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[6] M. A. Hamon, J. Chen, H. Hu, Y. Chen, M. E. Itkis, A. M. Rao, P. C. Living Coordination Polymerization of Allene
Eklund, R. C. Haddon, Adv. Mater. 1999, 11, 834, and references
therein. Derivatives Bearing Hydroxy Groups by
[7] See, for example: L. Dai, Polym. Adv. Technol. 1999, 10, 357, and p-Allylnickel Catalyst
references therein; M. S. P. Shaffer, A. H. Windle, Adv. Mater. 1999,
11, 937; J. Sandler, M. S. P. Shaffer, T. Prasse, W. Bauhofer, K. Schulte, Masanori Taguchi, Ikuyoshi Tomita,* and
A. H. Windle, Polymer 1999, 40, 5967. Takeshi Endo*
[8] See, for example: B. Z. Tang, H. Y. Xu, Macromolecules 1999, 32,
2569; J. Fan, M. Wan, D. Zhu, B. Chang, Z. Pan, S. Xie, J. Appl. Polym. Synthetic polymers such as poly(vinyl alcohol) and poly(2-
Sci. 1999, 74, 2605; C. Downs, J. Nugent, P. M. Ajayan, D. J. Duquette,
K. S. V. Santhanam, Adv. Mater. 1999, 11, 1028; G. Z. Chen, M. S. P.
hydroxyethyl methacrylate)bearing hydroxy groups in their
Shaffer, D. Coleby, G. Dixon, W. Zhou, D. J. Fray, A. H. Windle, Adv. repeating units are, because of their unique polar character
Mater. 2000, 12, 522. and reactivities, useful starting materials for the preparation
[9] D. B. Romero, M. Carrard, W. A. de Heer, L. Zuppiroli, Adv. Mater. of many functional compounds. [1] Nevertheless, with the
1996, 8, 899; Y. Saito, S. Uemura, K. Hamaguchi, Jpn. J. Appl. Phys.
exception of methods that involve the protection and
1998, 37, L346.
[10] S. A. Curran, P. M. Ajayan, W. J. Blau, D. L. Carroll, J. N. Coleman, deprotection of hydroxy groups, their use in well-defined
A. B. Dalton, A. P. Davey, A. Drury, B. McCarthy, S. Maier, A. synthesis has been limited.[2]
Strevens, Adv. Mater. 1998, 10, 1091. Living polymerization, a technique which is insensitive to
[11] H. Ago, K. Petritsch, M. S. P. Shaffer, A. H. Windle, R. H. Friend, polar functional groups on the monomers, is thus a suitable
Adv. Mater. 1999, 11, 1281.
[12] R. H. Baughman, C. Changxing, A. A. Zakhidov, Z. Iqbal, J. N.
method to prepare well-defined polymers directly from
Barisci, G. M. Spinks, G. G. Wallace, A. Mazzoldi, D. de Rossi, A. G. monomers bearing hydroxy groups. The living coordination
Rinzler, O. Jaschinski, S. Roth, M. Kertesz, Science 1999, 284, 1340; M. polymerization of allene derivatives by [{(p-allyl)NiO-
Gao, L. Dai, R. H. Baughman, G. M. Spinks, G. G. Wallace, SPIE, in COCF3}2] (1) is therefore attractive because this complex is
press.
able to polymerize monomers having a variety of functional
[13] S. Huang, L. Dai, A. W. H. Mau, J. Phys. Chem. B 1999, 103, 4223; Y.
Yang, S. Huang, H. He, A. W. H. Mau, L. Dai, J. Am. Chem. Soc. 1999, groups, such as alkoxy,[3a±c] aryl,[3d] alkyl,[3e±f] amide,[3g] and
121, 10 832; S. Huang, A. W. H. Mau, T. Turney, P. White, L. Dai, J. carboalkoxy[3h] moieties. Herein we investigate the coordina-
Phys. Chem. B 2000, 104, 2193; Q. Chen, L. Dai, Appl. Phys. Lett. tion polymerization of allenes bearing hydroxy groups (2 a ±
2000, 76, 2719; D. Li, L. Dai, S. Huang, A. W. H. Mau, Z. L. Wang, 2 c) mediated by 1 (Scheme 1).
