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Ion-Selective Crown Ether Dyes.

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500
/
t
L50.
[l]
[2]
1400
d
350
[3]
300 .
[4]
[5]
0.2
0.3
0.6 0.7 0.8 0 9 1.0 1.1 1 2
[ i l l l / ~ N a @+
l
Fig. I . Plot of R, uersus [(l/];[Na ] ( 3 2 C = 3 0 5 K); the solid line (method
A) is the curve for minimization of R, for each of 5 experimental points ( x ),
corresponding t o iteration of the values for Kr and the limiting relaxation
rate in the complex from ( I ) and Nam (equation (2) of reference [6a]).
0.1
04
05
The dashed line (method B) corresponds t o Simplex optimization [8a] using
the equation of Liue and Chan [8b] with simultaneous iteration on K f ,
R:, and the relaxation rate for free Nae Rp.
[6]
[7]
181
Table 1 . Complexation constant K r and limiting relaxation rates for free
(R:) and hound (R:) Nae obtained by method A and method B.
T CKI
279.2
290.6
305.2
321.5
R:
A
229
229
229
R,B
A
B
223
226
232.5
I95
848
691
575
B
861
691
565.5
600
Kr [I m o l '~1
A
B
750
240
75
749
241
77.5
12.2
A strong complex is indeed formed between ( I ) and
NaCIO,, in pyridine solution, with a formation constant Kf
of lo3 to 10lmol-' in the temperature range from 5 to
50°C. From the temperature dependence of Kf it follows
that :
AH:= -17kcal mo1-I
( - 7 1 kJ m&1[9J)
AS,"= -48 cal mol-' K-' (-201 J mol-' K-'L9]).
Usually, only mildly negative entropy terms (ca. -10 to
-50 Jmol-' K-'[''l) are found for inclusion of Na' into
the preformed central cavities of cyclic natural or synthetic
ionophores in solvents such as HzO or CH30H. It is unlikely
that only the change from such protic solvents to pyridine
could account for this large difference in complexation entropies. Rather, the strongly negative entropy term found here
is highly reminiscent of a cyclization entropy, as if Na@complexation locks the ligand molecule (I) into a single highly
organized conformation: one in which most (if not all)["1
the ether oxygens form van der Waals bonds with the enclosed
sodium cation, accounting for the magnitude of the enthalpy
change. The complex formation in solution is enthalpy-driven.
The Na@-Cloy distance is likely to increase upon complex
Hence, we feel that the interaction of (1) and
Na@is best described as a wrapping of the heptadentate ligand
(I), most probably in a stepwise manner[1oC1,around the
sodium cation. Pyridine, a weakly polar aprotic solvent capable
of cation solvation, is a solvent of type B in the recent classification by Jackman and Lange['21. From the relatively large
equilibrium constants Kf found in pyridine, we feel confident
that molecules of the same type as (1 )[Zbl will produce anionic
activation in anumber of organic solvents of type B"'], particularly at low temperatures.
Received: August 3, 1978 [Z 79 IE]
German version: Angew. Chem. 90, 902 (1978)
Angew. Chem. Int. Ed. Engl. 17 ( I 978) No. 11
[9]
[lo]
[I I]
1121
E. Weber, F. Mgtle, Tetrahedron Lett. 1975, 2415; W Russhqfer, G.
Oepen, F. Voyrle, Chem. Ber. 11 1, 41 9 ( I 978).
a) Synthesized by twofold nucleophilic substitution of 1,ll -dibromo3,6,9-trioxaundecane with 2-nitrophenol in EtOH/DMF/KOH, reduction of the di-nitro compound with Raney-Ni and subsequent acetylation
of the diamine; h) F . Viigtle, H . Sieger, Angew. Chem. 89, 410 (1977);
Angew. Chem. Int. Ed. Engl. 16, 396 (1977).
B. Tummler, G. Maass, E. Weher, W Wehner, F . Viigtle, J. Am. Chem.
Soc. 99, 4683 (1977); B. Tummler, G. Maass, F. Voytle, H. Siegrr, U .
Heimann, E . Weber, ibid., in press.
P. Laszlo, Angew. Chem. 90, 271 (1978); Angew. Chem. Int. Ed. Engl.
17, 254 (1 978).
