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Manganese Complexes with УEnd-OnФ and Spirocyclic Bonded 3 5-Phosphazene Ligands.

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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,).
2 RRP(S)SX
3 2 RRP(S)SBr
RRP(S)SS(S)PRR
1
3
2
R=R'=tBuCH,O; b, R=R'=iPrO:
R = R = P h O ; e, R=tBu, R'=MeO
a,
c,
R=R=MeO;
>P(S);-C-C-Br
I 1
I
R"OH/Base
*
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
types.
d,
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.
'
3
Manganese Complexes with "End-On" and
Spirocyclic Bonded 03,h5-PhosphazeneLigands**
I
;P(S)S-OR"
5
B
A
Whereas the double ylide A reacts with, e. 9 . . TiCI,"] or
(C3H5)2Pd[21
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
P=S
groupf4]. We have now found that with
R2N-P(=NR)*
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.
;P(S)S-i\'RY
6
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,
RR'P(S)S-OR'
RR'P(S)SCI
+
R'
fc'
R'OSiMe,
1'1
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):
s=+97.
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%
yield.
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.
136
I
7
5
Experimental
-
3
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
moiety
~
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
[**I
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
The angle between the S-P-N(
1) and C-P-N(2)
planes is 92.9'. I n contrast to the planar ring containing
the Si atom, the other ring is puckered (angle between the
planes S-Mn-N(
1) and S-P-N(
1) = 20.8").
Received: July 28, in altered form
October 29, 1981 [Z 998 IE]
German version: Angew. Chem. 94 (1982) 149
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1982. 169-174
[I] E. Niecke, R. Kroher, S. Pohl, Angew. Chem. 89 (1977) 902; Angew.
Chem. I n f . Ed. Engl. 16 (1977) 864.
[2] W. Keim, R. Appel, A. Storeck, C. Kriiger, R. Goddard, Angew. Chem. 93
(1981) 91; Angew. Chem. Int. Ed. Engl. 20 (1981) 116.
[3] 0. J. Scherer. A. Nahrstedt, Angew. Chem. 91 (1979) 238; Angew. Chem.
Inf. Ed. Engl. 18 (1979) 234.
141 0. J. Scherer, H. Jungmann, Angew. Chem. 91 (1979) 1020; Angew. Chem.
Int. Ed. Engl. 18 (1979) 953.
[6] 'H-NMR [CaD,CD,: -60°C: 6=0.45 (s, ISH), 0.22 ( s , 9H), -0.17 (S,
9 H ) : 20°C: 6=0.45 (5, I8H), 0.24 ( s , I8H)]. "P('H)-NMR [Ct,D,CD,;
-60°C as well as 20°C: 6 = - 1.6 (s)]. '3C(1H/-NMR [C,DsCD3:
-60°C: 6CO = 227 (s); the appearance of a single C O signal is a n indication of a rranr-configuration in 31. IR [n-hexane: metalcarbonyl region:
v=2030 (s), 1935 (vs), 1904 (w) cm-'1.
Table I. 8-0xabicyclo[3.2. I]oct-6-en-3-ones 2 by reaction of a-haloketones 1
and furan in TFE/furan ( I : 1 v/v) at room temperature with triethylamine
(Method A: molar ratio I :2) o r sodium trifluoroethoxide (Method B: molar
ratio 1 : 1) as base. All products except 2g are known.
Educt
1
Method
Reaction
time
A
A
B
B
A
B
A
A
25 d
29 d
5d
6d
Id
4d
3d
10 d
75 min
A
75 min
A
Id
B
Product
2
Yield
[Oh]
a
45
56
a
b PI
b [b]
e=b[b]
d
d
e=d
f
T["C/torr] [a]
M.p. P C ]
I
120-140/12
41-42
120-140112
33-35
ii}
93
130-150/ 12
70-9010.3
13-16
70-90/0.001
88-89
90- 120/0.001
88-89
60-70/0.002
43-44
68
55
g [c]
52
h
84
[a] Kugelrohr temperature. [b] The product contains at maximum 6% of the
C-2/C-4 epimers. M.p. of isomerically pure 2b: 45-46°C. [c] 'H-NMR
(CDC13): 6=5.25 (s, I-H, 5-H), 6.65 (s, 6-H, 7-H); 1R (CHCl3): 1765 c m - '
(C=O).
tones can not only be prepared by chlorination of ketones,
but also via several other routes, by C-C coupling reactions. Thus, the [4+ 3]-cycloaddition of allylium-2-olates
opens u p promising applications in synthetic chemistry.