Chem. Phys. Lett. 2000, 316, 349.
[14] L. Dai, J. Macromol. Sci. Rev. Macromol. Chem. Phys. 1999, 39, 237,
and references therein. R
•
[15] D. Sazou, C. Georgolios, J. Electroanal. Chem. 1997, 429, 81; P. M. OCOCF3 R OCOCF3
2
McManus, R. J. Cushman, S. C. Yang, J. Phys. Chem. 1987, 91, 744; Ni Ni
A. G. MacDiarmid, J. C. Chiang, W. S. Huang, B. D. Humphrey, N. D. PPh3 a b n
PPh3
Somasiri, Mol. Cryst. Liq. Cryst. 1985, 125, 309. 1 R R
[16] The polyaniline-encapasulated nanotubes gave IR absorption peaks at
1514 (CˆC stretching of the benzenoid rings), 1622 (CˆC stretching of CH3
the quinoid rings), 1359 (C N stretching), and 1197 cm 1 (electronic-
R: CH2 OH CH OH C OH
like absorption of NˆQˆN, where Q represents the quinoid ring),
consistent with reported data.[14] XPS measurements indicated a CH3 CH3
decrease in the carbon content to 71.08 % and concomitant increases (2a) (2b) (2c)
to 12.11, 5.81, and 11.00 % for nitrogen, sulfur, and oxygen, respec-
tively, after the electrodeposition of polyaniline. The calculated C:N Scheme 1. Living coordination polymerization of allene derivatives that
atomic ratio of 6.7 is close to that of aniline (C:N ˆ 6), suggesting the contain hydroxy moieties (2 a ± 2 c).
formation of a continuous polyaniline coating with a thickness greater
than the XPS detection depth (typically, 10 nm; see Figure 3). The
corresponding atomic ratios of 3.8 for O:S and 4.7 for N:S indicated a The polymerization of 2,3-butadiene-1-ol (2 a)[4a] by 1 ([2 a]/
high doping level of the polymer coating by H2SO4 .[17] Further [1] ˆ 60) was carried out in the presence of PPh3 ([PPh3]/[1] ˆ
evidence for the electrodeposition of polyaniline on the nanotube 1.0) in EtOH at 50 8C (Table 1, entry 1). The polymerization
surface comes from Raman scattering measurements. Whilst the
Raman spectrum of the bare nanotubes shows an intense peak at
was complete within 3 h and a white powdery polymer
1584 cm 1, attributable to the E2g mode of the multiwall nanotubes, (poly(2 a)) was obtained in 96 % yield. The 1H NMR spectrum
with a shoulder centered at 1322 cm 1 associated with the amorphous of poly(2a) indicated that it consists of both the 1,2- and the
graphite,[2] the corresponding Raman spectrum for the polyaniline- 2,3-polymerized units (labeled a and b in Scheme 1) in a ratio
coated nanotubes reveals broad bands around 1600, 1495, and
1390 cm 1, typical for polyaniline.[18] An additional peak at
1330 cm 1 is associated with the stretching vibration of the -C-N‡- [*] Dr. I. Tomita
polaron groups, indicating the conducting nature of the polymer Department of Electronic Chemistry
coating. Interdisciplinary Graduate School of Science and Engineering
[17] L. Dai, J. Lu, B. Matthews, A. W. H. Mau, J. Phys. Chem. B 1998, 102, Tokyo Institute of Technology
4049. Nagatsuta 4259, Midori-ku, Yokohama 226-8502, (Japan)
[18] A. H.-L. Goff, M. C. Bernard, Synth. Met. 1993, 60, 115. Fax: (‡ 81) 45-924-5489
[19] L. Dai, White, J. W. Polymer 1997, 38, 775, and references therein. E-mail: [email protected]
[20] Z. L. Wang, P. Poncharal, W. A. de Heer, Microsc. Microanal. 2000, 6, Prof. Dr. T. Endo, M. Taguchi
224. Research Laboratory of Resources Utilization
[21] R. P. Gao, Z. L. Wang, Z. G. Bai, W. A. de Heer, L. Dai, M. Gao, Phys. Tokyo Institute of Technology
Rev. Lett. 2000, 85, 622. Nagatsuta 4259, Midori-ku, Yokohama 226-8503, (Japan)
[22] G. Shi, S. Jin, G. Xue, C. Li, Science 1995, 267, 994. Fax: (‡ 81) 45-924-5276
E-mail: [email protected]

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Table 1. Living coordination polymerization of 2 by 1.
