Polycondensation of bis(diazocarbonyl) compounds with aromatic diols and cyclic ethers: Synthesis of new type of polyetherketones

Article abstract of DOI:10.1021/ma100494a

A series of new polyetherketones was prepared by Rh-catalyzed polycondensation of bis(diazocarbonyl) compounds 1a-c with aromatic diols 2A-C in cyclic ethers (THF, THP, and 1,4-dioxane). In addition to the expected insertion of diazo-bearing carbon of 1a-

Full text of DOI:10.1021/ma100494a

Macromolecules 2010, 43, 4589–4598 4589
DOI: 10.1021/ma100494a
Polycondensation of Bis(diazocarbonyl) Compounds with Aromatic Diols
and Cyclic Ethers: Synthesis of New Type of Polyetherketones
Eiji Ihara,* Kotaro Saiki, Yuko Goto, Tomomichi Itoh, and Kenzo Inoue*
Department of Material Science and Biotechnology, Graduate School of Science and Engineering, Venture
Business Laboratory, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
Received March 4, 2010; Revised Manuscript Received April 14, 2010
ABSTRACT: A series of new polyetherketones was prepared by Rh-catalyzed polycondensation of bis-
(diazocarbonyl) compounds 1a-c with aromatic diols 2A-C in cyclic ethers (THF, THP, and 1,4-dioxane). In
addition to the expected insertion of diazo-bearing carbon of 1a-c into O-H of 2A-C releasing N2, unexpected
incorporation of the ring-opened cyclic ethers between the diazo-bearing carbon of 1a-c and phenolic oxygen of
2A-C occurred, providing the polymer main chains with additional oxyalkylene units. The extent of cyclic ether
incorporation relative to the expected insertion depended on the kind of the cyclic ether: THF, 95-98%; THP,
26-32%; 1,4-dioxane, 11-21%. Polyetherketones with a variety of main chain structures can be prepared by the
new polycondensation.
Introduction
linker to impart enough solubility to resulting polymers. By
employing rhodium acetate dimer, Rh2(OAc)4, as a most com-
Diazocarbonyl compounds have been demonstrated to be
versatile reagents that can be used in a variety of reactions,1,2
mostly represented by transition-metal-catalyzed cyclopropana-
tion of olefins. In addition, not only for organic synthesis, utility
of diazocarbonyl compounds as a monomer for polymer synthesis
has also been demonstrated in the metal-mediated polymerization
to afford C-C main chain polymers bearing substituents on all
of the main chain carbon atoms.3 In addition to linear polymers,
we have succeeded in preparing cross-linked polymers by copoly-
merization using bifunctional diazocarbonyl compounds [bis-
(diazocarbonyl) compounds] as a comonomer.4
To our knowledge, polycondensation using bis(diazocarbonyl)
compounds as a monomer has not been reported so far, although
the formation of a variety of main chain structures will be
expected by using the reactions of a diazocarbonyl group with
other functional groups. For example, Rh-catalyzed O-H inser-
tion of diazocarbonyl compounds with alcohol is one of the
common reactions,1,2 which could be applied for polycondensa-
tion of bis(diazocarbonyl) compounds with diols. Interesting to
note is that the resulting polymer main chain consists of carbonyl
and ether linkages (Scheme 1), and variation in the combination
of R3 and R4 groups in the monomers will enable us to control the
physical properties of the products. Herein, we will describe the
results of Rh-catalyzed polycondensation of bis(diazocarbonyl)
compounds with aromatic diols, which indeed afforded poly-
mers with carbonyl and ether linkages in the main chain (poly-
etherketones), whereas unexpected incorporation of ring-opened
cyclic ether (THF, THP, and 1,4-dioxane) units accompanied to
afford additional oxyalkylene [-O-(CH2)n-] units in the poly-
mer main chain.
monly used catalyst for the O-H insertion,1,2 the reaction of 1a
with bisphenol A (2A) was conducted in various solvents, such as
CH2Cl2, 1,2-dichloroethane, toluene, and cyclic ethers. However,
when the reaction was conducted in the chlorinated solvents and
toluene at 0-80 °C, the resulting polymeric products (Mn =
1500-4300) obtained in 20-50% yields exhibited very compli-
cated appearance in their 1H NMR spectra, which did not allow
us to identify the polymer structures. The results suggest that in
these solvents, in addition to the expected insertion of diazo-
bearing carbon into O-H, some unexpected reactions occur
between the functional groups, even though CH2Cl2 is the most
commonly used solvent for the Rh-catalyzed reaction of diazo-
carbonyl compounds.1 The unexpected reactions could be N2-
releasing CdC formation between two diazocarbonyl groups and
oligomerization of the diazocarbonyl group, as we have reported
for monofunctional diazoketones in previous publications.3d,4
Polymers with well-defined structures were obtained in the cyclic
ethers (THF, THP, and 1,4-dioxane), as will be described in detail
in the following.
For example, when a 1:1 mixture of 1a and 2A was reacted in the
presence of a catalytic amount of Rh2(OAc)4 in a ratio of
[1a]/[2A]/[Rh2(OAc)4] 50:50:1, a polymeric product 3aA, whose
GPC-estimated Mn (PMMA standards) was 11 900, was obtained
after purification with preparative recycling GPC (Scheme 2, run 1
1
in Table 1). In the H NMR spectrum shown in Figure 1, in
addition to signals assignable to H’s derived from 1a and 2A, we
can observe unexpected signals at 3.95, 3.62, and 1.85 ppm in a
1:1:2 ratio, which could be ascribed to the ring-opened framework
of THF, as illustrated in Scheme 2.
To confirm the incorporation of the ring-opened THF frame-
work, a model reaction for the polymerization was conducted
between diazoacetophenone (monofunctional counterpart to 1a)
and 4-t-butylphenol (Scheme 3). Because a Rh-catalyzed equi-
molar reaction of the compounds in THF afforded a polymeric
product with an unidentified structure as a main product, a 10-
fold excess of the phenol was employed in the model reaction. As
a result, along with a small amount of an undesirable polymeric
product, we obtained a product of normal (expected) O-H
Results and Discussion
As a bis(diazocarbonyl) compound for the polycondensation,
we first employed bis(aryldiazoketone) 1a, in which two diazoa-
cetophenone moieties are connected with a SiMe2CH2CH2SiMe2
*Corresponding author. Tel/Fax: þ81-89-927-8547. E-mail: ihara@
eng.ehime-u.ac.jp.
r 2010 American Chemical Society
Published on Web 04/23/2010
pubs.acs.org/Macromolecules

4590 Macromolecules, Vol. 43, No. 10, 2010
Ihara et al.
