Polymerization of Methyl Methacrylate and Styrene
J. Am. Chem. Soc., Vol. 119, No. 45, 1997 10991
connected to a Shimadzu UV spectrophotometric detector set at 270
nm and a CR-6A computing integrator.
5 × 3H, 4 × ring CH
3.78 (s, 3H, OCH ), 7.08-7.16 (m, 2H ArH), 7.20-7.27 (m, 2H ArH);
(CDCl ) 20.6 (CH ),
CON), 25.1, 25.7, 29.5 and 29.7 (4 × ring CH
29.3 [(CH C], 30.2 [(CH C], 35.6 (CH CON), 38.0 (CH CH CON),
51.7 (OCH ), 67.8 and 67.9 (C-1, C-3), 84.5 (CON), 121.5 and 121.6
(C-4, C-7), 127.2 and 127.3 (C-5, C-6), 144.8 and 145.5 (C-3a, C-7a),
3
and CH
3
CON), 1.6-2.0 (m, 2H, CH
2
CON),
3
Peak areas were determined by integration of HPLC chromatograms.
Allowance for differing chromophores was made either by determining
the extinction coefficients at 270 nm of the isolated products or by the
reinjection of solutions of known concentration to assess peak response
ratios for the UV detector. The adjusted peak areas were converted
into relative product yields and normalized to 100%.
δ
C
3
3
3
3
)
3
3
)
3 3
2
2
2
+
+
175.3 (CdO); m/z 384 (M + Na) , 362 (M + H) .
Methyl 7-Hydroxy-2,5,5,7-tetramethyl-2-((1,1,3,3-tetramethyl-2,3-
The reaction products were isolated using preparative reverse-phase
HPLC on a Rainin Instruments Dynamax-60A 8µm 250 × 21.4 mm
dihydro-1H-isoindol-2-yl)oxy)octanoate (11c): δ
(CH CCH COH], 1.2-1.3 (m, 2H, CH CH CON), 1.30 [s, 6H, (CH
COH], 1.34, 1.36, 1.44, 1.46 and 1.53 (5 × s, 5 × 3H, 4 × ring CH
and CH CON), 1.52 (s, 2H, CH OH), 1.6-2.0 (m, 2H, CH
(s, 3H, OCH ), 7.06-7.14 (m, 2H ArH), 7.21-7.26 (m, 2H ArH);
(CDCl ) 20.6 (CH ),
28.6 [(CH COH], 31.9 and 32.1 [(CH
COH], 35.0 (CH CON), 38.4 (CH CH
COH), 67.8 and 67.9 (C-1, C-3), 72.4 [(CH
and 121.6 (C-4, C-7), 127.2 and 127.3 (C-5, C-6), 144.7 and 145.4
H 3
(CDCl ) 1.04 [s, 6H,
)
3 2
2
2
2
3 2
) -
C
18 preparative column. Compounds were detected by a Soma UV
3
detector S-310A fitted with a 1.0 mm preparative cell. Solvent flow
rates were variable depending upon the methanol-water ratio and the
back-pressure which was kept less than 2500 psi by a Gilson 303 pump
3
2
2
CON), 3.76
3
δ
C
3
3
CON), 25.0, 25.7, 29.5 and 29.7 (4 × ring CH
CCH COH], 33.7 [(CH CCH
CON), 51.7 (OCH ), 53.1 (CH
2
3
3
-1
fitted with a 25 cm min preparative head and 803C manometric
module.
3
)
2
3
)
2
2
2
3
)
2
2
-
-
2
2
3
NMR spectra were recorded on a Varian Gemini-200 (200MHz)
3 2
) COH], 84.5 (CON), 121.5
spectrometer, using deuterated chloroform as solvent. Chemical shifts
1
+
+
for H NMR spectra are relative to residual CHCl
3
(δ 7.24 ppm) and
(C-3a, C-7a), 175.3 (CdO); m/z 442 (M + Na) , 420 (M + H) .