Entry Monomer [2]/[1] a:b[a] Yield [%][b] Mn ( 103)[c] Mw/Mn[c]
1 2a 60 40:60 96 9.6[d] 1.13[d]
2 2b 60 50:50 98 4.6 1.13
3 2c 50 35:65 94 6.4 1.08

[a] The ratio of 1,2- and 2,3-polymerized units, determined by 1H NMR

spectroscopy. [b] Yields after precipitation with hexane. [c] GPC (THF,
polystyrene standard). [d] Determined by GPC measurement performed
after the reaction with ethyl vinyl ether.

of about 40:60. Poly(2 a) is soluble in polar organic solvents

such as MeOH, EtOH, DMSO, and DMF but insoluble in
hexane, benzene, CH2Cl2 , THF, and water. In the reaction Figure 2. GPC traces a) before, and b) after postpolymerization with 3.
with ethyl vinyl ether, the hydroxy group attached to the
polymer was converted quantitatively to acetal moieties and
the resulting polymer was soluble in MeOH, THF, benzene, tional blocks, should be possible. To the best of our knowl-
hexane, and CH2Cl2 .[5] Gel permeation chromatographic edge, this is the first example of a living polymerization
(GPC) analysis of the acetal-containing polymer revealed reaction capable of the polymerization of a wide variety of
that the number-average molecular weight (Mn) and the functionalized monomers.
molecular weight distribution (Mw/Mn) are 9.6  103 and 1.13,
Experimental Section
respectively (THF, polystyrene standard; see Table 1). The
living nature of the present system was confirmed by Typical living polymerization reaction: EtOH (2.0 mL), a solution of 1
polymerization reactions with different ratios of [2 a]/[1] (0.10 m, 0.2 mL, 0.020 mmol) in toluene, a solution of PPh3 (1.0 m, 20 mL,
(Figure 1). That is, the molecular weight of the polymers 0.020 mmol) in toluene, and 2 a (0.084 g, 1.2 mmol, [2 a]/[1] ˆ 60) at 0 8C
were placed under a nitrogen atmosphere in a test tube equipped with a
obtained after conversion of the hydroxy groups to the acetal three way tap and a magnetic stirrer bar. The mixture was stirred at 50 8C
moieties increased linearly as the ratio of [2 a]/[1] increased, for 3 h. After the complete conversion of 2 a (monitored by gas
and Mw/Mn remained narrow ( 1.13). chromatography), the solution was precipitated with hexane and dried in
vacuo to give poly(2 a) (0.081 g; 96 %). 1H NMR (300 MHz, [D6]DMSO,
25 8C): d ˆ 1.96 (br, 2 H  b; ˆC-CH2-Cˆ), 2.75 (br, 1 H  a; -CH < ), 3.34
(br, 2 H  a; > C-CH2-O-), 3.48 (br, 2 H  b; ˆC-CH2-O-), 4.03 (br, 1 H;
OH), 4.80 (br, 2 H  a; > CˆCH2), 5.42 (br, 1 H  b; > CˆCH-O-); a and b
are shown in Scheme 1; a:b ˆ 0.40:0.60; 13C NMR (100 MHz, [D6]DMSO,
25 8C): d ˆ 24.0, 24.9 (-CH2-), 30.1, 31.6 (> CH-), 60.0 (> CH2-CH2-OH),
69.1 (ˆCH-CH2-OH), 129.5, 129.8, 130.0 (ˆCH2), 132.4, 133.0, 133.1, 134.6,
134.8, 139.4 (ˆCH-CH2-OH, > CˆCH2 , and > CˆCH-CH2-OH); IR
(CHCl3):nÄ ˆ 3389 (O H), 2966, 2928, 1452, 1369 (C H), 1682, 1633
(CˆC), 1053 cm 1 (C O).
