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Hydrogenolysis of Trisubstituted DichlorophosphoranesЧA New Method for Deoxygenation of Oxophosphoranes.

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CAS Registry numbers:
( 4 a ) , 2304-94-1;( 4 b ) , 63216-38-6;( 4 c ) , 63216-39-7;( 4 d j , 3303-84-2;( 4 e j .
63216-40-0;
( 5 a ) . 5105-78-2:( 5 h i , 6321 6-41-1;(5 c), 63216-42-2;( 5 d ) , 57294( h h ) , 63216-44-4;
(6c), 63216-45-5:
( 7 a ) , 63216-46-6;
38-9;(Se),63216-43-3;
( 7 b ) , 63216-47-7:(7c), 63216-48-8;( 7 d ) , 63216-50-2;( a h ) , 63216-51-3;
( 8 d ) . 63216-53-5:( l o ) , 63216-54-6,
( 1 1 ), 63216-55-7;trihutylstannyl azide,
17846-68-3;cis-4-cyclohexen-1,2-dicarboxylicanhydride, 935-79-5:succinic
thioanhydride, 3194-60-3
[CH3CN: h,,,(~)=230 (sh, 16300), 244 (18400), 277nm (sh,
SSOO)] also complies with expectations. Secondary photolysis
of (4) to ( 3 ) and other products can largely be avoided.
The complete absence of &-cleavage on photolysis of (3)
is surprising.
H . R. Kricheldorf, E. Leppert, Synthesis 1976, 329.
[2] J . L u i j t m , M . Janssen, G. J . M . can der Kerk, Rec. Trdv. Chim. Pays-Bas
81, 202 (1962).
[3] H . R. Kricheldorf, E. Leppert, Makromol. Chem. 158, 223 (1972).
141 R. H . Sifferd, !T du Viyneaud, J . Biol. Chem. 108, 753 (1935).
[5] P. H . Bentley, H . Gregory, A. H . Laird, J . S . Morley, J. Chem. Soc.
1964, 61 30.
[6] M . Hont, I/: du Vigneaud, J. Biol. Chem. 127, 43 (1939).
[7] E. Scknabel, Justus Liebigs Ann. Chem. 702, 188 (1967).
[S] W L . F . Armarego, P. A . Reece. J. Chem. Soc. Perkin Trans. I 2313
(1 974).
Compound (1) (2.0g, 11.2 mmol) is dissolved in (2) (90g)
and irradiated for 3d with eight low-pressure mercury lamps
(253.7nm) in a Rayonet reactor at 30 to 35°C. Excess (2)
is distilled off, and compound (3) (1.05g) crystallizes from
the oily residue at -20°C after addition of C H 3 0 H (50ml).
Chromatography of the mother liquor on S O 2 (3OOg) with
benzene ( 5 1) yielded unreacted ( I ) (320mg), (4) (IWmg),
and (3) (860mg; total yield 64%; m.p. 88"C, CH30H).
[I]
1,6-cis-7,8-Diphenyl-2,5-dioxabicyclo[4.2.0]oct-7-ene
(3)f6]:
6,7-Dipheny1-2,3-dihydro-l,4-dioxocin
(4)[61:
By Gerd Kaupp and Michael Stark[*]
Irradiation of 1,2-diphenylcyclobutenederivatives generally
leads to elimination of diphenylacetylene (a-cleavage) or to
oxidative formation of cyclobuta[l]phenanthrenes (dehydrocyclization)[', '1. The reaction course depends upon whether
the phenyl groups can undergo free rotation after excitation
of the cis-stilbene chroniophore, or whether the partial rotations are sterically hinderedf31.We now report a P-cleavage,
a rare event in photolyses of cyclobutenes['.4], which permits
a ready synthesis of dihydrodioxocin (4) starting from the
bicyclic (3).
Photoaddition of diphenylacetylene (1 ) to p-dioxene (2)[51
affords (3) ['H-NMR (CCl,): 6=7.75-7.15 (IOH, m), 4.95
(2 H, s), 4.0-3.5 (4 H, sym. AA'BB')]L6]. cis-Linkage of the
rings in (3) is confirmed by catalytic hydrogenation to the
symmetrical ('H- and "C-NMR spectra) derivative ( 5 ) (m.p.
134-135°C)[6]. Compound (3) displays a UV spectrum having pronounced fine structure [CH3CN: h,,,(~)=225 (22500),
229 (sh, 20500), 294 (16600), 298 (sh, 16500), 315 (sh, 10400),
319nm (sh, 8500); EPA, 77K: 228, 233, 236.5, 284 (sh), 296.5,
309, 322 nm] and an intense fluorescence spectrum showing
only a hint of fine structure even at 77K [cyclohexane:
=; ; : .?