2-(1-Phenyl-2-((2,4,4-trimethylpent-2-yl)oxy)ethoxy)-1,1,3,3-tet-
ramethyl-2,3-dihydro-1H-isoindole (12): δ (CDCl ) 0.80 (s, 3H, ring
1
3
for C NMR spectra are relative to the central peak of the triplet
resonance due to CDCl (δ 77.0 ppm).
3
H
3
HPLC-electrospray mass spectra were obtained with a Single
Quadrupole VG Platform II mass spectrometer, coupled to a MassLynx
data system.
CH ), 0.97 [s, 9H, (CH ) ], 1.21 and 1.25 [2 × s, 2 × 3H, (CH ) CO],
3
3
3
3 2
1.25 (s, 3H, ring CH ), 1.49 (s, 5H, ring CH and CH CO), 1.68 (s,
3
3
2
3H, ring CH ), 3.44 (dd, J 4.8, 9.7, 1H, CH CHON), 3.83 (dd, J 7.8,
3
2
New compounds were isolated by preparative HPLC and character-
ized by the NMR data listed below (J values are given in hertz; ring
9.7, 1H, CH CHON), 4.83 (dd, J 4.8, 7.8, 1H, CHON), 6.94-7.44 (m,
2
+
+
9H, ArH); m/z 446 (M + Na) , 424 (M + H) .
CH
3
refers to methyl substituents on the isoindole, and primed numbers
2-(((4,4-Dimethyl-1-phenyl)pentyl)oxy)-1,1,3,3-tetramethyl-2,3-di-
of carbon refer to the monosubstituted phenyl ring).
Methyl 2-Methyl-2-((1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-
hydro-1H-isoindole (13b): δ (CDCl ) 0.73 (s, 3H, ring CH ), 0.88
H
3
3
[s, 9H, (CH ) ], 1.2-1.4 [m, 2H, (CH ) CCH ], 1.24, 1.46, 1.64 (3 ×
3
3
3
3
2
2
0
-yl)oxy)-3-((2,4,4-trimethylpent-2-yl)oxy)propanoate (7): δ
.97 [s, 9H, (CH CO], 1.37
C], 1.13 and 1.14 [2 × s, 2 × 3H, (CH
and CH CON), 1.39 (s, 3H, ring CH ), 1.49 (s, 5H,
and CH CO), 1.60 (s, 3H, ring CH ), 3.41 (d, 1H, J 8.1,
), 3.77 (s, 3H, OCH
H
(CDCl
3
)
s, 3 × 3H, 3 × ring CH ), 1.66-1.87 (m, 1H, CH CHON), 2.04-2.24
3
2
3
)
3
3
)
2
(m, 1H, CH CHON), 4.61 (dd, J 5.9, 8.3, 1H, CHON), 6.92-7.40 (m,
2
(s, 6H, ring CH
3
3
3
9H, ArH); δ (CDCl ) 25.3, 25.7, 29.3, 30.2 and 30.3 [4 × ring CH
C
3
3
ring CH
OCH
3
2
3
3 3 3 3 2 2 2
and (CH ) C], 29.4 [(CH ) C], 31.0 (CH CHON), 40.3 (CH CH -
2
), 3.65 (d, 1H, J 8.1, OCH
2
3
), 7.06-7.14 (m,
CHON), 67.0 and 68.0 (C-1, C-3), 89.0 (CHON), 121.4 and 121.9 (C-
4, C-7), 127.0 and 127.1 (C-5, C-6), 127.4, 128.0 and 128.1 (C-2′,
C-3′, C-4′), 143.9 (C-1′), 145.2 and 145.5 (C-3a, C-7a); m/z 388 (M +
+
2
H) .
