Novel lithium cation complexants

Tetrahedron Letters No. 21, pp 1861 - 1862, 1978. 0 Persamon Press Lti. Printed in Ureat Britain.

s02,00/0

004~4039/78/0515-1861.

NOVELLITHIUMCATIONCCMPLEXANTS by Jean Grandjean and Pierre (a) Universit6 (b) Universit6

Laszlo::(a),

J.P.

de Liege - Sart-Tilman

des Sciences

et Techniques

Picavet

and Henri Sliwa::(b)

par 4000 Liege 1 - Belgium 59650 Villeneuve

de Lille,

(Received in UK 21 March 1978; accepted for publication

Two of us have recently cycloundecane

prepared’

new derivatives

d’Ascq

- France.

28 March 1978)

of l,lO-dioxa-4,7-diaza-ll-phospha-

Q) .

We report

here the complexing

Complexation

induces downfield

spectrometer

(Fig.)

aptitude

shifts

of these crowns 1,2 towards alkali

of the proton resonances

metal cations.

measured with a Varian T-60

(Table).

A&r) 10'

H3hNoNP-OR C

0'

H3CHNu

1

Using the observed solution

indicate

(K = 8-10 M-l) weak. Several

obtained

constants from the best

strong binding

we have extracted’ K and the limiting fits

of the lithium

from the data in acetonitrile chemical

of the theoretical cation

shift

6B in the bound

curves to the experimental

(K > 300 M-l),

while the sodium

and potassium lithium

(K = 5 M-l) complexes of these 11-crown-5 analogs (1, are rather 3-6 , cyclic decapeptides7 and cryptands 8 complexes with crown ethers

have been characterized. reported

stoichiometry,

at 35’C the stability

form. The K values points

1:l

R : CH3, C&

with 12-crown-44,

But such a selectivity 14-crown-43y5,

towards lithium

and the (2.1.1)

1861

as we find here has only been

cryptand8.

With a diameter of -ca.

Nq. 21

1862

R

salt

resonance

LiC104

C2%

NCH3

NaC104

CzHs

NCH3

NaSCN

‘ZH5

NCH3

NaSCN

CH3

NCH3

NaSCN

(II3

CCH3

KSCN

‘ZH5

NCH3

a) + 0.4 Hz, downfield

1.2 i,

the lithium

ion can fit

hole dimensions

are within

The lithium-complexing

this

in conjunction

of the lithium

with 12-crown-4

143.6

10.1

> 300

137.7

4.2

10

139.9

6.4

8

139.9

6.2

9

208.7

9.9

8

136.3

2.8

5

‘)at

35’C,+

15%

of 1.2-l .6 i 3. Strong interactions

12-crown-4,

14-crown-4,

and the (2.1.1)

with Li+

cryptand,

whose

range.

avidity

A number of important alkylation upon the structure

K(M-l)c

: summaryof the results.

into a cavity

with 11-crown-S,

A@z)b

b) + 0.6 Hz

from TMS Table

are indeed observed

IBM

10

of

(1, should be extremely useful

reactions

have rates

ion pairs , to drive

present’.

and/or

products

Derivatives

such reactions

for

synthetic

purposes.

very much dependent

of this

towards formation

type could be used, of specific

products . ACKNOWL~S

.

This work is part of the program “Binding of ions by organic subsidized

by Fonds de la Recherche Fondamentale Collective,

and bio-molecules”

Belgium.

REFERENCES.

(1) H. Sliwa and J.P. Picavet, Tetrahedron Letters, 1583 (1977). (2) D. Live and S.I. Chan, J. Am. Chem. Sot., 98; 3769 (1976). (3) J.J.

Christensen,

D.J. Eatough, and R.M. Izatt,

Chem. Rev.,

74, 351 (1974).

(4) F.A.L. Anet, J. Krane, J. Dale, K. Daasvatn and P.O. Kristiansen, 27, 3395 (1973). (5) C. J. Pedersen,

Fed. Proc.

(Fed. Am. Sot.

Exp. Biol.)

Acta Chem. Stand.,

, 27_, 1305 (1968).

(6) J. Dale and J. Krane, J. Chem. Sot., Chem. Connn., 1012 (1972). (7) I.L. Karle, J. Am. Chem. Sot., !4& 4000 (1974). (8) J.M. Lehn and J.P. Sauvage, Chem. Coma., 440 (1971); J. Am. Chem. Sot., 97_, 6700 (1975). (9) For instance : J.C. Dalton and B.G. Stokes, Tetrahedron Letters, 3179 (1975); T.M. Chan and B.S. Ong, ?etrahedron (10) C. Ouannes, G. Dressaire

Letters,

and Y. Langlois,

319 (1976).

Tetrahedron

Letters,

815 (1977).