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Novel Coordination of (Benzoylmethylene)triphenylphosphorane in a Nickel Oligomerization Catalyst.

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2.05 (s, 3H, CH3), 3.69 (hept., IH, J=7Hz, tert. H), 6.15
and 6.28 (AB, 2H, J=6Hz, vinyl-H), 6.75-7.80 (m, 15H,
phenyl-H); 13C-NMR (CDCI3): 6= 164.9 (C+N), 51.0 (NCH), 24.2 and 22.4 (isopropyl-CH3); UV (cyclohexane):
1.,,,=337 (4.20), 250 (4.00) sh, ,lmi,=283 (3.63); IR (KBr):
V C = N = 1630cm- (m).The preparation and spectroscopic data
of (8b)-(8e)
closely resemble those given for (8a).
in the planar PC20Ni five-membered ring indicate a delocalized system with typical P-C and P-Ni bond lengthsr3].
As in the triphenylphosphane coordinated via P2 to Ni, both
the phenyl groups attached to PI are oriented in a propellerlike arrangement. The Ni-C1 o-bond is unusually short
(1.893m- l o ) ; in comparable Ni-Ph compounds[41values of
1.96-2.00 m- l o are observed. This finding might be explained
in terms of a strong electron affinity of the 0,P-ligand. ESCA
analyses confirm this assumption.
Received: March 20, 1978 [Z 968 IE]
German version: Angew. Chem. 90, 497 (1978)
c4f-bnc3
CA3
[I]
[2]
[3]
[4]
[S]
[6]
[7]
[S]
[9]
[lo]
Survey: A. J. Waring, Adv. Alicycl. Chem. I, 129 (1966); references
cited therein.
2,4-Cyclohexadienimines described so far: P. Claus, H! Vycudilik,
Monatsh. Chem. 101, 396 (1970); P . Claus, W Vycudilik, W Rieder,
ibid. 102, 1571 (1971); R . Okazaki, Y. Inagaki, N . Inamoto, J. Chem.
SOC.Chem. Commun. 1974, 414; Y. Inagaki, R. Okazaki, N . Inamoto,
Bull. Chem. SOC.Jpn. 49, 1142 (1976); R. Adams, E. Angello, R. S .
Colgroue, J. Am. Chem. SOC.77, 5617 (1955).
Survey: G. Quiiikert, Angew. Chem. 87, 851 (1975); Angew. Chem.
Int. Ed. Engl. 14,790 (1975);Pure Appl. Chem. 33, 285 (1973),references
cited therein.
W Dannenberg, H . Perst, Justus Liebigs Ann. Chem. 1975, 1873, references cited therein.
Survey: G. Quinkert, Angew. Chem. 84, 1157 (1972); Angew. Chem.
Int. Ed. Engl. 11, 1072 (1972), references cited therein.
H . J . Bestrnann, J . Lienerr, L. Mott, Justus Liehigs Ann. Chem. 718,
24 (1968); cf. G. R. Krow, Angew. Chem. 83,455 (1971); Angew. Chem.
Int. Ed. Engl. 10, 435 (1971); references cited therein.
The configuration at the C=N bond has not yet been established
only one stereoisomer is observed for ( 8 a ) and ( 8 b ) whereas
stereoisomers can be detected for ( S c ) and ( a d ) .
H. Perst, Tetrahedron Lett. 1970, 4189.
Attempted conversion of ( 5 ) into (8) led to dienone-phenol rearrangement (cf. [I]).
H. H. Eckhardt, H . Persf, to be published.
C64
c1=
C13
Fig. 1. Molecular structure of the complex ( I ) in the crystal.
The formation of ( I ) according to
(cod)zNi
+
Ph3P
Novel Coordination of (Benzoy1methylene)triphenylphosphorane in a Nickel Oligomerization C a t a l y s t [ * * ]
By Wilhelm Keim, Frank H . Kowaldt, Richard Goddard, and
Carl Kriiger[*]
The oligomerization of ethylene to linear a-olefins
is of substantial technical interest[']. On reacting
Ph3PLCH-CO-Ph
with Ni(PPh3)4 or Ni(cod)z/Ph3P
[cod = 1,5-cyclooctadiene]in toluene we obtained a compound
of the composition C4&60P2Ni ( I ) , the first well defined
and readily crystallizable complex, which converts ethylene
in high selectivity and activity into a-olefins or also polyethylenes in the absence of cocatalysts such as are required e.g.
by catalysts of the Ziegler type.
