Abstract
General considerations related to the use of sugars and closely
related compounds as reagents for molecular and macromolecular synthesis
are presented. For the first time, we have used unprotected carbohydrates
to initiate polymerizations. A variety of dicyanoalkenes and -arenes
react with sugars in the presence of alkali to give conjugated polymers.
Both cyclopolymerization and polymerization at only one of two cyano
groups are observed, and some qualitative mechanistic issues related
to these observations are discussed. In some cases, a sugar alkoxide
is the active initiating reagent. Characterization of the resulting
polymers is reported. Alkaline sugar reagents have also been used
in Knoevenagel reactions to synthesize CN-PPV oligomers and a related
conjugated polymer in good yields. The use of the polysaccharide
chitosan as a polycation allows the absorption spectrum of the polythiophene
HPURET to shift to longer wavelengths than other polycations in
electrostatically assembled films.
Key words
polymers - carbohydrates - oligosaccharides - Knoevenagel reactions - polysaccharides
- polycations
References
<A NAME="RC10402SS-1">1 </A>
Shirakawa H.
Angew.
Chem. Int. Ed.
2001,
40:
2574
<A NAME="RC10402SS-2">2 </A>
MacDiarmid AG.
Angew.
Chem. Int. Ed.
2001,
40:
2581
<A NAME="RC10402SS-3">3 </A>
Heeger AJ.
Angew.
Chem. Int. Ed.
2001,
40:
2591
<A NAME="RC10402SS-4">4 </A>
Groenendaal L.
Jonas F.
Freitag D.
Pielartzik H.
Reynolds JR.
Adv.
Mater.
2000,
12:
481
<A NAME="RC10402SS-5">5 </A>
Electronic
Materials: The Oligomer Approach
Müllen K.
Wegner G.
Wiley;
Weinheim:
1998.
<A NAME="RC10402SS-6">6 </A>
Phthalocyanines:
Properties and Applications
Vol. 1-4:
Leznoff CC.
Lever ABP.
VCH;
New York:
1989-1995.
<A NAME="RC10402SS-7">7 </A>
McKeown NB.
Phthalocyanine Materials
Cambridge University
Press;
New York:
1998.
<A NAME="RC10402SS-8">8 </A>
Thomas AL.
Phthalocyanine Research and Applications
CRC;
Boca
Raton, Florida:
1990.
<A NAME="RC10402SS-9">9 </A>
Matsuoka M. In
Infrared Absorbing Dyes
Matsuoka M.
Plenum;
New York:
1990.
Chap.
5.
<A NAME="RC10402SS-10">10 </A>
Moser FH.
Thomas AL.
The
Phthalocyanines
CRC;
Boca Raton,
Florida:
1983.
<A NAME="RC10402SS-11">11 </A>
Kobayashi S.
J.
Polym. Sci. Part A: Polym. Chem
1999,
37:
3041
<A NAME="RC10402SS-12">12 </A>
Gross RA.
Kumar A.
Kalra B.
Chem.
Rev.
2001,
101:
2097
<A NAME="RC10402SS-13">13 </A>
Kothakota S.
Mason TL.
Tirrell DA.
Fournier MJ.
J. Am.
Chem. Soc.
1995,
117:
536
<A NAME="RC10402SS-14">14 </A>
Lichtenthaler FW.
Cuny E.
Martin D.
Rönninger S.
Weber T.
Carbohydrates as Organic Raw Materials
Lichtenthaler FW.
VCH;
Weinheim:
1991.
p.207-246
<A NAME="RC10402SS-15">15 </A>
Frost JW.
Draths KM.
Chem. Br.
1995,
31:
206
<A NAME="RC10402SS-16">16 </A>
Frost J.
The
Chem. Engineer
1996,
16:
32
<A NAME="RC10402SS-17">17 </A>
Robyt JF.
Essentials of Carbohydrate Chemistry
Springer;
New
York:
1998.
p.80
<A NAME="RC10402SS-18">18 </A>
Robyt JF.
Essentials of Carbohydrate Chemistry
Springer;
New
York:
1998.
p.50-60
<A NAME="RC10402SS-19">19 </A>
Daub J.
Rapp KM.
Salbeck J.