Scheme 1. O-H Insertion of Diazocarbonyl Compound with Alcohol and its Application to Polycondensation Affording Polyetherketone
Scheme 2. Polycondensation of 1a with Aromatic Diols in THF
a
Table 1. Polymerization of 1a with 2A∼2C and Cyclic Ethers (THF, THP, and 1,4-Dioxane) Catalyzed by Rh2(OAc)4
(x0 þ x00)/(y0 þ y00)c
96:4
b
b
run
diol
ether
temp
yield (%)
product
Mn
Mw/Mn
1
2
3
4
5
6
7
8
9
10
2A
THF
THF
THF
THP
1,4-dioxane
THF
THP
THF
THP
1,4-dioxane
RT
40.8
35.1
44.9
27.3
24.0
24.1
29.1
28.6
36.1
24.7
3aA
3aA
3aA
6aA
8aA
3aB
6aB
3aC
6aC
8aC
11 900
10 000
5200
13 400
13 100
16 500
11 900
10 400
14 400
11 400
2.07
1.77
1.31
1.64
1.44
1.39
1.38
1.86
1.85
1.81
0 °C (41 h)
50 °C
RT
RT
RT
RT
RT
RT
RT
95:5
96:4
29:71
18:82
98:2
29:71
96:4
27:73
11:89
2B
2C
a Polymerization period =17 h; solvent (ether) = 5 mL, 1a = ca. 0.1 g, [1a]/[diol]/[Rh2(OAc)4] = 50:50:1. b Mn and Mw/Mn were obtained by GPC
calibration using standard PMMAs and dibutyl sebacate in THF solution. c x0 þ x00 = ether-incorporated unit; y0 þ y00 = normal insertion unit.
insertion 4 and a product incorporating ring-opened THF 5 in 1.3
and 86.8% isolated yields, respectively, whose 1H NMR spectra
are shown in Figure 2. Compared with the spectrum of 4
(Figure 2a), there appear three additional signals at 3.97, 3.64,
and 1.87 ppm with an intensity ratio of 1:1:2 in the spectrum of 5
(Figure 2b). Considering the relative intensity of the additional
signals to the other signals and 13C and 2D (H-H and H-C)
NMR spectra, the structure of 5 can be clearly identified as that
having a ring-opened THF between the diazoketone- and phenol-
derived moieties.
Although this type of reaction giving 5 is unprecedented at
least to our knowledge, the mechanism for the formation of 5 can

Article
Macromolecules, Vol. 43, No. 10, 2010 4591
be estimated from the reported mechanism for the formation of
4.1 The reaction would be initiated by a nucleophilic attack of
a THF-oxygen to the carbene-carbon of Rh-carbene complex,
which should be formed by the reaction of the Rh complex with a
diazoketone. Then, the resulting oxonium ylide complex would
be attacked by a phenolic-oxygen in one of two possible path-
ways. In path A, the attack of the phenolic-oxygen occurs at one
of two carbons adjacent to the oxygen in the THF-derived five-
membered ring, resulting in the ring-opening of THF to give a
THF-incorporated product such as 5 after elimination of the Rh-
complex. In path B, the phenolic-oxygen attacks at a Rh-bearing
carbon, followed by eliminations of THF and the Rh complex to
give a normal insertion product such as 4.
Pd-mediated ones,3d,4 and so on, as we also suggested as the
aforementioned reason for the formation of unidentifiable pro-
ducts in chlorinated solvents and toluene. The low yield due to the
contamination of the low Mn unidentifiable product is a common
trend observed in all polymerizations in Tables 1 and 2. Poly-
merization at 0 °C did not affect the polymerization result (run 2
in Table 1), and raising the temperature to 50 °C afforded a lower
Mn polymer (run 3). In addition, longer reaction periods at room
temperature did not improve the yield or Mn of the products.
The THF-incorporating polycondensation of 1a also pro-
ceeded with 4,40-biphenol 2Band 2,6-naphthalenediol2C, afford-
ing polymers 3aB and 3aC (Scheme 2, runs 6 and 8 in Table 1),
respectively. (See the Supporting Information for 1H NMR
spectra for the polymers.) In a similar manner as with 1A,
incorporation of the ring-opened THF predominates in those
polymerizations as the ratios listed in Table 1 indicate, and the
isolated yields of the polymers were rather low after the removal
of the low-molecular-weight products by using preparative re-
cycling GPC.
Comparison of the 1H NMR spectrum of 5 (Figure 2b) with
that of 3aA demonstrates that the polymer predominantly has the
ring-opened THF framework in the main chain. The small signal
at 5.18 ppm in the spectrum of 3aA can be assigned to the CH2
between carbonyl carbon and ether oxygen resulting from the
normal insertion as in the formation of 4 (the related signal of 4
appears at 5.25 ppm in Figure 2a), indicating the presence of the
framework in a very small extent. The selectivity for the THF-
incorporation in the polymerization is in good accordance with
that in the model reaction ([4]/[5] 2:98): the relative signal
intensity between those at 5.18 and 4.67 ppm (the signal for
-(CdO)-CH2-O- of THF-incorporated framework) shows
the ratio is 4:96 ([without THF]/[with THF]). The yield of
3aA calculated based on the main chain structure was relatively
low (40.8%), basically because a significant amount of a low-
molecular-weight product was removed by preparative recycling
GPC, which also brings about rather narrow molecular weight
When THP was used as a solvent instead of THF for the
polycondensation of 1a with bisphenol A (2A) (run 4 in Table 1),
the appearance in 1H NMR of the obtained polymer 6aA with Mn=
13 400 indicated that the ether linkage in the product was totally
different from the aforementioned pattern for 3aA with THF
1
(Scheme 5, Figure 3). Therefore, in the H NMR spectrum of
6aA shown in Figure 3, five signals centered at 3.91, 3.58, 1.78, 1.70,
and 1.57 ppm (the last one overlaps with signals from Me derived
from 2A and H2O) with nearly equal intensities appear, which can
be ascribed to the ring-opened structure of THP. To confirm the
structural assignment, a model reaction of diazoacetophenone with
1
distributions for polycondensation products. In the H NMR
spectrum of the low-molecular-weight product removed by
the purification, we observed additional signals that cannot
be identified along with the predominant signals of 3aA. We
assume that these low-molecular-weight products derived
from some side reactions such as a coupling reaction forming a
-C(dO)-CHdCH-C(CdO)- linkage, polymerization as in
Figure 1. 1H NMR spectrum for 3aA (run 1 in Table 1).
Figure 2. 1H NMR spectra of (a) 4 and (b) 5.
Scheme 3. Model Reaction of Diazoketone with Phenol in THF

4592 Macromolecules, Vol. 43, No. 10, 2010
Ihara et al.
a
Table 2. Polymerization of 1b and 1c with 2A∼2C and Cyclic Ethers (THF, THP, and 1,4-Dioxane) Catalyzed by Rh2(OAc)4
etherb
product
yield (%)
Mn
Mw/Mn
(x0 þ x00)/(y0 þ y00)c
97:3
b
b
run
1b or 1c
diol
1
2
3
4
5
6
7
8
1b
2A
THF
THP
1,4-dioxane
THF
THP
THF
THP
THF
THP
1,4-dioxane
THF
THP
THF
THP
3bA
6bA
8bA
3bB
6bB
3bC
6bC
3cA
6cA
8cA
3cB
6cB
3cC
6cC
30.8
40.4
40.1
37.7
35.7
28.2
25.3
27.6
26.2
25.5
38.7
27.8
35.7
36.5
10 500
12 000
15 400
14 700
16 700
27 000
17 500
10 400
7600
1.23
1.63
1.78
1.43
1.82
2.05
1.92
1.36
1.21
1.25
1.41
1.54
1.69
2.44
27:73
11:89
98:2
27:73
96:4
26:74
97:3
32:68
21:79
98:2
2B
2C
2A
1c
9
10
11
12
13
14
9000
2B
2C
13 400
10 700
17 200
12 200
32:68
98:2
37:63
a Polymerization period =17 h; solvent (ether) = 5 mL, 1b or 1c = ca. 0.1 g, [1b,c]/[diol]/[Rh2(OAc)4] = 50:50:1. b Mn and Mw/Mn were obtained by
GPC calibration using standard PMMAs and dibutyl sebacate in THF solution. c x0 þ x00 = ether-incorporated unit; y0 þ y00 = normal insertion unit.
