced pressure, and the product dried
in vacuo for 24 h to give 0.40 g of 7 as a light yellow liquid.
1H NMR (300 MHz, CDCl3, δ): 0.77-1.39 (m, 180H),
2.54-2.62 (m, 1H), 2.73-2.82 (m, 1H), 2.86 (s, 6H), 4.54
(t, J ) 6.3 Hz, 1H), 7.17 (d, J ) 7.5 Hz, 1H), 7.52 (m, 2H),
8.29 (m, 2H), 8.51 (d, J ) 8.4 Hz, 1H).
Dansyl-Labeled Poly(tert-butylstyrene) (PTBS-Dan-
syl) (9). A mixture of N-propyl-5-dimethylaminonaphthalene-
1-sulfonamide (8)34 (0.0833 g, 0.285 mmol) and potassium
tert-butoxide (0.317 g, 0.283 mmol) in 15 mL of dry DMA
was placed in a flame-dried flask. The reaction was stirred
under argon for 1 h before the dropwise addition of a solution
of 10:1 poly(tert-butylstyrene)-c-poly(vinyl benzyl chloride)
(PTBS-VBC) (1.0041 g, 0.57 mmol) in 5 mL of DMA. An
additional 5 mL of DMA was added via syringe, and the
reaction was allowed to stir overnight. The reaction was
determined complete by phenolphthalein indictor and titration
with standardized HCl. The mixture was extracted with
hexanes (3 × 20 mL), washed with DMF (5 × 50 mL), and
concentrated under reduced pressure. The polymer was taken
back up into ether and washed with water (3 × 50 mL).
The organic phase was dried over MgSO4 and the ether
removed under reduced pressure. The polymer was then
dissolved in 3 mL of chloroform, precipitated into 500 mL
of methanol, filtered, and dried in vacuo.1H NMR (300 MHz,
CDCl3, δ): 0.3-2.5 (m, 254H), 2.91 (br s, 6H), 3.13 (br s,
2H), 4.2-4.8 (br m, 4H), 6.00-7.28 (br m, 100H), 7.55 (br
m, 2H), 8.18 (br s, 1H), 8.5 (br s, 1H), 8.36 (br s, 1H).
General Procedure for Synthesis of Octadecyl Acry-
lates (12 and 13). A 500-mL three-necked round-bottomed
flask with stir bar, addition funnel, and condenser was
charged with octadecanol (31.427 g, 110.37 mmol), N,N-
dimethylaniline (10 mL, 86.32 mmol), and 60 mL of
dichloromethane. The mixture was warmed to dissolve the
alcohol, and a solution of acryloyl chloride (11 mL, 130
mmol) in 50 mL of dichloromethane was added dropwise.
Following addition, the reaction was gently refluxed over-
night. The mixture was cooled and alternately washed with
water and 10% HCl. The organic phase was dried over
MgSO4, concentrated under reduced pressure, and dried
1
in vacuo to give 35.09 g of 12 as a viscous oil (95%). H
NMR (300 MHz, CDCl3, δ): 0.88 (t, J ) 7.8 Hz, 3H),
1.25 (s, 28H), 1.55-1.75 (m, 4H), 4.14 (t, J ) 6.9 Hz, 2H),
5.80 (dd, J ) 1.8 and 10.5 Hz, 1H), 6.11 (dd, J ) 10.5 and
17.4 Hz, 1H), 6.39 (dd, J ) 1.8 and 17.4 Hz, 1H). Octadecyl
methacrylate (13)1H NMR (300 MHz, CDCl3, δ): 0.80
(t, J ) 6.6 Hz, 3H), 1.18 (s, 28H), 1.4-1.7 (m, 4H), 1.85
(t, J ) 0.9 and 1.5 Hz, 3H), 4.05(t, J ) 6.9 Hz, 2H), 5.45
(q, J ) 1.5 and 1.8 Hz, 1H), 6.01 (dd, J ) 0.9 and 1.8 Hz,
1H).
Amine-Terminated p-Methyl Red (14). p-Methyl red
(7.89 g, 29.3 mmol) was suspended in 225 mL of dichlo-
romethane. To this suspension was added carbonyldiimida-
zole (10.0 g, 61.67 mmol), resulting in a rapid emission of
CO2. The mixture was stirred at ambient temperature for 4
h, and the starting material was observed to dissolve to form
a bright red homogeneous solution. This solution was
transferred to an addition funnel and added dropwise over 3
h to a solution of 1,6-hexanediamine (13.6 g, 117 mmol) in
200 mL of dichloromethane. After the addition, the resulting
solution was allowed to stir for 24 h at room temperature.
The reaction was filtered, and the filtrate was washed with
water (10 × 60 mL), dried over MgSO4, and dried in vacuo
1
to yield 8.57 g of 14 as a red solid (80%). H NMR (300
MHz, CDCl3, δ): 1.25 (m, 4H), 1.60-1.67 (m, 4H), 2.69
(t, J ) 6.6 Hz, 2H), 3.10 (s, 6H), 3.47 (q, J ) 6.3 Hz, 2H),
6.21 (t, J ) 6 Hz, 2H), 6.76 (d, J ) 9 Hz, 2H), 7.86 (s, 4H),
7.89 (d, J ) 9 Hz, 1H).
General Procedure for the Synthesis of p-Methyl Red-
Labeled Acrylamides (15 and 16). A solution of 14 (1.82
g, 5 mmol) and triethylamine (2 mL, 14 mmol) in 50 mL of
dichloromethane was added to a 100-mL round-bottomed
flask. Acryloyl chloride (0.60 mL, 7.09 mmol) was then
added dropwise via syringe. The reaction was allowed to
stir for 24 h at room temperature before the mixture was
transferred to a separatory funnel and the organic phase was
washed with water. The organic phase was set aside, and
the aqueous phase was washed with dichloromethane until
the dichloromethane was colorless. The organic phases were
combined, washed with water (3 × 50 mL), and dried over
MgSO4. The solvent was removed under reduced pressure,
and the product was dried in vacuo to give 1.95 g of 15 as
a red solid (96.5%). 1H NMR (300 MHz, CDCl3, δ): 1.30-
1.7 (m, 8H), 3.11 (s, 6H), 3.34 (q, J ) 6.6 Hz, 2H), 3.46 (q
J ) 6.6 Hz, 2H), 5.61 (dd, J ) 2.1 and 10.2 Hz, 1H), 5.8
(34) Summers, W. A.; Lee, J. Y.; Burr, J. G. J. Org. Chem. 1975, 40, 1559-
1561.
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Vol. 8, No. 3, 2004 / Organic Process Research & Development