Schöberl U. In
Carbohydrates
as Organic Raw Materials
Lichtenthaler FW.
VCH;
Weinheim:
1991.
p.323-350
<A NAME="RC10402SS-20">20 </A>
Synthesis
2001,
312-343
<A NAME="RC10402SS-21">21 </A>
Bigelow HE.
Palmer A.
Opolonick N.
Org. Synth. Coll. Vol. 2
Wiley;
New
York:
1943.
p.57
<A NAME="RC10402SS-22">22 </A>
Galbraith HW.
Degering EF.
Hitch EF.
J. Am. Chem. Soc.
1951,
73:
1323
<A NAME="RC10402SS-23">23 </A>
Kornblum N. In
Organic Reactions
Vol. II:
Wiley;
New York:
1944.
p.262-340
<A NAME="RC10402SS-24">24 </A>
Wassmundt, F. W.; Plourde, D. M.;
Pedemonte, R. P. presented at the 203rd National Meeting
of the American Chemical Society, San Francisco, California, 1992,
April 5-10; Book of Abstracts, ORGN 310.
<A NAME="RC10402SS-25">25 </A>
Sauter HP.
Makowka C.
Res. Discl.
1989,
302:
411 ;Chem. Abstr. 1990 , 112 , 7093x
<A NAME="RC10402SS-26">26 </A>
Robyt JF.
Essentials of Carbohydrate Chemistry
Springer;
New
York:
1998.
p.63
<A NAME="RC10402SS-27">27 </A>
Lubineau J.
Auge J.
Bienayme H.
Queneau Y.
Scherrmann MC.
Carbohydrates as Organic Raw Materials II
Descotes G.
VCH;
Weinheim:
1993.
p.99-112
<A NAME="RC10402SS-28">28 </A>
Lubineau J.
Auge J.
Bienayme H.
Lubin N.
Queneau Y. In
Cycloaddition Reactions in Carbohydrate Chemistry
Vol.
494:
Giuliano RM.
American
Chemical Society Symposium Series; Washington, D.C. 1992.
p.147-157
<A NAME="RC10402SS-29">29 </A>
Aoi K.
Suzuki H.
Okada M.
Macromolecules
1992,
25:
7073
<A NAME="RC10402SS-30">30 </A>
Bisht KS.
Deng F.
Gross RA.
Kaplan DL.
Swift G.
J.
Am. Chem. Soc.
1998,
120:
1363
<A NAME="RC10402SS-31">31 </A>
Bon SAF.
Haddleton DM.
Polymer
Preprints
1999,
40(2):
248
<A NAME="RC10402SS-32">32 </A>
Haddleton DM.
Ohno K.
Biomacromolecules
2000,
1:
152
<A NAME="RC10402SS-33">33 </A>
Butler GB.
J.
Polym. Sci. Part A: Polym. Chem.
2000,
38:
3451
<A NAME="RC10402SS-34">34 </A>
Nagasaki Y.
Yasugi K.
Yamamoto Y.
Harada A.
Kataoka K.
Biomacromolecules
2001,
2:
1067
<A NAME="RC10402SS-35">35 </A>
Miles MG.
Wager JS.
Wilson JD.
Siedle AR.
J. Org.
Chem.
1975,
40:
2577
<A NAME="RC10402SS-36">36 </A>
Rixman MA.
Sandman DJ.
Macromolecules
2000,
33:
248
<A NAME="RC10402SS-37">37 </A>
Butler GB. In
Encyclopedia of Polymer Science and Technology
2nd
ed., Vol. 4:
Mark HF.
Bikales NM.
Overberger CG.
Menges G.
Wiley-Interscience;
New
York:
1986.
p.566
<A NAME="RC10402SS-38">38 </A>
Wöhrle D.
Adv.
Polym. Sci.
1972,
10:
35
<A NAME="RC10402SS-39">39 </A>
Naito K, and
Ikezaki T. inventors; Japanese Kokai, JP 6191912.
; Chem. Abstr. 1986 , 105 , 217629h
<A NAME="RC10402SS-40">40 </A>
Keller TM.
CHEMTECH
1988,
18:
635
<A NAME="RC10402SS-41">41 </A>
Hanack M.
Lang M.
Chemtract, Org. Chem.