Scheme 4. Proposed Mechanism for Propagation in the Presence of THF
4-t-butylphenol was conducted in THP under a similar condition
([diazoketone]/[phenol] 1:10) as that in THF described above. As a
result, a mixture of 4 and a THP-incorporated product 7 was
with respect to the ring-opening incorporation can be reasonably
ascribed to the higher propensity for the ring-opening reaction for
THF than for THP under the condition. It is interesting to note that
THP and 1,4-dioxane (see below) participate in the ring-opening
reaction, which, we propose, proceeds in a mechanism analogous to
cationic ring-opening polymerization of cyclic ethers, although
THP and 1,4-dioxane have very low cationic ring-opening
homopolymerizability.5
The polycondensation of 1a with 2B and 2C as aromatic diols
in THP also proceeded to give polymers 6aB and 6aC, respec-
tively, having ring-opened THP in their main chains with similar
incorporation selectivities of THP (runs 7 and 9 in Table 1).
1
obtained in 51.8 and 26.8% yields, respectively, and a H NMR
spectrum for 7 is shown in Figure 4, whose comparison with
Figure 3 allowed us to confirm the presence of the ring-opened
THP in the polymer main chain of 6aA. Corresponding to the ratio
of the yields of 4 and 7 ([4]/[7] 66:34), the composition in the
polymerization determined by the relative signal intensity between
the signals at 5.18 and 4.67 ppm in Figure 3 shows the predomi-
nance of the normal insertion: [without THP]/[with THP] 71:29.
The observed difference between THF and THP in the selectivity

Article
Macromolecules, Vol. 43, No. 10, 2010 4593
Scheme 5. Polycondensation of 1a with Aromatic Diols in THP and 1,4-Dioxane
Figure 3. 1H NMR spectrum for 6aA (run 4 in Table 1).
Figure 5. 1H NMR spectrum for 8aA (run 5 in Table 1).
2A, a ring-opened framework of 1,4-dioxane was incorporated in
the main chain of the product 8aA (Scheme 5, run 5 in Table 1).
The assignment of the signals derived from the ring-opened 1,4-
dioxane structure in the 1H NMR spectrum in Figure 5 was again
confirmedbycomparison of the signalsto those of an 1,4-dioxane
incorporated model product 9 (Figure 6) obtained from the
model reaction described in Scheme 7. The ratio of the yield
of 4 to 1,4-dioxane-incorporated compound 9 ([4]/[9] 90:10) is
even higher than that observed in the model reaction in THP
(Scheme 6), and the selectivity for the reaction was reflected in the
polymerization, where the composition between the two types of
the linkages was 82:18 ([without 1,4-dioxane]/[with 1,4-dioxane]).
The composition was determined from the relative signal intensity
between those at 5.17 and 4.77 ppm in Figure 5. The analogous 1,4-
dioxane-incoporated polymer 8aC was obtained from the poly-
merization using 2C as an aromatic diols (run 10 in Table 1),
Figure 4. 1H NMR spectrum for 7.
Similarly, when 1,4-dioxane was used as another six-mem-
bered cyclic ether as a solvent for the polymerization of 1a with

4594 Macromolecules, Vol. 43, No. 10, 2010
Ihara et al.
although a product of the polymerization of 1a with 2B was an
insoluble solid because of its low solubility derived from the low
degree of 1,4-dioxane incorporation.
examined, and the results are summarized in Table 2. For these
polymerizations, the incorporation of ring-opened ethers em-
ployed as a solvent was observed in similar manners as described
with 1a, furnishing a variety of polyetherketones (Scheme 8). (See
Whereas we can expect that similar polymerization should
proceed with the use of another six-membered cyclic ether
trioxane6 and a three-membered ether 1,2-epoxybutane, which
have high reactivity for cationic ring-opening polymerization, the
reaction of 1a with 2A under similar conditions using these cyclic
ethers afforded polymeric products, whose structures cannot be
1
the Supporting Information for H NMR spectra for the poly-
mers in Table 2.) However, when 1,4-dioxane was used as a
solvent, because of low solubility of the products derived from the
low degree of solvent incorporation, well-defined polymers were
not obtained, except in the case of using bisphenol A as a diol
(8bA (run 3) and 8cA (run 10)).
1
identified from their H NMR spectra. For the reaction with
trioxane, which is solid at room temperature (mp 59-62 °C), the
reaction was conducted at >65 °C or at room temperature by
using Et2O, CH2Cl2, or toluene as a solvent. The model reaction
of diazoacetophenone with 4-t-butylphenol and trioxane in
CH2Cl2 as a solvent gave 4 alone in a 63.6% yield, whereas the
reaction in 1,2-epoxybutane did not afford any identifiable
product. These results suggest that the efficient incorporation
of the ring-opened cyclic ether is the essential condition for the
polymerization to afford well-defined main chain structures. In
addition, although our proposed mechanism for THF-incorpora-
tion described in Scheme 4 is closely related to the propagation
mechanism for the cationic polymerization of THF, the reacti-
vities of cyclic ethers for cationic polymerization and ring-opening
insertion in this study are not simply related.
Conclusions
We have demonstrated that bis(diazocarbonyl) compounds can
be utilized as a monomer for polycondensation for the first time.
The reaction of bis(diazocarbonyl) compounds with aromatic
Scheme 8. Polycondensation of 1b and 1c with Aromatic Diols in THF,
THP, and 1,4-Dioxane
The polymerizations of 1b and 1c bearing -SiMe2- and
-SiMe2-O-SiMe2- linkers, respectively, as bis(diazocarbonyl)
compounds with aromatic diols 2A∼2C in the cyclic ethers were
Figure 6. 1H NMR spectrum for 9.
Scheme 6. Model Reaction of Diazoketone with Phenol in THP
Scheme 7. Model Reaction of Diazoketone with Phenol in 1,4-Dioxane

Article
Macromolecules, Vol. 43, No. 10, 2010 4595
diols in cyclic ethers afforded polyetherketones with a variety of
structures as a result of incorporation of ring-opened cyclic ethers.
Despite the rather low polymer yields in this study, bis(dia-
zocarbonyl) compounds can be regarded as a useful class of
monomers for polycondensation because of their versatile reactiv-
ities with various functional groups. The further investigation
along this course is underway in our laboratory.
(Ph), 125.6 (Ph), 54.2 (-CHdN2), 7.6 (-SiMe2-[CH2]2-
SiMe2-), -3.8 (-Si[CH3]2-). Anal. Calcd for C22H26N4O2-
Si2 0.3H2O: C, 60.05; H, 6.09; N, 12.73. Found: C, 60.78; H,
3
5.89; N, 11.74. 1c: 1H NMR (400 MHz, CDCl3, δ): 7.71 (d, J=
7.6 Hz, 4H, Ph-H), 7.58 (d, J=6.8 Hz, 4H, Ph-H), 5.91 (s, 2H,
-CHdN2), 0.35 (s, 12H, -Si[CH3]2-). 13C NMR (100 MHz,
CDCl3, δ): 186.5 (CdO), 145.3 (Ph), 137.3 (Ph), 133.3 (Ph),
125.8 (Ph), 54.3 (-CHdN2), 0.72 (-Si[CH3]2-). Anal. Calcd
for C20H22N4O3Si2 0.8H2O: C, 54.97; H, 5.44; N, 12.82. Found:
3
Experimental Section
C, 54.23; H, 5.05; N, 12.01.
