Abstract
The synthesis of α,ω-terminally functionalized polyenes with arenes or hetarenes at
one end and either an aldehyde or a triethoxysilyl function at the other end, capable
of reacting with H-terminated or oxidized silicon surfaces, is described. Analogous
to known Wittig reactions, polyenedialdehydes 1 and 3 , the latter derived from 1 and phosphonium chloride 2 in a twofold Wittig olefination, were converted with phosphonium bromides 4 to give the (all-E )-arylpolyenaldehydes 5 and 6 . A terminal alkyl chain was introduced in dialdehydes 1a and 3a by reaction with P ,P -didecyldibenzophospholium bromide 8 , resulting in polyenals 9 . Wittig olefination of 5c and 9a with phosphonium chloride 2 afforded the (2-thienyl)tridecahexaenal 7 and the docosahexaenal 10 . With respect to monolayer formation on oxidized Si(100) surfaces, (9-anthryl)- and
(2-thienyl)-ω-functionalized polyenetriethoxysilanes 16 and 17 were prepared in a reaction sequence involving the introduction of a terminal triple
bond with [3-(trimethylsilyl)prop-2-ynyl]triphenylphosphonium bromide (11 ), desilylation of the resulting arylpolyeninetrimethylsilanes 12 , 13 with Bu4 NF3H2 O, and subsequent hydrosilylation of the arylpolyenines 14 , 15 using triethoxysilane under dichlorocyclooctadienylplatinum(II) catalysis.
Key words
aldehydes - electron transfer - hydrosilylations - Wittig reactions
References
<A NAME="RT00701SS-1">1 </A>
Wezstein M.
Dissertation
University of Stuttgart;
Germany:
1999.
<A NAME="RT00701SS-2">2 </A>
Maier S.
Port H.
Wolf HC.
Effenberger F.
Schlosser H.
Synth. Met.
1989,
29:
E517
3a </A>
Arrhenius TS.
Blanchard-Desce M.
Dvolaitzky M.
Lehn JM.
Proc. Natl. Acad. Sci. USA
1986,
83:
5355
3b </A>
Lehn J.-M.
Angew. Chem., Int. Ed. Engl.
1990,
29:
1304
<A NAME="RT00701SS-4">4 </A>
Effenberger F.
Wolf HC.
New J. Chem.
1991,
15:
117
<A NAME="RT00701SS-5">5 </A>
Würthner F.
Vollmer MS.
Effenberger F.
Emele P.
Meyer DU.
Port H.
Wolf HC.
J. Am. Chem. Soc.
1995,
117:
8090
6a </A>
Vollmer MS.
Würthner F.
Effenberger F.
Emele P.
Meyer DU.
Stümpfig T.
Port H.
Wolf HC.
Chem.-Eur. J.
1998,
4:
260
6b </A>
Vollmer MS.
Effenberger F.
Stümpfig T.
Hartschuh A.
Port H.
Wolf HC.
J. Org. Chem.
1998,
63:
5080
<A NAME="RT00701SS-7">7 </A>
Hirsch T.
Port H.
Wolf HC.
Miehlich B.
Effenberger F.
J. Phys. Chem. B
1997,
101:
4525
<A NAME="RT00701SS-8">8 </A>
Hartschuh A.
Port H.
Wolf HC.
Miehlich B.
Endtner JM.
Vollmer MS.
Effenberger F.
J. Lumin.
1998,
76 & 77:
655
<A NAME="RT00701SS-9">9 </A>
Knorr S.
Grupp A.
Mehring M.
Grube G.
Effenberger F.
J. Chem. Phys.
1999,
110:
3502
10a </A>
Endtner JM.
Effenberger F.
Hartschuh A.
Port H.
J. Am. Chem. Soc.
2000,
122:
3037
10b </A>
Port H.
Hartschuh A.
Hennrich M.
Wolf HC.
Endtner JM.
Effenberger F.
Mol. Cryst. Liq. Cryst.
2000,
344:
145
<A NAME="RT00701SS-11">11 </A>
Effenberger F.
Niesert C.-P.
Synthesis
1992,
1137
12a </A>
Bubeck C.
Effenberger F.
Häußling L.
Neher D.
Niesert C.-P.
Ringsdorf H.
Adv. Mater.
1992,
4:
413
12b </A>
Schmelzer M.
Roth S.
Niesert C.-P.
Effenberger F.
Li R.
Thin Solid Films
1993,
235:
210
13a </A>
Tillmann N.
Ulman A.
Penner TL.
Langmuir
1989,
5:
101
13b </A>
Sailor MJ.
Lee EJ.
Adv. Mater.
1997,
9:
783
14a </A>
Harder P.
Bierbaum K.
Woell C.
Grunze M.
Heid S.
Effenberger F.
Langmuir
1997,
13:
445
14b </A>
Heid S.
Effenberger F.
