Calix[4]arenes in the 1,3-alternate conformation [Elektronische Ressource] / Crenguta Dordea

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2006
• Nombre de lectures: 53
• Langue: English
• Poids de l'ouvrage: 14 Mo

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Dissertation
zur Erlangung des Grades
„Doktor der Naturwissenschaften“



am Fachbereich Chemie, Pharmazie und Geowissenschaften
der Johannes Gutenberg-Universität Mainz












Crenguta Dordea
geb. in Sibiu (Hermannstadt)


Mainz, 2006&RQWHQWV

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1. Definition and nomenclature 1
1.1. Synthesis 2
1.1.1. One–pot procedure 2
1.1.2. Stepwise Syntheses 3
1.1.3. Fragment condensation 3
1.2. Conformations 4
1.3. Funtionalization of calix[4]arenas 6
1.3.1. Modification of calix[4]arenes at the narrow rim 7
1.3.2. Modification of calix[4]arenes at the wide rim 10
1.4. Characteristics of the DOWHUQDWH conformation, potential modification 11
1.5. References 12
&KDSWHU. $OWHUQDWHcalix[4]arenes, selectively functionalizated by amino groups 15
2. Introduction 15
2.1. Tetraamines, QDUURZULP 17
2.2. Tetraamines, ZLGHULP 21
2.2.1. Distally functionalization of the wide rim tetraamines 21
2.2.2. Proximally functionalization of the wide rim tetraamines 24
2.3.TetraaminesQDUURZZLGHULP 27
2.4. Octaamines 30
1 2.5. Characterization by H-NMR 32
2.6. Single Crystal X-Ray Analyses 38
2.8. Experimental part 44
2.9. References 61
&KDSWHU. Ligands for Lanthanides and Actinides 63
3. Introduction 63
3.1. Tetra-CMPO derivatives 66
3.2. Two CMPO combined with two picolinamide functions in the same side of the
DOWHUQDWH conformation 69
3.3. Octa-CMPO derivatives of calix[4]arenes in all possible conformations 70
3.4. Tetra CMPO, tetra picolinamides in the DOWHUQDWH conformation 73 3.5. Two CMPO combined with acidic functions at the same side of the DOWHUQDWH
conformation 74
3.6. Extraction results 75
3.7. X-ray analysis 76
3.8. Experimental part 79
3.9. References 90
&KDSWHU. Conformational Properties of Cyanomethoxy Calix[4]arenas 93
4. Introduction 93
4.1. Synthesis 94
4.2. Conformational studies 97
4.3. X-Ray structures 104
4.4. Experimental part 109
4.5. References 114
&KDSWHU. Cobalt Bis(dicarbollides)(1-) combined with CMPO as ligating functions attached
to the calix[4]arene skeleton 115
5. Basics of carboranes 115
5.1. Nomenclature 116
5.2. The main properties of Cosan 117
5.3. Calix[4]arene in FRQH conformation bearing a combination of Cosan and CMPO
groups. 118
5.4. Experimental part 124
5.5. References 129
&KDSWHU. Perylene imide dyes attached to the calix[4]arene fixed in DOWHUQDWH
conformation. 130
6. Introduction and synthesis 130
1 6.1. H-NMR characterization 133
6.2. Experimental part 135
6.3. References. 138
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1In 1872, Adolph von Baeyer studied reactions of phenols with aldehydes, but the products of these
2reactions remained uncharacterized for nearly 70 years. Then, in the 1940s, Zinke and Ziegler
suggested a cyclic tetrameric structure for the product of the based-induced reaction between S-
3substituted phenols with formaldehyde (,). A similar structure was proposed by Niederl and Vogel for
the product of the acid-induced reaction between resorcinol and aldehydes (,,).

5
+2 2+
R R
+2 2+
2++
5 2 2 5
++2
2++2
R R
+2 2+5
, ,,

4,5 6,7About 40 years later, Gutsche and Högberg studied these base- and acid-induced condensations
showing that both are extremely useful methods to synthesize these cyclic oligomers. C. D Gutsche
has chosen name “calixarenes” for the cyclic oligomers since they look like an ancient Greek vase,
known as “calix crater”, while “arene” refers to the aromatic rings. So, the term “calixarene” describes
the shape of the cyclic tetra- or pentamers, when they assume the “FRQH” conformation and is added as
an extension to the name. Larger cyclic oligomers are also called calix[n]arenes. The [n] represents the
number of the aromatic units.
The analogy with an ancient vase reveals the edges of the molecule as XSSHU- and ORZHU-rim and the
ring is called DQQXOXV (Fig. 1). Replacing the terms XSSHU and ORZHU by ZLGH and QDUURZ rim is
preferable because this is independent of the orientation.

4 4

)LJXUH. Formula of S-WHUW-butylcalix[4]arene in the FRQH conformation in a) spatial and b) planar representation.
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To indicate from which phenol S-substituent calix[4]arene is derived, often is mentioned also the
substituent. For example the product derived from S-WHUW-butylphenol in the abbreviated nomenclature
is S-WHUW-butylcalix[4]arene. In a more detailed nomenclature of calix[n]arenes this name is retained
and the substituents are named also specifying their positions by numbers as shown the figure 2.


)LJXUH. Structure and numbering of calix[4]arenes: 25, 26, 27, 28-tetrahydroxycalix[4]arene; 2, 8, 14, 20-tetramethyl-4,
6, 10, 12, 16, 18, 22, 24-octahydroxy calix[4]arene.

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2QH–SRWSURFHGXUH
On a laboratory scale the WHUWbutyl-calixarenes are available by alkali-catalysed condensation of S
WHUWbutylphenol with formaldehyde (scheme 1).

HO
R

6FKHPH. Formation of calix[n]arenes by one-pot condensation of WHUWbutylphenol with formaldehyde.

Under proper reaction conditions (solvent, temperature, base, aldehydes), the cyclic tetra-, penta-,
hexa- hepta- and octamer can be formed.
a) the pre-condensation of with aqueous CH O using 0.045 eqv. NaOH with respect to the phenol 2
8followed by 2 h refluxing in toluene yields about 50 % of .
b) the heating of with formalin with 0.034 eqv. KOH with respect to the phenol followed by 4 h
9refluxing in xylene yields about 83-88 % of .
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