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Carbon MonoxideWater as a Reducing Agent Formation of Selane from Selenium.

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both cycloreversions the gain in aromatic resonance energy is
already utilized in the transition state; for (6) it is about
3.2 k 1.0 kcal/mol smaller than for "~,p-dibenzene"[~'.
Despite the highly negative heat of reaction of ca. -35 kcal/
mol the transition state occurs late, i. e. it lies on the side of
the components. The weakly negative entropy of activation,
on the other hand, shows that the arenes are formed in a
highly ordered transition state, which still has no new degrees of freedom. Hence, in the retrocleavage the adduct (6)
passes through a reaction profile typical for Dieis-Alder reactions in the reverse direction, and the frontier orbital modell']
developed for the forward reaction should hold here too.
Table 1. Di- and tetra-substituted 5,5'-dimethyl-2,2- spirobiindans [a]
f 9)
Received: October 29, 1979 [Z 428 I€]
German version: Angew. Chem. 92, 307 (1980)
111 Exceptions are the reaction of benzene with dehydrobenzene [R. G. Miller,
M. Stiles, J. Am. Chem. SOC.85. 1798 (1963)l and with dicyanoacetylene [E.
Ciganek, Tetrahedron Lett. 1967, 33211.
[2] W. Grimme, E. Schneider, Angew. Chem. 89,754 (1977); Angew. Chem. Int.
Ed. Engl. 16, 717 (1977).
[3] L. A. Paquefre, J. C HoweN, Tetrahedron Lett. 1970. 2259.
141 The errors are the double standard deviations of the linear regression used for
the kinetic analysis; R = 1.986 cal K ' mol I .
[ 5 ] For equal strain energy in "o,p'-dibenzene" and in {6), the difference in their
heats of decomposition is equal to the negative difference in the heats of hy-4.8 t0.5 kcal/mol) and naphthalene
drogenation of benzene (AHhydr(ll
= 1.7 0.5 kcal/mol) to their 1.4-dihydro compounds. The calculation was carried out using the data given in J. D. Cox, G. Alcher: Thermochemistry of Organic and Organometallic Compounds. Academic Press,
London 1970, and the standard heats of formation of cyclohexadienes 161 and
tetralin (71.
161 R B. Turner, B. J. Mallon. M. Tichy, W van E. Doering, W. R. Roth, G.
Schroder, J. Am. Chem. SOC.95, 8605 (1973).
171 W. D. Good, S. H. Lee, J. Chem. Thermodyn. 1976, 643.
[8] a) R. Sustmann, Pure Appl. Chem. 40,569(1974); b) K. N. Houk, Acc. Chem.
Res. 8, 361 (1975).
(10) [bl
["I Optically Active Aromatic Spiranes, Part 10. This work was supported by
the Osterreichischer Fonds zur Forderung der wissenschaftlichen Forschung
(Project No. 3033).-Part 9: [I].
0 Verlag Chemre. GmbH, 6940 Weinherm, 1980
(in acetone)
+ 45.0"
Received: November 2, 1979 [Z 430 IE]
German version: Angew. Chem. 92, 318 (1980)
[I] H. Neudeck, B. Richter, K. Schlogl, Monatsh. Chem. 110, 931 (1979).
(2) A. Meyer, H. Neudeck, K. Schlogl, Chem. Ber. 110, 1403 (1977).
(31 H. Neudeck, K. Schlogl, Chem. Ber. IiO, 2624 (1977).
[4] H. Neudeck, K. Schlogl. Monatsh. Chem. 110. 541 (1979).
cf. S.
151 Note added inproofi For the isomeric 1 ,i'-spirobi[benz(e]indan]-system,
Imajo, A. Nakamura, K . Shmgu, A . Karo, M. Nakagawa, J. C. S . Chem. Commun. 1979, 868.
161 On the C D of 2,2-spirobiindanes see: E. Langer, H. Lehner, H. Neudeck, K.
Schlogl. Monatsh. Chem. 109, 987 ( 1 978); chiroptical properties of I,i'-spirobiindans: J. H. Brewster, R. ?i Prudence, J. Am. Chem. SOC.9s. 1217 (1973).
and references cited therein.