The structure of the complex ( I ) followed from spectroscopic data ('H- and 13C-NMR,IR, MS) and from a crystal
structure analysis['] (cf. Fig. 1). The nickel atom is surrounded
in an almost square planar arrangement by a triphenyl moiety,
a o-bonded phenyl group and a bidentate ylide ligand bonded
via 0 and P (deviations from planarity of +0.07m-" for
C1, 0; -0.07m-" for PI, P2). The bond lengths and angles
Prof. Dr. W. Keim ['I, Dr. F. H. Kowaldt
lnstitut fiir Technische Chemie und Petrolchemie der Technischen Hochschule
Alte Maastrichter Strasse 2, D-5100 Aachen (Germany)
Dr. R. Goddard, Dr. C. Kriiger
Max-Planck-Institut fiir Kohlenforschung
Lembkestrasse 5, D-4330 Miilheim-Ruhr 1 (Germany)
['I Author to whom correspondence should be addressed.
[**I This work was supported by the Deutsche Forschungsgemeinschaft.
[*I
466
+
Ph
Ph,P=CH-CO-Ph-
- 2 cod
PhSP'
PPhz
\N:>y
'0-
'ph
(1)
proceeds via a novel type of phenyl rearrangement leading
to a phenyl-metal bond. A 1,2-migration of a phenyl group
in phosphorus ylides catalyzed by nickel compounds is already
Reaction of a toluene solution of the complex ( I ) with
ethylene (50bar) at 50°C affords n-olefins which are up to
99 % linear and consist of up to 98 % of cl-olefins. The olefins
up to C30analyzed by gas chromatography are present in a geometrical distribution. Activities of 6000 mol ethylene per mol
of complex (1) are achieved. When the reaction of ( I ) with
ethylene is carried out in n-hexane as suspension medium,
however, high molecular linear polyethylene is formed.
Procedure
A solution of triphenylphosphane (26.2 g, 0.1 mol) and (benz~ylmethylene)triphenylphosphane[~~
(38 g, 0.1 mol) in toluene
(900ml) is added dropwise to a solution of bis(cyc1ooctadiene)nickel(o)(27.5g, 0.1 mol) in toluene (600ml) at 0°C and
the mixture stirred for 24 h at room temperature and a further
2 h at 50°C. It is then evaporated to dryness in a vacuum
at 50°C. The toluene distilled over contains almost
quantitatively the liberated 1,5-cyclooctadiene.The brownishred crude reaction product is dissolved in toluene at 50-70°C
and treated with a small amount of n-octane. On cooling
to O"C, 48.5 g (69 %) of compound ( I ) crystallizes out.
Received: April 12, 1978 [Z 981 IE]
German version: Angew. Chem. 90,493 (1978)
Angew. Chem. I n t . Ed. Engl. 17 ( 1 9 7 8 ) N o . 6
CAS Registry numbers:
(1 ), 66674-76-8;(Cod),Ni, 1295-35-8; Ph3P, 603-35-0; Ph3P=CH-CO--Ph,
859-65-4
[l]
[2]
[3]
141
[S]
[6]
W Keim, R. S. Bauer, H . C. Chung, P. Glockner, US-Pat. 3635937
(1969); W Keim, R. f. Mason, P . Glockner, US-Pat. 3647914 (1972);
DOS 2054009 (1972); Eur. Chem. News, Sept. 16, 60 (1977).
Cell data: a= 14.4341(6), b = 16.2935, c=9.6575(6) m-”, CI=103.897(2),
!3=97.636(2),~=80.177(3)”,V=2162.4m-30, space group Pi, Z = 2 , with
.
reflections (k=1.5418
a toluene molecule at 7, d , = l . 2 5 7 g ~ m - ~9123
m-I”), 1646 unobserved (20); R=0.067, R,=0.099.
B. L. Barnett, C. Kriiger, J. Cryst. Mol. Struct. 2, 271 (1972); D. 3 .
Brauer, C . Kriiger, P . 3 . Roberts, I!-H, R a y , Chem. Ber. 107, 3706
(1974).
C . Kriiger, Y - H . Euy, Angew. Chem. 85, 1051 (1973); Angew. Chem.
Int. Ed. Engl. 12, 998 (1973); D. J . Brauer, C. Kriiger, P . 3 . Roberts,
Z - H . Tyay, ibid. 88, 52 (1976) and 15, 48 (1976), respectively; K . Jonas,
D. J. Brairer, C. Kriiger, P . 3 . Roberts, Y - H . Tsay, J. Am. Chem. SOC.
98. 74 ( I 976).
F. Heydenreich, A . Mollbach, G . Wilke, H . Dreeskamp, E. G. Hoffmann,
G . Schroth, K . Seeuogel, W. Stempfle, Isr. J. Chem. 10, 293 (1972).
F . Rumirez, S. Dershowitz, J. Org. Chem. 22,43 (1957).
N-Terminal Cyclization of Peptides with N,”-Carbonyldiimidazole or N ,N’-Thiocarbonyldiimidazole
The significance of the procedure lies in the fact that it
provides a convenient entry to such modified peptides which
are of interest for the study of structure activity-relations
of peptide hormones. Previous methods13’ required relatively
drastic conditions and their scope is therefore very limited.
