Hyperbranched polymers are highly branched, three-dimensional

macromolecules which are closely related to dendrimers

and are typically prepared via a one-pot polycondensation of

AB_(n≥2) monomers.^1 Although hyperbranched macromolecules

lack the uniformity of monodisperse dendrimers, they still

possess many attractive dendritic features such as good solubility,

low solution viscosity, globular structure, and multiple end

groups.^1-3 Furthermore, the usually inexpensive, one-pot synthesis

of these polymers makes them particularly desirable

candidates for bulk-material and specialty applications. Toward

this end, hyperbranched polymers have been investigated as both

rheology-modifying additives to conventional polymers and as

substrate-carrying supports or multifunctional macroinitiators,

where a large number of functional sites within a compact space

becomes beneficial

Gorodetskaya, Irina A.

Gorodetsky, Alon A.

Grubbs, Robert H.

Vinogradova, Ekaterina V.

English

Caltech Authors - Main

Supporting Information for 
 
Functionalized Hyperbranched Polymers via Olefin Metathesis 
 
Irina A. Gorodetskaya, Alon A. Gorodetsky, Ekaterina V. Vinogradova, Robert H. Grubbs 
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and 
Chemical Engineering, California Institute of Technology, Pasadena, California 91125 
 
 
 
Table of Contents 
1) Materials and Instrumentation                                                                                                       S2 
2) Synthesis of 4 (with full characterization)                                                                                     S2 
3) Functionalization procedure/synthesis of 5                                                                                   S3 
4) Reaction scheme and experimental procedures (with full characterizations) for 6 and 7            S3 
5) Polymerization procedure for 8                                                                                                     S4 
 
 
 
 
 
 
 
 
 
 
 
 
 
S2 
Materials.  All reagents, except for catalyst 1 and 1-pyrenebutyric acid were purchased 
from Aldrich at the highest available purity and used without further purification.  Catalyst 1 was 
obtained from Materia, Inc., and 1-pyrenebutyric acid (≥97%) was purchased from Fluka.  The 
synthesis of 2 and its polymerization to 3 with 1 have been reported previously.
1
 
Instrumentation.  NMR spectra were obtained using a Varian Mercury-300 spectrometer; 
samples were dissolved in (methylene chloride)-d2. 
Size exclusion chromatography (SEC) analysis was performed using a Wyatt triple detector 
system equipped with a triple angle light scattering (miniDAWN TREOS, with a laser wavelength 
of 658 nm) detector, a viscometer (ViscoStar) detector, and a refractive index (Optilab rEX) 
detector—all operating at 25
o
C.  Viscotek ViscoGEL I-Series (one mixed bed medium MW and 
one mixed bed high MW) columns were used for SEC with THF as the eluent and a Shimadzu LC-
10AD pump operating at 1 mL/minute. 
Fluorescence measurements were conducted using an ISS K2 fluorimeter (5 mm path 
length), equipped with a 250 W xenon lamp as excitation source.  Emission spectra were obtained 
by exciting at 346 nm and monitoring the emission between 300 and 700 nm.  UV-Vis spectra 
were recorded on a Beckman DU 7400 spectrophotometer. 
 
Synthesis of 4-(4-pent-4-enyloxy-butyl)-pyrene (4).  1-Pyrenebutanol (1.0 g, 3.6 mmol) 
was combined with potassium hydride (35% suspension in mineral oil, 1.0 g, 8.7 mmol) in 10 mL 
of toluene in a 50 mL round bottom flask equipped with a stir bar.  The suspension was stirred at 
room temperature until gas evolution ceased, at which point 5-bromo-pentene (0.6 mL, 5.0 mmol) 
was slowly added to the reaction flask.  The solution was subsequently heated at reflux for 10 h.  
The reaction mixture was then cooled to room temperature, and the unreacted potassium hydride 
was neutralized with a small amount of iPrOH before the solution was filtered and concentrated 
under reduced pressure.  The product was purified by silica gel chromatography, eluting with 5% 
EtOAc in hexane, and recrystallized from cold (0 
o
C) hexane to give a quantitative yield of pure 4 
as a yellowish crystalline solid.  
1
H NMR (300 MHz, CD2Cl2, ppm): 8.32 (d, J = 9 Hz, 1H), 8.19–
7.97 (m, 7H), 7.90 (d, J = 7.8 Hz, 1H), 5.83 (m, 1H), 5.04–4.91 (m, 2H), 3.49–3.35 (m, 6H), 2.09 
(m, 2H), 1.93 (m, 2H), 1.79–1.59 (m, 4H).  
13
C NMR (300 MHz, CD2Cl2, ppm): δ 139.17, 137.80, 
131.99, 131.50, 129.33, 128.04, 127.89, 127.58, 126.99, 126.37, 125.49, 125.33, 125.18, 125.04, 
 
S3 
124.11, 114.82, 71.08, 70.66, 33.81, 30.95, 30.40, 29.62, 29.11.  HRMS(FAB+) m/z: 342.1987 
[M]
+•
. 
 
