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Conversion of an Iodomethyl(phosphane)- into a Methylenephosphorane-Complex Example of a Nucleophile-Catalyzed Isomerization Reaction.

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has to be pointed out that the liposomes are not destroyed by
the osmotic shock. Electron miscoscopy proved that the precipitate consisted of spherical vesicles.
In addition, the possibility of obtaining scanning electron
micrographs of the polymer liposomes (Fig. 3) also hints at
their great stability. In contrast, the monomer vesicles are destroyed during sample preparation.
These stable lipid bilayer vesicles could be of use as models for the study of cell-cell interactions or as carriers for biologically active substances. Preliminary experiments have already shown that mixed membranes consisting of polymerizable and natural lipids and proteins, respectively, can be realized at the gas-water interface. These mixed systems are of
special interest for the investigation of interactions with natural cell systems. Synthetic lipids with different polymerizable groups161(vinyl and butadiene derivatives) can also be
used for these experiments instead of the excessively rigid
polydiacety lenes.
Fig. 3. Scanning electron micrograph of large, multilamellar (Ib) polymer vesicles ISI-40 scanning electron microscope, acceleration voltage I5 kV.
(10 mmol) is added to POcl3 (15 mmol) dis(4c): (4b)13d1
solved in anhydrous CCI, (25 ml). After standing stoppered
overnight the mixture is refluxed for 6 h. The solvent and excess POC13 are evaporated in uucuo, and the residue is heated
with water (50 ml) for 30 min. The mixture is extracted with
ether and the product recrystallized.
(la): (4a)l3"] is reacted with oxalyl chloride to obtain the
acid chloride1*'.The acid chloride (10 mmol) dissolved in anhydrous chloroform (10 ml) are added dropwise at 0 "C to a
mixture of tetraethyleneglycol(5 mmol) and anhydrous pyridine (15 mmol) dissolved in anhydrous chloroform (20 ml).
The mixture is stirred overnight at room temperature and
worked up with ether.
(16): (ld) is obtained from N-methyliminodiethanol and
the acid chloride of (4a) as described for (la). (ld) is quaternized with CH3Br in anhydrous acetone at 0 "C.
(lc): A mixture of the acid chloride of (4a) and N,N-bis(2hydroxyethyl)-2-aminoethanesulfonic acid in anhydrous
chloroform/pyridine is refluxed overnight. (lc) crystallizes
on chilling.
(2): 1,2-Bis(l0,l2-hexacosadiynoyl)glycerol, m. p. 6566 "C (from light petroleum), was obtained using a general
procedure described in ref. "'1. This product was acylated
with f3-bromoethylphosphoricdichloride according to Eibl et
uLfiol,hydrolyzed, and reacted with N(CH3)3 and Ag2C03.
(3): 2-(10,12-Hexacosadiynoyl)-3-stearoylglycerol iodohydrin, m. p. 34-36 "C (ether/methanol), was obtained by
stepwise acylation of racemic glycerol iodohydrin["I. This
product is phosphorylated with silver di-tert-butyl phos-
0 Verlag Chemie, GmbH, 6940 Weinheim, 1980
phate['21.The tert-butyl protecting groups are removed by
gaseous HCl in anhydrous CHC13["].
Received: July 23. 1980 [Z 614 IE]
German version: Angew. Chem 92, 962 (1980)
CAS Registry numbers
(la). 75495-20-4(Ib), 75495-21-5;f l c ) .75495-22-6,
(Id),73510-24-4;(2), 7549523-7; (3), 75495-24-8;( 4 4 . 73510-21-1;(4a) acid choride, 75495-25-9:(46).
75495-26-0;( 4 ~ ) 75495-27-1.
tetraethyleneglycol. I 12-60-7:N-methyliminodiacid, 10191ethanol. 105-59-9N,N-bis(z-hydroxyethy1)-2-aminoethanesulfonic
18-1: 1,2-bis(hexacosa-lO,12-diynoyl)glycerol, 75495-28-2; 3-bromethylphosphoric dichloride, 4167-02-6; 2-(hexacosa-l0.I2-diynoyl)-3-stearoylglycerol
iodohydrin, 75506-21-7;silver di-rerf-butyl phosphate, 18281-42.0
[I] H. T. Tien: Bilayer Lipid Membranes. Marcel Dekker. New York 1974,A.
D. Bangham, M. W. Hill. N. G. Hill, Methods Membr Biol. 11, 38 (1974).
121 a) J. M. Gebicki, M. Hicks, Chem. Phys. Lipids 16. 142 (1976);W. R. Hargreaues, D. W. Daemer, Biochemistry 17, 3759 (1978);b) M. K. Join, C. J. A .
oan Echteld, F. Ramirer, J. de Gier, G. H. de Haas, L. L. M. uan Deenen, Nature 284, 486 (1980);c) T. Kunifake, J. Macromol. Sci.-Chem. A 13. 587
(1979);J. H. Fender, Acc. Chem. Res. 13, 7 (1980);K. Degucht. J. Mino. J.
Colloid Interface SCI.65. 155 (1978);R. A . Mortara, F. H. Quina. H. Charmooich, Biochem Biophys. Res. Commun X I , I080 (1978);d ) Y. Okahata.