Carbon Monoxide/Water as a Reducing Agent:
Formation of Selane from Selenium[']
By Noboru Sonoda, Kiyoshi Kondo, Kiyoyuki Nagano,
Nobuaki Kambe, Fumihiko Morimoto"]
One of the striking applications of carbon monoxide in organic or inorganic chemistry is its use as reducing agent. In
[*I Prof. Dr. K. Schlogl, Dr. H. Neudeck
Institut fur Organische Chemie der Universitat
Wahringerstrasse 38. A 1090 Wien (Austria)
acid in benzene to the bishexadiene (9), in which the two vinyl groups are essentially fixed in the orthogonal planes. Finally, catalytic dehydrogenation of (9) (Pd- -C in boiling
dioxane with passage of 0 2 ) afforded the desired product
(10) in 90% yield as colorless crystals of m.p. 185-189 "C
(from benzene/methanol). (9) could also be dehydrogenated
with dichlorodicyanobenzoquinone in benzene (3 h at 20 "C)
to give (10) in 70% yield.
The configuration (2R) (cf. iz.31)
and the enantiomeric purity @=loo%) of (+)-(lo)clearly follow from those of the
educt (+)-(2R)-(1)[*].
By Horst Neudeck and Karl Schlogl[''
Optically active 2,2'-spirobiindanes of known chirality and
enantiomeric purity-such as ( + ) - ( 2 R ) - ( l ) , R1= RZ= Hare accessible via chiral tricarbonylchromium complexes of
the corresponding 1-oxoindans['I. This enables the synthesis
of numerous 5 3 ' 4 - and 5,5',6-trisubstituted 2,2'-spirobiindan~.'~.~],
which are of particular interest for testing approximations for chirality functions['?
We have now synthesized the title compound, a hitherto
unknown spirosystem
containing two mutually orthogonal naphthalene units, which should be of interest, inter
alia, because of its chiroptic properties (cf. 16]).
Optically pure ( 2 R ) - ( l ) ( R i = R 2 = H , [ L Y ] ~ = +4.6" in
acetone)12]was acylated with succinic anhydride/A1CI3in nitrobenzene to the bis-oxo acid (2) (cf. Table 1) whose dimethy1 ester (3) could be smoothly hydrogenated with H2/
Pd--C in 2-propanol to the bis-butyrate (4). The corresponding dicarboxylic acid (5) could be cyclized with polyphosphoric acid (5 h, 100°C) to the biscyclohexenone (6). The
hydrocarbon (7) was accessible from (6) by hydrogenation
(H2/Pd --C in propanol/benzene), and the diol (8) by reduction with LiAIH,. (8) was dehydrated with p-toluenesulfonic
[a) All compounds are thin-layer chromatographically pure; their structures are
confirmed by 'H-NMR and mass spectra. [b] 'H-NMR (CDCI,): 6=8.01 (m.
2H), 7.73 (m, 2H), 7.50 (m, 4H). 7.24 ( s , 2H), 3.33 (s, 4H), 3.20 (s, 4H). 2.69 (s,
6H); UV (n-heptane): A,,, [nml (Ige): 233 (5.30), 258 (4.43), 285 (4.37), 292
(4.38). 297 (4.34), 312 (3.95). 319 (3.72), 327 (4.03); 1. :"= + 124.0 (c=2.0 in
CHCId; C D (n-heptane): A [nm] (Ae): 231 ( - 312), 239 ( + SSS), 267 ( + 2.89), 292
(-6.32), 311 (-0.92). 312 (-1.27). 321 (-0.66). 324 (-0.36). 328 (-1.81).
C27H24 (348.5).
( + )-(2R)-5,5'-Dimethyl-2,2-spirobi(2,3-dihydro-lHc yclopenta[a]naphthalene)A Chiral Spirohydrocarbon Containing
Orthogonal Naphthalene Units[**]
( '1
Prof. Dr N. Sonoda ['I, Dr. K. Kondo, K. Nagano, N. Kambe,
F. Morimoto
Department of Petroleum Chemistry, Faculty of Engineering,
Osaka University
Suita, Osaka 565 (Japan)
Author to whom correspondence should be addressed.