Synthesis of the pyrene functionalized hyperbranched polymer (5).  3 (163 mg, 0.646 
mmol in monomer), 4 (167 mg, 0.485 mmol, 0.75 equiv.), and 1 (3 mg, 3.53 µmol) were combined 
in 2 mL of dry CH2Cl2 under an inert atmosphere.  The reaction mixture was stirred at 40ºC for 10 
h with venting through a bubbler.  Subsequently, the solution was concentrated before the product 
was redissolved in a small amount of CH2Cl2, loaded on a short silica plug, rinsed with CH2Cl2, 
and eluted with THF.  The purified product was characterized by 
1
H NMR spectroscopy and triple 
detector–SEC, both of which indicated clean and complete addition of 4 (~ 0.75 equivalents per 
repeat unit in 3). 
 
 
Synthesis of the linear pre-monomer, cycloocten-4-ol.  A 250 mL round bottom flask 
equipped with a stir bar and an addition funnel was charged with 1,5-cyclooctadiene (8.6 g, 79.1 
mmol).  A solution of mCPBA (11.1 g, 64.1 mmol) in chloroform (180 mL) was added to the 
reaction flask drop-wise via the addition funnel.  The reaction mixture was stirred for 10 h and then 
filtered.  The filtrate was transferred to a separatory funnel and washed sequentially with saturated 
aqueous solutions of NaHSO3 (3 times), NaHCO3 (once), and NaCl (once).  Purification by silica 
gel chromatography, eluting with 10% EtOAc in hexane, gave 4.2 g (43% yield) of the epoxide 
product.  
1
H NMR (300 MHz, CD2Cl2, ppm): δ 5.57 (m, 2H), 3.00–2.95 (m, 2H), 2.46–2.36 (m, 
2H), 2.18–1.93 (m, 6H).  
13
C NMR (300 MHz, CD2Cl2, ppm): δ 129.35, 56.95, 28.68, 24.20. 
A 1 M THF solution of LAH (17.0 mL, 17.0 mmol) was slowly added via syringe to the 
solution of the epoxide (4.21 g, 33.9 mmol) in THF (23 mL) at room temperature and the mixture 
was stirred for 10 h.  The reaction was then quenched with sodium sulfate decahydrate and stirred 
vigorously for 20 minutes.  The mixture was subsequently filtered through a pad of Celite, washed 
 