Efficient Synthesis of
8-0xa bicyclol3.2.l]oct-6-en-3-ones,
Preparatively Useful 14 31-Cycloadducts**
+
By Baldur Fohlisch*, Eberhard Gehrlach, and Rorf Herter
The title compounds 2, accessible by cycloaddition of
allylium-2-olates to furans have proven to be valuable
educts for the synthesis of natural products and biologically active analogues. Previously, however, the cycloadducts could only be synthesized using tedious and expen.-ive methodS[za.3iL4.5.71. We have now found a method in
which not only a-bromoketones but also the less expensive
and more stable a-chloroketones can be reacted with readily available bases.
The a-haloketones la-h react with furan in 2,2,2-trifluoroethanol (TFE), a very weakly nucleophilic and powerful ionizing solvent, in the presence of triethylamine or
sodium 2,2,2-trifluoroethoxide generated in situ to give 8oxabicyclo[3.2. I]oct-6-en-3-ones 2 (Table 1). The yields are
good, and work-up is simple. The bicyclic compounds
2b-f are formed stereoselectively. By reduction of 2f or
2g with the Zn/Cu couple, the unsubstituted ketone 2,
R'-R"= H, is also accessible in good yields. a-Chloroke-
Received: April 21, 1981 [Z 993 IE]
German version: Angew. Chem. 94 (1982) 144
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1982. 241-249
[2] a) H. M. R. Hoffmann, Angew. Chem. 85 (1973) 877; Angew. Chem. Int.
Ed. Engl. 12 (1973) 819.
[3] a) H.Takaya, S. Makino, Y.Hayakawa, R. Noyori, J. Am. Chem. SOC.100
(1978) 1755.
[4] J. Mann, A. A. Usmani, J. Chem. Sor. Chem. Commun. 1980, I 1 19.
[S] H. Sakurai, A. Shirata, A. Hosomi, Angew. Chem. 91 (1979) 178: Angew.
Chem. Inr. Ed. Engl. 18 (1979) 163.
171 H. M. R. Hoffmann, J. Matthei, Chem. Ber. 113 (1980) 3837.
Optically Active Glycerol Derivatives from
1,3(R) :4,6(R)-Di-O-benzylidene-D-mannitolThe First Structural Analogues of Moenomycin A**
By Thomas Schubert and Peter Welzel*
Morpain and Tisserand recently reportedI5l that optically
active glycerides are accessible from D-mannitol derivatives of type 2 in fewer steps than from the "classical"
educt 1"'. Presumably, di-0-benzylidene compound 3 is
Rol
HO
2
1
a
b
c
d
R'
R'
R'
R'
X
CH,
CH,
CH,
CH,
CH,
H
H
H
H
H
H
CH,
H
CH,
CH,
CH,
CI
CI
Br
CI
1
e
f
g
h
R'
R'
R'
CH,
CI
CI
H
CH, H
CI
H
CI
CI
-(CH2),-
R'
X
CH,
CI
CI
CI
CI
CI
Br
H
0
OH
OR
1
2
3,R=H
4, R
5, R
[*] Prof. Dr. B. Fohlisch, E. Gehrlach, Dr. R. Herter
lnstitut fur Organische Chemie, Biochemie und Isotopenforschung der
Universitat
Pfaffenwaldring 55, D-7000 Stuttgart 80 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
Angew. Chem. Int. Ed. Engl. 21 11982) No. 2
= Cl8H3.l
= C&41
[*] Prof. Dr. P. Welzel, Dr. Th. Schubert
Abteilung fur Chemie der Universitat
Postfach 102148, D-4630 Bochum (Germany)
[**I This work was supported by the Fonds der Chemischen lndustrie and
by Hoechst AG.
0 Verlag Chemie GmbH, 6940 Weinheim. 1982
0570-0833/82/0202-0137 $02.50/0
I37
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bonded, onф, spirocyclic, phosphazene, complexes, уend, ligand, manganese
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