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O O-Dialkylthiophosphonosulfenyl BromidesЧ A New Class of Reactive Organophosphorus Compounds.

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the rotational spectrum could become an important tool in
cell and membrane research. The experimental result that
rotation ceases when the membrane permeability is increased may explain why electrically induced fusion of
monomeric vesicles is observed only occasionally and not
reproducibly. In permeable membranes the breakdown
voltage can no longer be reached so that fusion cannot be
initiated. For the purpose of electric field induced fusion,
the occurrence of rotation in a n alternating field thus represents an accessible criterion for the integrity of biological
and artificial membranes.
Received: November 11, 1981 [Z 1 IE]
German version: Angew. Chem. 94 (1982) 151
[I] a) U. Zimmermann, J. Vienken, G. Pilwat, Z. Nafurforsch. C36 (1980)
173: b) C. Holzapfel, J. Vienken, U. Zimmermann, J . Membr. Biol.. in
[2] H. A. Pohl, J. S. Crane, Biophys. J. 11 (1971) 711.
[3] E. Jeltsch, U. Zimmermann, Bioekctrochem. Bioenerg. 6 (1979) 349.
[4] D. Day, H. H. Hub, H. Ringsdorf, Isr. J. Chem. 18 (1979) 325: H. H. Hub,
B. Hupfer, H. Koch, H. Ringsdorf, J. Macromol. Sci.-Chem. A 15 (1981)
Stereoselectivity and Relative Reactivity in the
Reaction of Organotitanium and -zirconium Reagents
with Carbonyl Compounds**
By Manfred T. Reetz*, Rainer Steinbach,
Jiirgen Westermann. Rarf Urz, Bernd Wenderoth,
and Roland Peter
Organotitanium and -zirconium compoundsl’a.b.2a.c1
such as 1-6 react far more selectively than their lithium-,
magnesium- and zinc analogues.
R T i ( 0 - i - C3H,),
R2Ti(O- i-C3H7)2
la, R = CH,
3a, R = CH,
3b, R CD3
l b , R = CD3
Ic. R n-C,H,
I d , R CH,=CHCHi
Addition of la, lc, 2, 4, and 5 to 2-phenylpropanal
leads preferentially to the “Cram products” (erythro :threo
u p to 93 :7). Other zirconium reagents react similarly,
whereas the analogous lithium and magnesium reagents
display far less diastereodifferentiation (=2 : 1).
Asymmetric induction in the construction of steroid side
chains can be realized particularly easily with titanium reagents, but not with zirconium reagents. Reaction of 13
with Id or l b leads to formation of the diastereomers 14a
and 15a or 14b and 15b in the ratio > 9 0 : 10 and 96 :4,
respectively. Furthermore, a titanium enolate derived from
0-methylestrone undergoes an erythro-selective aldol addition, whereby practically only one of the four possible
diastereomers is formed.
In order to test whether Cram’s “cyclic model” is applicable in the case of titanium and zirconium reagents, benzil
21 was allowed to react with la, 2, 3 or 4 to give 25
( d J - threo)
26 (meso- erythro) ( > 98 :2, 60 :40, 93 : 7
and 98 :2, respectively). This is a reuersal of the 1,2-asymmetric induction observed on reaction with 5, methylli-
[*I Prof. Dr. M. T. Reetz, R. Steinbach, J. Westermann, R. Urz,
B. Wenderoth, R. Peter
Fachbereich Chemie der Universitat
Hans-Meerwein-Strasse, D-3550 Marburg (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
Angew. Chem. Inr. Ed. Engl. 21 (1982) No. 2
a, R
CH,=CHCH2; b, R = CD,
thium or methylmagnesium bromide (25 :26 in the ratios
of 19:81, 15:85, and 28:72 respectively) and thus supports Anh’s open-chain modelL5I.Reaction of 27 with l a or
4 yields exclusively the erythro isomer (29:30 in the ratio
> 99 :l), indicating intermediary formation of the sterically less strained chelate 28.
