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Direct Formation of the -Ferrocenylisobutyl Cation from Ferrocene and Isobutyraldehyde.

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and benzonitrile were removed in uacuo, and the residue sublimed at 80--85"C/0.01 torr, yielding 56 mg of (7f) ['H-NMR
(CCI4/CDCl3 10 : 1): 6 = 3.66 (s, 3 H), 7.2-7.7 (m, 9 H)].
Received: June 28, 1978 [Z 37 IE]
German version: Angew. Chem. YO, 731 (1978)
CAS Registry numbers:
(4), 1076-59-1; ( 5 ~ ) .138-89-6; ( S b ) , 1122-04-9; ( 5 ~ 1 ,715-99-1; ( S d ) ,
27318-25-8: f 5 e ) . 885-1 1-0: (Sf), 53603-63-7; ( 6 a ) , 67523-67-5; ( 6 b ) ,
67523-68-6; ( 6 c ) , 67523-69-7; ( 6 d ) , 67523-70-0: (6e), 67523-71-1 : (6f),
67523-72-2; ( 7 ~ 1 ,7050-85-3: ( 7 6 1 , 67523-73-3; ( 7 ~ ) . 67523-74-4; ( 7 d ) ,
67523-75-5: ( 7 e ) . 67523-76-6; ( 7 j ) , 67523-77-7
C . Wrntrup, H! Reichen, Helv. Chim. Acta 5Y, 2615 (1976); C . Wentrup,
H.-M! Winter, Angew. Chem. YO. 643 (1978); Angew. Chem. Int. Ed.
Engl. 17. 609 (1 978).
W Reichrn, C . Wentrup, Helv. Chim. Acta 59, 2618 (1976).
A. M e y r r , Ann. Chim. Phys. 191, 1, 252 (1914).
All new compounds were characterized by elemental analysis and spectroscopic data.
E. Muller, B . Narr, 2. Naturforsch. 1 6 8 , 845 (1961).
E. Crrgat, R. Putter, Chem. Ber. 99, 2361 (1 966).
1. U g i . Isonitrile Chemistry. Academic Press, New York 1971, pp. 24&
This reaction is of preparative importance because (6) can
were much
readily be converted into (7); previous
more complicated.
Procedure
Synthesis of (6): Compounds ( 1 ) (1.86mmol) and (2)
(1.8m1, 20mmol) are dissolved in TFA (10ml) and stirred
at room temperature for 3 h. Compound ( 5 ) is added ( 5 ml,
70mmol),stirringcontinued for 15min, and the mixture slowly
neutralized with saturated NaHC03 solution until the greenish
brown color turns to orange. The mixture is treated with
10% caustic soda (100ml) and CH2CI2(100ml). The phases
are separated, the organic phase is extracted one more with
10% caustic soda (100ml) and twice with water (2.x 100ml)
and the combined aqueous solutions are finally extracted
twice with CH2C12.The aqueous phase is acidified with sulfuric
acid until incipient precipitation of (6) gives rise to a yellowish
white turbidity. After extracting three times with CH2C12, the
combined extracts are dried with sodium sulfate, and the
solvent removed under reduced pressure. Compound (6) is
obtained as a red oil which slowly crystallizes. It is recrystallized
from ether and cyclohexane; yield 2.65g (80%), m.p. 82°C.
Received: June 30, 1978 [Z 38 IE]
German version: Angew. Chem. YO. 734 (1978)
Direct Formation of the a-Ferrocenylisobutyl Cation
from Ferrocene and I s o b u t y r a l d e h y d e [ * * ]
By Rudolf Herrmann and Ivar Ugi[*]
We suspected that ferrocene ( I ) can undergo electrophilic
substitution by isobutyraldehyde (2) in trifluoroacetic acid
(TFA) to form ( 3 ) , which equilibrates with (4). Evidence
favoring this idea comes from (a) the formation of highly
stable r-ferrocenylalkyl cations from x-ferrocenylalkanols in
TFA"', (b) the enhancement of electrophilic reactivity of carbony1 compounds by O-protonationt2],and (c) the role played
by the r-ferrocenylisobutyl cation (4)[41 in the chemistry of
r-ferrocenylisobutylamine ( 7)[31.Compound (7) is the asymmetrically inducing chiral reference system for peptide syntheses by stereoselective four-component condensati~n[~I.