Block copolymerization reaction: EtOH (2.0 mL), a solution of 1 (0.10 m,
0.2 mL, 0.020 mmol) in toluene, a solution of PPh3 (1.0 m, 20 mL,
0.020 mmol) in toluene, and 2 a (0.056 g, 0.80 mmol, [2 a]/[1] ˆ 40) at 0 8C,
Figure 1. Dependence of Mn (*) and Mw/Mn (&) of poly(2 a) on the ratio of were placed under a nitrogen atmosphere in a test tube equipped with a
monomer to initiator ([2 a]/[1]). three way tap and a magnetic stirrer bar. The mixture was stirred at 50 8C
for 3 h. After the complete conversion of 2 a (monitored by gas
chromatography), a portion of the solution (ca. 50 mL) was removed, and
The coordination polymerization of allenes bearing secon- 3 (0.096 g, 1.0 mmol, [3]/[1] ˆ 50) was added to the remaining solution.
dary and tertiary hydroxy groups (2 b[4b] and 2 c,[4b] respec- After postpolymerization at 50 8C for 3 h, the product was precipitated with
water and dried in vacuo to give the block copolymer (0.137 g, 90 %). GPC
tively) also proceeds smoothly to give narrowly dispersed
measurements of both poly(2 a) sampled before the addition of 3 and the
polymers in high yields (Table 1, entries 2 and 3).[6] block copolymer were performed after the treatment with ethyl vinyl ether.
The block copolymerization of 2 a with 1,2-heptadiene ((3) 1
H NMR (300 MHz, CDCl3 , 25 8C, TMS): d ˆ 0.82 (br, 3 H  n; -CH3), 1.12
n-butylallene)[4c] by the sequential addition of monomers to 1 (br, 4 H  n ‡ 2 H  n  c ‡ 2 H  n  d; -CH2-, > C-CH2-, and ˆC-CH2-,),
further confirmed the living nature of the polymerization. 1.96 (br, 2 H  m  b ‡ 2 H  n  d, ˆC-CH2-Cˆ), 2.55 (br, 1 H  m  a ‡
1 H  n  c; -CH < ), 3.40 (br, 2 H  m  a; > C-CH2-O-), 3.53 (br, 2 H 
That is, after the polymerization of 2 a ([2a]/[1] ˆ 40), 3 was m  b; ˆC-CH2-O-), 4.07 (br, 1 H  m; OH), 4.76 (br, 2 H  m  a ‡ 2H 
added to the polymer solution ([3]/[1] ˆ 50) and the post- n  c; > CˆCH2), 5.18 (br, 2 H  m  b ‡ 2 H  n  d; > CˆCH-O-,); a and
polymerization was conducted at 50 8C for 3 h; a block b are shown in Scheme 1 a:b ˆ 0.43:0.57, c and d represent the 2,3- and the
copolymer was obtained quite effectively, as confirmed by 1,2-polymerized units, respectively, in poly (3) segment c:d ˆ 0.10:0.90, m
and n represent the ratio of poly (2 a) and poly (3), respectively, in the block
GPC measurements (Figure 2).[7]
copolymer m:n ˆ 0.39:0.61; 13C NMR (100 MHz, CDCl3 , 25 8C, TMS): d ˆ
These results show that well-defined poly(alcohol)s can be 14.0 (-CH3), 22.5, 24.0, 27.5 (-CH2-), 30.1, 31.6, 35.6 (> CH-), 60.0 (> CH2-
prepared without a multiple-step protection ± deprotection CH2-OH), 69.1 (ˆCH-CH2-OH), 110.3, 128.4, 128.6, 130.0 (ˆCH2), 132.2,
process, and that the polymerization of allene derivatives by 1 132.1, 134.6, 134.8 (ˆCH-CH2-OH, > CˆCH2 , and > CˆCH-CH2-OH); IR
can yield polymers bearing a variety of functional groups. This (CHCl3):nÄ ˆ 3395 (O H), 2957, 2928, 2858, 1464, 1379 (C H), 1674, 1637
(CˆC), 1095 cm 1 (C O).