Noticeable 1,3- and 1,4-asymmetric induction is observed on addition of l a and 4 to 3-hydroxybutyraldehyde
or phthalaldehyde (diastereomeric ratios u p to 70 :30 and
83 : 17, respectively).
The rate of addition of the reagents to ketones decreases
along the series 4 = 6 > 3 > l a = 5 . In the titanium series itself: ally1 > methyl > n-butyl. The highly reactive but not
uery basic tetramethylzirconium 6 adds to sterically highly
hindered compounds, particularly in cases in which methyllithium, la or 5 fail. Titanium or zirconium reagents
react selectively with ketones in the presence of ester
groups, but lactonization can occur.
Received: November 2, 1981 [Z 994 IE]
German version: Anyew. Chem. 94 (1982) 133
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1982. 257-268
[I] a) M. T. Reetz, J. Westermann, R. Steinbach, Angew. Chem. 92 (1980)
933: Anyew. Chem. Inr. Ed. Enyl. 19 (1980) 902: b) M. T. Reetz, R. Steinbach, J. Westermann, R. Peter, ibid. 92 (1980) 1044 or 19 (1980) 101 I .
[2] a) B. Weidmann, D. Seebach, Helu. Chim. Acro 63 (1980) 245 I : c) B.
Weidmann, C. D. Maycock, D. Seebach, ibid. 64 (198 I ) 1552.
[S] N. T.Anh, Top. Curr. Chem. 88 (1980) 40.
0,O-Dialkylthiophosphonosulfenyl BromidesA New Class of Reactive Organophosphorus
By Jan Michalski*, Marek Potrzebowski. and
Andrzej topusiriski
We report that the reaction of elemental bromine with
dithiophosphoric acid derivatives 1 (X = H) leads to a new
(*] Prof. Dr. 1. Michalski, Dip1.-Chem. M. Potrzebowski, Dr. A. Lopusinski
Polish Academy of Sciences
Centre of Molecular and Macromolecular Studies
PL-90-362 t o d z , Boczna 5 (Poland)
0 Verlag Chemie GmbH. 6940 Weinheim, 1982
0570-0833/82/0202-0135 $02.50/0
class of compounds, the sulphenyl bromides 3, in quantitative yield. The reaction proceeds via the disulphides 2,
which can be used advantageously as educts. The bromides 3 are also formed in quantitative yield by the action
of Br, on trimethylsilyl esters 1 (X = SiMe,).
3 2 RRP(S)SBr
R=R'=tBuCH,O; b, R=R'=iPrO:
R = R = P h O ; e, R=tBu, R'=MeO
I 1
By Otto J . &hererr, Jurgen Kerth.
Barbara K . Balbach and Manfred L. Ziegler
Until now the complex chemistry of 03,h5-phosphazenes
A [aminobis(imino)phosphoranes] and B [amino(imino)thiophosphoranes] has been limited to two reaction
By analogy, 0-methyl butyldithiophosphonate l e (X = H)
reacts to give 3e. The sulfenyl bromides 3 can be isolated
in a pure statel]', but decompose at room temperature
(within a few days) to the bromides RRP(S)Br and sulfur.
The bromides 3 react readily at room temperature or below with various nucleophiles giving a variety of novel or
difficultly accessible organophosphorus compounds.
Manganese Complexes with "End-On" and
Spirocyclic Bonded 03,h5-PhosphazeneLigands**
Whereas the double ylide A reacts with, e. 9 . . TiCI,"] or
to give the transition metal chelate complexes
L , M m R ' R " with a four-membered ring framework,
obtainable with platinum by other rneansl3l, reaction of B
with (Ph3P)2F't(C2H4)led to "side-on'' coordination of the
groupf4]. We have now found that with
1, Mn(C0)5Br forms the complex 3
which contains an "end-on" bonded 03,h5-phosphazene ligand, while with RR'N-P(S)=NR
2, it forms the phosphorus spiro compound 4 whose ring framework consists
of two four-membered rings each of which contains four
different elements.
Compounds of type 5 react with trimethylsilyl chloride
to give in high yield sulfenyl chlorides 7 which, due to
their reactivity, are suitable educts for the synthesis of
other organophosphorus compounds'*].