Use of [D4]methanol leads to very small enhancement of the 23Na
relaxation rate, perhaps because of a small K r in this solvent and/or
(more likely) a small quadrupolar coupling constant when mostly oxygen
atoms are coordinated to Nae. As in an earlier study of sodium-complexation by sugars 161, use of pyridine as the solvent allows for sizable
effects.
a) C . DeteUier, J . Grundjean, P. Laszh, J. Am. Chem. Soc. 98, 3375
(1976); b) J . Grundjean, P. Laszlo, Helv. Chim. Acta 40, 259 (1977).
We havechecked that line broadening due to chemical exchange between
sites having different chemical shifts has a negligible effect under the
conditions of this study.
a) S . N . Deming, S . S . Morgan, Anal. Chem. 4 5 , 278A (1973); b) D .
Liue, S . 1. Chan, J. Am. Chem. Soc. 98, 3769 (1976).
Standard deviations are 5.9klmol-' and 2 l J m 0 l - ' K - ~ on the
enthalpy and entropy of complexation respectively,
a) R. M. Izatt, R. E . Terry, 8. L. Haymore, L. D . Hansen, N . K .
Dalfey, A . G . Auondet, J . J . Christensen, J. Am. Chem. Soc. 98, 7620
(1976); b) Ch. U . Zust, P. U . Friih, W Simon, Helv. Chim. Acta 54,
495 (1973); c) P. B. Chock, F. Eggers, M . Eigen, R. Winkler, Biophys.
Chem. 4, 239 (1977).
Cf. I:H. Suh, W Saenger, Angew. Chem. 90, 565 (1978); Angew. Chem.
Int. Ed. Engl. 17, 534 (1978).
L. M. Jackman, B. C . Lange, Tetrahedron 33, 2737 (1977).
Ion-Selective Crown Ether Dyes
By 1.Peter Dix and Fritz Vogtle[*]
A molecular combination of dyes with crown ethers is desirable for a variety of reasons: one point of interest is the
influence of selective complex formation with alkali or alkaline
earth metal ions"', made possible by crown ether structural
units, on the absorption of the chromophore. Moreover, crown
ether dyes should be suitable for detection of phase transfer
of salts and for the study of ion transport through lipophilic
media['].
We have therefore incorporated crown ethers into dye molecules in such a manner that the chromophore is influenced
directly on complexation with cations: the dimethylamino
group in the azo dyes methyl orange, methyl red, etc. was
111 - / 8 /
formally replaced by a "crown ether amine" group. In order
to synthesize compounds (1) to ( 8 ) , we first prepared the
N-phenyl crown ether amines (9) to (11) of various ring
widths and transformed them by azo coupling into ( 1 ) to ( 8 ) .
[*] Prof. Dr. F. Vogtle ['I, Dipl.-Chem. J. P. Dix
[ '1
Institut fur Organische Chemie und Biochemie der Universitat
Gerhard-Domagk-Strasse 1, D-5300 Bonn (Germany)
To whom correspondence should be addressed
857
Compound ( 9 ) was converted into the p-nitrosodimethylaniline-analogous crown ether (12); reduction of (12) gave
(I 3 ) and ( I 5 ) ; Vilsmeyer reaction of ( 9 ) afforded the aldehyde
(1 4 ) (see Table 1 for data).
In order to compare various dye systems, the dimethylamino
groups of the diphenylmethane dye Michler’s hydro1 blue
and the triphenylmethane dyes malachite green and crystal
violet were successively replaced by “crown ether amine
{
R
chromophore including the nitrogen of the crown ether amine
because the lone pair contributing to resonance will be affected
to a greater or lesser extent by the positive charge of the
guest ion, depending upon the nature of the ion
As shown by the UV spectra of the p-nitrophenyl azo dyes
(3)-(5),
considerable characteristic differences are observed
for the various cations as compared with the only slightly
ionically active “parent dye” (21) with a dimethylamino group
(Table 2).
\ /
w
1161-1181
1191
groups”. Synthesis of compounds (1 6)-(20)
was achieved
by Friedel-Crafts reaction of ( 9 ) with carbonyl compounds
(data for the isolated leuco compounds X = H, see Table 1).
Table 2. Difference ( A l ) between the strongest absorption band of the crown
ether dyes ( 3 ) - ( 5 ) and the reference substance ( 2 1 ) before and after addition
ofsalt (in acetonitri1e);concentrationsofligand, salt 5 1 : 10. - : hypsochromic
shift, : bathochromic shift.