suggests that the designed synthesis of macromolecules, such
as block copolymers with a versatile combination of func- Received: March 7, 2000 [Z 14816]

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[1] a) Polyvinyl Alcohol Developments (Ed.: C. A. Finch), Wiley, New formed have been utilized for intramolecular C C bond
York, 1992; b) ªHydrogels for Medical and Related Applicationsº formation,[4] but there is no report on the intermolecular
(Ed.: J. D. Andrade), ACS Symp. Ser., Vol. 31 Washington, 1976.
[2] See, for example: A. Hirao, H. Kato, K. Yamaguchi, S. Nakahama,
version, probably because reduction of the a-alkoxy radical
Macromolecules 1986, 19, 1294 ± 1299. by the metal hydride competes with C C bond formation.
[3] a) I. Tomita, Y. Kondo, K. Takagi, T. Endo, Macromolecules 1994, 27, Since organotellurium compounds are excellent precursors
4413 ± 4414; b) I. Tomita, Y. Kondo, K. Takagi, T. Endo¹ Acta Polym. for carbon-centered radicals,[5, 6] we envisaged that silyl
1995, 46, 432 ± 436; c) I. Tomita, M. Ubukata, T. Endo, React. Funct.
tellurides would act as silyl radical precursors which do not
Polym. 1998, 37, 27 ± 32; d) K. Takagi, I, Tomita, T. Endo, Macro-
molecules 1997, 30, 7386 ± 7390; e) K. Takagi, I. Tomita, T. Endo, Chem. contain reducing hydrido groups.[7] We examined reactions of
Lett. 1997, 1187 ± 1188; f) T. Endo, K. Takagi, I. Tomita, Tetrahedron silyl tellurides in the presence of several radical acceptors and
1997, 53, 15 187 ± 15 196; g) K. Takagi, I. Tomita, T. Endo, Macro- found a new coupling reaction of phenyl trimethylsilyl
molecules 1998, 31, 6741 ± 6747; h) K. Takagi, I. Tomita, T. Endo, Chem. telluride (1), carbonyl compounds, and phenyl isocyanide
Commun. submitted.
[4] Allene monomers (2 a, 2 b, 2 c, and 3) were prepared by reported
[Eq. (2)]. Here we report on this new three-component
methods. See: a) L. Brandsma, H. D. Verkruijsse, Synthesis of Acety- coupling reaction, which is of both mechanistic and synthetic
lenes, Allenes and Cumulenes, Elsevier, New York, 1981, pp. 188 ± 189; interest.
b) M. Kimura, S. Tanaka, Y. Tamaru, Bull. Chem. Soc. Jpn. 1995, 68,
1689 ± 1705; c) L. Brandsma, H. D. Verkruijsse, Synthesis of Acetylenes,
Allenes and Cumulenes, Elsevier, New York, 1981, pp. 157.
[5] The reaction of poly(2 a) with ethyl vinyl ether (twofold excess with
respect to the hydroxy moieties) was carried out in the presence of p-
toluenesulfonic acid (1.0 mol %) in DMSO at 50 8C for 10 min.