+ CISiMe,
3c: A solution of Br2 (1.6 g, 10 mmol) in 5 mL of CC1,
was added to a stirred solution of 2c (3.14 g, 10 mmol) in
10 m L of CCI, at -25°C. Solvent was removed at 05 "C/5 torr, yielding 3c (4.7 g) as a yellow oil. 3c could be
added to cyclohexene in CH2CI2at 0 ° C to give the 2-bromocyclohexyl compound (MeO),P(S)SC6H loBr(type 4) in
88% yield; b.p.= 105-108"C/0.0I
torr, "P-NMR (C6H6):
7a: Me3SiC1 (1.3 g, 12 mmol) was added to a stirred solution of 5a (3.5 g, 10 mmol) (R=R'=R"=rBuCH,O) in
20 mL of CH2CI2at - 1O"C, and the mixture stirred for 20
min at - 5 "C. After removal of the solvent and trimethylsilyl ether at 0 ° C under reduced pressure, 7a (3.0 g) was
obtained; 3'P-NMR (CH,C12): 6= +79.5. 7a reacts with
piperidine to give the piperidide (m.p.=67"C) in 86%
Received: July 8, 1980 [Z 988 IE]
publication delayed at authors' request
German version: Angew. Chem. 94 (1982) 134
[I] All the new compounds were characterized by elemental analysis and
"P-NMR spectroscopy (standard: ext. HAPOI); I'P-NMR: 3n,
6= +74.7; 3b, 6 = +70.7; 3c, 6 = +79.9: 3d, 6= +69.8; 3e, IS= + 110.7.
[2] a) L. Almasi, A. Hantz, Chem. Eer. 97 (1964) 66 I ; L. Almasi, L. Paskucz,
ibid. 98 (1965) 3546: b) L. Almasi, A. Hantz, Monarsh. Chem. 99 (1968)
1045, and references cited therein: c) A. Lopusinski, J. Michalski, W. J.
Stec, Justus Liebigs Ann. Chem. 1977. 924.
0 Verlag Chemie GmbH. 6940 Weinheim. 1982
3 can be isolated from hexane as permanganate-colored,
extremely air-sensitive crystals which are readily soluble in
ether, benzene, n-hexane, and dichloromethane. In solution, 3 exhibits dynamic behavior: the intramolecular exchange of the B I - ( C O ) ~ M
from one to the other imino group, which at room temperature occurs rapidly on
the NMR time scale, is measurably slowed down at low
temperatures (AG: = 51 kJ. mol-1)[61.When 3 and Ph3P
(molar ratio 1 :2) are warmed for 2.5 h at 40°C in hexane,
uncoordinated double ylide 1 is formed in high yield together with a mixture offac-Mn(CO),(PPh,),Br [ca. 80%:
"P-NMR (CD,C12, -50°C): 6=35.2(s)] and merMn(CO)3ce-(PPh3)2Br[ca. 20%; 31P-NMR:6= 54.5 (s)].
4 forms yellow-brown, slightly air-sensitive crystals
from ether which are readily soluble in CH2C12 and
CH3CN, moderately soluble in ether and benzene, and
sparingly soluble in n-hexane. The NMR data ( e . g . the
four expected singlets from the C O groups are found in the
I3C('H) spectrum) of 4, as well as the X-ray structure analysis confirm the tetrahedral environment of the P atom.
[*] Prof. Dr. 0. J. Scherer, J. Kenh
Fachbereich Chemie der Universitat
Postfach 3049, D-6750 Kaiserslautern (Germany)
Prof. Dr. M. L. Ziegler, B. K. Balbach
Anorganisch-chemisches Institut der Universitat
Im Neuenheimer Feld 270, D-6900 Heidelberg I (Germany)
This work was supported by the Fonds der Chemischen Industrie.
0570-0833/82/0202-0J36 $02.50/0
Angew. Chem. Inr. Ed. Engl. 21 (1982) No. 2
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class, bromides, compounds, dialkylthiophosphonosulfenyl, reactive, organophosphorus, new
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