Angew. Chem.
Ed. Engl. 19 (1980) No. 4
this connection, there has been increasing interest in developing catalysts active at low temperature for the water gas
shift reaction, and in establishing a convenient homogeneous
hydrogenation system using carbon monoxide and water['].
During the course of our studies on the selenium-catalyzed
carbonylation of various compounds with carbon monoxideL3],we found that metallic selenium is readily reduced to
selane (H2Se) by carbon monoxide and water in the presence
of base under mild conditions [eq. (l)].
Se + CO + H 2 0
H2Se + C 0 2
The yield of HzSe is quantitative. The reaction proceeds at
25"C/1 bar CO, but is accelerated at higher pressure and
temperature. To obtain solvent-free H2Se14],water can be
used as reaction solvent; in this case 60 "C and 5 bar were required. Acidification of the reaction mixture with sulfuric
acid liberated HzSeIsl,which was trapped in a receiver cooled
to - 196 "C (see Experimental).
We assume that the reaction proceeds via carbonyl selenide16' [eq. (2)J.
Se + CO
+ H2Se
+ C02
Murai, Tetrahedron Lett 1975. 1969 K. Kondo, K. Muraia, N . Miyoshr. S.
Murai, N . Sonoda, Synthesis 1979, 735, K. Kondo, N . Sonoda, H. Sakurai,
Chem. Lett. 1974, 1429; K . Kondo, N . Sonoda, S. Tsutsumr, ibid. 1972. 373.
[4] In organic solvents such as acetonitrile and tetrahydrofuran, the reaction proceeded more smoothly than that in water
I51 Production of H2Se: D. L. Klayman, T S. Grffin. J. Am. Chem. SOC.9.5, 197
(1973); F. Fehb in G. Brauer: Handbook of Preparative Inorganic Chemistry.
Vol. 1. Academic Press, New York 1963, p. 418; H. Reinboldt in HoubenWeyl-Miiller: Methoden der Organischen Chemie. Vol. 1X. Thieme, Stuttgart 1955, p. 953.
[61 K. Kondo, S. Yokoyama, N . Miyoshi, S. Murai, N. Sonoda, Angew. Chem. 91.
760 (1979); Angew. Chem. Int. Ed. Engl. 18, 691 (1979); K. Kondo, S. Yokoyama. N . Miyoshi, S. Murai, N. Sonoda, ibid. 91, 761 (1979) and 18. 692
(1979), respectively.
X-Ray Structure Analysis of
Bis( 0,
a Bicyclic Dimer Held Together by q6-C6H5/Sn"
By J. L. Lefferts, M. B. Hossain, K. C. Molloy, D. van
der Helm, and J. J. Zuckerman"]
The tin(I1) dithiophosphate ester Sn[SzP(OC6H5)2]2,
m. p.
125.5-126.5 "C, has been synthesized by the reaction of dimethoxytin(I1) with 0,O'-diphenyldithiophosphoric acid
(molar ratio 1:2) in benzene:
It could prove possible to develop a catalytic cycle on this basis.
Sn(OCH3)?+ ~ H S P ( S ) ( O C ~ H+S2CH30H
+ Sn[S2P(OC6Hs)2]2
and characterized by t19"Sn Mossbauer [Z.S. = 3.78 0.02;
Q.S. =1.06t0.04 mm/s] and mass [m/e=682 (2.9%) M + ]
spectrometry, as well as by elemental analysis. A triclinic single crystal o,f space group P i [ a = 10.499(5), b = 13.948(7),
c=9.291(4) A; a=99.18(6)', p=95.71(5)", y=91.80(5)"] was
studied by MoKa X-radiation and refined to a final R value
of 2.9% for 5517 reflections.