Addition to water precipitated a polymer in 98 % yield whose acetal
content was confirmed to be quantitative by 1H NMR spectroscopy.
The polymer thus obtained is soluble in various organic solvents
The coupling reaction of 1,[8] benzophenone, and phenyl
including MeOH, THF, benzene, hexane, and CH2Cl2 .
[6] Both poly(2 b) and poly(2 c) have high solubility in THF, a poor solvent isocyanide proceeded under mild thermal conditions, and the
for poly(2 a). Thus, the GPC measurements were performed without group-transfer product 2 a (R1 ˆ R2 ˆ Ph) was formed in 82 %
treatment with ethyl vinyl ether. yield after heating at 100 8C for 12 h in propionitrile. The
[7] Since the block copolymer is soluble in THF, benzene, and CH2Cl2 tellurium atom plays a crucial role in this reaction, and the use
which reflects the solubility of poly(3) segment, the GPC measurement
was also performed directly without treatment with ethyl vinyl ether,
of the corresponding silyl selenide or sulfide led to complete
and gave a unimodal elution peak (Mn ˆ 8.3  103, Mw/Mn ˆ 1.12). recovery of the starting materials. In addition, various silyl
and stannyl hydrides did not promote C C bond formation,
and either the recovery of the starting materials or the
reduction of the carbonyl group was observed. Monitoring the
reaction in CD3CN by 1H NMR spectroscopy indicated that
Novel Group-Transfer Three-Component the formation of the a-silyloxytelluride 3 competed with that
Coupling of Silyltellurides, Carbonyl of 2 a and that the amount of 3 gradually decreased with the
Compounds, and Isocyanides** progress of the reaction. Indeed, isolated 3 reacted with
Hiroshi Miyazoe, Shigeru Yamago,* and
Jun-ichi Yoshida*

Silyl and stannyl radicals add to the carbonyl oxygen atom

to generate a-alkoxy radicals, and this is an elemental step in
the radical-mediated reduction of carbonyl compounds with
silyl and stannyl hydride reagents.[1, 2] Addition of the
a-alkoxy radicals to radical acceptors would form a new phenyl isocyanide at 100 8C to give 2 a in 92 % yield. The
C C bond [Eq. (1)].[3] Indeed, a-stannyloxy radicals thus coupling reaction was inhibited by the addition of 2,2,6,6-
tetramethylpiperidine-N-oxyl (TEMPO) radical (1.0 equiv)
and mainly afforded silylated TEMPO 4 (63 %); this suggests
the intermediacy of trimethylsilyl radicals. The reaction
proceeded faster in polar solvents such as propionitrile,
DMF, and pyridine than in nonpolar solvents such as toluene,
[*] Prof. S. Yamago, Prof. J.-i. Yoshida, H. Miyazoe and the smooth reaction in basic media also ruled out the
Department of Synthetic Chemistry and Biological Chemistry
involvement of carbocation intermediates.[9]
Graduate School of Engineering, Kyoto University
Kyoto 606-8501 (Japan) The present reaction is generally applicable to a variety of
Fax: (‡ 81) 75-753-5661 ketones and aldehydes, and its scope and efficiency are
E-mail: [email protected], summarized in Table 1. Aromatic ketones reacted smoothly
[email protected] and gave the desired adducts in high yields when almost
[**] This work was partly supported by a Grant-in-Aid for Scientific equimolar quantities of each reagent were used (entries 1 ± 6).
Research from the Ministry of Education, Science, Sports, and
Culture, Japan. We thank Professor S. Okazaki, Professor M. Oyama,
Aliphatic ketones and aldehydes also gave the desired adducts
and T. Morikawa of the Department of Material Chemistry of Kyoto in good yields (entries 7 and 8), but they were slightly less
University for the ESR measurement and valuable discussions. reactive than aromatic ketones. The reaction of benzaldehyde

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