вход по аккаунту


New Tungsten-Iridium Dinuclear Complexes Containing Cyclopentadienyl and Hydrido Bridges.

код для вставкиСкачать
Facile Synthesis of Racemic Cysteine
By Jiirgen Martens, Heribert Offermanns, and
Paul Scherberich'"
Until now racemic cysteine has only been synthetically
accessible via expensive multi-step syntheses['].
In the course of our investigations on the synthesis of
natural and unnatural amino acids['] and amino acid deriv a t i v e ~ [we
~ ] have now found a facile and efficient synthesis for DL-cysteine hydrochloride . H 2 0 (3). The key intermediate, 2,2-dimethyl-3-thiazoline ( I ) , can be obtained in
92% yield in a one-pot reaction from chloroacetaldehyde,
sodium hydrogen sulfide, ammonia and acetone. This
reaction is based on the fundamental studies of Asznger et
( I ) : 350 mg of a 45% aqueous soIution of chloroacetaldehyde (2.0 mol) is added between 0 and 1O"C, over 45 min,
to a suspension of sodium hydrogen sulfide (135 g, 2.4
mol) in acetone (450 mL, 6.1 mol), 235 g water, and ammonia
(93 g, 5.5 mol). After 25 min at 5- 1O"C, the organic and
aqueous phases are separated. Fractional distillation of the
organic phase (88--89"C/100 mbar) gives 106 g (1) (92%)
as a colorless liquid.
(2): Hydrocyanic acid (50 mL, 1.3 mol) is added over 60
min to a stirred solution of ( I ) (I15 g, 1 mol) in 100 mL
methanol at 5-10°C. After 30 min at 15-20°C, the solution of (2) obtained is directly further reacted.
(3): A solution of (2), as prepared above, is dropped over
60 min into 1000 mL (ca. 11 mol) conc. hydrochloric acid
at 20-30°C. After 3 h stirring at 40-50°C the mixture is
diluted with 600 mL water, the methanol and acetone distilled off, the resulting solution refluxed for 4-5 h, clarified with activated charcoal and the solvent removed. Ammonium chloride, which does not dissolve upon digestion
of the residue in 400 mL methanol, is filtered off. The
methanolic filtrate is evaporated to dryness and the residue recrystallized from 20% hydrochloric acid ; (3) forms
thick colorless crystals. The latter are suction-filtered,
washed with cold 20% hydrochloric acid, and dried in a
fluidized bed dryer at 20--40°C. 122.9 g (70%) of (3) is
obtained from two crystallization fractions; the product is
found to be pure by thin layer chromatography.
Received: December 5, 1980 [Z 797 IE]
German version: Angew. Chem. 93. 680 (1981)
CAS Registry numbers: (I), 66692-88-4; (%)-(2), 78249-03-3; (DL)-(3/ . HCI,
10318-18-0; acetone, 67-64-1 ; chloraldehyde, 107-20-0; sodium hydrogen
sulfide, 16721-80-5
111 J . P. Greenstein. M . Winitz: Chemistry of the Amino Acids, Vol. 3, Wiley,
New York 1961, p. 1892.
121 W. M . Weigeri, H . Offermanns, P. Sckerbericli. Angew. Chem. 87, 372
(1975); Angew. Chem. Int. Ed. Engl. 14. 330 (1975).
131 A . Kleemann, B. Lekmann, J. Martens, Angew. Chem. 91, 858 (1979); Angew. Chem. Int. Ed. Engl. 18. 797 (1979); A . Kkemann, W. Leuchienberger. J . Martens, H . Weigel. ibid. 92. 640 (1980); 19. 627 (1980).
(41 F. Asinger. H . Offermanns, Angew. Chem. 79. 953 (1967); Angew. Chem.
Int. Ed. Engl. 6, 907 (1967); M . Thiel, F. Asinger, K . Schrniedel. Justus
Liebigs Ann. Chem. 611. I21 (1958).
151 The isolated intermediates and i 3 j gave correct elemental analysis and
spectroscopic data.
Anhydrous hydrocyanic acid adds to the azomethine
group of ( I ) to give the 2,2-dimethylthiazolidine-4-carbonitrile (2) in almost quantitative yield.