Materials. THF was dried over Na/K alloy and distilled before
use. THP (TCI, > 98.0%) and 1,2-epoxybutane (TCI, > 99.0%)
were dried over CaH2 and used without further purification.
1,3,5-Trioxane (TCI, > 99.0%), dehydrated 1,4-dioxane (Kanto
Chemical, > 99.5%), bisphenol A (Wako, > 95%), 4,40-biphenol
(TCI, > 99.0%), 2,6-dihydroxynaphthalene (Wako), 4-t-butyl-
phenol (Nacalai, 98%), and Rh2(OAc)4 (AZmax, 99%) were used
as received. Diazoacetophenone was prepared according to the
literature.7
Polymerization Procedure. As a typical procedure, copoly-
merization of 1a with 2A in THF (run 1 in Table 1) was described
as follows.
Under a N2 atmosphere, 1a (106 mg, 0.244 mmol), 2A (55.7
mg, 0.244 mmol), and Rh2(OAc)4 (2.2 mg, 4.9 ꢀ 10-3 mmol)
were placed in a Schlenk tube. After THF (5.0 mL) was added,
the mixture was stirred at room temperature for 17 h. After the
volatiles were removed under reduced pressure, a MeOH solu-
tion of HCl (1N, 10 mL), aqueous solution of HCl (1N, 10 mL),
and CHCl3 (20 mL) were added to the residue. The organic layer
was extracted with a separatory funnel, and the aqueous layer
was extracted with 30 mL of CHCl3. The combined organic
layer was washed with 50 mL of 1 N aqueous solution of HCl
and 50 mL of saturated aqueous solution of NaCl, dried over
Na2SO4. The solid obtained after removal of volatiles under
reduced pressure was purified by using preparative recycling
GPC to give a polymer as a brownish yellow solid (67.8 mg,
40.8%).
Measurements. 1H (400 MHz) and 13C (100 MHz) NMR
spectra were recorded on a Bruker Avance 400 spectrometer
using tetramethysilane as an internal standard in chloroform-d
(CDCl3) at room temperature (monomers) or at 50 °C
(polymers).
Molecular weights (Mn) and molecular weight distributions
(Mw/Mn) were measured by means of gel permeation chromato-
graphy (GPC) on a Jasco-ChromNAV system equipped with a
differential refractometer detector using tetrahydrofuran as
eluent at a flow rate of 1.0 mL/min at 40 °C, calibrated with
poly(MMA). The column used for the GPC analyses was
a combination of Styragel HR4 (Waters; 300 mm ꢀ 7.8 mm
i.d., 5 μm average particle size, exclusion molecular weight of
600K for polystyrene) and Styragel HR2 (Waters; 300 mm ꢀ 7.8
mm i.d., 5 μm average particle size, exclusion molecular weight
of 20K for polystyrene), and poly(MMA) standards (Shodex
M-75, Mp=212 000, Mw/Mn=1.05, Mp=50 000, Mw/Mn=1.02,
Mp=22 00, Mw/Mn=1.02, Mp =5720, Mw/Mn=1.06, Mp =
2400, Mw/Mn=1.08) and dibutyl sebacate (MW=314.5) were
used for the calibration.
Purification by preparative recycling GPC was performed on
a JAI LC-918R equipped with a combination of columns of a
JAIGEL-3H (600 mm ꢀ 20 mm i.d., exclusion molecular weight
of 70K for polystyrene) and a JAIGEL-2H (600 mm ꢀ 20 mm
i.d., exclusion molecular weight of 5K for polystyrene) for
polymers and a combination of columns of a JAIGEL-2H and
a JAIGEL-1H (600 mm ꢀ 20 mm i.d., exclusion molecular
weight of 1K for polystyrene) for monomers 1a-c and the
products of model reactions 4, 5, 7, and 9, using CHCl3 as
eluent at a flow rate of 3.8 mL/min at 25 °C. The sample solution
(3 mL containing ca. 0.3 g of the crude product) was injected and
recycled before fractionation.
Elemental analyses were performed on a YANAKO MT-5
analyzer at Integrated Center for Science (INCS) in Ehime
University. Probably because of the presence of Si-containing
or aromatic moiety in the main chains, elemental analyses of all
the polymers in this study did not give satisfactory results.
Preparation of Bis(diazocarbonyl) Compounds (1a-1c). The
preparation of bis(4-diazoacetylphenyl)dimethylsilane (1b) by
diazo-transfer reaction7 of bis(4-acetylphenyl)dimethylsilane
was described in our previous publication.4 1,2-Bis[(4-diazoa-
cetylphenyl)dimethylsilyl]ethane (1a) and 1,3-bis(4-diazoacetyl-
phenyl)-1,1,3,3-tetramethyldisiloxane (1c) were prepared by
applying the procedure for 1b to 1,2-bis[(4-acetylphenyl)di-