By analogy with the hydantoins (3), thiohydantoins ( 5 )
are obtained by reaction with N,N’-thiocarbonyldiimidazole
( 4 ).
(5)
R1 = ( S ) - 3 - I n d o l y l m e t h y l , R 2 = (S)-CH2-CH(CH3)2
R3 = A s p ( C H 2 P h ) - P h e - N H z
Peptides (6) containing an N-terminal p-amino acid cyclize
with (2) to form 2,4-pyrimidinediones (7).
By Franz Esser and Otto Roes[*]
We have found that N,N’-carbonyldiimidazole (2)“’ reacts
smoothly and without racemization under very mild conditions with C-terminally protected peptides to give hydantoin
peptides of type ( 3 ) [ ( 3 c ) and ( 3 d ) after removal of the
benzyl protecting group]. This cyclization can also be carried
out on a solid phase[”.
(3a)
(3h)
(3c)
(3d)
R’
R2
R3
(S)-CH2COZCH,Ph
H
(S)-3-Indolylmethyl
(R)-3-Indolylmethyl
(S)-CHzPh
(S)-3-Indolylmethyl
(S)-CH2--CH(CH3),
(S)-CH2-CH(CH3)2
NH2
Met-Gly-NH2
Asp-Phe-NH2
Asp-Phe-NH2
R’ = (S)-CH2Ph, R 2 = NH2
Characteristic data for six selected products are compiled
in Table 1. Ring formation is readily seen in the I3C-NMR
spectra. The expected signals (Table
are accompanied
by a typical shift of the C, signals of the second amino acid
unit relative to the corresponding signals of the open-chain
compounds. Diastereomers such as ( 3 c ) and (3d) can be
unequivocallydistinguished. The expected molecular ions were
observed in the mass spectra of ( 3 a ) and (7), and the species
(8) containing the hydantoin ring could be detected as key
fragment in the case of ( 3 b)[51.
That the compounds synthesized were indeed N-terminally
cyclized structures and not ureas of type ( 9 ) was proved
as follows: For example amino acid analysis of ( 3 c) revealed
a Trp :Leu :Asp :Phe ratio of 0.27 :0.46 : 1.01 : 1.O on acidic
Table 1. Selected data of compounds produced.
____
Reactant
~-
(1 a)
(I b )
(1c)
(1 c ‘ )
(1 d )
(1c)
(6)
ProdUCt
Method
(30)
(3b i
(3c )
(3c)
(3d)
(5)
(7)
A
.__
H-Asp(CH,Ph)-Phe-NH
H-Gly-Trp-Met-Gly-Pol [f]
H-Trp-Leu-Asp(CH2Ph)-Phe-NH2
H-Trp-Leu-Asp(CH2Ph)-Phe-BzPol [g]
H-D-Trp-Leu-Asp(CH2Ph)-Phe-BzPol [g]
H-Trp-Leu-Asp(CH2Ph)-Phe-NH2
H-P-Ala-Phe-NH2
____
B
A
B
B
A
A
Yield
M.P. [“C]
(dec.)
Rr [d]
[”/.I
88
40 [a]
60 [b]
94 [c]
74 [c]
91
77
166-1 69
136
161-162
158--160
152-154
103-1 I5
133-1 35
0.96
0.24
0.2
0.2
0.23
0.83
0.6
I3C-NMR [el
( c = l , DMF)
-131.8
- 18.61
~
44.7
18.60
- 27.34
- 6.54
-
_155.6
157.7
155.8
-
158.9
184.3
148.4
[a] Based on amino acid linked to the Merrifield resin: after ammonolytic cleavage. [b] After hydrogenolytic debenzylation. [c] Based on amino acid linked to
benzhydrylamine resin; after acidolytic cleavage. [dl Eluent: CHC13: MeOH:H,O=65:25:4. [el Signal of the C-atom of the newly introduced CO or CS group
(TMS=O, in [DeIDMSO); Dr. K . H.Pook, Ingelheim. [fl Pol=Merrifield resin. [g] BzPol= benzhydrylamine resin.
[*] Dr. F. Esser, Dr. 0 . Roos
C. H. Boehringer Sohn, Abteilung Pharmachemie
Postfach 200, D-6507 Ingelheim (Germany)
Angew. Chem. Int. Ed. Engl. 17 (1978) N o . 6
degradatiod6] and a ratio of 0.99 :0.95 :0.97 : 1.0 on alkaline
hydrolysis[71.The incomplete regeneration of the first two
amino acids on acid hydrolysis can only be rationalized by
467
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nickell, coordination, oligomerization, triphenylphosphonium, benzoylmethylene, novem, catalyst
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