close

Вход

Забыли?

вход по аккаунту

?

Bis(1 2 4 6-tetraphenyl- and Bis(1-methyl-2 4 6-tri-phenyl-5-phosphorinyl)iron.

код для вставкиСкачать
Table 1. Yields of the reaction products from allylphosphonates ( 1 ) and alkyl halides X-R'
(1)
X-R'
Yield
1x1
83
92
89
56
78
82
3s
55
40
82
61
77
94
84
91
83
[a] T H P tetrahydropyran-2-yl
pure reduction of (2) still affords pure trans olefin. For
example, alkylation of a mixture of cis- and trans-2-butenylphosphonate ( l a ) with benzyl bromide followed by reduction
afforded trans-1-phenyl-bpentene exclusively[4!
[4] P. Vittorelli, 7: Winkler. H . J . Hansen, and H . Schmid, Helv. Chim.
Acta 51, 1457 (1968).
[S] J . Wratherston, W Roelofs, A . Comrau, and C. J . Sunders, Can. Entomol.
103. 1741 (1971).
[ 6 ] F . L. M Pattison, J . B. Stothers, and R . G . Woolford, J. Amer. Chem. SOC.
78, 2255 (1956).
Bis(l,2,4,6-tetraphenyl- and Bis(l-methyl-2,4,6-triphenyl-h5-phosphorinyl)iron
Finally, the present method was applied to the synthesis of
trans-1 1-tetradecenal, which is the sex attractant of the eastern
spruce budworm, Choristoneurafumiferana Clemen~[~'.
Starting with readily available bromide (4)[61and ( I a), and using
the same procedure as described above, we obtained trans-I 1tetradecenol ( 5 ) in 73 YOyield, which was readily converted
into the aldehyde in 95 YOyield.
trans-1-Phenyl-Zpentene (3), R =H , R'
By Gottfried Mark1 and Claus Martin"]
Phosphorins (phosphabenzenes) from transition metal complexes with coordination via both the n-electron system, as
in the x-aromatic complex ( I ) [ ' ] , and the free electron pair,
as in complexes of type (2)['1 and (3)13]. In contrast, pyridinetransition metal x-complexes have hitherto only been accessible by indirect
= CHzC6H5
n-Butyllithium (12mmol) was added to a stirred solution of
( l a ) (2.92g, IOmmol) in THF (20mI) at -60°C under a
positive pressure of argon and stirred at this temperature
for 1 h. Benzyl bromide (1.7g, 10mmol) in THF (5ml) was
added dropwise to the solution. After stirring for an additional
30min at -6O"C, the reaction mixture was allowed to warm
to room temperature. The mixture was quenched by the addition of 10% aqueous NH4CI and the product was isolated
by extraction with ether. Distillation of the crude product
afforded2.33g(83%)oftheadduct (2),R=H, R' =CHzC6Hs
(b. p. 144YJO.3 torr). A solution of this adduct (1.4g, 5mmol)
in dry ether (100ml) was cooled in an ice bath and LiAIH4
(0.11 g) was added. After stirring for 1 h at O'C, a few drops
of water were added and the resulting mixture was filtered
through celite. The solid was washed with ether and the combined filtrates were evaporated. The resulting crude product
was purified by distillation to yield 0.65 g (89X ) of ( 3 ) , R =H,
R' =CH2C6Hs (b. p. 88"C/14 torr). The overall yield of the
olefin did not decrease when the two steps were performed
successively without purification of the intermediate.
We have studied the reaction of 1,2,4,6-tetraphenyl-X5-phosphorin-I-yllithium ( 5 a ) and the corresponding I-methyl compound ( S b ) with the transition metal salts AgN03, Hg(OAc)2,
and FeCl,.
R
R
(5a), R' = CsH5
(Sb). R' = C H 3
P R
Received: March 15, 1974 [Z 20 IE]
German version: Angew. Chem. 86,415 (1974)
(7h).
R'
= CH3
[l] G . Looielle, C. R. Acad. Sci. C270, 86 (1970).