Table 1. Data of the synthesized crown ether dyes. Correct elemental analyses
or high resolution mass spectra and uniform thin layer chromatograms were
obtained for all the compounds listed.
Added
salt
-
~
Cpd.
X
R
n
M.p.
[“Cl
p-SO Na
o-COONa
p-NOz
1
1
1
138-145
139-149
132-134
P-NOZ
2
p-NOz
m-NOz
p-COOEt
H
H
3
H
2
3&35
H
p-NO
3
1
oil [h]
127
p-NHz
p-cno
1
i
46
80
145-151
8C-85
H
Cz04H
H
CsHC1402
H
CI
H
CsHC140z
H
C6HCLOz
I
1
1
1
111-116
95-97
110
115
rbi
4445
H
1
H
C6Hs
C6Hs
1
1
14
1
1
oil
1
125-127
1
1
I
oil
PI
-
A,,
Complex with
[nml [a1 (m.p. Wl)
41 8
474
LiClO
(254-256)
NaSCN
(I 68-1 7I )
KSCN [b]
(145)
474 [c]
477
471
435.5
440
413
NaC104
(153-156)
KSCN
(1 37-142)
420
NaSCN
(160)
421.5
610
117-121
622
426.5
1
588.0
587.0
489.5
470
[a] In acetonitrile. [b] Although detected unequivocally (NMR, MS) this
compound could not be obtained absolutely pure. [c] In methanol. [d]
R = .D-(CHI)~N-C&.
.
The selective inclusion of alkali metal, alkaline earth metal,
ammonium, and heavy metal ions, as well as H 3 0 + in such
crown ether dyes should exert a selective influence on the
858
+
LiC104
Lit
NaC104
NaSCN
NaI
KI
KSCN
RbI
CSI
Mglz
Ca(SCN),
NaI,
Ba(SCN),
CUCI,
(CH3)3CNH3SCN
NHiSCN
ZnCI,
( 3)
- 10
- 9.5
- 8.5
- 8.5
-
-
0
1.5
0
0
1.5
7.5
[a1
rai
- 19
+
Difference ( A i ) [nm]
(4)
(5)
- 4
- 3.5
- 10
- 7
20
-
- 6.5
- 4.5
13
26
-120
-117.5
-
- 7
- 7.5
- 5.5
- 4.5
- 5
- 5.5
- 5
- 7
(21 I
+1
0
+1
-11
3
-13
[41
- 7
+i
-
+1
- 2
- 2
- 8
0.5
[a] -2 to -10; very dependent upon salt concentration.
On variation of the ring width, the expected selective complexation occurs with added alkali and alkaline earth metal
ions, which led to widely varying shifts or changes in intensity
of the absorption bands. The alkali metal ion fitting into
the crown ether cavity leads to the greatest hypsochromic
shift: Li+/Na+ for (3), K + for ( 4 ) , Cs+ for ( 5 ) . As is also
shown by Table 2, the change in the absorption bands is
the greatest for the [18]crown dye ( 4 ) and Ba2+ ions
(A).= 120nm). Much smaller changes in absorption are
observed for the smaller and larger crown ether amines ( 3 )
and (5) ; neither significant wavelength shifts on addition
of ions (e.g. AA= + 1 nm for Ba2+I4])nor ion selectivity of
light absorption are observed for the parent dye (21 ).
Table 2 shows that the anions have very little effect on
the absomtion.
The appearance of the band at 357nm on addition of Ba2+
salts to ( 4 ) could be due to the fact that this cation has
such a drastic effect on the ‘‘lone’’ electron pair of the amino
nitrogen, because its volume fits the crown ether cavity and
because of its high charge density [cf. ( 4 a ) . M +c--t ( 4 b ) .M+],
that almost exclusively the nitro-substituted azobenzene acts
as chromophore (&.,ax 332 nmr3]).
Angew. Chem. Int. Ed. Engl. 17 ( 1 9 7 8 ) N o . 1 1
The ability of the crown ether dyes to form stable complexes
was also evidenced by the isolation of a number of crystalline
alkali metal salt complexes (Table 1).