1995,
8:
131
<A NAME="RC10402SS-42">42 </A>
Jones, M. T. unpublished experiments 1994 .
<A NAME="RC10402SS-43">43 </A>
Kim I.-B.
Rixman MA.
Tsai Z.-H.
Wu D.
Njus JM.
Stark JC.
Hankins J.
Sandman DJ.
Macromolecules
2001,
34:
7576
<A NAME="RC10402SS-44">44 </A>
Tsai Z.-H.
Sandman DJ.
J. Porphyrins Phthalocyanines
2001,
5:
564
<A NAME="RC10402SS-45">45 </A>
Horiguchi E.
Shirai K.
Jaung J.
Furusyo M.
Takagi K.
Matsuoka M.
Dyes and Pigments
2001,
50:
99
<A NAME="RC10402SS-46">46 </A>
Kim, I.-B.; Njus, J.; Sandman, D.
J.; Macromolecules , to be submitted.
<A NAME="RC10402SS-47">47 </A>
Mague JT.
Eduok EE.
J. Chem. Crystallogr.
2000,
30:
311
<A NAME="RC10402SS-48">48 </A>
Hassner A.
Stumer C.
Organic
Syntheses Based on Name Reactions and Unnamed Reactions
Pergamon;
Oxford,
UK:
1994.
p.205
<A NAME="RC10402SS-49">49 </A>
House HO.
Modern Synthetic Reactions
2nd
ed.:
Benjamin/Cummings;
Menlo
Park, California:
1972.
p.646-653
<A NAME="RC10402SS-50">50 </A>
Schlick U.
Teichert F.
Hanack M.
Synthetic
Metals
1998,
92:
75
<A NAME="RC10402SS-51">51 </A>
Moratti SC. In
Handbook of Conducting Polymers
2nd ed.:
Skotheim TA.
Elsenbaumer RL.
Reynolds JR.
Marcel
Dekker;
New York:
1998.
p.343-361
<A NAME="RC10402SS-52">52 </A>
Kraft A.
Grimsdale AC.
Holmes AB.
Angew. Chem. Int. Ed.
1998,
37:
402
<A NAME="RC10402SS-53">53 </A>
Kauffman H.
Ber.
Dtsch. Chem. Ges.
1917,
50:
515
<A NAME="RC10402SS-54">54 </A>
Holm MJ.
Zienty FB.
Terpstra MA.
J. Chem. Eng. Data
1968,
13:
70
<A NAME="RC10402SS-55">55 </A>
Kim D.-J.
Kim S.-H.
Zyung T.
Kim J.-J.
Cho I.
Choi SK.
Macromolecules
1996,
29:
3657
<A NAME="RC10402SS-56">56 </A>
Kim M.
Sandman DJ.
J. Macromol. Sci.-Pure Appl. Chem.
2001,
A38:
1291
<A NAME="RC10402SS-57">57 </A>
Lehn J.-M.
Supramolecular Chemistry
VCH;
Weinheim:
1995.
p.139
<A NAME="RC10402SS-58">58 </A>
Decher G.
Science
1997,
277:
1232
<A NAME="RC10402SS-59">59 </A>
Kim M.
Sandman DJ. In
Electrical,
Optical, and Magnetic Properties of Organic Solid State Materials
V , In Materials Research Society Symposium
Proceedings
Vol. 598:
Ermer S.
Reynolds JR.
Perry JW.
Jen AK.-Y.
Bao Z.
Materials Research
Society; Warrendale, PA 2000.
p.Paper
BB 3.12
<A NAME="RC10402SS-60">60 </A>
Kuball H.-G.
Höfer T. In
Circular
Dichroism: Principles and Applications
Berova N.
Nakanishi K.
Woody RW.
Wiley-VCH; Weinheim 2000.
p.133-158
<A NAME="RC10402SS-61">61 </A>
Okada S.
Peng S.
Spevak W.
Charych D.
Acc. Chem. Res.
1998,
31:
229
<A NAME="RC10402SS-62">62 </A>
Baek M.-G.
Sevens RC.
Charych DH.
Bioconjugate Chem.
2000,
11:
777
<A NAME="RC10402SS-63">63 </A>
Madison PH.
Long TE.
Biomacromolecules
2000,
1:
615
