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Formation of Oxazolidinones and Oxazinanones by Reaction of Allylamines and of Homoallylamines with Carbon Dioxide and Iodine via Intramolecular Cyclization.

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trogen and methanol. In addition to Sa, traces ( < 1%) of E-1,2-bis[3,6bis(trifluoromethyl)pyridazin-4-yl]ethenewere also isolated (cf. 141).
[91 Review: 1. Fleming: Frontier Orbitals and Organic Chemicat Reactions.
Wiley, New York 1976, Chap. 4, p. 86ff; Grenrorbitale und Reaklionen
organischer Verbindungen. Verlag Chemie, Weinheim 1979, Chap. 4, p.
133 ff, and references cited therein.
[lo] Dr. A. Heidenreich, Prof. Dr. A. Schweig (Universitat Marburg), private
[ I I] G. Seitz, R. Mohr, W. Overheu, R. Allmann, M. Nagel, Angew. Chem. 96
(1984)885;Angew. Chem. Ini. Ed. Engl. 23 (1984)890.
Herein we report on the synthesis of oxazolidinone and
oxazinanone derivatives by reaction of allylamines and homoallylamines, respectively, with carbon dioxide and iodine via intramolecular cyclization under extremely mild
Treatment of allyl- or homoallylamines with carbon
dioxide in MeOH, followed by treatment with I2 at ambient temperature for 20 h, gave iodoalkyloxazolidinones
[Eq. (e)] o r iodoalkyloxazinanones [Eq. (f)], respectively, in
Formation of Oxazolidinones and Oxazinanones by
Reaction of Allylamines and of Homoallylamines
with Carbon Dioxide and Iodine via Intramolecular
By Takashi Toda' and Yoshinori Kitagawa
Recently, much attention has been focused on the utilization of carbon dioxide in organic synthesis."] However,
almost all reactions of these types are carried out in the
presence of biotin (or its analogues),[21metal complexes,[3*
large amounts of phosphorus compounds,[41strong bases
under high pressure,[51 or combinations of these methods.['.'] Furthermore, the reaction conditions are often
rather severe.
We have been interested in carbon dioxide fixation via
ammonium carbamates under mild conditions: without a
catalyst, at atmospheric pressure, and, if possible, at ambient temperature. Since several aliphatic amines form stable carbamates 1 [Eq. (a)],['] these salts were expected to
Table I . Yields and some physical properties of the oxazolidinones and
oxazinanones. The yields in parentheses are those obtained after prolonged
reaction in the presence of Cs2C0, (see text).
Reac- Amine
(in KBr)
[cm - '1
= alkyl; R' = alkyl, H
61 (70) 117-118.5
60 (90) 83-84
offer certain advantages in carbon dioxide fixation. We
have indeed reported several such reactions.['l For example, intermolecular reactions between ammonium carbamates and oxiranes (or their synthons) give carbamate derivatives including cyclic carbamates [Eqs. (b)-(d)].
R' R2 0
R' = R2 = alkyl, a r y l
R' = alkyl; R2 = H
R = alkyl
R'= H
R = R'
52(80) 134.5-136[a] 1735
41 (60) 142.5-144[a] 1680
+ 1
[a] Decomposition.
[*I Prof. Dr. T. Toda, Dr. Y. Kitagawa
Department of Industrial Chemistry,
Faculty of Engineering, Utsunomiya University
Utsunomiya 321 (Japan)
[**IUtilization of Carbon Dioxide in Organic Synthesis via Ammonium
Carbamates, Part 8.
0 VCH Verlagsgesellschaft m b f f . E)-6940 Weinheim, 1987
fairly good yields (40-709'0). The results and some physical
properties of the products are summarized in Table 1. Pro-
OS70-0833/87/0404-0334 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 26 (1987) No. 4
longed reaction for a week in the presence of Cs2C03 or
Na2C03raised the yields to 70-90%. Since isolation of the
intermediate ammonium carbamates is not necessary and
the oxazolidinones and oxazinanones are the only isolable
products, the reactions constitute one-pot procedures.