methylsilyl]ethane8 and 1,3-bis(4-acetylphenyl)-1,1,3,3-tetramethyl-
disiloxane,9 respectively. Yields for the diazo-transfer reactions
were 75.1% for 1a and 32.4% for 1b. 1a: 1H NMR (400 MHz,
CDCl3, δ): 7.70 (d, J=7.6 Hz, 4H, Ph-H), 7.52 (d, J=6.8 Hz,
4H, Ph-H), 5.92 (s, 2H, -CHdN2), 0.62 (s, 4H, -SiMe2-
[CH2]2-SiMe2-), 0.26 (s, 12H, --Si[CH3]2-). 13C NMR (100
MHz, CDCl3, δ): 186.5 (CdO), 145.4 (Ph), 136.8 (Ph), 133.8
Other Rh-catalyzed polymerizations of bis(diazocarbonyl)
compounds with diols in cyclic ether were carried out in a
1
similar procedure. 3aA: H NMR (400 MHz, CDCl3, δ): 7.85
(d, J=7.2 Hz, -SiMe2-Ph[-H]-[CdO]-), 7.54 (d, J=7.2 Hz,
-SiMe2-Ph[-H]-[CdO]-), 7.09 (d, J = 8.0 Hz, -O-Ph-
[-H]-CMe2-), 6.76 (d, J = 8.0 Hz, -O-Ph[-H]-CMe2-),
5.16 (s, -[CdO]-CH2-O-Ph- [minor repeating unit without
THF incorporation]), 4.67 (s, -[CdO]-CH2-O-CH2- [major
repeating unit with THF incorporation]), 4.0-3.9 (m,
-CH2-O-Ph-CMe2-), 3.7-3.5 (m, -[CdO]-CH2-O-
CH2-), 1.9-1.7 (br, -O-CH2-[CH2]2-CH2-O-), 1.61 (s,
-Ph-C[CH3]2-Ph-),0.65(s,-SiMe2-[CH2]2-SiMe2-),0.25(s,
-Si[CH3]2-). 6aA: 1H NMR (400 MHz, CDCl3, δ): 7.95-7.82 (m,
-SiMe2-Ph[-H]-[CdO]-), 7.61-7.49 (m, -SiMe2-Ph[-H]-
[CdO]-), 7.15-7.03 (m, -O-Ph[-H]-CMe2-), 6.85-6.67 (m,
-O-Ph[-H]-CMe2-), 5.17 (s, -[CdO]-CH2-O-Ph- [major
repeating unit without THP incorporation]), 4.67 (s, -[CdO]-
-CH2-O-CH2- [minor repeating unit with THP incorporation]),
3.91 (t, J=5.8 Hz, -CH2-O-Ph-CMe2-), 3.58 (t, J=6.2 Hz,
-[CdO]-CH2-O-CH2-), 1.82-1.74 (m, -CH2-CH2-O-
Ph-CMe2-), 1.74-1.66 (m, -[CdO]-CH2-O-CH2-CH2-),
1.60 (s, -Ph-C[CH3]2-Ph-), 1.65-1.46 (m, -O-CH2-
CH2-CH2-CH2-CH2-O-), 0.66 (s, -SiMe2-[CH2]2-Si-
Me2-), 0.26 (s, -Si[CH3]2-). 8aA: 1H NMR (400 MHz, CDCl3,
δ): 7.95-7.80 (m, -SiMe2-Ph[-H]-[CdO]-), 7.61-7.47 (m,
-SiMe2-Ph[-H]-[CdO]-), 7.14-7.01 (m, -O-Ph[-H]-
-CMe2-), 6.86-6.66 (m, -O-Ph[-H]-CMe2-), 5.17 (s,
-[CdO]-CH2-O-Ph- [major repeating unit without 1,4-diox-
ane incorporation]), 4.77 (s, -[CdO]-CH2-O-CH2- [minor
repeating unit with 1,4-dioxane incorporation]), 4.09-4.04 (m,
-CH2-O-Ph-CMe2-), 3.83-3.78 (m, -[CdO]-CH2-O-
CH2-), 3.78-3.71 (m, -O-CH2-CH2-O-CH2-CH2-O-),
1.60(s,-Ph-C[CH3]2-Ph-),0.66(s,-SiMe2-[CH2]2-SiMe2-),
0.26 (s, -Si[CH3]2-). 3aB: 1H NMR (400 MHz, CDCl3, δ): 7.86 (d,
J = 7.2 Hz, -SiMe2-Ph[-H]-[CdO]-), 7.54 (d, J = 7.6 Hz,
-SiMe2-Ph[-H]-[CdO]-), 7.42(d, J=8.0 Hz, -O-Ph[-H]-),
6.91 (d, J = 7.6 Hz, -O-Ph[-H]-), 5.24 (s, -[CdO]-
-CH2-O-Ph- [minor repeating unit without THF incorpo-
ration]), 4.69 (s, -[CdO]-CH2-O-CH2- [major repeating
unit with THF incorporation]), 4.01 (t, J = 5.6 Hz,-CH2-
O-Ph-CMe2-), 3.64 (t, J=5.6 Hz, -[CdO]-CH2-O-
CH2-), 1.95-1.79 (br, -O-CH2-[CH2]2-CH2-O-), 0.65

4596 Macromolecules, Vol. 43, No. 10, 2010
Ihara et al.
(s, -SiMe2-[CH2]2-SiMe2-), 0.25 (s, -Si[CH3]2-). 6aB:
1H NMR (400 MHz, CDCl3, δ): 7.96-7.82 (m, -SiMe2-Ph-
[-H]-[CdO]-), 7.61-7.49 (m, -SiMe2-Ph[-H]-[CdO]-),
7.46-7.33 (m, -O-Ph[-H]-), 7.00-6.87 (m, -O-Ph[-H]-),
5.23 (s, -[CdO]-CH2-O-Ph- [major repeating unit without
THP incorporation]), 4.67 (s, -[CdO]-CH2-O-CH2- [minor
repeating unit with THP incorporation]), 3.97 (t, J = 5.6 Hz,
-CH2-O-Ph-CMe2-), 3.59 (t, J = 5.6 Hz, -[CdO]-CH2-
O-CH2-), 1.86-1.77 (br, -CH2-CH2-O-Ph-CMe2-),
1.76-1.67 (br, -[CdO]-CH2-O-CH2-CH2-), 1.62-1.52
(m, -O-CH2-CH2-CH2-CH2-CH2-O-), 0.70-0.60 (m,
-SiMe2-[CH2]2-SiMe2-), 0.26 (s, -Si[CH3]2-). 3aC: 1H NMR
(400 MHz, CDCl3, δ): 7.90-7.80 (m, -SiMe2-Ph[-H]-
[CdO]-), 7.61-7.46 (m, -SiMe2-Ph[-H]-[CdO]- and
-O-naphthalene[-H]-), 7.11-7.00 (m, -O-naphthalene-
[-H]-), 5.26 (s, -[CdO]-CH2-O-naphthalene- [minor repeat-
ing unit without THF incorporation]), 4.69 (s, -[CdO]-
CH2-O-CH2- [major repeating unit with THF incorporation]),
4.11-4.01 (m, -CH2-O-naphthalene-), 3.69-3.59 (m,
-[CdO]-CH2-O-CH2-), 1.98-1.79 (br, -O-CH2-
[CH2]2-CH2-O-), 0.64 (s, -SiMe2-[CH2]2-SiMe2-), 0.25 (s,
CH2-O-CH2-), 3.78-3.70 (s, -O-CH2-CH2-O-CH2-
CH2-O-), 1.59 (s, -Ph-C[CH3]2-Ph-), 0.59 (s, -Si[CH3]2-).