S4 
with THF, and concentrated.  Purification by silica gel chromatography with a 30% EtOAc in 
hexane eluent afforded 4.0 g (95% yield) of a clear colorless oil.  
1
H NMR (300 MHz, CD2Cl2, 
ppm): δ 5.73–5.53 (m, 2H), 3.75 (m, 1H), 2.33–2.23 (m, 2H), 2.17–2.03 (m, 2H), 1.94–1.75 (m, 
2H), 1.71–1.44 (m, 4H).  
13
C NMR (300 MHz, CD2Cl2, ppm): δ 130.67, 129.95, 73.09, 38.29, 
36.92, 26.13, 25.47, 23.30.  HRMS(EI+) m/z: 126.1041 [M]
+•
. 
(6).  Cycloocten-4-ol (0.3 g, 2.4 mmol), 1-pyrenebutyric acid (1.0 g, 3.5 mmol), DMAP 
(0.6 g, 4.8 mmol), and Et3N (1.3 mL, 9.5 mmol) were dissolved in 10 mL of dry CH2Cl2. 2,4,6-
Trichlorobenzoyl chloride (1.16 g, 4.8 mmol) was then slowly added to the reaction mixture, and 
the reaction was stirred for 10 h.  The unreacted benzoyl chloride was neutralized with a small 
amount of iPrOH before the solution was filtered and concentrated.  The product was then purified 
by silica gel chromatography, eluting with 5% EtOAc in hexane, to give 0.9 g (95% yield) of a 
semi-crystalline, bright yellow material.  
1
H NMR (300 MHz, CD2Cl2, ppm): δ 8.33 (d, J = 9.6, 
1H), 8.21–7.98 (m, 7H), 7.89 (d, J = 8.1, 1H), 5.76–5.60 (m, 2H), 4.86 (m, 1H), 3.38 (t, J = 7.6, 
2H), 2.44–2.29 (m, 4H), 2.22–2.08 (m, 4H), 1.98–1.56 (m, 6H).  
13
C NMR (300 MHz, CD2Cl2, 
ppm): δ 173.04, 136.77, 131.98, 131.49, 130.47, 130.34, 130.20, 129.28, 128.02, 128.00, 127.77, 
127.15, 126.43, 125.54, 125.45, 125.42, 125.37, 125.28, 124.01, 76.01, 34.83, 34.33, 33.30, 28.45, 
27.54, 26.14, 25.49, 22.88.  HRMS(FAB+) m/z: 396.2084 [M]
+•
. 
(7).  Cycloocten-4-ol (0.5 g, 4.0 mmol) was combined with tBuOK (0.7 g, 6.0 mmol) in dry 
THF (8 mL) at room temperature.  Upon addition of MeI (0.4 mL, 6.0 mmol) the reaction mixture 
was heated to 35 
o
C and stirred for 10 h.  The remaining unreacted tBuOK was neutralized with a 
small amount of iPrOH before the solution was filtered and concentrated.  Purification by silica gel 
chromatography, eluting with 5% EtOAc in hexane, afforded 0.15 g (27% yield) of clear colorless 
oil 7.  
1
H NMR (300 MHz, CD2Cl2, ppm): δ 5.71 (m, 2H), 3.23 (s, 3H), 3.20 (m, 1H), 2.39–2.27 
(m, 2H), 2.17–1.36 (m, 8H).  
13
C NMR (300 MHz, CD2Cl2, ppm): δ 130.67, 129.90, 82.52, 56.15, 
34.48, 33.33, 26.31, 26.20, 23.17.  HRMS(EI+) m/z: 140.1201 [M]
+•
. 
 
Synthesis of pyrene functionalized linear polymer (8).  Monomers 6 (100 mg, 0.25 
mmol) and 7 (12.0 mg, 0.08 mmol) were dissolved in dry CH2Cl2 (1 ml) under an argon 
atmosphere.  Catalyst 1 (5 mg, 6 µmol) was added to the reaction flask, and the solution was stirred 
at 45ºC for 24 hours.  Upon consumption of the monomers, the volatiles were removed under 
reduced pressure.  The product was then redissolved in a small amount of CH2Cl2, loaded on a 
 
S5 
short silica plug, rinsed with CH2Cl2, and eluted with THF.  The purified product was characterized 
by 
1
H NMR spectroscopy and triple detector–SEC (Mw ~ 38K, Mw/Mn ~ 1.45). 


Functionalized hyperbranched polymers via olefin metathesis

Supporting Information for 
 
Functionalized Hyperbranched Polymers via Olefin Metathesis 
 
Irina A. Gorodetskaya, Alon A. Gorodetsky, Ekaterina V. Vinogradova, Robert H. Grubbs 
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and 
Chemical Engineering, California Institute of Technology, Pasadena, California 91125 
 
 
 
Table of Contents 
1) Materials and Instrumentation                                                                                                       S2 
2) Synthesis of 4 (with full characterization)                                                                                     S2 
3) Functionalization procedure/synthesis of 5                                                                                   S3 
4) Reaction scheme and experimental procedures (with full characterizations) for 6 and 7            S3 
5) Polymerization procedure for 8                                                                                                     S4 
 
 
 
 
 
 
 
 
 
 
 
 
 S2 
Materials.  All reagents, except for catalyst 1 and 1-pyrenebutyric acid were purchased 
from Aldrich at the highest available purity and used without further purification.  Catalyst 1 was 
obtained from Materia, Inc., and 1-pyrenebutyric acid (≥97%) was purchased from Fluka.  The 
synthesis of 2 and its polymerization to 3 with 1 have been reported previously.1 
Instrumentation.  NMR spectra were obtained using a Varian Mercury-300 spectrometer; 
samples were dissolved in (methylene chloride)-d2. 
Size exclusion chromatography (SEC) analysis was performed using a Wyatt triple detector 
system equipped with a triple angle light scattering (miniDAWN TREOS, with a laser wavelength 
of 658 nm) detector, a viscometer (ViscoStar) detector, and a refractive index (Optilab rEX) 
detector—all operating at 25oC.  Viscotek ViscoGEL I-Series (one mixed bed medium MW and 
one mixed bed high MW) columns were used for SEC with THF as the eluent and a Shimadzu LC-
10AD pump operating at 1 mL/minute. 
Fluorescence measurements were conducted using an ISS K2 fluorimeter (5 mm path 
length), equipped with a 250 W xenon lamp as excitation source.  Emission spectra were obtained 
by exciting at 346 nm and monitoring the emission between 300 and 700 nm.  UV-Vis spectra 
were recorded on a Beckman DU 7400 spectrophotometer. 
 