T Kunitake. J. Am. Chem. SOC. 101, 5231 (1979);E. Baumgartner. J.-H
Fuhrhop, Angew. Chem. Y2. 564 (1980);Angew. Chem. Int. Ed. Engl. 19,
550 (1980).
131 a) G. Wegner. Makromol. Chem. 154, 35 (1972);R. H Buughman. Contemp.
Top Polym. Sci. 2, 205 (1977);b) D. Day, H. Ringsdorf, J. Polym. Sci. Polym Lett. Ed. 16, 205 (1978); c) B. Tteke, G. Lieser. G. Wegner. J. Polym.
Sci. Polym. Chem. Ed. 17, 1631 (1979);d ) B. Tieke, G. Wegner. D. Naegeb.
H . Ringsdo$, Angew. Chem. 88. 805 (1976);Angew. Chem. Int. Ed. Engl.
15,764(1976);e) D. Naegele, H. Ringsdorf, J. Polym. Sci. Polym Chem. Ed.
15. 2821 (1977).
[4]a) D. Day. H.-H. Hub, H. Ringsdorf, Isr. J. Chem. 18, 325 (1979);b) H.-H.
Hub, B. Hupfer, H. Rmgsdorf, Am. Chem. SOC., Org. Coatings Plastics
Chem. Div. Prepr. 42. 2 (1980); c) H. Koch. Diploma thesis, Universitat
Mainz 1980; B. Hupfer, Ph. D. thesis, Universitat Mainz, scheduled for
151 a ) G. N Patel, J. D. Wift. Y. P.Khanna, J. Polym. S o . Polym. Phys. Ed. 18,
1383 (1980); b) D. R. Day. H. Ringsdorf, Makromol. Chem. 1x0, 1059
161 K. Dorn, H. Schupp, Ph. D.thesis. Universitat Mainz, scheduled for 1981
[7] All reactions were carried out with exclusion of moisture. All new compounds yielded correct elemental analyses, as well as appropriate IR. 'Hand "C-NMR, and F D mass spectra.
IS] F. H. Marson. R. A . Volpenheim. J. Lipid Res. 3, 281 (1962).
[9]F. R. Pfeiffer, C. K . Mino. J. A. Weisbach, J. Org. Chem. 3S, 221 (1970).
[ 101 H. Etbl, D. Arno/d, H. U . Welfrien,0. Wesphal, Justus Liebigs Ann. Chem.
709. 226 (1967).
1111 G. H. de Haas. L. L. M. van Deenen, Rec. Trav. Chim. Pays-Bas 80, 951
[I21 P. P. M. Bonsen, G. H. de Haas, Chem. Phys. Lipids 1, 100 (1967).
Conversion of an Iodomethyl(phosphane)- into a
Methylenephosphorane-Complex: Example of a
Nucleophile-Catalyzed Isomerization Reaction"]
By Ruiner Feser and Helmut Werner"'
Dedicated to Professor Fritz See1 on the occasion of his
65th birthday
The pronounced Lewis-base behavior of C5H5Rh(PMe3)z
(1) can be exploited for the synthesis of cationic hydrido-, alkyl-, and halo-complexes of the type [C5H5RhR(PMe3)2]
( R = H , Me, Et, MeCO, PhCO, C1, I, etc.)121. We have now
also attempted the preparation of a cationic iodomethyl complex. Such a compound containing a carbenoid ligand
should be readily convertible into cations of the type
+ ~ , ) (L=PR3,
[C5H5Rh(CH2X)(PMe3)2J(X = halogen, OCH3, etc.). Ylide
complexes were hitherto prepared either by reaction of a
Prof. Dr. H. Werner, Dip].-Chem. R. Feser
lnstitut fur Anorganische Chemie der Universitat
Am Hubland. D-8700Wiirzburg (Germany)
Angew. Chem. Int. Ed. Engl. 19 (1980) No. I 1
suitable substrate with a free ylidei3]or of a methylene complex with a n~cleophile'~~.
The synthesis of the iodomethylbis(phosphane)-complex
(2) was accomplished by the rapid, smooth reaction of (1)
with diiodomethane.
The synthesis of the methylenephosphorane-metal complex from a phosphane-metal complex and dihalomethane is
not new. Thus the reaction of C O ( P M ~with
~ ) ~CH2Cl2leads
to (Me3PCH2)2CoC12161,
and that of Pt(PPh3), with CH2CII to
As an important step in their
one-pot synthesis of (Me3PCH2)2CoC12,
Klein and Hammed6]
postulated the formation of a halomethyl(ph0sphane)-complex which reacts very rapidly via [ C O ( C H , P M ~ ~ ) ( P M ~ ~ ) ~ C ~ ]
as a further non-isolated intermediate to give the product.
Our investigations demonstrate for the first time the sequence
C5H,Rh(PMe3)2+ CH212+ IC5H5Rh(CH21)(PMe3)2]I
The product is a colorless solid which is moderately soluble
in polar organic solvents. (2) is stable for several days in
CH3N02and CH30H, whereas in dimethyl sulfoxide a rapid
reaction takes place, giving [C,H5RhI(PMe3)2]I.