[2] E . J . Corey and G. 7: Kwiarkowski, J. Amer. Chem. SOC.88, 5654 (1966).
[3] J . Reucrofz and P. G. Sammes, Quart. Rev. Chem. Soc. 25, 135 (1971),
and references cited therein.
408
['I
Prof. Dr. G. Mark1 and Dipl.-Chem. C. Martin
Fachbereich Chemie der Universitat
84 Regensburg, Universitatsstrasse 31 (Germany)
Angew. Chem. internar. Edit. / Voi. 13 (1974)
No. 6
Theanions''lof(5u) and (5hl.whicharesensitiveto moisture,
can be obtained as deep blue-red solutions by reaction of
2,4,6-triphenylphosphabenzene( 4 ) with phenyl- and methyllithium, respectively, in benzene or T H F ; they can be isolated
as relatively stable deep red salts of the tetrabutylammonium
ion"].
( 5 u ) and ( 5 b ) undergo redox reactions with AgN03 and
H ~ ( O A C silver
) ~ ; or mercury is deposited and the phosphorin
( 4 ) regenerated. It has yet to be established whether o-complexes having P-Ag or P-Hg bonds play an intermediate
role in these reactions.
Treatment of ( 5 u ) and ( 5 b ) with FeClz in T H F (reaction
conditions as for ferrocene formation from cyclopentadienyl
anion and FeCI2) affords deep brown solutions from which
brownish red neutral compounds ( 7 a ) and ( 7 b ) can be isolated by chromatography (SiOJight petroleum); they form
fine, felted, lustrous needles on crystallization from benzene/
light petroleum.
( 7 u ) , m.p. 231'C; mass spectrum (70eV, T0=180"C): 858
( M + , 5 % ) ; 'H-NMR: ~=2.34--3.57 (m, 40H), 4.72 (br. d,
4 phosphorin-H). 3 J p = 10 Hz.
(7b), m.p. 192°C; mass spectrum (70eV, T0=160"C): 734
( M + , 21 %); 'H-NMR: t=2.15-3.20 (m, 30H), 4.63 (br. d,
4 phosphorin-H), 3Jp.. H = 8 Hz, 9.96 (d, 6 H), 'JP-.H= 5 HZ
(methyl-H).
The results 'of elemental analysis, osmometric molecularweight determination, and mass spectrometry clearly indicate
a metathetic reaction yielding [C23HI ,P-R'12Fe. The 'HNMR spectrum of ( 7 h ) permits tentative conclusions regarding structure. Whereas the methyl protons of 1,l-dimethyl2,4,6-triphenyl-h5-phosphorin(6 b ) appear as a doublet at
T = 8.27, the corresponding signal of ( 7 b ) exhibits a
pronounced upfield shift (T = 9.96).
*
R
&
-
P
m
R
P atom on going from the phosphorin (4) ( - 178.2 ppm)
to the n-complex ( I ) ( - 4.3 ppm). These data and the findings
of 'H-NMR spectroscopy strongly suggest structure ( 7 ) with
central bonding of the iron over the phosphorin 6% system
resembling that in dibenzenechromium and the metallocenes.
Received: March 29. 1974 [ Z 26 I t ]
G e r m a n version: Angew C'hem. X6.445 (1974)
-__ -. .-
[I] J . Deherirz a n d
t / . NArh, Chem. Ber 103. 2541 (19701.
[2] J . Drhurirz a n d H . Ndrh, J. Organometal. Chem. 4Y. 453 (1977)
[3] K . C . Dush. J . Ehrr/ein, a n d H . Schnridhoirr, Synth. Inorg. Metalorg.
Chem. 1Y73. 375.
[4] E. 0. Frscheu a n d K . Ofe/r,C h e m . Ber. 93. 1156 (1960).
[5] T h e anions of ( 5 ) a n d the 1,lLdisubstituted phosphorins ( 6 1 having
a formal 3dn-2p,
double bond a r e isoelectronic. According 10 C N D O ' ?
calculations [ A . Schweig a n d H. Oehling, Tetrahedron Lett. 1970, 49411
thehs-phosphorins ( 6 ) arearomatic6rrsystems with so "'pi' "do * ? hybridt/.ition at the P atom.
[6] C . Morrin, Dissertation. Untversitat Regensburg, planned for 1974.
[7] J . S . Wtiiiyh a n d R. W F
tiden.
J. Amer. Chem Soc. 7Y. X46 (19571.
[XI
E h y e l a n d H. D. Rorh. Angew. Chem. 76, 145 (1964); Angew. Chem.