3bB: 1H NMR (400 MHz, CDCl3, δ): 7.88 (d, J = 7.6 Hz,
-SiMe2-Ph[-H]-[CdO]-), 7.58 (d, J=8.0 Hz, -SiMe2-Ph-
[-H]-[CdO]-), 7.41 (d, J=8.4 Hz, -O-Ph[-H]-), 6.91 (d, J=
8.0 Hz, -O-Ph[-H]-), 5.21 (s, -[CdO]-CH2-O-Ph- [minor
repeating unit without THF incorporation]), 4.67 (s, -[Cd
O]-CH2-O-CH2- [major repeating unit with THF in-
corporation]), 4.06-3.94 (m, -CH2-O-Ph-CMe2-), 3.68-
3.56 (m, -[CdO]-CH2-O-CH2-), 1.94-1.77 (m, -O-CH2-
1
[CH2]2-CH2-O-), 0.58 (s, -Si[CH3]2-). 6bB: H NMR (400
MHz, CDCl3, δ): 8.01-7.80 (m, -SiMe2-Ph[-H]-[CdO]-),
7.68-7.48 (m, -SiMe2-Ph[-H]-[CdO]-), 7.47-7.31 (m,
-O-Ph[-H]-), 7.01-6.79 (m, -O-Ph[-H]-), 5.22 (s, -[Cd
O]-CH2-O-Ph- [minor repeating unit without THP incor-
poration]), 4.66 (s, -[CdO]-CH2-O-CH2- [major repeating
unit with THP incorporation]), 4.01-3.89 (m, -CH2-O-
naphthalene-), 3.63-3.52 (m, -[CdO]-CH2-O-CH2-),
1.87-1.75 (br, -CH2-CH2-O-naphthalene-), 1.75-1.63 (br,
-[CdO]-CH2-O-CH2-CH2-), 1.61-1.39 (m, -O-CH2-
CH2-CH2-CH2-CH2-O-), 0.60 (s, -Si[CH3]2-). 3bC: 1H
NMR (400 MHz, CDCl3, δ): 7.93-7.83 (m, -SiMe2-Ph[-H]-
[CdO]-), 7.63-7.52 (m, -SiMe2-Ph[-H]-[CdO]- and
-O-naphthalene[-H]-), 7.11-7.01 (m, -O-naphthalene-
[-H]-), 5.26(s, -[CdO]-CH2-O-naphthalene- [major repeat-
ing unit without THF incorporation]), 4.67 (s, -[CdO]-CH2-
O-CH2- [minor repeating unit with THF incorporation]),
4.11-4.00 (m, -CH2-O-naphthalene-), 3.68-3.58 (m, -[Cd
O]-CH2-O-CH2-), 1.97-1.79 (m, -O-CH2-[CH2]2-CH2-
O-), 0.58 (s, -Si[CH3]2-). 6bC: 1H NMR (400 MHz, CDCl3, δ):
8.01-7.76 (m, -SiMe2-Ph[-H]-[CdO]-), 7.67-7.35 (m,
-SiMe2-Ph[-H]-[CdO]- and -O-naphthalene[-H]-),
7.21-6.96 (m, -O-naphthalene[-H]-), 5.26 (s, -[CdO]-
CH2-O-naphthalene- [major repeating unit without THP in-
corporation]), 4.65 (s, -[CdO]-CH2-O-CH2- [minor repeating
unit with THP incorporation]), 4.07-3.95 (m, -CH2-O-
naphthalene-), 3.62-3.50 (m, -[CdO]-CH2-O-CH2-), 1.89-
1.77 (br, -CH2-CH2-O-naphthalene-), 1.76-1.64 (br, -[Cd
O]-CH2-O-CH2-CH2-), 1.63-1.37 (m, -O-CH2-CH2-
CH2-CH2-CH2-O-), 0.58 (s, -Si[CH3]2-). 3cA: 1H NMR
(400 MHz, CDCl3, δ): 8.03-7.78 (m, -SiMe2-Ph[-H]-
[CdO]-), 7.73-7.48 (m, -SiMe2-Ph[-H]-[CdO]-), 7.09 (d,
J=7.6 Hz, -O-Ph[-H]-CMe2-), 6.75 (d, J=8.0 Hz, -O-Ph-
[-H]-CMe2-), 5.18 (s, -[CdO]-CH2-O-Ph- [minor repeat-
ing unit without THF incorporation]), 4.69 (s, -[CdO]-
CH2-O-CH2- [major repeating unit with THF incorporation]),
3.99-3.89 (m, -CH2-O-Ph-CMe2-), 3.67-3.58 (m, -[Cd
O]-CH2-O-CH2-), 1.91-1.76 (br, -O-CH2-[CH2]2-CH2-
O-), 1.61(s, -Ph-C[CH3]2-Ph-), 0.35(s, -Si[CH3]2-). 6cA:1H
NMR (400 MHz, CDCl3, δ): 7.97-7.83 (m, -SiMe2-Ph[-H]-
[CdO]-), 7.68-7.56 (m, -SiMe2-Ph[-H]-[CdO]-), 7.14-7.03
(m, -O-Ph[-H]-CMe2-), 6.85-6.67 (m, -O-Ph[-H]-
CMe2-), 5.18 (s, -[CdO]-CH2-O-Ph- [major repeating unit
without THP incorporation]), 4.67 (s, -[CdO]-CH2-O-CH2-
[minor repeating unit with THP incorporation]), 3.92 (t, J=6.0 Hz,
-CH2-O-Ph-CMe2-), 3.58 (t, J = 6.6 Hz, -[CdO]-
CH2-O-CH2-), 1.82-1.74 (m, -CH2-CH2-O-Ph-CMe2-),
1.74-1.67 (m, -[CdO]-CH2-O-CH2-CH2-), 1.60 (s, -Ph-
C[CH3]2-Ph-), 1.64-1.51 (m, -O-CH2-CH2-CH2-CH2-
CH2-O-), 0.39-0.30 (m, -Si[CH3]2-). 8cA: 1H NMR (400
MHz, CDCl3, δ): 7.96-7.82 (m, -SiMe2-Ph[-H]-[CdO]-),
7.68-7.51 (m, -SiMe2-Ph[-H]-[CdO]-), 7.14-7.01 (m,
-O-Ph[-H]-CMe2-), 6.85-6.66 (m, -O-Ph[-H]-CMe2-),
5.17 (s, -[CdO]-CH2-O-Ph- [major repeating unit without
1,4-dioxane incorporation]), 4.78 (s, -[CdO]-CH2-O-
CH2- [minor repeating unit with 1,4-dioxane incorporation]),
4.09-4.05 (m, -CH2-O-Ph-CMe2-), 3.84-3.79 (m,
-[CdO]-CH2-O-CH2-), 3.79-3.75 (m, -O-CH2-CH2-
O-CH2-CH2-O-), 1.60 (s, -Ph-C[CH3]2-Ph-), 0.36 (s, -Si-
[CH3]2-). 3cB:1H NMR (400 MHz, CDCl3, δ):7.88(d, J=8.4 Hz,
1
-Si[CH3]2-). 6aC: H NMR (400 MHz, CDCl3, δ): 7.99-7.81
(m, -SiMe2-Ph[-H]-[CdO]-), 7.63-7.49 (m, -SiMe2-
Ph[-H]-[CdO]- and -O-naphthalene[-H]-), 7.22-7.02 (m,
-O-naphthalene[-H]-), 5.23 (s, -[CdO]-CH2-O-naph-
thalene- [major repeating unit without THP incorporation]),
4.67 (s, -[CdO]-CH2-O-CH2- [minor repeating unit with
THP incorporation]), 4.06-3.99 (m,-CH2-O-naphthalene-),
3.63-3.55 (m, -[CdO]-CH2-O-CH2-), 1.89-1.79 (br,
-CH2-CH2-O-naphthalene-), 1.77-1.68 (br, -[CdO]-