The lability of the carbon-iodine bond in (2) is confirmed
by the reactions with various nucleophiles. Reaction with trimethylphosphane in nitromethane at room temperature
Table 1. ' H - and "P-NMR data of (2)-(6),
in CD3N02[6 values. TMS mt. ('H) and 85'16 H3P04 ext. ("P); J
5.67 d x I
J p H = 1.2
5.90 t
1.75 d x vt
Jpn = 5.3
1.10 d x d x t
Jnhn = 2.0,
3 J p H z4.R
1.90 d
1.80 d x d
5.63 d x d
J n h n =0.4,
J p n = 1.5
= 11.2
1.72 d x vt
J ~ h =
n I .O
5.63 d x t
J n h H =0.4.
= 1.2
5.47 d
1.73 d x vt
= 0.8
36.5 d x t
J p p = 7.4
J n h H = 129.5,
1.90 d
J p p = 10.4
= 13.2
2.37 d x t
Jnhn = 2.4.
1.60 d x d
J y H = 11.2
tion of one of the two trimethylphosphane groups from rhodium to the carbon of the carbenoid ligand. In no case have
+ [L,M(CH,PMe3)X]
A remarkable feature of the conversion (2)+ (4) is the migra-
38.5 d x d
J=6.0, J'=10.4 [bj
2.13 s
= 5.0
1.80 d
J ~=H
= 1.6.
= 0.5
J ~ h p =
34.5 "I"
Jnhr = J r p = 8.5
[a] The signal for the CH, protons disappears owing to several couplings in the background noise. [b] Assignment of coupling constants to Jnhp and
leads after 30 h to almost quantitative formation of the dicationic methylenephosphorane complex
(2) + PMe,
is not possible.
we previously been able to demonstrate the dissociation of a
[CSH5RhR(PMe3)2] (R = H, Me, MeCO, etc.) either with
nucleophiles or with electrophile~[~.~1.
The possibility thus arises that the isomerization (2) + (4) proceeds intramolecularly, and formation of a four-center transition state
No reaction is observed with triphenylphosphane under the
same conditions. With triethylamine the nitrogen-ylide complex corresponding to (3) is not formed, but surprisingly the
compound (4) isomeric with (2).
(with participatation of the catalyst) would be plausible.
Received: June 9, 1980 [ Z 615 IEj
German version: Angew. Chem. 92, 960 (1980)
The anion is apparently of no significance for this conversion: The complex [C5H5Rh(CHzI)(PMe3)2]BF4,obtained
from (2) and [CPh3]BF4,likewise reacts smoothly with NEt,,
to give the ylide complex [CSH5Rh(CH2PMe3)(PMe3)I]BF,.
That not only neutral, but also anionic nucleophiles catalyze the isomerization (2)+ (4), is shown by the reaction of
(2) with NaOMe in methanol. Instead of the expected prodUCt [ C S H ~ R ~ ( C H ~ O M ~ )(which
( P M ~is~readily
) ~ ~ ~accessible
via another routeIsl), (4) is formed quantitatively. With the
weaker base SMe- a mixture of [C5H5Rh(CH2SMe)(PMe3),JI (5) and [CSHSRh(SMe)(CH2PMe3)PMe3]I(6) is
formed; the latter mentioned compound is-as shown in an
independent experiment-the product of a rapid secondary
reaction of (4) with NaSMe.
Angew. Chem. IRI. Ed. Engl. 19 (1980)No. 11
CAS Registry numbers:
( I ) . 69178-15-0; (2). 75522-37-1; (3), 75522-38-2; (4). 75522-39-3; (S), 75522-40-6,
(6). 7552241-7: [CsH5Rh(CH20Me)(PMe3)211.
7552242-8 CHz12,75-1 1-6
[ l ] Basic Metals, Part 25. This work was supported by the Deutsche Forschungseemeinschaft. the Fonds der Chemischen Industrie, and bv gifts of chemical
from BASF AG. Ludwigshafen. and DEGUSSA, Hanau. We thank A. Hohn
for valuable assistence with the experiments.-Part 2 4 H. Werner. i?. Jurhanr, Z. Anorg. Allg. Chem., in press.
121 H. werner,R. F ~ w. ~
~ chern.
, ~ e 112,
~ 834
. (1979).
131 H,Schm,dbnur, Act, ,-hem. Res, 8.62 (1976).
141 W K. Wong. W. Tam, J. A. Gladysz, J. Am. Chem. Sac. IOI.5440(1979); and
references cited therein.
~ ~ ; ? " ~ Angew.
~ ~ Chem.
~ ~ gg,; 61 r(1976);
Angew, Chern. Int, Ed.
Engl. 15, 42 (1976).
[7] J. R. Moss, J. C. Spiers, J. Organomet. Chem. 182, C20 (1979).
0 Verlag Chemie. CmbH, 6940 Weinheim, 1980
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complex, example, reaction, phosphane, isomerization, iodomethyl, methylenephosphorane, conversion, nucleophilic, catalyzed
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