Moreover, purification of the products is very easy. The
structures of the products were deduced from their elemental analyses and from the IR or NMR spectra. As
listed in Table 1, all the oxazolidinones exhibit their C=O
absorption band near 1730 cm-', which is in agreement
with a five-membered carbamate. The characteristic,
strong C=O absorptions for the oxazinanones are observed around 1685 cm-'. The scope and limitations of
this reaction are now being studied.
Experimental Procedure
A solution of allylamine (4.0 mmol) in MeOH (4mL) in an ice-cooled bath
was saturated with C 0 2 . l 2 (2 mmol) was added to the solution, and C02was
admitted for a n additional 5 min. The reaction mixture was then stirred for
20 h under C 0 2 at room temperature. The excess iodine was removed by addition of aqueous Na2S20,, and the MeOH was removed in vacuo at 40°C.
Extraction with ethyl acetate, drying over Na,SO,, a n d removal of the solvent gave 5-iodomethyl-2-oxazolidinone,
which was purified by recrystallization from ethyl acetate. The reaction of the homoallylamines was carried out
similarly. Reaction for one week in the presence of Cs2COs (2 mmol) raised
the yields to the values shown in parentheses in Table 1.
Received: October 22, 1986;
revised: January 2, 1987 12 1961 IE]
German version: Angew. Chem. 99 (1987)366
CAS Registry numbers:
amine I. 107-11-9;product I, 107175-73-5;amine 2,69957-80-8;product 2,
107175-74-6;amine 3,52853-55-1;product 3, 107175-75-7;amine 4, 10717579-1; product 4, 107175-76-8;amine 5, 107175-80-4;product 5, 107175-77-9;
amine 6, 2524-49-4;product 6, 107175-78-0;amine 7, 3399-73-3;product 7,
107200-84-0;carbon dioxide, 124-38-9;iodine, 7553-56-2.
[ I ] Reviews: M. E. Vol'pin, 1. S. Kolomnikov, Organomel. React. 5 (1975)
3 13; S. Inoue, N. Yamazaki: Organic and Bioorganic Chemistry of Curbon Dioxide. Kodan-sha, Tokyo 1980, and references cited therein.
121 N. Matsumura, T. Ohba, S. Yoneda, Chem. L e f f .1981, 317; T. Bodnar,
S. J. LaCroce, A. R. Cutler, J. Am. Chem. SOC.I02 (1980)3928.
131 H. Kisch, R. Millini, L J . Wang, Chem. Ber. 119 (1986) 1090; P. Binger,
H.-J. Weintz, ibid. 117 (1984) 654; G. Burkhart, H. Hoberg, Angew.
Chem. 94 (1982) 75;Angew. Chem. Inf. Ed. Engl. 21 (1982)76; Angew.
Chem. Suppl. 1982, 147;D. J. Darensbourg, R. K. Hanckel, C. G. Banch,
M. Pala, D. Simmons, J. N. White, J. Am. Chem. SOC.107 (1985)7463;
T. Aida, S. Inoue, ibid. I05 (1983) 1304;T. Tsuda, Y. Chujo, T. Saegusa,
ibid. 102 (1980)431; Y. Inoue, R. Ohashi, M. Toyofuku, H. Hashimoto,
Nippon Kagaku Kaishi 1985, 533;T. Fujinami, T. Suzuki, M. Kamiya, S .
Fukuzawa, S. Sakai, Chem. Lett. 1985, 199; B. Demerseman, R. Mahe.
P. H. Dixneuf, J. Chem. Soc. Chem. Commun. 1984. 1394; F. Sato, S .
lijima, M. Sato, ibid. 1981. 180; A. Dohring, P. W. Jolly, Tetrahedron
Lett. 21 (1980) 3021; J.-E. Backvall, 0.Karlsson, S. 0. Ljunggren, ibid.
21 (1980)4985; H. Sugimoto, 1. Kawata, H. Taniguchi, Y. Fujiwara, J.
Organomef.Chem. 2666 (1984)C44.
[4] H. J. Bestmann, G. Schmid, Tetrahedron Leff. 1977. 3037; G . Ege, K.
Gilbert, ibid. 1979. 4253.