CH2-O-CH2-CH2-), 1.63-1.54 (m, -O-CH2-CH2-CH2-
CH2-CH2-O-), 0.72-0.59 (m, -SiMe2-[CH2]2-SiMe2-),
0.27 (s, -Si[CH3]2-). 8aC: 1H NMR (400 MHz, CDCl3, δ):
7.99-7.79 (m, -SiMe2-Ph[-H]-[CdO]-), 7.63-7.43 (m,
-SiMe2-Ph[-H]-[CdO]- and -O-naphthalene[-H]-),
7.22-7.02 (m, -O-naphthalene[-H]-), 5.27 (s, -[CdO]-
CH2-O-naphthalene- [major repeating unit without 1,4-di-
oxane incorporation]), 4.79 (s, -[CdO]-CH2-O-CH2- [minor
repeating unit with 1,4-dioxane incorporation]), 4.21-4.15
(m, -CH2-O-naphthalene-), 3.90-3.84 (m, -[CdO]-CH2-
O-CH2-), 3.81-3.76 (m, -O-CH2-CH2-O-CH2-CH2-
O-), 0.71-0.58 (m, -SiMe2-[CH2]2-SiMe2-), 0.26 (s, -Si-
1
[CH3]2-). 3bA: H NMR (400 MHz, CDCl3, δ): 7.88 (d, J =
8.0 Hz, -SiMe2-Ph[-H]-[CdO]-), 7.58 (d, J = 8.0 Hz,
-SiMe2-Ph[-H]-[CdO]-), 7.09 (d, J = 8.8 Hz, -O-Ph-
[-H]-CMe2-), 6.75 (d, J = 9.2 Hz, -O-Ph[-H]-CMe2-),
5.15 (s, -[CdO]-CH2-O-Ph- [minor repeating unit without
THF incorporation]), 4.66 (s, -[CdO]-CH2-O-CH2- [major
repeating unit with THF incorporation]), 3.94 (t, J = 5.8 Hz,
-CH2-O-Ph-CMe2-), 3.61 (t, J = 6.2 Hz, -[CdO]-CH2-
O-CH2-), 1.91-1.75 (m, -O-CH2-[CH2]2-CH2-O-), 1.61
1
(s, -Ph-C[CH3]2-Ph-), 0.59 (s, -Si[CH3]2-). 6bA: H NMR
(400 MHz, CDCl3, δ): 8.05-7.77 (m, -SiMe2-Ph[-H]-
[CdO]-), 7.65-7.43 (m, -SiMe2-Ph[-H]-[CdO]-), 7.14-
6.97 (m, -O-Ph[-H]-CMe2-), 6.85-6.64 (m, -O-Ph-
[-H]-CMe2-), 5.15 (s, -[CdO]-CH2-O-Ph- [major repeat-
ing unit without THP incorporation]), 4.65 (s, -[CdO]-
CH2-O-CH2- [minor repeating unit with THP incorporation]),
3.95-3.85 (m, -CH2-O-Ph-CMe2-), 3.60-3.51 (m, -[Cd
O]-CH2-O-CH2-), 1.82-1.73 (m, -CH2-CH2-O-Ph-
CMe2-), 1.73-1.65 (m, -[CdO]-CH2-O-CH2-CH2-), 1.60
(s, -Ph-CMe2-Ph), 1.64-1.43 (m, -O-CH2-CH2-CH2-
CH2-CH2-O-), 0.59 (s, -Si[CH3]2-). 8bA: 1H NMR (400
MHz, CDCl3, δ): 7.99-7.79 (m, -SiMe2-Ph[-H]-[CdO]-),
7.67-7.43 (m, -SiMe2-Ph[-H]-[CdO]-), 7.15-6.98 (m,
-O-Ph[-H]-CMe2-), 6.86-6.64 (m, -O-Ph[-H]-CMe2-),
5.15 (s, -[CdO]-CH2-O-Ph- [major repeating unit without
1,4-dioxane incorporation]), 4.76 (s, -[CdO]-CH2-O-CH2-
[minor repeating unit with 1,4-dioxane incorporation]), 4.09-
4.02 (m, -CH2-O-Ph-CMe2-), 3.84-3.78 (m, -[CdO]-

Article
Macromolecules, Vol. 43, No. 10, 2010 4597
-SiMe2-Ph[-H]-[CdO]-), 7.60 (d, J=8.0 Hz, -SiMe2-Ph-
[-H]-[CdO]-), 7.42 (d, J=8.8 Hz, -O-Ph[-H]-), 6.91 (d, J=
8.4 Hz, -O-Ph[-H]-), 5.24 (s, -[CdO]-CH2-O-Ph- [minor
repeating unit without THF incorporation]), 4.69 (s, -[CdO]-
CH2-O-CH2- [major repeating unit with THF incorporation]),
4.01 (t, J=5.8 Hz, -CH2-O-naphthalene-), 3.65 (t, J=6.2 Hz,
-[CdO]-CH2-O-CH2-), 1.94-1.80 (m, -O-CH2-[CH2]2-
CH2-O-), 0.35 (s, -Si[CH3]2-). 6cB: 1H NMR (400 MHz,
CDCl3, δ): 7.98-7.83 (m, -SiMe2-Ph[-H]-[CdO]-), 7.68-
7.56 (m, -SiMe2-Ph[-H]-[CdO]-), 7.47-7.33 (m, -O-Ph-
[-H]-), 7.00-6.81 (m, -O-Ph[-H]-), 5.24 (s, -[Cd
O]-CH2-O-Ph- [minor repeating unit without THP incor-
poration]), 4.68 (s, -[CdO]-CH2-O-CH2- [major repeating
unit with THP incorporation]), 3.97 (t, J = 5.2 Hz, -CH2-
O-Ph-), 3.60 (t, J = 6.2 Hz, -[CdO]-CH2-O-CH2-),
1.86-1.77 (br, -CH2-CH2-O-Ph-), 1.76-1.67 (br, -[CdO]-
CH2-O-CH2-CH2-), 1.62-1.52 (m, -O-CH2-CH2-CH2-
CH2-CH2-O-), 0.36 (s, -Si[CH3]2-). 3cC: 1H NMR (400
MHz, CDCl3, δ): 7.92-7.83 (m, -SiMe2-Ph[-H]-[CdO]-),
7.64-7.54 (m, -SiMe2-Ph[-H]-[CdO]-), (m, -O-naph-
thalene[-H]-), 7.11-7.04 (m, -O-naphthalene[-H]-), 5.28
(s, -[CdO]-CH2-O-naphthalene- [major repeating unit with-
out THF incorporation]), 4.69 (s, -[CdO]-CH2-O-CH2-
[minor repeating unit with THF incorporation]), 4.07 (t, J=6.0
Hz,-CH2-O-naphthalene-), 3.65 (t, J = 6.0 Hz, -[CdO]-
CH2-O-CH2-), 1.98-1.81 (m, -O-CH2-[CH2]2-CH2-O-),
0.35 (s, -Si[CH3]2). 6cC: 1H NMR (400 MHz, CDCl3, δ):
8.01-7.81 (m, -SiMe2-Ph[-H]-[CdO]-), 7.71-7.41 (m,
-SiMe2-Ph[-H]-[CdO]- and -O-naphthalene[-H]-),
7.22-6.98 (m, -O-naphthalene[-H]-), 5.28 (s, -[CdO]-
CH2-O-naphthalene- [major repeating unit without THP in-
corporation]), 4.68(s,-[CdO]-CH2-O-CH2- [minor repeating
unit with THP incorporation]), 4.06-3.97 (m, -CH2-O-
naphthalene-), 3.63-3.54 (m, -[CdO]-CH2-O-CH2-), 1.88-
1.78 (br, -CH2-CH2-O-naphthalene-), 1.77-1.66 (br, -[Cd
O]-CH2-O-CH2-CH2-), 1.63-1.51 (m, -O-CH2-CH2-
CH2-CH2-CH2-O-), 0.35 (s, -Si[CH3]2-).