New Tungsten-Iridium Dinuclear Complexes
Containing Cyclopentadienyl and Hydrido Bridges
The crude thiazolidine (2) can be directly further
reacted. Using aqueous hydrochloric acid, the desired (3) is
obtained in 709'0 yield (relative to ( I ) ) in a one-pot reacti
By Paul S. Pregosin, Antonio Togni, and
Luigi M. VenanziL'l
We have previously shown that neutral monomeric hydrido complexes of platinum(ir)""l and iridium(riI)['blreact
with cationic species to form dimeric complexes containing one or more bridging hydrido ligands.
As an extension of this work we report here the new dinuclear complex (la) obtained by reacting (2) with (3a).
["I Prof. Dr.
[*I Dr. J. Martens, Dr. H. Offermanns, Dr. P. Scherberich
Degussa A G
Postfach 2644, D-6000 F r a n k f u d M a i n (Germany)
0 Verlag Chemie GmbH. 6940 Weinheim. 1981
L. M. Venanzi, Dr. P. S . Pregosin, A. Togni (Ciba-GeigyFellow)
Laboratorium fur Anorganische Chemie
ETH-Zentrum, Universitatstrasse 6, CH-8092 Zurich (Switzerland)
0570-0833/81/0808-0668 $02.50/0
Angew. Chem. Int. Ed. Engl. 20 (198t) No. 8
Cation (3a) is produced in situ as previously described for
the formation of (36) and ( 3 ~ ) ~ " .
the cyclopentadienyl moiety is present as a bridging q 5 :q'-fuIvaIene.
The mechanistic pathway leading to (1) is likely to involve the initial formation of [(q5-CSH5),W(p-H),Ir(PEt,),]+, which is analogous to (4) and contains the
structural unit (A), followed by the oxidative addition of a
(3a).L = PEt3; (3b). L = PMePh2;
( 3 ~ )L, = PPh,
Compound ( l a ) is a green solid and is stable in air for several days. It is moderately soluble only in polar organic
solvents and the solutions obtained decompose rapidly in
the presence of oxygen.
Support for the proposed structure for ( l a ) stems from
its 'H-, I3C- and 3iP-NMR spectra (in CD2C12):
'H-NMR: 6 = - 17.57 [H 1, 'J(HI,H2)=3.7 Hz, 'J(W,Hl)=95.2
Hz]; - 18.86 [H2, 2J(H1,H2)=2J(H2,H3)=2J(H2,P1)=3.7 Hz,
'J(H2,P2)=47.6 Hz, 'J(W,H2)=92.4 Hz]; -23.78 [H3, 'J(H3,PI),
'J(H3,P2)= 16.8, 28.4 Hz]; 6.42 [(IH), 6.36 (IH), 5.09
I3C-NMR: 6 ~ 8 5 . 5[C9(2H), HS-H8,
5.34 (5H), H9-HI3;
(2131; 110.3 [C4, 'J(Pl,C4)=84.2 Hz, 'J(P2,C4)=8.3 Hz]; 95.1 [C5
or C8, 'J(PI,C)=7.4 Hz]; 93.6 [C8 or C5, 'J(PI,C)=5.5 Hz]; 91.2
[C6 or C71; 89.9 [C7 or C6]; 20.3, 19.8, [PCH2, 'J(P,C)=25 Hz]; 8.0,
7.8 [PCHZCH,]. 3'P-NMR: 6=6.2 [PI, 2J(PI,P2)=11.8 Hz]; 4.7
cyclopentadienyl C-H bond, resulting in the formation of
structural unit (B). (Hydrogen-abstraction reactions occur
easily and often irreversibly in Ir' cornplexeslg1.) A species
of type (B) (M = Rh) has been postulated to explain the H/
D-exchange observed in compound (4)[31.
A vigorously stirred deep-red suspension of
[Ir(cod)(PEt3)']PF6(0.539 g, 0.79 mmol) (cod = 1,5-cyclooctadiene) in 25 mL EtOH at 0°C was treated with H2 for 15
min. A solution of (2) (0.250 g, 0.79 mmol) in 15 mL EtOH
was added to the resulting clear pale-yellow solution and
stirring continued for an additional 0.5 h. Solvent was
evaporated (with cooling) until precipitation began and
this was followed by rewarming to room temperature and
subsequent recrystallization at - 22". The green microcrystalline ( l a ) formed was recrystallized again from EtOH to
afford the product: yield 0.218 g (31%).
