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Isomerization of Dimethylphosphane Sulfide on Transition Metals.

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C 0 M M U N I CAT1 0N S
P-bonded complexes (5a-b) occurs in which the ligand
is now bonded as thiophosphinic acid.
Thus the conversion of ( 1 ) into (2) proceeds under relatively mild conditions on a metal. Thiophosphinic acid ( 2 )
is apparently only stable in the complexed state since ( I )
is immediately regenerated from the free ligand.
(
(5)
Isomerivltion of Dimethylphosphane Sulfide on Transition Metals[**]
0
+
7
H3
S = PI - H
+ (3)
On reaction of ( 1 ) with IMn(C0)S ( 3 c ) the temperatures
for CO substitution and isomerization of ( 4 c ) to (5c) are
almost identical (70°C) and (OC)41MnP(CH3)2SH( 5 c ) is
therefore formed directly.
By Ekkehard Lindner and Hans Dreher"]
Dedicated to Professor Eugen Miiller on the occasion of his
70th birthday
In principle secondary phosphane sulfides ( 1 ) and thiophosphinic acids ( 2 ) , R2HPS and R2PSH, can be assumed to
exist in a tautomeric equilibrium"]:
I<
I
I1 P S
I
H
(1)
B
:P-SH
I
H
(2)
At room temperature, however, the system lies completely
on the side of (1)[21.
Temperature-dependent 'H-NMR studies have shown that
the P-H bond in (CH3)2HPS (1) is cleaved only above
180°C,and it appears rather unlikely that the thiophosphinic
acid (CH,),PSH (2) can exist under these conditions.
Accordingly[21,compound ( I ) initially coordinates via sulfurc3'to carbonylmetal systems such as XMn(CO), (3a-b)
with replacement of one CO ligand to form the S-isomeric
complexes (4a-b), which are sparingly soluble in cyclohexane:
Available evidence suggests that the isomerization of ( 4 )
to ( 5 ) proceeds via an intramolecular mechanism. The compositions and structures of the yellowish brown and orange
monomeric diamagnetic linkage isomers ( 4 a - b ) and (5a--c)
follow from elemental analysis and mass, IR, 'H-NMR, and
31P-NMR spectra (see Table I).
Table 1. 'H-NMR spectra of (CH,),HPS ( I ) and the hromotetracarbonylmanganese complexes ( 4 b ) and ( 5 6 ) (solution in CDCI,, TMS as standard.
recorded at 60 MHz).
Cpd.
Coupling constants
J CHzl
(I)
(46)
14
14
(5b)
8
448
490
-
Chemical shifts
6 [PPml
4.5
4.5
-
-
4.5
1.9
1.9
2.0
1.4
7.0
-
-
3.7
[a] The large coupling constant of 45&500 Hz is characteristic of all protons
bonded directly to phosphorus [4].
(4)
If the temperature is raised by about 5°C in each case,
then quantitative isomerization to the cyclohexane-soluble
~~~
[*I
Prof. Dr. E. Lindner and Dip].-Chem. H. Dreher
Lehrstuhl fur Anorganische Chemie I1 der Universitat
74 Tiibingen 1, Auf der Morgenstelle (Germany)
[**I The Behavior of Mono- and Diorganylphosphane Sulfides towards
Metal Carbonyl Systems, Part 4. This work was supported by the Deutsche
Forschungsgemeinschaft and the Fonds der Chemischen 1ndustrie.-Part
3: ref. [3].
416
Procedure:
(CH3)2HPS ( 1 ) (4mmol) and ( 3 a ) or ( 3 b ) (4mmol) are
heated together to 40 or 50°C, respectively, in cyclohexane
(30ml)until evolution of gas has ceased; the mixture is filtered
and the precipitate is washed with cold light petroleum. Recrystallization from CH2Cl2/light petroleum affords analytically
pure (4a) or ( 4 6 ) . To prepare (Sa-b) a suspension of
(4a-b) in cyclohexane is heated to 45 or 55"C, respectively,
until dissolution is complete. Themixture is filtered, the solvent
removed under vacuum, and the product recrystallized from
light petroleum.
Received: December 6, 1974 [Z 185 IE]
German version: Angew. Chem. 87, 447 (1975)
Publication delayed at authors' request
Angew. Chem. inremar. Edit. 1 Vol. 14 ( 1 9 7 5 ) 1 No. 6
CAS Registry numbers:
i l l . 6591-05-5; /hi.