383 nm,Qfl=0.32;EPA,77 K:ca.355 (sh),369, cu. 385 nm
(sh)]. Disrotatory opening of the bicyclic (3) to the eight-membered ring (4) with a quantum yield @=0.33 competes with
fluorescence. The symmetrical structure of (4) is confirmed
by the 'H-NMR spectrum [CCI,: 6 = 7.2-6.9 (IOH, m), 6.53
(2H, s), 4.08 (4H, br s, AvI 2=2Hz)][6]. The UV spectrum
[*I Univ.-Doz. Dr. G.Kaupp, Dip].-Chem. M. Stark
Chemisches Lahoratorium der Universitat
Albertstrasse 21, D-7800 Freiburg (Gerinany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemisehen Industrie.
552
A solution of compound (3) (l.Og, 3.8mmol) in benzene
(500ml) is irradiated for 1h with a high-pressure mercury
lamp (Hanau TQ 150) through a Pyrex filter under Nz at
25 "C. After concentration, compound (4)(850 mg) crystallizes
from C H 3 0 H (15ml) at -20°C. The mother liquor still contains 30mg of (4) (total yield 88%; m.p. 114"C, CH30H)
and 30mg of (3).
Received: June 8, 1977 [Z 756 IE]
German version: Angew. Chem. 89,555 (1977)
CAS Registry numbers:
( 1 ), 501-65-5:( 2 1 , 543-75-9;( 3 ) . 63163-65-5;( 4 ) , 63163-66-6;
( 5 ) , 6316367-7
G. Kuupp, Angew. Chem. and Angew. Chem. Int. Ed. Engl., in press.
[2] G. Kuupp, M . Srurk, Chem. Ber.. in press. H . H . White, J . P. Anhalt,
Tetrahedron Lett. 1965, 3937.
[3] G. Kaupp, M . Stark, E. Teuf'l, Lecture at Chemiedozententagung in Marburg (March 23, 1977).
[4] J. M . Labrum, J . Kolc, J . Mirhl, J. Am. Chem. Soc. Y6, 2636 (1974).
Cyclobutenediones: N . Obata, 7: Takiiawa, J. Chem. Soc. Chem. Commun.
1971, 587: 0. L . Chapman, C . L . Mcliirosh, L . L. Barber, ihid. 1971, 1162.
[S] R. I . M e l t i e r , A. D . Lewis, A. Fischman, J . Org. Chem. 2 4 , 1763 (1959).
[6] All new compounds gave correct elemental analyses. ( 3 j and ( 5 j are
stable up to at least 210°C ( > 6 h ) ; ( 4 ) rapidly changes above 160°C.
[I]
Hydrogenolysis of Trisubstituted Dichlorophosphoranes-A New Method for Deoxygenation of 0 x 0 phosphoranes
By Mitsuo Masaki and Noboru Kakeyay]
Although tertiary phosphanes are versatile reducing agents,
their use in industry is very limited, mainly owing to the
lack of economical methods for regenerating the reagents
from oxophosphoranes, i. e. from their oxidation products.
We recently reported a convenient method for the reduction
of the oxophosphoranesI'], involving their treatment with
oxaIyl chloride and reduction of the resulting dichlorophosphoranes with thiols in the presence of trimethylamine[zl. We
have now found an even simpler method, which is illustrated
by equations (a) and (b).
[*] Dr. M. Masaki, N. Kakeya
Polymer Research Laboratory, Ube Industries, Ltd.
Minami-kaigan, Goi, Ichihara. Chiba 290 (Japan)
Aiigew. Chem. l n r . Ed. Eiiyl. 16 ( 1 9 7 7 ) N o . 8
Table 1. Reduction of oxophosphoranes ( I ) to phosphanes ( 3 ) .
[a] Chlorination and hydrogenolysis were performed under conditions similar t o the case of I I a ) (see Experimental).
[b] Chlorination conditions: 1 h a t 60°C and then 1.5 h at 100°C: hydrogenolysis conditions: 18O"C, 2 h.
When tri-n-butyl(oxo)phosphorane(1 a) is treated with an
equimolar amount of chlorine under carbon monoxide pressure in carbon tetrachloride at room temperature, an exothermic reaction occurs to give tri-n-butyl(dich1oro)phosphorane
( 2 u ) and carbon dioxide. The formation of (Za) was confirmed by treatment of the reaction mixture with aniline and
triethylamine to give tri-n-butyl(pheny1imino)phosphorane
[isolated in 94% yield based on ( I a)].
The dichloro compound ( 2 u ) underwent hydrogenolysis
at 160°C and cu. 98 bar of hydrogen without any catalyst
to give tri-n-butylphosphonium chloride, which was easily
converted into the free base ( 3 a ) either by neutralization
with sodium hydrogen carbonate or by thermal dissociation
in refluxing toluene (further examples are shown in Table 1).
Oxo(tripheny1)phosphorane ( I c) is known to be converted
into the corresponding dichloro compound ( 2 c ) by phosgeneL3].The reaction of eq. (a) takes place with ease even
under conditions where phosgene is scarcely formed from
carbon monoxide and chlorine without catalyst. When a solution of chlorine in carbon tetrachloride is treated with ca.
59 bar of carbon monoxide at 60°C for 1 h, neither phosgene
nor oxalyl chloride was formed and the major amount of
chlorine is recovered.