Synthesis of 4-(4-pent-4-enyloxy-butyl)-pyrene (4).  1-Pyrenebutanol (1.0 g, 3.6 mmol) 
was combined with potassium hydride (35% suspension in mineral oil, 1.0 g, 8.7 mmol) in 10 mL 
of toluene in a 50 mL round bottom flask equipped with a stir bar.  The suspension was stirred at 
room temperature until gas evolution ceased, at which point 5-bromo-pentene (0.6 mL, 5.0 mmol) 
was slowly added to the reaction flask.  The solution was subsequently heated at reflux for 10 h.  
The reaction mixture was then cooled to room temperature, and the unreacted potassium hydride 
was neutralized with a small amount of iPrOH before the solution was filtered and concentrated 
under reduced pressure.  The product was purified by silica gel chromatography, eluting with 5% 
EtOAc in hexane, and recrystallized from cold (0 oC) hexane to give a quantitative yield of pure 4 
as a yellowish crystalline solid.  1H NMR (300 MHz, CD2Cl2, ppm): 8.32 (d, J = 9 Hz, 1H), 8.19–
7.97 (m, 7H), 7.90 (d, J = 7.8 Hz, 1H), 5.83 (m, 1H), 5.04–4.91 (m, 2H), 3.49–3.35 (m, 6H), 2.09 
(m, 2H), 1.93 (m, 2H), 1.79–1.59 (m, 4H).  13C NMR (300 MHz, CD2Cl2, ppm): δ 139.17, 137.80, 
131.99, 131.50, 129.33, 128.04, 127.89, 127.58, 126.99, 126.37, 125.49, 125.33, 125.18, 125.04, 
 S3 
124.11, 114.82, 71.08, 70.66, 33.81, 30.95, 30.40, 29.62, 29.11.  HRMS(FAB+) m/z: 342.1987 
[M]+•. 
 
Synthesis of the pyrene functionalized hyperbranched polymer (5).  3 (163 mg, 0.646 
mmol in monomer), 4 (167 mg, 0.485 mmol, 0.75 equiv.), and 1 (3 mg, 3.53 µmol) were combined 
in 2 mL of dry CH2Cl2 under an inert atmosphere.  The reaction mixture was stirred at 40ºC for 10 
h with venting through a bubbler.  Subsequently, the solution was concentrated before the product 
was redissolved in a small amount of CH2Cl2, loaded on a short silica plug, rinsed with CH2Cl2, 
and eluted with THF.  The purified product was characterized by 1H NMR spectroscopy and triple 
detector–SEC, both of which indicated clean and complete addition of 4 (~ 0.75 equivalents per 
repeat unit in 3). 
 