Since crown ether (or ~ryptand[~I)
structural units can be
incorporated into many other dye systems, novel quantitative
data can be obtained on the selective modification of host
molecules containing chromophores by guest particles in various media.
Received: March 13, 1978 [Z 963 IE]
German version: Angew. Chem. YO, 893 (1978)
Publication delayed at authors' request
CAS Registry numbers:
( I ), 66769-43-5; ( 2 j , 66769-42-4; ( 3 ) , 66750-14-9; (3). NaSCN, 66758-65-4:
Table 2, complexes with (3) (from top to bottom), 66758-50-7; 66758-48-3;
66758-47-2; 66758-45-0; 66758-44-9; 66758-64-3; 66758-62-1 ; 66758-61-0;
66770-06-7;66758-60.9; 66758-58-5; 66758-57-4; 66758-55-2; 66758-54-1:( 4 j ,
66750-29-6; Table 2, complexes with ( 4 ) (from top to bottom), 66750-21-8;
66750-19-4; 66750-18-3; 66750-16-1: 66750-15-0; 66750-32-1; 66750-31-0;
66750-30-9; 66769-28-6; 66750-28-5; 66769-26-4; 66922-21-2; 66922-20-1 ;
(5 j,66750-27-4;Table2,complexeswith
(5)(fromtopto bottom), 66750-26-3;
66750-24-I ; 66750-23-0; 66769-39-9; 66769-41-3; 66750-06-9; 66769-38-8;
66750-04-7; 66750-03-6; 66750-02-5; 66769-36-6; 66769-34-4; 66750-01-4;
( 6 j , 66750-13-8; ( 7 ) , 66750-12-7; ( 8 ) , 66750-11-6; ( 9 j , 66750-10-5;
( Y j . N a C I O , , 66750-00-3; ( l o ) , 66750-09-2; (lO).KSCN, 66769-32-2; ( l l ) ,
66750-08-1; (12), 66750-07-0; ( 1 2 j . N a S C N . 66769-30-0; ( 1 3 j , 66750-05-8;
( 1 4 ) , 66749-96-0; (151 66769-99-1; ( 1 6 a ) , 66749-95-9; ( 1 6 b j , 66749-94-8;
( I 7 a j , 66749-93-7: ( I 7 b ) , 66769-40-2: ( l S a j , 66749-92-6; ( 1 8 b ) , 66749-91-5;
( 1 9 a j , 66149-90-4; ( 1 9 b j , 66749-98-2; ( 2 0 a j , 66749-97-1; (ZObj, 66769-24-2;
(21 j , 2491-74-9
[I]
[2]
[3]
[4]
[5]
Review: F. Vogtle, E. Weber, Kontakte (Merck) 1977, ( l ) , 11; 1977 (Z),
16; 1Y77, (3), 34.
Reviews: W Burgermeister, R. Winkler-Oswatitsch, Top. Curr. Chem.
69,91 (1977); Yu. A. Ouchinnikov, V: 7: Ivanow, A . M . Shkrob: Memhraneactive Complexones. Elsevier, Amsterdam 1974; C . J. Duncan: Calcium
in Biological Systems. Cambridge University Press 1976.
J. Grifithsr Colour and Constitution of Organic Molecules. Academic
Press, London 1976.
MgIz is an exception, inducing a hypsochromic shift.
In addition to a shift of equilibrium in favor of the complex, cryptand
systems should give rise to greatest cation selectivity.
Carbonylation of Transition-Metal Carbyne Complexes, a New Method for the Synthesis of MetalSubstituted K e t e n e s [ * * ]
By Fritz R. Kreissl, Wovgang Uedelhoven, and Karl EberIP]
Dedicated to Professor E . 0 . Fischer on the occasion of his
60th birthday
Only a few examples of reactions of carbon monoxide with
carbene- and carbyne-complexes have so far been reported
in the literature. One example is the reaction of a mixture
of methoxy(pheny1)carbenepentacarbonylchromium and 1vinyl-2-pyrrolidone with CO at 150atm and 80°C to give
a highly substituted vinyl ketone; methoxy(pheny1)ketene was
postulated as intermediate['].
If, however, p-tolylcarbynecarbonyl(cyclopentadieny1)trimethylphosphane complexes of molybdenum and tungsten[']
are allowed to react with CO, carbonylation at the carbyne
carbon already takes place at normal pressure and -30°C:
[*] Dr. F. R. Kreissl, Dipl.-Chem. W. Uedelhoven, Dip1.-Chem. K. Eherl
Anorganisch-chemisches Institut der Technischen Universitat Miinchen
Lichtenbergstrasse 4, D-8046 Garching (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft.