Amino Sugars and N-Glycosides by Oxyamination of
Unsaturated Carbohydrate Derivatives[**]
By IngoEfDyong, Quan Lam-Chi, Gerhard Schulte, Bert FraserReid, and John L. Primeuuyl
The synthesis of amino sugars has so far remained a difficult
problem. Only 2-amino-2-deoxyaldoses have become more
readily accessible through studies by Lemieux et al."], but
in the case of all other amino sugars (e.g. 3-amino-3-deoxyaldoses) recourse is still being made to tedious multi-step syntheses. As has been found independently by each of our
research groups, the single-step cis-oxyamination of olefins
developed by Sharpless et ul.rzl provides a particularly useful
and widely applicable method in carbohydrate chemistry for
the synthesis of nitrogen-containing sugar derivatives.
3,4,6-Tri-O-acetyl-D-glucal
( I ) reacts with chloramine-T,
the sodium salt of N-chloro-p-toluenesulfonamide,
in the presence of catalytic amounts of O S O ~ [to~ give
I the four products
( 2 ) - ( 5 ) , which can easily be separated by chromatography
on silica gel with toluene/diisopropyl ether/2-propanol
(20:4: 1) and are readily isolable in crystalline form. (2) [m.p.
159-1 6 0 T , [ct]$' = 70.9" (CHC13),yield 10.3
after acetylation to ( 2 a ) [m.p. 125-226"C, [.]6"= $74.4" (CHCL,)],
is identical with the known 1,3,4,6-tetra-O-acetyl-N-toluenesulfonyl-cc-D-gl~cosamine~~~.
Compounds (3)-(5)
are tri-0acetyl-N-tosyl-cc-D-glucosylamines [total yield 30.6 %]. Reac-
OAc
(6)
rOAc
T
rOAc
rOAc
IkTos
Experimentctl
(1)
A glass cylindrical vessel containing a solution of ( I a)
(2.18g, 10mmol) and chlorine (0.71 g, 10mmol) in carbon
tetrachloride (15ml) was charged in an autoclave, which was
then pressurized with CO to ca. 59 bar at 25°C. The reaction
mixture was shaken for IOmin, during which the temperature
of the mixture rose to 60°C at the highest by an exothermic
reaction. The reaction mixture in the vessel was stripped of
solvent and toluene (50ml) was added. Some (ca. 35ml) of
the toluene was evaporated to remove the remaining carbon
tetrachloride. The vessel containing the resultant toluene solution of ( 2 u ) was charged in an autoclave, which was pressurized with hydrogen to ca. 98 bar. The mixture was shaken
at 160°C for 1.5h, and then neutralized with aqueous
NaHC03. According to gas chromatography the reaction
mixture contained 1.82 g of (312) and 0.21 g of (1 a ) .
Received: May 23, 1977 [Z 761 IE]
German version: Angew. Chem. 89, 558 (1977)
CAS Registry numbers:
( I a ) , 814-29-9; ( I b), 78-50-2; ( I c ) . 791-28-6: ( Z a i , 17417-07-1; ( Z b ) ,
22402-74-0: ( ? c ) , 2526-64-9; ( 3 a ) , 998-40-3; (361,4731-53-7; (3c), 603-35-0
M. Musaki, K . Fukur, Chem. Lett. 1977, 151.
[2] Reduction of trisubstituted dichlorophosphoranes of type ( 2 ) with various reducing agents were previously known; reduction with molecular
hydrogen is new (see references cited in Ref. [I]).
131 G . W u m c k , K . Winrerhrrger. H . Geierkaas, Z. Anorg. Allgem. Chem.
369, 33 ( I 966).
[l]
Aiigew. Chpm. l i i t .
x,],
+
E d . E i l g l . 16 ( 1 9 7 7 ) NO. 8
~OAC
(2), R = H
( 2 a j . R = Ac
OR'
( 3 ) , R' = H, R2 = R 3 = Ac
( 4 ) , R' = R3 = Ac, R2 = H
(5/,R' = R2 = Ac, R 3 = H
r OAC
rOAc
HO
@oEt-Ho@OH
( l o j , R = Tos
(11). R = H * HC1
(12)
-~
["I
Prof. Dr. 1. Dyong, Q. Lam-Chi, G. Schulte
Organisch-Chemisches lnstitut der Universitat
Orleans-Ring 23, D-4400 Munster (Germany)
Prof. Dr. B. Fraser-Reid, J. L. Primeau
Guelph-Waterloo Centre for Graduate Work in Chemistry
University of Waterloo
Waterloo, Ontario N2L 3G1 (Canada)
p*] Synthesis oC Biologically Important Carbohydrates, Part 12. This work
was supported by the Landesamt fur Forschung des Landes Nordrhein-Westfalen, the Fonds der Chemischen Industrie, and the National Research Council
of Canada: -Part I 1 : I . Dyony. R . Knollmann, N. Jersch, H. Luftmann, Chem.
Ber., in press.
553
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hydrogenolysis, deoxygenative, method, oxophosphoranes, dichlorophosphoranesчa, trisubstituted, new
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