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Photoresponsive complexing stilbene α,α′ disubstituted by ethylene dioxy side arms

Photoresponsive complexing stilbene α,α′ disubstituted by ethylene dioxy side arms

Tetrahedron Letters,Vo1.30,No.34,pp Printed in Great Britain PHOTORESPONSIVE 0040-4039/89 $3.00 + .oo Pergamon Press plc 4509-4512,1989 COMPLEXING...

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Tetrahedron Letters,Vo1.30,No.34,pp Printed in Great Britain

PHOTORESPONSIVE

0040-4039/89 $3.00 + .oo Pergamon Press plc

4509-4512,1989

COMPLEXING STILBENE

Q,Q’

DISUBSTITUTED

BY ETHYLENE DIOXY SIDE ARMS. J.PH.SOUMILLION=*,

J.WBILERZ, X.DE MANI,

R.TOUILLAUXx, J.P.DECLERCQs,

B.TINANTx.

1) Laboratory of Physical Organic Chemistry. 2) Laboratory of Quantum Chemistry. 3) Laboratory of Physical Chemistry and Cristallography. Catholic University of Louvain, Place Louis Pasteur,l, B-1348, Louvain-la-Neuve, Belgium.

Suptlrarv:A photoresponsive stilbene molecule showing complexing ability has been synthesized. Its cis-trans isomerization under direct irradiation has been examined and the corresponding phenanthrene by-product has been prepared. The extracting ability versus Li, Na and K cations were measured. A stable complex with sodium thiocyanate has been isolated and characterized.

One of the recent developments

in the use of macrocyclic ligands

was the idea proposed by Shinkai to construct host molecules containing a photoresponsive

chromophore

(I). This could lead to a photocontrol of the

binding ability of the host and models have been proposed, based on photoisomerization of azobenzenes

('-") or olefins ('). Geometrical changes

were also obtained by other mechanisms such as in the redox-switched crown ethers ("). Photocycloaddition cyclobutanocrown

was recently used in photoreversible

ethers (').

In most of these examples, the geometrical modifications

are not

sufficient to generate an all-or-nothing change of the complexing ability. In a model recently proposed by Irie and Kato, a thioindigo derivative with ethylenedioxy side groups was used(-), leaving the crown portion of the molecule in an open form. In order to test binding abilities, we synthesized a stilbene model bearing the complexing side arms directly on the double bond. These compounds were prepared by a method similar to the one adopted by Merz (**10) for the synthesis of stilbeno crown ethers: the tosylate of methoxy-2 ethanol was allowed to react with benzoin ("). The products were characterized by spectrometry and satisfactory data were obtained (+"). The structures, as determined by X-ray diffraction, are given below and the crystallographic

parameters are in reference ("). 4509

4510

i-4 Cis-trans or T-STO,

isomerization

('"). A photostationary

ted photodehydrocyclization (PheO,).

After

phenanthrene

clization dium

was

the course

of C-STO,

slowed

also

was

by direct

irradiation

of C-

not reached

due to the

expec-

to the corresponding

(by a factor

perchlorate,

isomerization

found

the

degassing,

down

of sodium

of the

was

state

freeze-thaw

In the presence

during

performed

of C-STO,

a carefully

by-product

suppressed. served

was

C-STO,

phenanthrene

formation of about

of the 6) but not

the cis/trans

was

increased.

to be favoured

ratio

ob-

The photocy-

in the presence

of so-

cations. *'

0'

(

0

0

0'

'0

,,(

1

'0

(

1

]=F&-& 0

O

8 0 T-St04 /

C-5304

A reversible with

visible

ligth

a mixture

equilibrated

when

The

PheO,

from

photocatalyzed

the dehydrocyclized

a mixture

spectrally

by-product

is always

inevitably cules

determine simple.

was prepared

present

do not show

Complexes

with

(").

with

The mixture

was

ratio.

by photoisomerization

in hexane

solution

starting

(I"). The product

a measurable.fluorescence:

by the

in the stilbene

association

interference

was

(").

dominated

are not strongly

without

by irradiating

and C- or T-STO,

a 2/1 T- to C-STO,

of C- and T-STO,

characterized

isomerization,

may be obtained

of iodine

reaching

C or T-STO, spectrum

PheO,,

Phe04

affected constants various

fluorescence samples.