151 The Kolbe-Schmidt reaction is a typical one of this type; for a recent
example, see L. A. Cate, Synthesis 1983. 385.
[6] Examples of carbonate ester formation from carbonate salts: G . Rokicki, w. Kuran, Bull. Chem. SOC.Jpn. 57(1984) 1662;J. A. Cella, S. w.
Bacon, J . Org. Chem. 49 (1984) 1122.
171 Carbon dioxide fixation reactions by charge transfer or photochemical
processes: S. W. Froelicher, B. S . Freiser, R. R. Squires, J. Am. Chem.
SOC.106 (1984)6863; K. Kitamura, S. Tazuke, Chem. Left. 1983. 1109;
S. Toki, S. Hida, S . Takamuku, H. H. Sakurai, Nippon Kagaku Kaishi
1984. 152.
181 T.Hayashi, Rikagaku Kenkyusho Iho I 1 (1932) 133; H. 8. Wright, M. B.
Moor, J . Am. Chem. SOC.70 (1948)3865; M. Kato, T. Ito, Bull. Chem.
Soc Jpn. 59 (1986)285.
[9] a) T. Toda, Chem. Letf. 1977, 951; Nippon Kagaku Kaishr 1982. 228; N.
Saito, K. Hatakeda, S. 110, T. Asano, T. Toda, Bull. Chern. SOC.Jpn. 59
(1986)1629: b) T. Asano, N. Saito, S. Ito, K. Hatakeda, T. Toda, Chem.
Angew. Chem. Inf. Ed. Engl. 26 (1987) No. 4
Left. 1978. 31 I ; c) for analogous reactions, see: Y. Yoshida, S. Inoue,
ibid. 1977, 1375;J. Chem. Sac. Perkin Trans. 11979. 3146: Y. Yoshida,
S. Ishii, T. Yamashita, Chem. Letf. 1984. 1571.
[lo] Very recently, Cardillo et al. reported similar reactions in which they
used Amberlyst A 26 as a catalyst. However, their concept of utilizing
carbon dioxide is different from ours: G. Cardillo, M. Orena, S. Sandri,
J. Org. Chem. 51 (1986)713.
Synthesis and Properties of
1-CycloheptatrienyIidene-2-cyclopentadienylideneethylene Derivatives
By Takashi Toda,* Norihiko Shimazaki, and
Toshio Mukai
is a novel system composed of fulvene and heptafulvene
units connected by a cumulative double bond. Compound
1 may be considered as a push-pull-type cumulene because of the resonance contribution of the form 1 '. Since
cumulenes have been intensively investigated,I'' this system
is interesting from the viewpoint of the chemistry of both
cumulenes and nonbenzenoid aromatic compounds.
Only a few examples of this type of compound have
been reported in the literature.f21As part of our investigation of compounds containing both cumulene and cycloheptatrienylidene units, we have already reported on cycloheptatrienylideneethylene derivatives 2, which dimerized when prepared.I3]
We have now synthesized derivatives of 1 (which may
be viewed as higher homologues of 2) and investigated
their properties (IR, NMR, and electronic spectra).
bromideL4'with the tetraarylcyclopentadienones 3a-cL5]afforded the corresponding cycloheptatrienylcyclopentadienylacetylenes 4a-c (Table 1). Treatment of these alkynols
a, Aryl = C,H,;
b. Aryl = p - CI - C,H4;
c. Aryl = p - Me0 - C,H,
with thionyl chloride in the presence of pyridine provided
a mixture"] of the corresponding chlorocyclopentadienyl['I, Dr. N. Shimazaki, Prof. Dr. T. Mukai
Department of Chemistry, Faculty of Science, Tohoku University
Sendai 980 (Japan)
1'1 Present address:
Department of Industrial Chemistry, Faculty of Engineering,
Utsunomiya University
Utsunomiya 321 (Japan)
[*] Prof. Dr. T. Toda
0 VCH Verlagsgesellschaft mbH. 0.6940 Weinheim, 1987
0570-0833/87/0404-0335 $ 02.50/0
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dioxide, intramolecular, allylamine, reaction, formation, cyclization, oxazolidinon, iodine, homoallylamines, oxazinanones, carbon, via
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