67.46 (-CH2-O-Ph-tBu), 34.06 (-C[CH3]3), 31.55 (-C-
[CH3]3), 26.35 (-O-CH2-[CH2]2-CH2-O-), 26.05 (-O-
CH2- [CH2]2-CH2-O-). Anal. Calcd for C22H28O3 0.2 H2O:
C, 76.80; H, 8.32. Found: C, 76.70; H, 7.60. 7: H NMR (400
3
1
MHz, CDCl3, δ): 7.95 (d, J=7.6 Hz, 2H, o-Ph[-H]-[CdO]-),
7.58 (t, J=7.4 Hz, 1H, p-Ph[-H]-[CdO]-), 7.47 (t, J=7.2 Hz,
2H, m-Ph[-H]-[CdO]-), 7.28 (d, J = 8.0 Hz, 2H, -O-Ph-
[-H]-tBu), 6.82 (d, J=8.8 Hz, 2H, -O-Ph[-H]-tBu), 4.73 (s,
2H, -[CdO]-CH2-O-), 3.94 (t, J=6.4 Hz, 2H, -CH2-O-
Ph-tBu), 3.60 (t, J=6.4 Hz, 2H, -[CdO]-CH2-O-CH2-),
1.84-1.77 (m, 2H, -CH2-CH2-O-Ph-tBu), 1.77-1.69 (m,
2H, -[CdO]-CH2-O-CH2-CH2-), 1.61-1.51 (m, 2H, -O-
CH2-CH2-CH2-CH2-CH2-O-), 1.29 (-C[CH3]3). 13C
NMR (100 MHz, CDCl3, δ): 196.70 (CdO), 156.81 (Ph), 143.16
(Ph), 135.02 (Ph), 133.51 (Ph), 128.71 (Ph), 127.98 (Ph), 126.19
(Ph), 113.94 (Ph), 73.92 (-[CdO]-CH2-O-), 71.77 (-[CdO]-
CH2-O-CH2-), 67.72 (-CH2-O-Ph-tBu), 34.07 (-C[C-
H3]3), 31.58 (-C[CH3]3), 29.42 (-[CdO]-CH2-O- CH2-
CH2-), 29.15 (-CH2-CH2-O-Ph-tBu), 22.70 (-O-CH2-
CH2-CH2-CH2-CH2-O-). Anal. Calcd for C23H30O3 0.1
3
1
H2O: C, 77.54; H, 8.54. Found: C, 77.39; H, 8.34. 9: H NMR
(400 MHz, CDCl3, δ): 7.91 (d, J = 7.6 Hz, 2H, o-Ph[-H]-
[CdO]-), 7.56 (t, J=7.2 Hz, 1H, p-Ph[-H]- [CdO]-), 7.43 (t,
J=7.4 Hz, 2H, m-Ph[-H]-[CdO]-), 7.27 (d, J=8.4 Hz, 2H,
-O-Ph[-H]-tBu), 6.83 (d, J=8.4 Hz, 2H, -O-Ph[-H]-tBu),
4.86 (s, 2H, -[CdO]-CH2-O-), 4.12-4.05 (m, 2H, -CH2-O-
Ph-tBu), 3.87-3.82 (m, 2H, -[CdO]-CH2-O-CH2-), 3.82-
3.76 (m, 4H, -O-CH2-CH2-O-CH2-CH2-O-), 1.29 (-C-
[CH3]3). 13C NMR (100 MHz, CDCl3, δ): 195.42 (CdO), 155.44
(Ph), 142.49 (Ph), 133.87 (Ph), 132.43 (Ph), 127.65 (Ph), 126.84
(Ph), 125.15 (Ph), 113.04 (Ph), 73.23 (-[CdO]-CH2-O-), 70.10
(-O-CH2-CH2-O-CH2-CH2-O-), 69.90 (-O-CH2-
CH2-O-CH2-CH2-O-), 68.80 (-[CdO]-CH2-O-CH2-),
66.33 (-CH2-O-Ph-tBu), 30.02 (-C[CH3]3), 30.49 (-C[C-
H3]3). Anal. Calcd for C22H28O4: C, 74.13; H, 7.92. Found: C,
73.74; H, 7.48.
Procedure for Model Reactions. As a typical procedure, a
reaction of diazoacetophenone with 4-t-butylphenol in THF
was described as follows.
Acknowledgment. This research was supported by the
Grants-in-Aid for Scientific Research (B) (no. 18350066) from
Japan Society for the Promotion of Science (JSPS).
Under a N2 atmosphere, diazoacetophenone (100.9 mg, 0.690
mmol), 4-t-butylphenol (1.03 g, 6.84 mmol), and Rh2(OAc)4 (3.3
mg, 7.5 ꢀ 10-3 mmol) were placed in a Schlenk tube. After THF
(14.0 mL) was added, the mixture was stirred at room tempera-
ture for 17 h. After workup procedure for the above polymeri-
zation was applied, purification with recycling-GPC in CHCl3
afforded 4 (34.1 mg, 0.127 mmol) and 5 (172.4 mg, 0.506 mmol)
in 1.3 and 86.8% yield, respectively.
Supporting Information Available: 13C NMR spectra for
products of model reactions 4, 5, 7, and 9. 1H NMR spectra for
polymers all the polymers in Tables 1 and 2 except for 3aA, 6aA,
and 8aA. This material is available free of charge via the Internet
at http://pubs.acs.org.
References and Notes
Other model reactions were carried out in similar procedures.
1
4: H NMR (400 MHz, CDCl3, δ): 7.99 (d, J = 7.6 Hz, 2H,
(1) Doyle, M. P.; Mckervey, M. A.; Ye, T. Modern Catalytic Methods
for Organic Synthesis with Diazo Compounds; John Wiley & Sons:
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o-Ph-H-[CdO]-), 7.59 (t, J=7.2 Hz, 1H, p-Ph-H-[CdO]-),
7.47 (t, J=7.6 Hz, 2H, m-Ph-H-[CdO]-), 7.29 (d, J=8.0 Hz,
2H, -O-Ph-H-tBu), 6.88 (d, J = 8.0 Hz, 2H,
-O-Ph-H-tBu), 5.23 (s, 2H, -[CdO]-CH2-O-), 1.28 (s,
9H, -C[CH3]3). 13C NMR (100 MHz, CDCl3, δ): 194.8 (CdO),
155.8 (Ph), 144.4 (Ph), 134.7 (Ph), 133.9 (Ph), 128.9 (Ph), 128.2
(Ph), 126.4 (Ph), 114.5 (Ph), 71.0 (-[CdO]-CH2-O-), 34.2
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3
1
C, 79.50; H, 7.56. Found: C, 79.41; H, 7.30. 5: H NMR (400
MHz, CDCl3, δ): 7.94 (d, J=7.6 Hz, 2H, o-Ph[-H]-[CdO]-),
7.58 (t, J=7.4 Hz, 1H, p-Ph[-H]-[CdO]-), 7.47 (t, J=7.2 Hz,
2H, m-Ph[-H]-[CdO]-), 7.28 (d, J = 8.4 Hz, 2H, -O-Ph-
[-H]-tBu), 6.82 (d, J=8.4 Hz, 2H, -O-Ph[-H]-tBu), 4.74
(s, 2H, -[CdO]-CH2-O-), 3.97 (t, J = 5.0 Hz, 2H,
-CH2-O-Ph-tBu), 3.64 (t, J = 5.4 Hz, 2H, -[CdO]-
CH2-O-CH2-), 1.93-1.80 (m, 4H, -O-CH2-[CH2]2-
CH2-O-), 1.29 (s, 9H, -C[CH3]3). 13C NMR (100 MHz,
CDCl3, δ): 196.64 (CdO), 156.76 (Ph), 143.21 (Ph), 135.01 (Ph),
133.51 (Ph), 128.71 (Ph), 127.97 (Ph), 126.19 (Ph), 113.94 (Ph),
73.86 (-[CdO]-CH2-O-), 71.47 (-[CdO]-CH2-O-CH2-),

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