internat. Edit. 3, 228 (1964): W Gritnnw. H . Hoffmrrirn. a n d E. I+&.
Angew.
Chem. 77. 34X (1965): Angew. Chem. internat. Edit. 4. 354 (1965)
[9] C! M u r k , C . H Diinyuri. M . M. Cr~rrdi/irId,a n d J . R. i u i i Wu:er. Top.
Phosphorus Chcm. 5, 227 (1967). especially p. 414: see also [ 2 ] .
Preparation and Reactions of Trifluoromethanesulfonic
Arenesulfonic Anhydrides"] [**I
By Franz Effnberyer and Klaiis Huthniucherl"
Dedicated to Professor Hrllmut Brrdereck on the occusion of
his 70th birthdajl
In the course of our investigations on new electrophilic agents,
we have reported on the preparation of trifluoromethanesulfonic carboxylic anhydrides and their high acylating potentialI2].We have now succeeded in obtaining the mixed sulfonic
anhydrides (3) from sulfonyl bromides ( I ) and silver trifluoromethanesulfonate (2).
Fe
R
W
P
-
C
H
K-SO,Br
,
f 1)
R
+ AgOSO,CF, -AgB; R-SOz-O-SO,CF,
(2)
(3)
I
CAr-H HOSOrCF,
R-SO,-Ar
We consider that this effect is interpretable only by assuming
that the P-CH3 groups are located directly above the phenyl
substituents, as depicted, the methyl protons thus experiencing
strong diamagnetic shielding. Similar conditions are found
in 1,4-p0ly(rnethylenebenzenes)~
'I and 1,6-methanocyclodecapentaenesIx1.The shift of the phosphorin proton signal from
T = 1.93 in ( 4 ) to 4.12 in ( 7 a ) and 4.63 in ( 7 h ) accords
with observations on the x-complex ( I ) ( ~ = 4 . 0 " ~ ) .
The -"P-NMR signals of ( 7 u ) lie at +45ppm (relative to
external I+.%POa)
and those of ( 7 b ) at + 5 5 ppm. Since o-complexation of phosphanes (PR,) with carbonylmetal compounds
leads to distinctly negative coordination shifts of the 3 1 P
resonance [(C,H,),P, ti31P==t-6.0ppm; (C,H,),PCr(CO)S,
- 55.3ppm: [(C,H,),P],Ni(CO),,
- 32.6ppm[']], the values
for (7u) and ( 7 b ) contraindicate o-bonded iron in the formally conceivable structure (8).
The large 3 1 P upfield shift in ( 7 a ) and ( 7 b ) relative to the
h'-phosphorins ( h ) , R'=alkyl or aryl [6"'P= +6.0ppm] is
comparable with the considerablc gain in shielding of the
A n g w . Chrm. inrrrnur. Edit.
1 Ih/.13 f
1 9 7 4 ) 1 No. 6
(4)
Since the anhydrides (3) are not stable in pure form, exact
physical data cannot be given; their structure, however, is
established unequivocally by 'H-NMR and by their reaction
with arenes, yielding aryl sulfones ( 4 ) (Table 1).
The extraordinary sulfonylating potential of the anhydrides
( 3 ) is apparent from the reaction with an arene as unreactive
as chlorobenzene, which is sulfonylated in high yield even
at 0 C (see Table 1). With sulfonyl halides, on the other
hand, sulfonesare formed from arenes only at elevated temperature and in the presence of Friedel-Crafts catalystsl3I.
The anhydrides (3) are thermolabile; in the absence of arenes
which can be sulfonylated they decompose in various ways
depending on the nature of R.
- .~
.
~
_.
['I
Prof. Dr. F. Effenberger a n d D i p L C h e m . K . Hulhmacher
Institut fur Organtsche Chemie der Universitiit
7 Stuttgart XO. Pfarrenwaldring 55 ( G e r m a n y )
This w o r k was supported by the Duutsche Forschunlrsgeme1nsch;lft
a n d the F o n d s der Chemischen Industrie.
["*I
409
Документ
Категория
Без категории
Просмотров
1
Размер файла
212 Кб
Теги
methyl, tetraphenyl, phosphorinyl, tri, iron, phenyl, bis
1/--страниц
Пожаловаться на содержимое документа