Received: December 19, 1980 [Z 800 IE]
German version: 93, 684 (1981)
The "Pi 'H}-NMR spectrum of the two non-equivalent
tertiary phosphorus atoms appears as an AB pattern. The
magnitude of 'J(Pl,P2) is consistent with a pseudo-cisorientation of the phosphorus atoms. The 'H-NMR spectrum between 6= - 17 and -24 ppm comprises three
groups of resonances, which may be assigned to H I , H2
and H3. The two lower field signals are assigned to H I and
H2 since they show '83W-satellites (natural abundance of
lx3W= 14.3%) with J(W,H)=90 Hz, consistent with onebond interactions. Reported 'J(W,H) values in related
complexes are 107 Hz for (4)13' and 60.3 and 59.7 Hz for
(Sa) and (5b)f41
respectively. A further relatively large splitting of the H2 signal stems from P2, and hence it can be
concluded that these two atoms occupy a pseudo-trans arrangement. H3 couples to two cis-phosphorus atoms and
H 1 but, interestingly, the trans-coupling 'J(H 1,H3) is quite
small (< 1.5 Hz).
[I] a) G. Bracher. D . M. Groue. L . M . Venanzi. F. Bachechi, P. Mura. L. Zambonelli, Angew. Chem. 90, 826 (1978); Angew. Chem. Int. Ed. Engl. I?,
778 (1978); G . Bracher. D . M . Groue. P S. Pregosin. L. M. Venanzi, ibid.
91, 169 (1979); 18, 155 (1979); b)A. Immirzi. A . Musco. P. S. Pregosin. L.
M. Venanzi. ibid. 92, 744 (1980); 19, 721 (1980).
(21 R . H. Crabtree. H . Felkin. T. Fillebeen-Khan. G. E. Morris. J. Organomet.
Chem. 168, 183 (1979).
(31 N . W . Alcock, 0 . W . Howarth, P. Moore. G . E . Morris. J. Chem. SOC.
Chem. Commun. 1979, 1160.
(41 A . Togni. Diplomarbeit, Eidgeniissische Technische Hochschule, Zurich
[S] A . Davison. S . S. Wreford, J. Am. Chem. SOC.96, 3017 (1974).
(61 K . I. Gell, J . Schwarfz.J. Chem. SOC. Chem. Commun. 1979, 244.
[7] R . J. Hoxmeier. J . R. Blickensderfer. H. D . Kaesz. Inorg. Chem. 18, 3453
181 M . Berry, N . J. Cooper, M. L . H. Green, S. J . Simpson. J. Chem. SOC.Dalton Trans. 1980, 29.
(91 A. D. English, T. Herskourfr,J. Am. Chem. SOC.99, 1648 (1977) and references therein.
(5a), R = H
(56). R = C ~ H S
The assignment of C5 and C8 in the '3C(IH)-NMR spectrum follows from the suggestions of Davison and Wreford'51,while the signal at 6= 110.3 may be assigned on the
basis of its positionr6', spin-lattice relaxation time and 31P
coupling pattern.
Complex ( l a ) appears to be a member of a general class
of compounds o f type ( I ) ; (Ib) and (Ic) can be prepared in
a similar way to ( l a ) (L= PMezPh o r PMePh,).
To our knowledge, the complexes of type ( I ) are the first
examples o f compounds containing both "C5H:-" and
"H -" bridging ligands. Although (q5:q'-C5H4) bridges
have been observed in complexes of zirconium@],molybdenum and
when bridging hydrides are presAnRew. Chem. Inr Ed. EnRI. 20 11981) No. 8
Double Ring-Opening of Bicyclic Oxaziridines to
N-(3-OxopropyI)amides by Jron(ii) Sulfate
By David St. C. Black and Lynn M . Johnstonel']
Dedicated to Professor Siegfried Hiinig on the occasion
of his 60th birthday
Iron(1r) sulfate has been shown to cleave C-alkyl-, Caryl-['. and C - ~ y a n o - [substituted
oxaziridines, the nature of the products depending on the particular substitution pattern. We now report that oxaziridines of type (2),
1'1 Dr. D. St. C. Black, L. M. Johnstone
Department of Chemistry, Monash University
Clayton, Vic. 3168 (Australia)
0 Verlaq Chemie GmbH. 6940 Weinheim, 1981
05?0-0833/81/0808-0669 $02.50/0
Без категории
Размер файла
436 Кб
dinuclear, containing, bridge, iridium, hydride, complexes, tungsten, cyclopentadienyl, new
Пожаловаться на содержимое документа