14100-30-2: (3bi, 14516-54-2:
i 3 c ) . 14879-42-6; / l a ) , 54751-04-1 : 14h). 54751-05-2:
( 4 c j . 54751-06-3; (5~). 54751-03-0; i 5 h i . 42593-43-1 ;
i S c i . 54751-07-4
K . Susar in: Methoden der organischen Chemie (Houben-Weyl-Miiller),
4th Edit., Vol. Xlljl. Thieme. Stuttgart 1955, p. 212.
[2] L . Muirr, Helv. Chim. Acta 49, 1249 (1966): references cited therein.
[3] E. Lindnrr and W-P. Meirr, J. Organometal. Chem. 67, 277 (1974).
[4] L. Mairr, Top. Phosphorus Chem. 2, 43 (1965).
[I]
hydrogenolysis of the 5-carbonyl group takes place as side
reaction.
The quoted ring coupling in the hydrogenated sulfone (3)
is proven by chemical correlation with the hydrogenated sulfone /9)"], whose structure is confirmed by the chemical
shift and coupling constant of the proton at C-I (6 = 3.48, broad
triplet, 5=8 Hz) (Table 1). From the positive Cotton effect
( A E * ~ ~ 1.64)it
=
would appear that the phenylsulfonylmethyl
group is R, i. e. in an equatorial position.
+
Synthesis of D-Norgestrel"'
By Gerhard Sauer, UIrich Eder, Gregor Haffer, Giinter N e d
and Rudolf Wiechert"]
D-Norgestrel[2s31 (17cc-ethynyl-18-methyl-19-nortestosterone ( 8 ) is a clinically proven, extraordinarily strong progestational and ovulation inhibiting steroid. The regioselective sulfonylmethylation of optically active 7a P-ethyl-6H-7,7a-dihydroindan-1,5-dione (/)I4]opens the possibility of a new, technically simpler synthesis of D-norgestrel.
Table 1. Prepared compounds 121, (3). and ( 9 )
+
(2). m.p. 124--125°C (CCI,): [x]u=
198" ( I '% in CHCI,): IR (KBr):
1750 (5-ring ketone). 1675 (unsat. ketone), I140 and 1300/1310 c m - ' (SO.):
U V ICHJOH): E Z I ~ = 1 1 700, E Z ~ I = 10400: CD (dioxane): A E , s , = -34.9.
A E ~ O Z+=1 1 . 8 , A ~ . j 1 =
1 +12.5: 'H-NMR (CDCIj):6=0.98(3H, t, J = 7 . 5 H z ,
CHJ-CHZ), 4.09 and 4.36 (2H. AB, J = 1 3 H z , C H z - S O z ) , 7.82 (2H, dd,
J = 8 H z , J = 2 H z . a r o m . H). 7.4-7.7 (3H. m a r o m . H).
13). m.p. 16&161'C (ethyl acetate): [ X I , = +82 (l';*,in CHCI,); IR ( K B r ) :
1732 (5-ring ketone), 1715 (6-ring ketone). 1310/1315 and 1 1 4 5 / 1 1 5 5 c m ~ '
+4.19: 'H-NMR (CDCI,): 6=0.94 (3H. t.
(SO,); CD (dioxane):
J = 7 . 2 Hz.CH,-CH2).2.Y8(l H.AB-X. J = 4 Hz. J = 1 6 Hz.CH-CH:SO,). 3.23 (1 H, m, W , ,=23Hz, CH-CH,-SO,).
4.06 ( I H. AB-X.
J = 4 . 6 Hz. J = 16 Hz. CH-CH,-SO,),
7.55-7.59 (3 H. m. arom. H). 7 M 7.98 (2 H. m, arom. H).
f9), m.p. 138--139°C (ethyl acetatejdiisopropyl ether): [XI"= +41" ( I 'Y,
in CHC1,); 1R (KBr): 1715 (6-ring ketone), 1140 and 1300 c m - ' (SO,); CD
(dioxane):
1.64; 'H-NMR (CDCI,): 6= 1.12 (3H. t. J = 7 H z . C H I CH2). I.l2(9H,s,(CH,),C), 2.R9 (1 H, AB-X, J = 2 . 8 Hz, J = 14 Hz, C H z S 0 2 ) .