Angew. Chem. I n t . Ed. Engl. 17 ( 1 9 7 8 ) No. 11
The products ( 2 a ) and (2b)c3] crystallize as bright-yellow
needles and are readily soluble in acetone or dichloromethane,
but insoluble in ether and pentane. On the basis of secondary
reactions[41 at the ketene function the two longwave v C 0
bands of the new compounds (in CH2C12: (2a) 1943s,
1855vs; (2b) 1930s, 1836vs cm-') can be assigned to the
carbonyl ligand, and the very strong bands at 2029 and
2022cm-' to the 11'-ketenyl ligand.
The 'H-NMR spectrum (CD2Clz) shows for (2b) four
signals of relative intensity 4 :5 :3 : 9, which correspond to
the aryl- (6 = 7.14), cyclopentadienyl- (6 = 5.35), methyl(6=2.33) and P-methyl protons (6=1.78). The signals at
6 = 5.35 and 1.78 appear as doublets owing to 31P-1Hcoupling
(5=2.2 and 9.2Hz).--In the 3'P('H}-NMR spectrum[51
(CD2Cl2,rel. to
ext.) a singlet accompanied by two
satellites is observed at 6 = - 14.99 with 1J('83W"P) = 174.0Hz.-Valuable information on the structure is
provided by the 13C('H}-NMR spectrum['] (CD2CI2, -4O"C,
&valuerel. to CDzC12= 54.2ppm; 31P-13Ccoupling constants
in Hz): W-CO (224.13; 17.1), CO-ketene (156.43), CsH4
(137.34, 131.19, 129.14), CsH5 (90.95), CH3 (20.93), PCH3
(19.63; 34.2), C-ketene (- 15.27; 7.3). The appearance of only
one signal for both metalcarbonyl C-atoms affords proof of
the trans orientation of the two CO-ligands, and thus also
of the phosphane- and the ketenyl-ligand. The last signal,
for the terminal ketene carbon with 6 = - 15.27, indicates
an extraordinarily large shielding for sp2-hybridized atoms[61.
Experimental
All operations should be carried out in dry (Na, P4010)
and N2-saturated solvents.-(2a):
A solution of 0.37 g
(3mmol) (2a)[2] in 30ml ether is treated at -30°C with
CO at a pressure of 1 at. The originally dark-red solution
slowly decolorizes and a bright-yellow precipitate separates
out. After ca. 5 h the crude product is decanted off and washed
twice with 20ml each of ether and pentane. Reprecipitation
from CH2Clz/ether/pentane affords fine yellow crystals; yield
0.29 g (69 %).--(2b): A solution of 0.46g (1 mmol) (I b)["
in 30ml ether is treated with CO and worked-up analogously
to (2a). Yellow crystals; yield 0.44 g (86%).
Received: July 5, 1978 [Z 85a lE]
Publication delayed at authors' request
German version: Angew. Chem. YO. 908 (1978)
CAS Registry numbers:
( l a ) , 68129-63-5; ( l b ) , 68129-64-6; ( 2 a ) , 68129-65-7; (2~). 68129-61-3:
" C , 14762-74-4
__
E . 0 . Fischer, B. Dorrer, Chem. Ber. 107, 2683 (1974); cf. also W A.
Herrmann, J . Plank, Angew. Chem. 90, 55 (1978); Angew. Chem. Int.
Ed. Engl. 17, 525 (I 978).
W.Uedelhouen, F. R. Kreissl, Chem. Ber., in press.
The corresponding chromium compound as well as analogous methylphenyl-, mesityl, ferrocenyl- and triphenylsilyl-derivativeshave also been
synthesized and characterized.
K . Eberl, F . R. Kreissl, unpublished results.
Bruker HFX 90, at 36.43 (3'P) or 22.63MHz (I%).
J. Fir/, W Runge, Angew. Chem. 85, 671 (1973); Angew. Chem. Int.
Ed. Engl. 12, 668 (1973); F. R. Kreissl, K . Eberl, W Uedelhouen, Chem.
Ber. 110, 3782 (1977).
859
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