The W

spectra

by the presence

of salt

have

their

shown

that

stoechiometries

their

of trace

emission

amounts

of PheO,

of these

and attempts

behaviour

are probably

moleto

is not

formed.

4511

The extracting ted by equilibrating aqueous

phase

ability

containing

Table

of the molecules

a dichloromethane an alkaline

1: Extraction

picrate.

Alkali

picrates

picrates

has been

molecules

extracted": K'

I.4

0.7

5.7

C-STO,

2.5

8.8

7.0

PheO,

1.2

5.2

0.9

96.1

I) In % of the aqueous y. Possible

error:

lo-" M in alkali

property This

extraction.

extracted

a more

cavity

sidearms,

compared

with

that

(21 ). This by the open

ability

complex,

shown

found

It is known

provided

below,

between

sodium anion was

ether

picrate,

molecule.

in the other

case cases

sodium

C-STO,

this

cation

must

that

our

of the comof the sodium presented

in

is preferentially

Li is the preferred difference

one when

the

be attributed

to

demonstrated

by

compound.

was

further

compound

is binded

and to a water

and sodium to the

molecule.

crystallographically

4

shows

variation

cations,

of the C-STO,

formed the

crown

a strong

was

the alkali

is used

to the thiocyanate

stereoscopically

7 lo-* M in host

known

However,

C- and T-STO,

af a complex

In this

spectrophotometrical-

3.3 lo-& M in alkali

phase:

a powerful

may be favourably

The complexing

cyanate.

with

between

12-crown-4

isolation

Organic

extractants.

by the C-STO,.

loose

as measured

phase:

6.

(5,zo ). Among

litterature

comparable

picrate

. Aqueous

hydroxide.

The comparison are poor

alkali

20.05

I) Dibenzo-18-crown

plexing

an

below.

.

T-STO,

molecules

tes-

with

are shown

Na‘

DB18C6_

the

of host

The results

of alkaline

Li'

the

synthesized

solutions

thio-

ethylenedioxy This

complex,

characterized

5

(").

4512

Acknowledaments: The authors wish to thank the IRSIA for a fellowship (XDM). The National Found for Scientific Research and the SPPS Belgium are thanked for financial support. REFERENCES:

(1) S.SHINKAI, T.NAKAJI, Y.NISHIDA, T.OGAWA, O.MANABE J.Am.Chem.Soc.,

102,5860(1980). S.SHINKAI, T.MINAKI, Y.KUSANO, O.MANABE, J.Am.Chem.Soc., 105,1851(1983). (3) S.SHINKAI, M.ISHIHARA, K.UEDA, O.MANABE J.Chem.Soc. Perkin Trans.II, 1174(1985). (4) S.SHINKAI, K.MIYAZAKI, O.MANABE, J.Chem.Soc. Perkin Trans.1, 449(1987), H.SASAKI, A.UENO, T.OSA, Chem.Letters, 1785(1986). I:; S.SHINKAI, K.INUZUKA, K.HARA, T.SONE, O.MANABE, Bull.Chem.Soc.Japan, 57,2150(1984). (7) S.AKABORI, Y.HABATA, M.NAKAZAWA, Y.YAMADA, Y.SHINDO, T.SUGIMURA, S.SATO, Bull.Chem.Soc.Japan, 60,3453(1987). (8) M.IRIE, M.KATO, J.Am.Chem.Soc., 107,1024(1985). (9) A.MERZ, R.TOMAHOGH, Angew.Chem.Int.Ed. Engl., 16,467(1977). (10) A.MERZ, M.EICHNER, R.TOMAHOGH, Liebigs Ann.Chem., 1774(1981). (11) The yields (unoptimized) in crystallized products are at least of 60%. (cis and trans are obtained in a 3/7 mixture separated by flash chromatography (Ethyl acetate/petroleum ether 2/l, 0.1% in triethylamine) and crystallized. M.p.: 46" (C-StO,) and 56O(T-STO,). (12) C-StO, : NMFt 200 MHz, S(ppm). IH: 3.42(6H,s), 3.68(4H,t), 3.91((4H,t), 7.2(10H,m). llC: 58.7, 69.6, 71.8, 142.8, 127.4, 127.5, 127.7, 128.6, 129.7, 135.1, 142.8. W(CH,CN): a.,,,:299 nm. T-STO,: NMR. IH: 3.24(6H,s), 3.43(4H,t), 3.62(4H,t), 7.36-7.82 (lOH,m). =3C: 58.6, 69.7, 71.4, 127.5, 127.6, 127.8, 128.3, 128.6, 134.2, 144.4. UV(CH,CN) &,_: 295 nm. (13) The crystallographic data were obtained with a Huber 4 cycle diffractometer using CuKa graphite monochromatized radiation (A =1.5418 A), solution by SHELXS-86 (1Q), refinement by SHELX-76 (I*). The structure of C-ST04 is discussed elsewhere ("'). C-STO,: mono$liniC, P21/a, a = 20.640(4), b = 9.542(l), c = 9.400(2)A, Z = 4, Dx = 1.19 gem-', final R index I3 = 96.17(2) V = 1840.6(6)A3 0.060 for 254; observed refleciions. T-ST04: mono:linic, P21/c, a = 9.541(2), b = 10.597(4), c = 9.109(3)A, B = 93.32(2) V = 919.4(4) A' 2 = 2, Dx = 1.19 gem-", final R index 0.056 for 145; observed refleciions. The list of atomic coordinate and molecular dimensions has been deposited with the Cambridge Data Center. (14) G.M.SHELDRICK in l'Crystallographic Computing 3", Eds G.M.SHELDRICK, C.KRUGER, R.GODDARD, Oxford University Press, p.175-189(1985). (15) G.M.SHELDRICK, SHELX-76 Program for Crystal Structure Determination, University of Cambridge (England). (16) Irradiation in pyrex tubes with W light from high pressure Hg lamp (4300 Hanau burner); STO, in CH,CN solvent. (17) Irradiation with 2 visible lamps (150W) in heptane. T-STO, was 3.10ms M and I, was 7.10-s M. (18) A 2 lOma M solution of T-STO, in heptane was irradiated in the presence of 2 10-4 M I,(quartz tube and 150 W high pressure Hg lamp. After reaching a 99% of T-STO, consumption, the residual C-STO,/PheO, mixture was chromatographed with ethyl acetate/hexane eluent (1:l) containing 0.1% of triethylamine. The yield of PheO, (pale yellow liquid) was 70%. (19) PheO,: NMR 200 MHz, 6(ppm), =H: 3.49(6H,s), 3.80(4H,t), 4.39(4H,t), 7.61(4H,m), 8.34(2H,m), 8.62(2H,m). W(CH,CN): the spectrum shows the characteristic shape and wavelength of a phenanthrene aromatic. (20) S.SHINKAI, M.ISIiIHARA, K.UEDA, O.MAMABE, J.Chem.Soc. Perkin TranS.2, 513(1985). (21) F.DE JONG, D.N.REINHOUDT, Adv.Phys.Org.Chem., 17,279(1980). (22) B.TINANT, J.P.DECLERCQ, J.WEILER, X-DE HAN, J.Ph.SOUMILLION, Acta tryst., under press. (2)

(Received in France 22 May 1989)