3.10(1 H.m, Wl,=24H2.CH--CH,--S0,).3.48(1
H.t,J=XHz.CH-OC(CH,),), 3.96 ( I H, AB-X, J z 5 . 8 Hz. J = 1 4 Hz. CHI-SO,), 7.48-7.62 ( 3
H. m, arom. H). 7.82-7.97 (2 H. m, arom. H).
181
171
91e = C'1I3, IZt = C2T15, t R u = C[C1I3l3. PI1 = C 6 f 1 5
Reaction of the (+)-enedione ( I ) with paraformaldehyde
and benzenesulfinic acid in a mixture of nitrilotriethanol
(triethan~lamine)[~]
and acetic acid[61at 50°C affords the sulfone (2) in 85 % yield (Table 1). Other bifunctional bases
such as N,N,N',N'-tetramethylethylenediaminecan be used ;
essential, however, is that base and acetic acid are used in a
volume ratio of about 3 : 1. Presence of a larger amount of
acetic acid accelerates the reaction, but the regioselectivity
is thereby reduced, and considerable amounts of doubly
alkylated products of varying structure are formed.
In acid solution (ethanol with 1 % aqueous 1 N hydrochloric
acid) with 6% palladium on charcoal (10%) as catalyst.
the sulfone (2) is hydrogenated to the trans-fused sulfone
(3) (Table 1). The yield of crystalline product is 75 %. Some
[*] Dr. G. Sauer, Dr. U. Eder, Dr. G. Haffer, Dr. G. Neef, and Prof. Dr
R. Wiechert
Schering AG. Berlin/Bergkamen
1 Berlin 65, Miillerstrasse 170-178
A n q r w . Chum. infernal. Edir.
(Germany)
/ Vol. 14 (1975) i No. 6
In non-polar solvents (pentane/benzene) (3) reacts with
the anion prepared from ethyl 7,7-ethylenedioxy-3-oxooctanoate (4)18' and sodium hydride to give high yields of
the ester ( 5 ) . This crude product is then cyclized. hydrolyzed,
and decarboxylated. The tricyclic compound (7) (cf. H u j m
et u ~ . [ ~ I ) was isolated as an oil and for this reason a more
detailed characterization was not carried out. Subsequent
hydrogenation, ketal cleavage, and cyclization afford 18methyl-19-norandrostenedione(7) in an overall yield of 35':,,
(from ( / I ) .
D-Norgestrel (8)I2l can be obtained from (7) by ethynylation; its structure, like that of (7), is confirmed by comparison
with authentic material.
Received: February 5, 1975 [ Z 195 IE]
German version: Angew. Chem. 87, 413 (1975)
CAS Registry numbers:
( 1 ), 33878-95-4; ( 2 ) , 54832-84-7: (3). 54832-85-8; ( 4 ) , 27428-41-7: ( 5 ) .
54851-83-1; (6). 24894-31-3; ( 7 ) . 21800-83-9: (8). 797-63-7: (9). 54832-86-9
[I]
[2]
[3]
[4]
[S]
[6]
[7]
[X]
Total Synthesis of Optically Active Steroids, Part 12.-Part 1 1 : U . Edrr,
G . Sauer, J . Rupprrr, G. Hufler. and R . Wiecherr, Chem. Ber., in press.
H . Smith. G. A. Hughes. G . H . Douglas, G. R . Wendr, G . C. Buzby.
j u i i . , R . A. E d g r m . J . Fisher, 7: Foell. B. Gadsby, D. H u r r l q , D. Hrrbsr,
A . B. A. Jansen. K . Ledig. B. J . McLoughlin. J . McMenamin. T W
Pattison. P. C. Phillips. R . Rees. J . Siddall, J . Siuda, L . L . Smirh. J .
T o k o l i m and D . H . P. Wcirson, J. Chem. SOC.1964. 4472.
C . Ruftr, H . Kosmol, E . Schrlidur, K . Kieslich, and H . Gihian. Liebigs
Ann. Chem. 702, 141 (1967).
a ) U . Edrr. G. Sauer, and R . Wtechrrr, Angew. Chem. 83, 492 (1971);
Angew. Chem. internat. Edit. 10, 496 (1971); b) Z . G. Hajos and D.
R . Parrish, J. Org. Chem. 39, 1615 (1974).
D. H . Kirk and !I Perrow. J. Chem. Soc. 1962, 1091.
H. Hellmann and K. Miiller. Chem. Ber. 98, 638 (1965).
Preparation of / Y ) : G. Sauer er a / . , to be published.
2. G. Hujos and D. R. Purrish, J. Org. Chem. 38, 3239. 3244 (1973).
417
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