CAS Registry numbers:
( I ) , 102-54-5: ( 2 1 , 78-84-2; (3). 51177-17-4: ( 4 ) , 67577-01-9: ( 5 ) . 6X-11-1;
( 6 1 , 63393-49-7; ( 7 ) . 64598-90-9
7: D . Turbirt, W E. Watts, J. Chem. Soc. Perkin I I 1974, 177, 185.
Y A . Palm. U . L. Haldna. A. J . Taluik in S. Putai: The Chemlstry
of the Carbonyl Group. Interscience, New York 1966, pp. 421 ff.
G . Eberle, I . Lagerlund. I . U g i , R. Urban, Tetrahedron 34, 977 (1978).
and references cited therein.
R. Urban, I . Ugi, Angew. Chern. 87, 67 (1975); Angew. Chem. Int. Ed.
Engl. 14, 61 (1975); R. Urban, G. Eberle, D. Marquarding, D. Rehn,
H . Rehn, I . Ugi, ibid. 88, 644 (1976) bzw. 15, 627 (1976); R. Urban,
D. Marquording, I . U g i , Hoppe-Seylers Z . Physlol. Chem.. in press.
V I . Sokoloa, P . K Petrovski, A. A . Kaidze, 0 . A. Reutlov, J. Organomet.
Chem. 76, C 15 (1974).
G . Eberle, I . U y i , Angew. Chem. 88, 509 (1976); Angew. Chem. Int.
Ed. Engl. 1 5 , 492 (1976).
A. Ratajczak, 5. Misterkiewicz, I. Organornet. Chem. Y I , 73 (1975).
Hydrosulfuration-Thionationof Unsaturated A m i d e s [ * * ]
Joint dissolution of (1 ) and (2) in TFA (each in a concentration of 1 mol/l) leads within a few minutes to the formation
of considerable amounts of (4), according to the 'H-NMR
spe~trum~~l.
Treatment of the reaction mixture after 30min at 20°C
with an excess of thioglycolic acid (5)163 'I affords up to 60 %
of S-(or-ferrocenylisobutyl)thioglycolic acid (6) while 35 % of
ferrocene ( I ) can be recovered. After 3 h, the yield of (6)
increases to 80% and ferrocene can no longer be isolated.
~
~.
By Howard Alper, Janie K . Currie, and Rajeeu Sachdeua[']
In 1973,Scheeren et al.[']reported that carbonyl compounds
could be converted into the corresponding thiocarbonyls by
the use of tetraphosphorus decasulfide and sodium bicarbonate
in acetonitrile or ether solvents. We have found this method
to be a very useful one for the synthesis of aromatic and
aliphatic thioketones['! However, when we applied this procedure to unsaturated amides, an interesting reaction occurred
to give a saturated thioamide.
a,P-Unsaturated amides ( I ), prepared by treatment of an
aromatic amine with acryloyl or methacryloyl chloride, react
with P,Slo and NaHC03 in acetonitrile to give the P-mercaptoalkyl thioamides (2) in 31-56% yields (Table 1). None
Organisch-chemisches Institut der Technischen Universitat Munchen
Lichtenbergbii,a>se 4, D-8036 Gaiching (Germany)
[**I This
work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
Angrw. Clwm. Int. Ed. Engl. 17 (i978) No. 9
['I, J. K Currie, R. Sachdeva
Department of Chemistry. University of Ottawa
Ottawa, Ontario KIN9B4 (Canada)
To whc.?: correspondence s.h.nu!d be addressed.
[*] Prof. Dr. H. Alper
[*] Prof. Dr. I. Ugi, DipLChem. R. Herrmann
['I
[**] We are grateful t o the National Research Council of Canada for support
of this work.
689
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formation, direct, cation, ferrocenylisobutyl, isobutyraldehyde, ferrocenyl
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