H ArH), 7.20-7.27 (m, 2H ArH); m/z 442 (M + Na) , 420 (M +
+
2-((2,2-Dimethylpropyl)oxy)-1,1,3,3-tetramethyl-2,3-dihydro-1H-
Na)
+
, 366 (M + H)
-(((6-Hydroxy-4,4,6-trimethyl-1-phenyl)heptyl)oxy)-1,1,3,3-tet-
ramethyl-2,3-dihydro-1H-isoindole (13c): δ (CDCl ) 0.73 (s, 3H, ring
CH ), 1.01 [s, 6H, (CH CCH COH], 1.2-1.4 (m, 2H, CH
CHON), 1.23 (s, 3H, ring CH
), 1.25 and 1.26 [2 × s, 2 × 3H, (CH
OH], 1.46 (s, 3H, ring CH
), 1.50 and 1.51 (2 × s, 2 × 1H, CH
.63 (s, 3H, ring CH ), 1.66-1.87 (m, 1H, CH CHON), 2.02-2.27
m, 1H, CH CHON), 2.80 (s, 1H, OH), 4.60 (dd, J 6.0, 8.1, 1H, CHON),
+
.
isoindole (10b): δ
H
(CDCl
3
) 1.01 [s, 9H, (CH
), 7.07-7.12 (m, 2H ArH), 7.20-7.26 (m,
) 24-32 (br hump, ring CH ), 27.2 [(CH C], 32.3
C], 67.4 (C-1, C-3), 87.6 (CH ), 121.5 (C-4, C-7), 127.2 (C-5,
C-6), 145.6 (C-3a, C-7a); m/z 284 (M + Na) , 262 (M + H) .
-((4-Hydroxy-2,2,4-trimethylpentyl)oxy)-1,1,3,3-tetramethyl-2,3-
dihydro-1H-isoindole (10c): δ (CDCl ) 1.15 [s, 6H, (CH CCH ON],
.33 [s, 6H, (CH ), 1.67 (s, 2H,
COH], 1.48 (br s, 12H, 4 × ring CH
CH COH), 3.29 (br s, 1H, OH), 3.87 (s, 2H, CH ON), 7.06-7.14 (m,
H ArH), 7.20-7.27 (m, 2H ArH); δ (CDCl ) 25-30 (br hump, ring
CH ), 27.8 [(CH CCH ON], 31.9 [(CH COH], 35.8 [(CH CCH
ON], 53.3 (CH COH), 67.5 (C-1, C-3), 71.3 (COH), 87.7 (CH ON),
21.4 (C-4, C-7), 127.3 (C-5, C-6), 145.0 (C-3a, C-7a); m/z 342 (M +
3
)
3
], 1.44 (br s, 12H, 4 ×
2
ring CH
H ArH); δ
(CH
3
), 3.62 (s, 2H, CH
2
H
3
2
[
C
(CDCl
3
3
3 3
)
3
3
)
2
2
2
CH
3
)
2
-
-
3
)
3
2
3
2
+
+
3
2
COH),
2
1
3
2
H
3
)
3 2
2
(
6
2
1
3
)
2
3
+
+
.94-7.42 (m, 9H, ArH); m/z 446 (M + Na) , 424 (M + H) .
Thermolysis of 11b,c in the Presence of 2. A MMA solution of
1b (0.01 M), 11c (0.01 M), 4 (internal standard, 0.01 M) and 2 (0.01
2
2
2
C
3
1
3
)
3 2
2
3
)
2
)
3 2
2
-
M) was heated at 60 °C for 1 h in the same manner as above. The
resulting solution was concentrated and followed by HPLC analysis.
2
2
1
+
+
Na) , 320 (M + H) .
Methyl 2-((1,1,3,3-Tetramethyl-2,3-dihydro-1H-isoindol-2-yl)-
oxy)-2,5,5-trimethylhexanoate (11b): δ (CDCl ) 0.92 [s, 9H, (CH C],
.1-1.3 [m, 2H, (CH CCH
], 1.35, 1.37, 1.46, 1.48 and 1.54 (5 × s,
Acknowledgment. We thank NOF Corp., Griffith Univer-
sity, and the Australian Research Council for financial assistance.
H
3
3 3
)
1
)
3 3
2
JA972240T