Metallic selenium (0.400 g, 5 mmol), water (10 g), and N methylpyrrolidine (1.04 ml, 10 mmol) are placed with a magnetic stirring bar in a 50-ml stainless steel autoclave, and the
apparatus is then flushed several times with CO and finally
charged with CO at 5 bar. The reaction is carried out at
60°C for 7 h with vigorous stirring. On completion of the
reaction (reaction mixture becomes pale yellow and homogeneous) the resulting gas (4.5 mrnol C 0 2 ) is collected in gas
sampler and analyzed. Cautious addition of well degassed
aqueous sulfuric acid ( 1 0 ~10
; ml, ca. 50 mmol) to the solidified solution mixture at - 78 "C followed by distillation
from the autoclave at - 5 "C/10 torr directly into a tube
cooled at - 196 "C gives H2Se containing COz. Trap-to-trap
distillation at - 41 to - 39 "C/760 torr affords pure H,Se
(b.p. -41.3"C). The yield (82%) was determined by gravirnetry after oxidation of H,Se with oxygen at room temperature in the presence of triethylamine (2.02 g, 20 mmol) in
THF (10 ml) to give selenium (0.320 g, 4.1 mmol) and water.
Received October 29, 1979 [Z 429 IE]
German version: Angew. Chem. 92, 317 (1980)
[I] A new system of utilizing the reducing ability of carbon monoxide, Part 1.
I21 H:C. Kang, C. H. Mauldin, T. Cole, W Slegeir, K. Cann, R. Pettit, J. Am.
Chem. Soc. 99, 8323 (1977); C.-H. Cheng, D. E. Hendriksen, R. Eisenberg,
ibid. 99, 2791 (1977); R. M. Laine,R. G. Rinker, P. Ford, ibid. 99, 252 (1977);
R. M. Laine,D. W . Thomas, L. W. Cory, S. E. Buttrill, ibid. too, 6527 (1978);
R. M. Laine,rbrd. 100,6451 (1978); C:H. Cheng, R. Eisenberg, ibid. 100, 5968
(1978); P. C. Ford, R. G. Rinker, C. Ungermann, R. M. Laine, V. Landis, S. A.
Moya, ibid. t00, 4595 (1978); K. Cann, T. Cole, W.Slegeir, R. Pettit, ibid. 100,
3969 (1978); T Yoshida, Y. Ueda, S. Otsuka, ibid. 100, 3941 (1978); R B.
King, C. C. Frazrer, R. M. Hones, A . D. King, Jr., ibid. 100, 2925 (1978); J. W
Rathke, H . M. Feder, ibid. 100, 3623 (1978).
131 N Sonoda, T. Yasuhara, K . Kondo, T. Ikeda, S. Tsutsumi, J. Am. Chem. SOC.
93, 6344 (1971); K. Kondo, N. Sonoda, S. Tsutsumi, J. Chem. SOC.Chem.
Commun. 1972, 307; K. Kondo, N. Sonoda, H. Sakurai, Bull. Chem. Soc.
Jpn. 48, 108 (1975); N. Sonoda, G. Yamamoto, K. Natsukawa, K. Kondo, S.
Angew. Chem. Int. Ed. Engl. 19 (1980) No. 4
Fig. 1. Molecular structure of dimeric bis(0,O'-diphenyldithiophosphato)tm(ii)
:Sn"[S2P(OC6Hs)2]2) held together by bifurcated, three-coordinated sulfur
atoms and 76-C6HSinteractions with the tin(li) lone electron pairs.
[*] Prof. Dr. J. J. Zuckerman, Dr. M. B. Hossain, Dr. J. L. Lefferts, Dr. K. C.
Molloy, Prof. Dr. D. van der Helm
University of Oklahoma. Department of Chemistry, Norman, OK 73019
[**I Oxy- and Thio-Phosphorus Acid Derivatives of Tin, Part 3. Our work is
supported by the U S . Office of Naval Research and the National Science Foundation (Grant No. CHE-78-26584) (J. J. Z.) and the National Cancer Institute,
U S . D.H.E.W. through Grant No. CA-17562 (0.
u. d. H.).-Part
2: K. C. Molloy, M. B. Hossain, D. van der Shelm, J. J. Zuckerman, Inorg. Chem. 18, 3507
0 Verlag Chemie, GmbH, 6940 Weinheim. 1980
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reducing, formation, agen, selenium, monoxidewater, carbon, selane
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