 
Synthesis of the linear pre-monomer, cycloocten-4-ol.  A 250 mL round bottom flask 
equipped with a stir bar and an addition funnel was charged with 1,5-cyclooctadiene (8.6 g, 79.1 
mmol).  A solution of mCPBA (11.1 g, 64.1 mmol) in chloroform (180 mL) was added to the 
reaction flask drop-wise via the addition funnel.  The reaction mixture was stirred for 10 h and then 
filtered.  The filtrate was transferred to a separatory funnel and washed sequentially with saturated 
aqueous solutions of NaHSO3 (3 times), NaHCO3 (once), and NaCl (once).  Purification by silica 
gel chromatography, eluting with 10% EtOAc in hexane, gave 4.2 g (43% yield) of the epoxide 
product.  1H NMR (300 MHz, CD2Cl2, ppm): δ 5.57 (m, 2H), 3.00–2.95 (m, 2H), 2.46–2.36 (m, 
2H), 2.18–1.93 (m, 6H).  13C NMR (300 MHz, CD2Cl2, ppm): δ 129.35, 56.95, 28.68, 24.20. 
A 1 M THF solution of LAH (17.0 mL, 17.0 mmol) was slowly added via syringe to the 
solution of the epoxide (4.21 g, 33.9 mmol) in THF (23 mL) at room temperature and the mixture 
was stirred for 10 h.  The reaction was then quenched with sodium sulfate decahydrate and stirred 
vigorously for 20 minutes.  The mixture was subsequently filtered through a pad of Celite, washed 
 S4 
with THF, and concentrated.  Purification by silica gel chromatography with a 30% EtOAc in 
hexane eluent afforded 4.0 g (95% yield) of a clear colorless oil.  1H NMR (300 MHz, CD2Cl2, 
ppm): δ 5.73–5.53 (m, 2H), 3.75 (m, 1H), 2.33–2.23 (m, 2H), 2.17–2.03 (m, 2H), 1.94–1.75 (m, 
2H), 1.71–1.44 (m, 4H).  13C NMR (300 MHz, CD2Cl2, ppm): δ 130.67, 129.95, 73.09, 38.29, 
36.92, 26.13, 25.47, 23.30.  HRMS(EI+) m/z: 126.1041 [M]+•. 
(6).  Cycloocten-4-ol (0.3 g, 2.4 mmol), 1-pyrenebutyric acid (1.0 g, 3.5 mmol), DMAP 
(0.6 g, 4.8 mmol), and Et3N (1.3 mL, 9.5 mmol) were dissolved in 10 mL of dry CH2Cl2. 2,4,6-
Trichlorobenzoyl chloride (1.16 g, 4.8 mmol) was then slowly added to the reaction mixture, and 
the reaction was stirred for 10 h.  The unreacted benzoyl chloride was neutralized with a small 
amount of iPrOH before the solution was filtered and concentrated.  The product was then purified 
by silica gel chromatography, eluting with 5% EtOAc in hexane, to give 0.9 g (95% yield) of a 
semi-crystalline, bright yellow material.  1H NMR (300 MHz, CD2Cl2, ppm): δ 8.33 (d, J = 9.6, 
1H), 8.21–7.98 (m, 7H), 7.89 (d, J = 8.1, 1H), 5.76–5.60 (m, 2H), 4.86 (m, 1H), 3.38 (t, J = 7.6, 
2H), 2.44–2.29 (m, 4H), 2.22–2.08 (m, 4H), 1.98–1.56 (m, 6H).  13C NMR (300 MHz, CD2Cl2, 
ppm): δ 173.04, 136.77, 131.98, 131.49, 130.47, 130.34, 130.20, 129.28, 128.02, 128.00, 127.77, 
127.15, 126.43, 125.54, 125.45, 125.42, 125.37, 125.28, 124.01, 76.01, 34.83, 34.33, 33.30, 28.45, 
27.54, 26.14, 25.49, 22.88.  HRMS(FAB+) m/z: 396.2084 [M]+•. 
(7).  Cycloocten-4-ol (0.5 g, 4.0 mmol) was combined with tBuOK (0.7 g, 6.0 mmol) in dry 
THF (8 mL) at room temperature.  Upon addition of MeI (0.4 mL, 6.0 mmol) the reaction mixture 
was heated to 35 oC and stirred for 10 h.  The remaining unreacted tBuOK was neutralized with a 
small amount of iPrOH before the solution was filtered and concentrated.  Purification by silica gel 
chromatography, eluting with 5% EtOAc in hexane, afforded 0.15 g (27% yield) of clear colorless 
oil 7.  1H NMR (300 MHz, CD2Cl2, ppm): δ 5.71 (m, 2H), 3.23 (s, 3H), 3.20 (m, 1H), 2.39–2.27 
(m, 2H), 2.17–1.36 (m, 8H).  13C NMR (300 MHz, CD2Cl2, ppm): δ 130.67, 129.90, 82.52, 56.15, 
34.48, 33.33, 26.31, 26.20, 23.17.  HRMS(EI+) m/z: 140.1201 [M]+•. 
 
Synthesis of pyrene functionalized linear polymer (8).  Monomers 6 (100 mg, 0.25 
mmol) and 7 (12.0 mg, 0.08 mmol) were dissolved in dry CH2Cl2 (1 ml) under an argon 
atmosphere.  Catalyst 1 (5 mg, 6 µmol) was added to the reaction flask, and the solution was stirred 
at 45ºC for 24 hours.  Upon consumption of the monomers, the volatiles were removed under 
reduced pressure.  The product was then redissolved in a small amount of CH2Cl2, loaded on a 
 S5 
short silica plug, rinsed with CH2Cl2, and eluted with THF.  The purified product was characterized 
by 1H NMR spectroscopy and triple detector–SEC (Mw ~ 38K, Mw/Mn ~ 1.45). 


Excited States and Photochemistry of Organic Molecules; VCH:

For reviews on hyperbranched polymers, see:(a)

http://authors.library.caltech.edu/14473/1/Gorodetskaya2009p2400Macromolecules.pdf

Functionalized hyperbranched polymers via olefin metathesis

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