Bierbaum K.
Grunze M.
Langmuir
1996,
12:
2118
14c </A>
Bierbaum K.
Kinzler M.
Woell C.
Grunze M.
Hähner G.
Heid S.
Effenberger F.
Langmuir
1995,
11:
512
<A NAME="RT00701SS-15">15 </A>
Effenberger F.
Götz G.
Bidlingmaier B.
Wezstein M.
Angew. Chem., Int. Ed. Engl.
1998,
37:
2462
16a </A>
Bumm LA.
Arnold JJ.
Cygan MT.
Dunbar TD.
Burgin TP.
Jones L.
Allara DL.
Tour JM.
Weiss PS.
Science
1996,
271:
1705
16b </A>
Cygan MT.
Dunbar TD.
Arnold JJ.
Bumm LA.
Shedlock NF.
Burgin TP.
Jones L.
Allara DL.
Tour JM.
Weiss PS.
J. Am. Chem. Soc.
1998,
120:
2721
17 </A>
Arbeitsvorschrift der BASF AG.
18a </A>
Pfander H.
Lachenmeier A.
Hadorn M.
Helv. Chim. Acta
1980,
63:
1377
18b </A>
Wolleb H.
Pfander H.
Helv. Chim. Acta
1986,
69:
1505
<A NAME="RT00701SS-19">19 </A>
von Braun J.
Fußgänger R.
Kühn M.
Liebigs Ann. Chem.
1925,
445:
201
20a </A>
Wang J.
Pappalardo M.
Keene FR.
Aust. J. Chem.
1995,
48:
1425
20b </A>
Kröhnke F.
Synthesis
1976,
1
<A NAME="RT00701SS-21">21 </A>
Sprintschnik G.
Sprintschnik HW.
Kirsch PP.
Witten DG.
J. Am. Chem. Soc.
1977,
99:
4947
<A NAME="RT00701SS-22">22 </A>
Ziessel R.
Lehn J.-M.
Helv. Chim. Acta
1990,
73:
1149; and references cited therein
<A NAME="RT00701SS-23">23 </A>
Effenberger F.
Schlosser H.
Synthesis
1990,
1085
24a </A>
Rüedi P.
Pure Appl. Chem.
1985,
57:
793
24b </A>
Kamber M.
Pfander H.
J. Chromatogr.
1984,
295:
295
25a </A>
Vetter W.
Englert G.
Rigassi N.
Schwieter U. In Carotenoids
Isler O.
Birkhäuser Verlag;
Basel:
1971.
p.189
25b </A>
Englert G. In Carotenoid Chemistry and Biochemistry
Britton G.
Goodwin TW.
Pergamon Press;
Oxford:
1982.
p.107
25c </A>
Englert G.
Pure Appl. Chem.
1985,
57:
801
25d </A>
Englert G.
Pure Appl. Chem.
1991,
63:
59
26a </A>
Jaffé H.
Orchin M.
Theory and Applications of Ultraviolet Spectroscopy
Wiley;
New York:
1962.
26b </A>
Das PK.
Becker RS.
J. Phys. Chem.
1982,
86:
921
26c </A>
Fabian J.
Hartmann H.
Light Absorption of Organic Colorants
Springer;
Berlin:
1980.
p.24
26d </A>
Hudson BS.
Kohler BE.
Schulten K. In Excited States
Vol. 6:
Lim EC.
Academic Press;
New York:
1982.
p.1-91
<A NAME="RT00701SS-27">27 </A>
Grandjean D.
Pale P.
Chuche J.
Tetrahedron
1991,
47:
1215
28a </A>
Vedejs E.
Marth CF.
Tetrahedron Lett.
1987,
28:
3445
28b </A>
Vedejs E.
Peterson MJ.
J. Org. Chem.
1993,
58:
1985
28c </A>
Vedejs E.
Cabaj J.
Peterson MJ.
J. Org. Chem.
1993,
58:
6509
28d </A>
Vedejs E.
Marth CF.
J. Am. Chem. Soc.
1988,
110:
3940
28e </A>
Wilson JF.
Tebby JC.
J. Chem. Soc., Perkin Trans 1
1972,
2713
<A NAME="RT00701SS-29">29 </A>
Eiter K.
Oediger H.
Liebigs Ann. Chem.
1965,
682:
62
30a </A>
Ahmed M.
Barley GC.
Hearn MTW.
Jones ERH.
Thaller V.
Yates JA.
J. Chem. Soc., Perkin Trans 1
1974,
1981
30b </A>
Miller RB.
Synth. Commun.
1972,
2:
267
<A NAME="RT00701SS-31">31 </A>
Alzeer J.
Vasella A.
Helv. Chim. Acta
1995,
78:
177
<A NAME="RT00701SS-32">32 </A>
Drew D.
Doyle JR.
Inorg. Synth.
1990,
28:
346
